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Chem. Rev.
2004, 104, 3893−3946 3893
Recent Advances in the Liquid-Phase Syntheses of Inorganic Nanoparticles

Brian L. Cushing,* Vladimir L. Kolesnichenko, and Charles J. O’Connor*
Advanced Materials Research Institute, University of New Orleans, New Orleans, Louisiana 70148-2820
Received October 28, 2003
Contents 3.3.1. Chelate Selection and Complex 3919

Formation
1. Introduction 3893 3.3.2. Limitations of the Pechini Method 3920
2. Nanoparticle Synthesis by Coprecipitation 3894 3.3.3. Oxide Syntheses with the Pechini Method 3920
2.1. Theory and Thermodynamics of 3895 4. Microemulsions 3921
Coprecipitation
4.1. Fundamentals of Microemulsions 3921
2.1.1. Nucleation 3895
4.1.1. Common Surfactants 3922
2.1.2. Growth 3896
4.1.2. Reverse Micelle Formation and Phase 3922
2.1.3. Ostwald Ripening 3896 Equilibria
2.1.4. Growth Termination and Nanoparticle 3896 4.1.3. Reaction Dynamics in Reverse Micelles 3923
Stabilization
4.1.4. Factors Influencing Surfactant Selection 3923
2.2. Coprecipitation Synthetic Methods 3897
4.2. Microemulsion Synthetic Methods 3923
2.2.1. Synthesis of Metals from Aqueous 3897
Solutions 4.2.1. Synthesis of Metals by Reduction 3923
2.2.2. Precipitation of Metals by Reduction from 3899 4.2.2. Synthesis of Alloys by Reduction 3925
Nonaqueous Solutions 4.2.3. Synthesis of Metal Oxides 3925
2.2.3. Precipitation of Metals by Electrochemical 3902 4.2.4. Syntheses of Other Inorganics 3926
Reduction 4.2.5. Synthesis of Core−Shell and 3928
2.2.4. Precipitation of Metals by 3902 Onion-Structured Nanoparticles
Radiation-Assisted Reduction 4.2.6. Microemulsion Syntheses in Supercritical 3929
2.2.5. Precipitation of Metals by Decomposition 3903 CO2
of Metallorganic Precursors 4.2.7. The Germ-Growth Method 3929
2.2.6. Precipitation of Oxides from Aqueous 3905 5. Hydrothermal/Solvothermal Processing of 3929
Solutions Nanoparticles and Nanocomposites
2.2.7. Precipitation of Oxides from Nonaqueous 3906 5.1. Principles of Hydrothermal and Solvothermal 3929
Solutions Processing
2.2.8. Coprecipitation of Metal Chalconides by 3907 5.2. Hydrothermal and Solvothermal Methods 3930
Reactions of Molecular Precursors 5.2.1. Solvothermal Processing of 3930
2.2.9. Microwave-Assisted Coprecipitation 3909 Nanocrystalline Oxides
2.2.10. Sonication-Assisted Coprecipitation 3910 5.2.2. Synthesis of Nanocrystalline Nitrides and 3930
3. Sol-Gel Processing 3911 Chalcogenides
3.1. Fundamentals of the Sol-Gel Process 3911 5.2.3. New Developments in Hydrothermal/ 3931
3.1.1. Precursors and the Partial-Charge Model 3911 Solvothermal Methods
3.1.2. Sol-Gel Chemistry of Metal Alkoxides 3912 6. Templated Syntheses 3932
3.1.3. Sol-Gel Chemistry of Aqueous Metal 3913 7. Biomimetic Syntheses 3934
Cations 8. Surface-Derivatized Nanoparticles 3937
3.1.4. Condensation Reactions of Hydrolyzed 3914 9. Acknowledgments 3939
Metals 10. References 3940
3.1.5. Xerogel and Aerogel Formation 3914
3.1.6. Gel Sintering 3914 1. Introduction
3.1.7. Controlling Particle Size and Morphology 3915
3.2. Sol-Gel Synthetic Methods 3915 The development of novel materials is a funda-
3.2.1. Sol-Gel Syntheses of Oxides 3915 mental focal point of chemical research; and this
3.2.2. Sol-Gel Syntheses of Other Inorganics 3916 interest is mandated by advancements in all areas
of industry and technology. A good example of the
3.2.3. Sol-Gel Processing of Nanocomposites 3916
synergism between scientific discovery and techno-
3.3. The Pechini Method 3919 logical development is the electronics industry, where
discoveries of new semiconducting materials resulted
* To whom correspondence should be addressed. B.L.C.: (504) 280- in the evolution from vacuum tubes to diodes and
1385 (phone); (504) 280-3185 (fax); [email protected] (e-mail).
C.J.O.: (504)280-6846(phone);(504)280-3185(fax);[email protected] transistors, and eventually to miniature chips. The
(e-mail). progression of this technology led to the development
10.1021/cr030027b CCC: $48.50 © 2004 American Chemical Society
Published on Web 08/20/2004
3894 Chemical Reviews, 2004, Vol. 104, No. 9 Cushing et al.
Brian L. Cushing received his B.S. in Chemistry from the University of Dr. Charles J. O’Connor is Distinguished Professor of Chemistry and the
West Florida (1994) and his Ph.D. in Inorganic Chemistry from the Director of the Advanced Materials Research Institute (AMRI) at the
University of New Orleans (1999). He previously held a postdoctoral University of New Orleans. He has been at the University of New Orleans
research position at the University of Texas at Austin and is currently a for 25 years following his Ph.D. in Inorganic Chemistry from the University
Research Specialist at the Advanced Materials Research Institute at the of Illinois in Chicago in 1976 and three years as an Instructor at the
University of New Orleans. His current research interests include interfacing University of Virginia. Dr. O’Connor has over 300 publications in refereed
magnetic nanoparticles with biologically active compounds. scientific journals and has active research programs in solid state
nanomaterials research, especially on magnetic nanomaterials.
at the Bottom” speech,1 if only for its historical

relevance. Several articles outlining the current
applications and speculating on the future impact of
nanotechnology are available.2-4 Discipline-specific
papers hypothesizing on the impact of nanotechnol-
ogy in fields ranging from automotive technology5 to
medicine6-8 to earth science9 to chemistry10-12 are
also common.
While articles offering highly detailed reviews of
specific synthesis techniques for preparing nanopar-
ticles are commonplace, they are usually quite nar-
row in scope. For researchers entering the field, or
for those already in the field but working with a very
Vladimir L. Kolesnichenko, born in Kiev (Kyiv), Ukraine, received his M.S. limited synthetic repertoire, developing a broad-
in Chemistry from Kiev State University and his Ph.D. in Inorganic based, working knowledge of the various state-of-the-
Chemistry from the Palladin Institute of General and Inorganic Chemistry art synthetic techniques constitutes an enormous
(Kiev, Ukraine). His research interests include transition metal cluster undertaking, complicated in part by the sheer volume
coordination chemistry and synthesis of functional nanocrystalline materials. of available literature and the rapid pace of develop-
He currently develops synthetic methodologies for magnetic nanoparticles ment. This survey is intended to address this gap by
and investigates their surface reactivities for different applications.
providing a relatively broad overview of synthetic
techniques.
of smaller and smaller electronic elements, resulting This survey focuses primarily on advances devel-
in chips with a higher density of circuitry and greater oped within the past five years in order to offer a
computing power. The size of these electronic circuits critical review of state-of-the-art methodology. The
and magnetic memory elements is approaching na- various preparative techniques will be discussed first
nometer dimensions, and as this realm is entered, followed by a discussion of novel properties and
scientists have found that properties of materials applications that are likely to fuel research into the
with nanometer dimensions can differ from those of coming decades. This review will discuss nanoparticle
the bulk material. syntheses by coprecipitation, sol-gel processing, micro-
Through the National Nanotechnology Initiative emulsions, hydrothermal/solvothermal methods, tem-
(http://www.nano.gov), a national strategic research plated syntheses, and biomimetic syntheses. Where
plan focuses on the development of new materials at appropriate, considerable background material is
the atomic, molecular, or macromolecular levels, on presented to provide the uninitiated reader with
the length scale of approximately 1-100 nm. These sufficient understanding of the underlying principles
research efforts are expected to provide a fundamen- and theories of the synthetic methodologies.
tal understanding of phenomena and materials at the
nanoscale and to create and use structures, devices,
and systems that have novel properties and functions 2. Nanoparticle Synthesis by Coprecipitation
due to their small and/or intermediate size, typically Many of the earliest syntheses of nanoparticles
under 100 nm. were achieved by the coprecipitation of sparingly
Any researcher entering the nanoscience arena soluble products from aqueous solutions followed by
should read Feynman’s 1959 “There’s Plenty of Room thermal decomposition of those products to oxides.
Liquid-Phase Syntheses of Inorganic Nanoparticles Chemical Reviews, 2004, Vol. 104, No. 9 3895
Coprecipitation reactions involve the simultaneous can be induced by altering other parameters related
occurrence of nucleation, growth, coarsening, and/or to solubility, most notably temperature and concen-
agglomeration processes. Due to the difficulties in tration.
isolating each process for independent study, the When the product contains only one or two ele-
fundamental mechanisms of coprecipitation are still ments (e.g. a metal, binary oxide, etc.), precipitation
not thoroughly understood. The following discussion reactions are relatively straightforward. In more
provides an overview of current coprecipitation theory. complicated ternary and quarternary systems, the
process becomes more complex, as multiple species
2.1. Theory and Thermodynamics of must be precipitated simultaneously (hence, the term
Coprecipitation coprecipitation).
Merely inducing precipitation of a compound, how-
The theory of coprecipitation is not a trivial subject. ever, does not guarantee that the product will be
Numerous books13,14 and review articles15-19 cover the nanoparticulate and/or monodispersed. The processes
topic much more thoroughly than the discussion of nucleation and growth govern the particle size and
presented here. As a brief overview, coprecipitation morphology of products in precipitation reactions.
reactions tend to exhibit the following characteris- When precipitation begins, numerous small crystal-
tics: (i) The products of precipitation reactions are lites initially form (nucleation), but they tend to
generally sparingly soluble species formed under quickly aggregate together to form larger, more
conditions of high supersaturation. (ii) Such condi- thermodynamically stable particles (growth).
tions dictate that nucleation will be a key step of the
precipitation process and that a large number of 2.1.1. Nucleation
small particles will be formed. (iii) Secondary pro-
cesses, such as Ostwald ripening and aggregation, The key to any precipitation process is the degree
will dramatically affect the size, morphology, and of supersaturation, S, given by
properties of the products. (iv) The supersaturation aAaB
conditions necessary to induce precipitation are usu- S) (3)
ally the result of a chemical reaction. As such, any Ksp
reaction conditions influencing the mixing process,
such as rate of reactant addition and stirring rate, where aA and aB are the activities of solutes A and B
must be considered relevant to product size, mor- and Ksp is the solubility product constant, or alter-
phology, and particle size distribution. natively by S ) C/Ceq, where C and Ceq are the solute
Although precipitation can be induced in any concentrations at saturation and at equilibrium,
number of ways, chemical reactions are by far the respectively. Indeed, the literature frequently refers
most common method for the synthesis of nanopar- to the difference in C and Ceq, ∆C ) C - Ceq, as the
ticles. Generally, chemical reactions are chosen that “driving force” for precipitation.17
result in products with low solubilities, such that the As nucleation begins in a supersaturated solution,
solution quickly reaches a supersaturated condition. there exists an equilibrium critical radius, R*:
The chemical reactions used to induce coprecipi-
R
tation can take numerous forms. For illustrative R* ) (4)
purposes, we consider the case of a simple addition ∆C
reaction for the formation of an electrolyte, AxBy: The term R is given by
xAy+(aq) + yBx-(aq) / AxBy(s) (1)

R) ( 2σSL
kT ln S )
νC∞ (5)
The equilibrium relationship between the product
where σSL is the surface tension at the solid-liquid
and its reactants is expressed as the solubility
interface, ν is the atomic volume of solute, k is the
product constant, Ksp:
Boltzmann constant, T is temperature, and S is the
supersaturation as defined in eq 3. Nucleated par-
Ksp ) (aA)x(aB)y (2) ticles with R > R* will continue to grow, while those
with R < R* will dissolve. The activation energy of
where aA and aB are the activities of cation A and the cluster formation is given by19
anion B in aqueous solution. Ksp values (and therefore
solubilities) tend to be very low for many hydroxides, 4πσSLR*2 16πσSL3ν2
carbonates, oxalates, and chalcogenides in aqueous ∆G* ) ) 2 2 2 (6)
3 3k T ln S
solutions, and the precipitation reactions for several
of these species are specifically discussed in later Thus, for stationary conditions, the homogeneous
sections. Tables of Ksp values are widely available in nucleation rate, RN, is then
reference volumes and in textbooks. Solubility data
for compounds in solvents other than water are
substantially more sparse.
Beyond simple addition/exchange reactions, pre-
RN ) ( )
dN 1
dt V
) A exp
-(∆G*)
kT [ ] (7)
cipitation can be induced by numerous other meth- where N is the number of nuclei formed per unit time
ods, such as chemical reduction, photoreduction, per unit volume, V, and A is a pre-exponential factor
oxidation, and hydrolysis. Alternatively, precipitation typically ranging from 1025 to 1056 s-1 m-3.
Combining eqs 6 and 7 exception to various approximations and assumptions
( )
of LSW theory, most notably the theory’s failure to
-16πσSL3ν2 adequately account for cooperative effects between
RN ) A exp (8) nuclei and the theory’s assumption of a steady change
3k3T3 ln2 S in solute concentration with time.30 Those authors’
revealing that RN is an exponential function of S. It criticisms are justified, insofar as the assumptions
follows that RN remains negligible until a certain in LSW theory have lead to frequent disagreements
critical supersaturation, S*, is reached. between theoretical and experimental results. None-
theless, most competing or expanded theories of
2.1.2. Growth Ostwald ripening are still based on the original LSW
model, and for the purposes of this discussion, the
The growth process of the precipitated particles is theory is adequate to make several important points
every bit as complicated as nucleation. The process concerning the precipitation of nanoparticles.
can be either diffusion-limited or reaction-limited. The mathematics involved in LSW theory are not
Experimental evidence suggests, however, that the rudimentary, and the reader is referred to the
overwhelming majority of precipitation reactions are literature for details of the derivations. The principles
diffusion-limited. As such, concentration gradients of LSW theory, however, are summarized as follows:
and temperature become the predominant factors (i) For a diffusion-controlled process, the average
determining growth rate as new material is supplied radius of the precipitate particles, rj, as a function of
to the particle surface via long-distance mass trans- time, t, is27
fer. The balance of that material, as a monomer,
crossing the surface of a spherical crystallite is given 3
by rj(t) ) xKt (12)
dr 1 1 where K is the coarsening rate, given by 4RD/9, and

dt δ r (
) DΩ + (Cb - Ci) ) (9) D is the diffusion current of solute across the grain
boundary. Particle size is thus proportional to the
where r is the crystal radius, t is time, D is the cube-root of time.
diffusivity of the monomer, Ω is the molar volume, (ii) During diffusion-controlled ripening, the num-
and δi is the thickness of the layer over which the ber density N of nucleated particles decays as27
concentration changes from Cb, the bulk solute
concentration, to Ci, the solute concentration in the 0.22Q0 0.22
vicinity of the crystal surface.20,21 N(t) ) ) (13)
h (t)
R 3 2DRt
The relationship between monomer concentration
and crystal size is established by the Gibbs-Thomson where Q0 is the total initial supersaturation. The
equation:22 number of solute particles therefore decreases as t-1
( )
1 + 2Ωγ during ripening.
Ce(r) = C∞ (10) (iii) The size distribution of particles is given by
RGTR
where γ is the interfacial tension, RG is the universal

gas constant, T is the temperature, and C∞ is a
f(R,t) ) [ ]
N(t)
p (F(t))
h (t) 0
R
(14)
constant.
Finally, the relationship between the rate of growth, where F(t) ≡ R/R h (t) and p0(F) is a time-independent
G, and the supersaturation ratio, S, can be expressed function of the absolute dimension of the grains, F.
as a power-law equation:17 Equations 1-14 provide several useful insights into
the precipitation of nanoparticles. To produce nano-
dL particles, the nucleation process must be relatively
G) ) kGSg (11) fast while the growth process remains relatively slow.
dt
The formation of particles with a narrow size distri-
where kG is the growth rate constant and g is the bution further requires that the nuclei of all species
growth order. present form simultaneously and without subsequent
nucleation of smaller particles. Park et al. have
2.1.3. Ostwald Ripening recently published a study specifically addressing the
Ostwald ripening (also referred to as coarsening) coprecipitation of nanoparticles.31
is the phenomenon by which smaller particles are
essentially consumed by larger particles during the 2.1.4. Growth Termination and Nanoparticle Stabilization.
growth process and is itself a topic of considerable Due to the thermodynamics discussed in section 2.1
investigation and postulation.23-29 This behavior can, that favor the maximization of the surface/volume
to some extent, be predicted by eq 10, which estab- ratio, the agglomeration of small particles precipi-
lishes that the solubility of particles increases with tated from solutions is practically inevitable in the
decreasing particle size. A detailed mathematical absence of a stabilizer. For the purposes of this
description of Ostwald ripening was first developed discussion, we are primarily interested in nanopar-
by Lifshitz and Slyozov and also independently by ticles that can be prepared as stable colloids or
Wagner; their combined models are today referred isolated as powdered products. It should be pointed
to as LSW theory.20,21 Some authors have taken out, however, that agglomeration can occur at any
stage during synthesis; aggregation and agglomera- solution to the metallic state in the presence of
tion of particles during precipitation is itself a subject gaseous H2 with proper adjustment of pH. These
of investigation.32 reactions are reviewed extensively elsewhere.37,38
There are generally two approaches to nanoparticle The electrochemical half-reaction and E° for boro-
stabilization: (a) steric repulsion between particles hydride ion are given by
caused by surfactants, polymers, or other organic
species bound to the nanoparticles’ surfaces (generi- B(OH)3 + 7H+ + 8e- / BH4- + 3H2O
cally referred to as capping ligands) and (b) electro- E° ) -0.481 V (18)
static (van der Waals) repulsions resulting from the
chemisorption of charged species (usually, though not Borohydride ions, however, should be employed
necessarily, H+ or OH-) at the surfaces. STM and judiciously, as they are known to reduce some cations
TEM studies of Pd clusters capped with tetrabutyl- to metal borides, particularly in aqueous systems.39-42
ammonium bromide have shown that, at least in The use of borohydride specifically for the precipita-
some cases, capping ligands indeed form monolayers tion of metal nanoparticles has recently been re-
at the particles’ surfaces.33 viewed.43
The reader will find that steric stabilization is Hydrazine hydrate is freely soluble in water, but
somewhat more common, probably due to issues since N2H4 is basic, the chemically active free-ion is
concerning the chemical stability of the nanoparticles normally represented as N2H5+:
at very high or very low pH values, and the literature
contains a dizzying variety of stabilizing agents used N2H4‚H2O / N2H5+ + OH- (19)
in nanoparticle syntheses. Consequently, our discus-
sions of synthetic methods in section 2.2 include or, in the case of hydrazine dihydrochloride,
detailed accounts of the methods of nanoparticle
stabilization where appropriate. A more thorough N2H4‚2HCl / N2H5+ + H+ + 2Cl- (20)
account of colloid stabilization is presented in section
8. The standard reduction potential for the hydrazinium
ion, N2H5+, is
2.2. Coprecipitation Synthetic Methods
N2 + 5H+ + 4e- / N2H5+ E° ) -0.23 V (21)
2.2.1. Synthesis of Metals from Aqueous Solutions
In theory, the reduction of any metal with an E°
Due to their widespread application as catalysts,34
more positive than -0.481 V or -0.23 V, respectively,
metals precipitated from aqueous solutions continue
should be possible at room temperature, given a
to be a thoroughly investigated subject (the role of
sufficient excess of reducing agent and proper control
nanomaterials in catalysis is specifically discussed
of pH. With respect to precipitating metals from
elsewhere35,36). The precipitation of metals from
solution, this would obviously include many first-row
aqueous or nonaqueous solutions typically requires
transition metal ions, such as Fe2+, Fe3+, Co2+, Ni2+,
the chemical reduction of a metal cation. Reducing
and Cu2+, but also many second- and third-row
agents take many forms, the most common of which
transition metals, as well as most post-transition
are gaseous H2, solvated ABH4 (A ) alkali metal),
elements and a few nonmetals. A brief survey of
hydrazine hydrate (N2H4‚H2O), and hydrazine dihy-
nanoparticles prepared by reduction from aqueous
drochloride (N2H4‚2HCl).
solutions is provided in Table 1.
For a typical reduction reaction of a transition
As a practical matter, the reduction of some metal
metal cation,
ions with E° > -0.481 V is either not feasible or
exceedingly difficult, but this is usually due to the
Mn+ + ne- f M0 (15) instability of the cation in aqueous environments.
there must, of course, be a corresponding oxidation However, in some instances, transition metal cations,
process of some species X, such that such as Rh3+, form stable complexes with hydrazine,
thereby greatly limiting the available options for
Xm - ne- f Xm-n (16) carrying out a reduction.50 We should further em-
phasize that consideration of pH and relative redox
In order for the electron transfer to occur, the free potentials is, at best, only a guide for predicting
energy change, ∆G, must be favorable. As a matter which metals may or may not be prepared by this
of convention, the favorability of oxidation-reduction method.
processes is reflected in the standard electrode The reduction of gold cations to gold metal is easily
potential, E°, of the corresponding electrochemical the single most thoroughly studied metal precipita-
half-reaction. tion reaction. Gold cations, usually in the form of
Since the E° values of all reactions are stated AuCl4-, are easily reduced by gaseous H2
relative to that of H2, the half-reaction and E° for H2
are, by definition, 2AuCl4-(aq) + 3H2(g) /
2Au(s) + 6H+(aq) + 8Cl-(aq) (22)
2H+ + 2e- / H2 E° ) 0.00 V (17)
although AuCl4- is so strongly oxidizing (E° ) +1.002
at standard temperature and pressure (STP). Nu- V) that weaker reducing agents such as carboxylates
merous metal ions can be reduced from aqueous or alcohols are usually sufficient. Tan et al. have
Table 1. Representative Sampling of Nanoparticulate Metals Precipitated from Aqueous Solutions

metal starting material reducing agent stabilizera notes avg diam (nm) ref
Co Co(OAc)2 N2H4‚H2O none ∼20 44
Ni NiCl2 N2H4‚H2O + NaOH CTAB reaction performed at 60 °C 10-36 45
Ni Ni(OAc)2 N2H4‚H2O + NaOH none (10-20) × (200-300) rods 44
Cu CuSO4 N2H4‚H2O SDS ∼35 44
Ag AgNO3 ascorbic acid Daxad 19 15-26 46
Ag AgNO3 NaBH4 TADDD 3-5 47
Pt H2PtCl6 potassium bitartrate TDPC 60 °C <1.5 48
Au HAuCl4 trisodium citrate S3MP simultaneous addition of not stated 49
reductant and stabilizer
a
CTAB ) cetyltrimethylammonium bromide (see section 4); SDS ) sodium dodecyl sulfate; Daxad 19 ) sodium salt of high-
molecular-weight naphthalene sulfonate formaldehyde condensate; TADDD ) bis(11-trimethylammoniumdecanoylaminoethyl)-
disulfide dibromide; TDPC ) 3,3′-thiodipropionic acid; S3MP ) sodium 3-mercaptopropionate
recently reported the synthesis of Au, Pt, Pd, and Ag

nanoparticles by reduction with potassium bitartrate;
all of the products formed stable colloids with the
addition of a suitable stabilizing agent.48
In many cases, an organic capping agent that is
normally used to prevent agglomeration can also
serve as the reducing agent. This is the case in the
well-known Turkevich process for the synthesis of
gold colloids.51 In their 1951 paper, Turkevich et al.
described a synthetic method for colloidal gold pre-
pared by boiling a mixture of dilute HAuCl4 and
sodium citrate.52 This method is still widely used
today and is the basis of a recently published labora-
tory experiment on Au monolayer self-assembly
designed for undergraduate students.53
Normally, if thiol stabilizing agents are used, the
reduction of AuCl4- in aqueous solution must be
performed with borohydride or similar reducing
agents because the complexes formed between AuCl4-
and thiols are too stable to be reduced by citrate or
other weak reducing agents. Yonezawa et al., how-
ever, have demonstrated that reduction of AuCl4-
with citrate in the presence of a thiol is possible, if
the thiol and citrate are added to the gold solution
simultaneously.49 Gold colloids with 2-10 nm dimen-
sions are achievable with this method, and narrow
size distributions are possible at high [thiol]/[Au]
ratios, as evidenced in Figure 1.
The reduction of metals with highly negative
reduction potentials requires reducing agents with Figure 1. (A) Size distribution of Au nanoparticles capped
considerably stronger reducing ability than that with mercaptopropionate (MPA) at various [MPA]/[Au]
ratios and (B) the relationship between average particle
afforded by most amines, hydroxycarboxylic acids, or diameter and [MPA]/[Au], where the bars represent the
alcohols. The reduction of ions such as Ni2+ (E° ) standard deviations of the particle sizes. (Adapted with
-0.257 V), Co2+ (E° ) -0.28 V), and Fe2+ (E° ) permission from ref 49. Copyright 1997 Chemical Society
-0.447 V) is therefore typically performed with of Japan.)
borohydride salts (eq 18).
Silver can similarly be reduced with borohydride Fe and Cu are not normally miscible in the equilib-
from aqueous Ag+ in a solution containing bis(11- rium state. The formation of the alloy may, however,
trimethylammoniumdecanoylaminoethyl)disulfide di- be facilitated by the incorporation of boron due to
bromide (TADDD), producing monodisperse nano- formation of Fe2B, as is known to be the case with
particles as small as 3.3 nm.47 In this case, the excess Fe1-xCox alloys prepared by reduction with KBH4 in
borohydride reduces the disulfide to a thiol that aqueous solution.55
serves as a capping ligand. The particles are easily Harris et al. heat-treated mixtures of CuO + CoO
redispersed into stable colloids in slightly acidified precipitated from aqueous solution to produce Cu80Co20
water. alloys. The samples were heated under flowing H2
While nanoparticulate Fe and Cu are easily re- at temperatures ranging from 200 to 650 °C, result-
duced individually with borohydride, Chow et al. ing in alloy particles with 10-20 nm particle sizes
prepared fcc Fe1-xCux (0.6 e x e 1) alloys with 30- with a broad size distribution. Heat treatment at 650
45 nm particle sizes by reduction of aqueous FeCl2 °C or above resulted in decomposition to the compos-
+ CuCl2 mixtures.54 The result is noteworthy in that ite metals.56
2.2.2. Precipitation of Metals by Reduction from

Nonaqueous Solutions
The stabilization of Au nanoparticles against ag-
glomeration in aqueous solutions by capping ligands
such as citrate is a well-documented process. Brust
et al., however, reported the synthesis of alkanethiol-
stabilized colloidal Au nanoparticles that are stable
almost indefinitely in nonpolar solvents.57,58 More-
over, the particles exhibited the rather unusual
ability to be fully redispersed into colloids after being
isolated as dry powders.
The synthesis method of Brust et al. is noteworthy
in that a two-phase reaction mixture was used to
carry out the gold reduction, similar to the technique
of Faraday. Starting from an aqueous solution of
AuCl4-, the tetrachloroaurate ions were transferred
to an organic phase by vigorously mixing the aqueous
solution with a solution of tetraoctylammonium
bromide (TOAB) dissolved in toluene (TOAB is a well-
known phase-transfer catalyst). After adding do-
decanethiol to the organic phase, an aqueous solution
of NaBH4 was subsequently introduced into the
mixture with rapid stirring. Colloidal gold (1-3 nm)
was formed in the organic phase and subsequently
isolated by vacuum evaporation or by precipitation
with methanol. The authors found that once the Figure 2. TEM image of Ag nanoparticles prepared in
products were isolated as dry powders, stable col- DMF (A) at room temperature and (B) under reflux
loidal suspensions could be reconstituted in any conditions. Both samples are capped with 3-(aminopropyl)-
trimethoxy silane that sometimes forms a thin silica shell,
number of nonpolar or weakly polar solvents, includ- as demonstrated by the inset in image B. (Reprinted with
ing toluene, pentane, and chloroform, but not alcohol permission from ref 77. Copyright 1999 American Chemical
or water. The authors further determined by IR and Society.)
X-ray photoelectron spectroscopy (XPS) that the
powder, even after washing, contains thiolate and hibited a narrow size distribution. It is not clear,
that the gold is present as Au0, which suggests that however, as to whether the particle size can be
the thiol binds as RSH as opposed to RS-. controlled, as the [PVP]/[Au] ratio did not appear to
The results of Brust et al. triggered a flurry of influence the particle size.
research into the thiol-based stabilization of colloidal In a similar reaction, silver nanoparticles have
nanoparticles. Among the more significant results been prepared by reduction of AgNO3 or AgClO4 by
from these investigations, numerous new thiol-, N,N-dimethylformamide (DMF), where 3-(amino-
amine-, silane-, phosphine-, and disulfide-based cap- propyl)trimethoxysilane served as the stabilizing
ping ligands have been identified,59-66 and several agent.77 The reaction probably involves the oxidation
techniques have emerged for the exchange of capping of DMF to a carboxylic acid:
ligands.67-70 This effectively allows the functionality
and chemical properties of the ligand shells to be HCONMe2 + 2Ag+ + H2O /
tuned.71,72 Stoeva et al. have modified Brust’s method
to allow the gram-scale synthesis of thiol-stabilized 2Ag0 + Me2NCOOH + 2H+ (23)
colloidal Au particles.73
Au nanoparticles reduced with borohydride and In this case, the size of the silver nanoparticles could
capped with mercaptosuccinic acid (MSA), HOOCCH2- be varied from 6 to 20 nm by adjustment of the
CH(SH)COOH, as reported by Chen et al., exhibit temperature as well as the [DMF]/[Ag] molar ratio.
the additional benefit of being dispersable in water The silane-based stabilizing agent is susceptible to
if the capped nanoparticles are precipitated as a hydrolysis and condensation, particularly at elevated
sodium salt.74 The sizes of the nanoparticles were temperatures and under acidic conditions, and some
controllable within the 1-3 nm range by variation of the Ag particles exhibited thin SiO2 coatings,
of the [MSA]/[Au] ratio. The method was later although this apparently did not lead to agglomera-
adapted to the synthesis of 1.4-5.7 nm metallic Ag.75 tion (Figure 2).
Han et al. developed a method for reducing gold in As previously mentioned, the ability of alcohols
nonaqueous solutions in which the solvent, in this such as ethanol to act as reducing agents for strongly
case formamide (HCONH2), also served as the reduc- oxidizing cations is well-known. Particle aggregation
ing agent.76 The reaction mechanism appears to in such reactions can, however, be problematic, even
involve a two-step process of ligand-exchange fol- in the presence of stabilizing agents. Reactions car-
lowed by reduction, and the reaction will not proceed ried out in polyalcohols such as ethylene glycol or 1,2-
in the presence of oxygen. The 30 nm particles were propanediol tend to yield more monodispersed prod-
stabilized by poly(vinylpyrrolidone) (PVP) and ex- ucts. Such polyols effectively act as bidentate chelating
agents for the solvated metal cations and, in some ing such reagents must therefore be carried out at
cases, also serve as reducing and/or stabilizing agents low temperatures and under inert atmosphere.
once the metal nanoparticles are precipitated. Viau Dye et al. reported as early as 1991 the synthesis
et al., for example, prepared monodispersed 4 nm Ru of numerous metal nanoparticles from alkalide and
particles by reduction of RuCl3 in various polyols; the electride solutions, including Au, Pt, Cu, Te, Ni, Fe,
polyols served as the reducing agents, and the Zn, Ga, Si, Mo, W, In, Sn, Sb, and Ti, as well as Au-
products were stabilized with dodecanethiol.78 A Cu, Au-Zn, Cu-Te, and Zn-Te alloys.82,83 The
similar technique has been used to successfully reactions were typically carried out at -50 °C and
reduce Ni2+ to Ni0 with hydrazine hydrate (eq 19) in resulted in 3-15 nm products. With the exception of
ethylene glycol solution, resulting in monodispersed Au, Pt, Cu, and Te, however, all of the products
9 nm particles.79 By eq 21, hydrazinium ions do not exhibited strong tendencies to oxidize on washing
normally exhibit sufficient reducing ability to reduce with methanol, even under inert atmosphere. More
Ni2+ to Ni0. In this case, excess NaOH was added to recently, Kirkpatrick et al. used lithium metal dis-
the reaction mixture, such that solved in naphthalene for the synthesis of nanopar-
ticulate mixed-phase Mg-Co composites.84
2Ni2+ + N2H5+ + 5OH- / 2Ni0 + N2 + 5H2O The trialkylborohydride reducing agents, ABEt3H
(24) (A ) Li, Na, or K), and solvated magnesium, Mg*,
also act as powerful reducing agents. Bönnemann et
The elevated pH, along with the 60 °C reaction al. have demonstrated that these reagents reduce an
temperature, greatly enhanced the reducing ability impressive array of electropositive metals from their
of N2H5+. This underscores the point that standard various salts in nonpolar organic solvents such as
reduction potentials, which are, by definition, taken toluene, dioctyl ether, or THF:85-87
at room temperature and in aqueous solutions,
should only be used as guides.
Similarly, Hou and Gao recently reported the xMXy + yABEt3H f xM + yAX + yBEt3 + xy/2H2
synthesis of monodispersed 3.7 nm Ni particles by (28)
reducing a Ni(acac)2 (acac ) acetylacetonate) solution
with NaBH4 at 100 °C where hexadecylamine served where My+ ) Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+,
as both stabilizer and solvent.80 The particles could Zn2+, Ru3+, Rh3+, Pd2+, Ag+, Cd2+, In3+, Sn2+, Re3+,
be redispersed in nonpolar solvents and did not Os3+, Ir3+, Pt2+, or Au+; A ) Li or Na; and X
exhibit indications of oxidation upon air exposure. represents the counterion. Others later adapted the
In cases where the Mn+ + ne- / M0 reduction method to the reduction of Mo3+ and W4+.88 The
necessary to produce metallic nanoparticles exhibits reaction in eq 28 typically results in 1-5 nm metal
a substantially negative E°, the use of an aqueous colloids, though the products tend to exhibit poor
solvent is precluded because the reducing agents crystallinity due to the relatively low reaction tem-
capable of supplying electrons to the metal will peratures (T < 70 °C). Interestingly, the above
reduce water, given that reaction is sensitive to both the reducing agent and
the solvent: substituting LiBEt3H for NaBEt3H and
2H2O + 2e- / H2 + 2OH- E° ) -0.8277 V THF for toluene results in the formation of 1-5 nm
(25) colloidal metal carbides (M2C).88
Sun and Murray et al. developed an analogous,
In these cases, solvents that are more stable must convenient elevated-temperature method of synthe-
be employed. sizing nanocrystalline cobalt and nickel and their
Thermodynamically, the strongest reducing agent alloys with tight size distributions (σ ) 7-10%).89-91
possible in solution is the solvated electron (es-), Their method involved the reduction of metal salts,
followed closely by the alkali-metal anion (A-). Either typically chlorides or acetates, in the presence of two
species may be generated by the dissolution of an types of capping ligands: strongly bound (carboxylic
alkali metal in an aprotic solvent such as dimethyl acid) and weakly bound (trialkyl phosphine and
ether or tetrahydrofuran (THF) in the presence of an phosphine oxide). Injecting a solution of reducing
alkali-metal complexing agent such as 15-crown-5 agents, long-chain 1,2-diol or LiBEt3H, into a pre-
ether: heated solution of metal salts and capping agents in
a high-boiling solvent (dioctyl or diphenyl ether)
2A0 + (15-crown-5) / A+(15-crown-5)A- (26) resulted in fast nucleation followed by slower nano-
The active reducing agent produced by eq 26 is crystal growth. Changing the ratio of the two capping
commonly referred to as an alkalide. Given a suf- ligands, as well as their chain length, allowed tuning
ficient excess of complexing agent, of the nanocrystal sizes. The reaction products formed
stable dispersions in nonpolar solvents due to the
A0 + 2(15-crown-5) / A+(15-crown-5)2es- (27) presence of carboxylic (oleic) acid groups covalently
attached to the nanocrystal surfaces (Figure 3).
and such products are called electrides. The above According to a recent report by Bönnemann et al.,
equilibrium is forced to the right by the extremely the reduction of metal salts, as well as the stabiliza-
strong complex formed between the alkalis and tion of colloids, can be performed by organoaluminum
chelate ethers.81 Both electride and alkalide solu- compounds:92-96
tions, while powerful reducing agents, are not ther-
mally stable and decompose in air; reactions involv- MXn + nAlR3 f M + nR2AlX + nR2 (29)
Figure 3. (A) Low-magnification TEM image of 8 nm Co-Ni alloy nanoparticles. (B, inset) Electron diffraction pattern
from 8 nm Co-Ni nanoparticles confirming the predominantly fcc structure. (C) TEM image of an ensemble of 8 nm fcc
Co nanoparticles. (D, inset) HRTEM image highlighting the multitwinned internal structure of Co nanoparticles. (E) TEM
image of an ensemble of 6 nm Fe nanoparticles. (F, inset) TEM image at higher magnification, in which the surface oxide
layer is clearly visible. (G) Image of an ensemble of 6 nm fcc FePt nanoparticles. (H, inset) HRTEM image of FePt
nanocrystals after annealing and forming of the face-centered tetragonal (fct) phase. (Reprinted with permission from ref
91. Copyright 1999 Materials Research Society.)
Table 2. Survey of Nanoparticulate Metals and Alloys That Have Been Precipitated by Reduction from
Nonaqueous Solutions
compd starting material solventa reductantb stabilizerc conditions product sized (nm) ref
Fe Fe(OEt)2 THF NaBEt3H THF 16 h at 67 °C 10-100 85
Fe Fe(acac)3 THF Mg* THF ∼8e 87
Fe20Ni80 Fe(OAc)2 EG EG EG reflux (150-160 °C) 6 (A) 98
Ni(OAc)2
Co Co(OH)2 THF NaBEt3H THF 2 h at 23 °C 10-100 85
Co CoCl2 THF Mg* THF ∼12 87
Co20Ni80 Co(OAc)2 EG EG EG reflux (150-160 °C) 18-22 (A) 98
Ni(OAc)2
Ni Ni(acac)2 HDA NaBH4 HDA 160 °C 3.7 (C) 80
Ni NiCl2 THF Mg* THF ∼94e 87
Ni Ni(OAc)2 EG EG EG reflux (150-160 °C) 25 (A) 98
Ru RuCl3 1,2-PD 1,2-PD Na(OAc) and DT 170 °C 1-6 (C) 78
Ag AgNO3 methanol NaBH4 MSA room temp 1-6 (C) 75
Ag AgClO4 DMF DMF 3-APTMS 20-156 °C 7-20 (C) 77
Au AuCl3 THF K+(15C5)2K- THF -50 °C 6-11 (C) 83
Au HAuCl4 formamide formamide PVP 30 °C 30 (C) 76
a
EG ) ethylene glycol; DMF ) dimethylformamide; HAD ) hexadecylamine; THF ) tetrahydrofuran; 1,2-PD ) 1,2-propanediol.
b
See text for descriptions of reducing agents. c MSA ) mercaptosuccinic acid; 3-APTMS ) 3-(aminopropyl)trimethoxysilane; PVP
) poly(vinylpyrrolidone); DT ) dodecanethiol. d (A) ) agglomerated; (C) ) colloidal/monodispersed e Estimated from BET surface
area assuming spherical shape.
where M ) metals of groups 6-11 and X ) acetyl- aluminum-coated nanoparticles open new pathways
acetonate. Nanoparticles of metal remain surrounded to the design and synthesis of heterogeneous cata-
by organoaluminum species that enable control of lysts.
their growth. Slow oxidation and derivatization of The techniques involving organoaluminum re-
these core-shell species allows the tailoring of their agents have recently been extended by the same
solubility and colloidal stability in different media. authors to include the metal carbonyl decomposition
The specific chemical reactivities of the organo- route.97 This resulted in the synthesis of 10 nm Co
nanoparticles with a narrow size distribution ((1.1 impurities were detected in their lattices resulting
nm) surrounded by organoaluminum species. Slow from the electrolysis.
air oxidation and peptization with suitable surfac-
tants lead to air-stable magnetic fluids. 2.2.4. Precipitation of Metals by Radiation-Assisted
Table 2 provides a summary of metals that have Reduction
been reported in the literature as being precipitated The most obvious example of radiation-assisted
from nonaqueous solutions. reduction is the photoreduction of aqueous AgNO3
solutions upon exposure to UV light. Huang et al.
2.2.3. Precipitation of Metals by Electrochemical adapted this method to the synthesis of Ag nanopar-
Reduction ticles by exposing a solution of AgNO3 to 243 nm
Although the method is not widely used, the radiation in the presence of poly(N-vinylpyrrolidone)
synthesis of powdered metallic nanoparticles is pos- (PVP) as stabilizer.103 The average particle size could
sible by electrochemical reduction. The method de- be varied from 15 to 22 nm by adjusting the [PVP]/
veloped by Reetz et al. involves the anodic dissolution [Ag+] ratio.
of a metal and the reduction of the intermediate At the extreme end of radiation-assisted reduc-
metallic salt at the cathode (usually Pt foil).99 The tions, all of the noble metals, as well as many other
reaction must be carried out in the presence of a electronegative metals, can be reduced in aqueous
stabilizer, such as a tetraalkylammonium salt, to solutions by exposure to γ-radiation. γ-rays decom-
prevent all of the particles from simply depositing pose H2O to H2, H2O2, •OH and •H radicals, and
(plating) at the cathode’s surface. aqueous, solvated electrons:104
In Reetz’s initial experiments, Pd metal was de-
γ-rays
posited from a 0.1 M solution of tetraoctylammonium H2O 98 •OH (2.8), eaq- (2.7), H2O2 (0.71),
bromide dissolved in a 4:1 mixture of acetonitrile- •
THF by applying a 0.1 mA/cm2 current at 1 V using H (0.55), H2 (0.45) (30)
a potentiostat. The monodispersed 4.8 nm particles
were collected by decantation/drying and were redis- where the numbers in parentheses represent the
persable in THF or toluene (Figure 4). The authors radical chemical yields expressed as the number of
also noted that increasing the current density re- species per 100 eV of energy absorbed.
sulted in a substantial decrease in particle size, such The reactions are usually performed under a
that 1.4 nm particles were obtained at 5.0 mA/cm2. nitrous oxide atmosphere that acts as a scavenger
for the hydrated electrons (eaq-):
Rodrı́guez-Sánchez et al. adapted the method to the
precipitation of 2-7 nm silver nanoparticles by
cycling a Ag|0.1 M tetrabutylammonium bromide in
N2O + eaq- + H2O f N2 + OH- + •OH (31)
acetonitrile|Pt cell from 1.35 V to -0.15 V at 500
The •OH and •H radicals are subsequently scavenged
mV/s for 5 min.100 The authors noted a similar
by short-chain alcohols such as methanol:
relationship between current density and particle size
as reported by Reetz. In a variation of this method, •
OH + CH3OH f H2O + •CH2OH (32)
Mohamed et al. were able to deposit Au nanorods by
adding Ag+ to the supporting electrolyte.101 •
Asenjo et al. have recently developed an analogous H + CH3OH f H2 + •CH2OH (33)
method for the preparation of nanoparticulate stron-
tium ferrites by electrolyzing acidic aqueous solutions The •CH2OH radical then serves as a reducing agent
of Sr2+ and Fe2+ chlorides and nitrates in a 40-80 for the metal accompanied by oxidation of the radical
°C temperature range.102 The spherical products were to an aldehyde:
typically on the order of ∼50 nm, although trace
Mn+ + n•CH2OH f M0 + nCH2O + nH+ (34)
In instances where the strong reducing power of eaq-

is necessary to perform the reduction, the nitrous
oxide atmosphere can be foregone, thereby allowing
some degree of control over the strength of the active
reducing agent.
The nanoparticle metals produced by radiolytic
reduction include Au (2 nm, stabilized in poly(vinyl
alcohol) or poly(vinylpyrrolidone)),105 Co (2-4 nm,
stabilized by polyacrylate),106 and Cu (20-100 nm in
poly(vinyl sulfate).107 20 nm particles of Ag stabilized
with sodium dodecyl sulfate have also been reported,
but the resulting colloidal suspensions were not
stable against agglomeration.108
The radiolytic reduction method is perhaps most
Figure 4. Mean particle diameter as a function of current
useful when enlarging colloidal metals or layering
density for Pd clusters precipitated electrochemically from dissimilar metals over one another, forming core-
acetonitrile-THF solution. (Adapted with permission from shell type arrangements. In these reactions, a metal
from ref 99. Copyright 1994 American Chemical Society.) colloid is usually prepared by a conventional chemical
Figure 5. Mechanism of Au nanoparticle enlargement

using γ irradiation. (Reprinted with permission from ref
110. Copyright 2000 American Chemical Society.)
route such as the Turkevich (citrate) method dis- Figure 6. TEM image of 20 nm Au nanoparticles (left)
produced by the Turkevich method and (right) after coating
cussed in section 2.2.1. The metal colloids are then with Ag by a radiation-assisted reduction method. (Re-
essentially used as seed particles for subsequent printed with permission from ref 110. Copyright 2000
growth of the same or a different metal from aqueous American Chemical Society.)
solutions. For instance, starting from a solution of
15 nm Au prepared by the citrate method, Henglein tially very useful method of preparing bi- and tri-
et al. enlarged the Au particles sequentially up to metallic nanoparticles.
diameters of 120 nm by adding aqueous Au(CN)2-
and methanol to the colloidal solution and irradiating 2.2.5. Precipitation of Metals by Decomposition of
with a 60Co source.109 The size distribution and Metallorganic Precursors
monodispersity of the nanoparticles do not appear to The thermolysis of organometallic precursors in the
be adversely affected throughout the process. presence of a polymer is one of the older methods of
In Henglein’s method, rather than the organic preparing colloidal metals. Typically, a metal complex
radicals directly reducing the metal cations, they such as Co2(CO)8 is decomposed at 130-170 °C under
instead charge the colloidal Au particles that subse- inert atmosphere in Decalin or ethylene glycol sol-
quently act as reducing agents for the aqueous vents:
Au(CN)2- ions:110
Co2(CO)8 f 2Co(s) + 8COv (37)
•
CH2OH + Aunx- f Aun(x+1)- + CH2O + H+ (35)
45 nm Co particles capped with PVP have been
Aun(x+1)- + Au(CN)2-(aq) f Au(n+1)x- + 2 CN- prepared by this approach.119 Originally, the poly-
(36) mers were thought to function as simple stabilizing
agents.120 Later, in their study of the thermolysis of
This mechanism is demonstrated schematically in Fe(CO)5, Smith and Wychick observed catalytic ac-
Figure 5. There is, of course, no requirement that the tivity by copolymers such as copoly(styrene-4-vinyl-
nanoparticle seeds and aqueous metal ions consist pyridine) and copoly(styrene-N-vinylpyrolidone).121
of the same metals. A dissimilar metal cation dis- The nitrogen-containing polymer chains were found
solved in the aqueous solution would essentially coat to effectively serve as nucleophiles (Nu), leading to
the surfaces of the existing metal colloid particles, the formation of ligated metal-cluster macromol-
creating a core-shell type composite. Henglein et al. ecules:
have published extensively on this method, and their
successes include nanocomposites of AucorePtshell,111 (n+1)Fe(CO)5 + xNu f [Fe(Nu)x][Fen(CO)m] (38)
PtcoreAushell,111 AucoreHgshell,112 AucorePbshell,113 Pdcore-
AushellAgshell,114 and the AucoreAgshell material shown x ≡ 2-6
in Figure 6.110 n ) 2, m ) 8
Very recently, Lee et al. have reduced aqueous
solutions of Ni2+ and NaPH2O2‚H2O to 100-300 nm n ) 3, m ) 11
Ni-P nanocomposites with synchrotron X-rays.115 n ) 4, m ) 13
The particle sizes could be controlled by adjusting the
temperature of the solution, although considerable Polymers such as polystyrene, which do not contain
aggregation of the products was observed. Nonethe- nitrogen and therefore do not function as nucleo-
less, this appears to be the first report of nanopar- philes, react only with [Fe(CO)4] intermediates gen-
ticles prepared by irradiation with synchrotron X- erated by thermolysis. In either case, the polymers
rays. effectively serve as nucleation sites for Fe. Because
Yeh et al. have reported the synthesis of Au-Ag, the polymers serve as catalysts,121 the functionality
Au-Pd, Ag-Pd, and Au-Ag-Pd nanoparticles by of the polymers profoundly influences the kinetics of
irradiating the appropriate mixtures of metal colloids the carbonyl decomposition reactions. It follows that
with an Nd:YAG laser.116-118 Although this method particle size can be controlled by varying polymer
cannot be classified as a precipitation reaction, since functionality, as well as reactant concentration.
the metals were already in colloidal form prior to Smith and Wychick were able to selectively prepare
irradiation, it is nonetheless noted here as a poten- 5-15 nm colloidal Fe particles in this manner.121
a fixed concentration of oleic acid, the length of the

nanodisks was directly proportional to the concentra-
tion of TOPO. As time progressed, the nanorods
dissolved and spherical 8 nm nanocrystals of -Co
with a tight size distribution appeared within a few
minutes as the final product. When the decomposi-
tion of Co2(CO)8 was performed in the presence of the
long-chain aliphatic amines instead of, or in addition
to, TOPO, the lifetime of nanodisks in solution
increased, which facilitated their preparation.127
Varying the reaction time and [capping ligand]/
[precursor] ratio allowed the synthesis of hcp-Co
nanodisks with sizes ranging from 2 × 4 to 4 × 90
nm, although the narrowest size distribution was
obtained for medium sized (4 × 35 nm) disks.
Thermal decomposition of Fe(CO)5 combined with
the polyol reduction of Pt(acac)2 in the same pot
resulted in formation of intermetallic FePt nanopar-
ticles.128 Their composition was controllable by ad-
justing the molar ratio of Fe and Pt precursors.
Particle size could be tuned by growing seed particles
followed by addition of additional reagents to enlarge
them in the range 3-10 nm (Figure 7).
The reaction between Co2(CO)8 and Pt(hfacac)2
Figure 7. (A) TEM micrograph of a 3-D assembly of 6 nm (hfacac ) hexafluoroacetylacetonate) resulted in the
as-synthesized Fe50Pt50 particles. (B) TEM micrograph of formation of bimetallic CoPt3 and CoPt nanopar-
a 3-D assembly of 6 nm Fe50Pt50 particles after replacing ticles.129 This reaction was performed under reflux
oleic acid-oleylamine with hexanoic acid-hexylamine. (C) in a toluene solution containing oleic acid as stabiliz-
HRSEM image of a ∼180 nm thick, 4 nm Fe52Pt48 nano- ing agent:
crystal assembly annealed at 560 °C for 30 min under 1
atm of N2 gas. (D) HRTEM image of 4 nm Fe52Pt48 Co2(CO)8 + Pt(hfacac)2 f
nanocrystals annealed at 560 °C for 30 min. (Reprinted
with permission from ref 128. Copyright 2000 American CoPt + Co(hfacac)2 + 8CO (39)
Association for the Advancement of Science.)
In contrast, when presynthesized Co nanoparticles
Van Wonterghem et al. substituted a surfactant were reacted with Pt(hfacac)2, the transmetalation
(Sarkosyl-0) for the polymers and carried out the redox reaction led to core-shell structured nanopar-
thermolysis of Fe(CO)5 in Decalin at T < 187 °C.122,123 ticles of Co@Pt:
Their method resulted in a ferrofluid of 8.5 nm Fe
with a 1.0 nm standard deviation. Ni, Cr, W, and Mo 2Co + Pt(hfacac)2 f Co/Pt + Co(hfacac)2 (40)
nanoparticles prepared by the thermolysis of metal
carbonyls have also been reported. Ge et al. later The resulting nanoparticles were coated with dodecyl
adapted the method to the synthesis of 10 nm isocyanide capping ligands and exhibited diameters
γ-(Fe44Ni56) alloy particles.124 of 6.27 nm (σ ) 0.58 nm). They were air-stable and
Further development of the metal carbonyl decom- dispersible in nonpolar solvents.
position method led to the use of capping ligands Alkene (olefin) complexes are similar to metal
instead of polymers for controlling the nanocrystal carbonyls in that they usually contain zerovalent or
growth and protecting the products from oxidation low-oxidation-state metals. Like carbonyls, alkene
and aggregation. Dinega et al. reported the discovery complexes decompose easily, liberating pure metal
of a new crystalline phase of metallic cobalt (-Co) and olefin ligands. This characteristic has been used
related to the β phase of manganese.125 This meta- advantageously for the development of new synthetic
stable phase appeared as a kinetically controlled methods for colloidal transition metals. The most
product of the thermal decomposition of Co2(CO)8 in commonly used ligands include 1,5-cyclooctadiene
hot toluene in the presence of trioctylphosphine oxide (COD), 1,3,5-cyclooctatriene (COT), and dibenzylidene
(TOPO); the same reaction performed in the absence acetone (DBA), in addition to the π-allyl ligands, such
of TOPO resulted in formation of a pure fcc Co phase. as cyclooctenyl (C8H13-).
More detailed study of this system performed by Chaudret et al. have applied this method exten-
Puntes et al. under a wide range of conditions sively to the synthesis of Co, Ni, Ru, Pd, Pt, CoPt,
revealed the stepwise character of the crystal CoRu, CoRh, and RuPt nanoparticles130-149 in addi-
growth.126,127 Rapid injection of cobalt carbonyl solution to Co and Ni nanorods.150,151 Solution syntheses
tion into a hot o-dichlorobenzene solution containing were typically performed in the presence of H2 or CO
both the labile ligand TOPO and the stronger ligand at room or slightly elevated temperature, yielding
oleic acid, followed by quenching of the reaction, 1-2 nm particles with clean surfaces. The authors
resulted in formation of different products. The initial have determined that the stabilizing agent poly-
product is hcp-Co with a nanodisk shape with dimen- (vinylpyrrolidone) (PVP) that is frequently used in
sions that are tunable from 4 × 25 to 4 × 75 nm. At this method exhibits practically no influence on the
saturation magnetization of Co and Ni nanoparticles The coprecipitation of metal cations as carbonates,

compared to the pure, bulk metals.133,140 bicarbonates, or oxalates, followed by their subse-
Recently this method was used for the synthesis quent calcination and decomposition, is a common
of colloidal Pt in 1-butyl-3-methylimidazolium hexa- method for producing crystalline nanoparticulate
fluorophosphate ionic liquid.152 The isolated nano- oxides. The calcination will, however, almost invari-
particles could be redispersed in the ionic liquid or ably lead to agglomeration or, at high temperatures,
in acetone or used under solventless conditions for aggregation and sintering. Fortunately, nanoparticu-
liquid-liquid biphasic, homogeneous, or heteroge- late hydroxide, carbonate, and oxalate precursors
neous hydrogenation of alkenes and arenes under tend to decompose at relatively low temperatures
mild reaction conditions. (<400 °C) due to their high surface areas, thereby
The cyclopentadiene complex of indium has been minimizing agglomeration and aggregation. As an
used for the synthesis of 15 nm uniform particles of example, Ce0.8Y0.2O1.9 (a fluorite-structured, oxide-ion
In metal protected with PVP or other capping conducting electrolyte for solid oxide fuel cells) was
ligands.153,154 Performing this reaction in the presence precipitated by the addition of oxalic acid to an
of long-chain amines yielded nanowires of In and aqueous solution of Ce(NO3)3 and Y(NO3)3, followed
In3Sn alloy with high aspect ratios.155 Similarly, by calcination.160 Calcining at 500 °C yielded 10 nm,
colloidal 5 nm Cu has been obtained from the slightly agglomerated, roughly spherical particles.
organometallic complex CpCu(tBuNC) in the presence Calcining at 1000 °C resulted in 100 nm aggregates
of CO and PVP (3.5 nm) or polydimethylphenylene with irregular shapes, although lower calcination
oxide (5 nm) in solutions of CH2Cl2 or anisole at room temperatures reduced aggregation considerably. CeO2
temperature.156 nanopowders, by contrast, have been prepared by
calcining the product of the precipitation between
2.2.6. Precipitation of Oxides from Aqueous Solutions Ce(NO3)3 and (NH4)2CO3, resulting in crystalline, 6
nm particles of CeO2 at calcination temperatures as
The precipitation of oxides, from both aqueous and
low as 300 °C.161 10-15 nm particles of NiO have
nonaqueous solutions, is somewhat less straightfor-
been similarly prepared by precipitating aqueous
ward than the precipitation of metals. Reactions for
Ni2+ solutions with (NH4)2CO3 and calcining the
the synthesis of oxides can generally be broken into
products at 400 °C.162
two categories: those that produce an oxide directly
and those that produce what is best termed a precur- Du et al. were able to prepare the Bi4Ti3O12
sor that must be subjected to further processing ferroelectric by calcining the product from the reac-
(drying, calcination, etc.). In either case, monodis- tion between a basic solution of TiO2 and Bi(NO3)3
persed nanoparticles of oxides, like those of metals, performed in acidic solution.163 Agglomerate sizes
frequently require a capping ligand or other surface- ranged from 16 to 48 nm after calcining between 500
bound stabilizer to prevent agglomeration of the and 800 °C. When the calcination temperature was
particles. kept at 500 °C or below, Bi4Ti3O12 appeared to
In those cases where calcination or annealing of crystallize in a metastable tetragonal phase previ-
the samples is necessary, some agglomeration will ously thought to be stable only at high temperatures.
be unavoidable. Nanoparticles can nonetheless be so In some rare instances, crystalline oxides can be
obtained, but there is little chance of the particles precipitated from aqueous solution, eliminating the
being monodispersed. For many of the reported need for a calcination step and greatly reducing the
syntheses of oxides, monodispersity of the products risk of agglomeration. This approach is most common
was neither a requirement nor a priority for the for simple binary oxides. 50-60 nm aggregates of 4
researchers involved. nm rutile-structured TiO2, for instance, can be pre-
The products of coprecipitation reactions, particu- pared by precipitating aqueous TiCl3 with NH4OH
larly those performed at or near room temperature, under ambient conditions and stabilizing the prod-
are usually amorphous. In those cases where hydrox- ucts with poly(methyl methacrylate).164
ides or carbonates of mixed metals are precipitated The direct coprecipitation of more complex ternary
from solution and subjected to a calcination or oxides, while somewhat uncommon, is nonetheless
postannealing process, it is extremely difficult to possible, particularly when the product assumes a
experimentally determine whether the as-prepared very thermodynamically favorable structure such as
precursor is a single-phase solid solution or a multi- spinel. In such cases, the precipitation reactions are
phase, nearly-homogeneous mixture of the constitu- normally carried out at elevated temperatures (50-
ent metal hydroxides-carbonates-oxides that react 100 °C), such that the hydroxide intermediates are
to form a single-phase mixed-metal oxide when condensed into oxides in the same reaction vessel as
heated. where coprecipitation was induced. Such “one-pot”
Many nanoparticulate metal oxides are prepared synthesis techniques render calcination steps un-
by calcining hydroxide coprecipitation products. necessary. Fe3O4, for example, has been prepared as
Albuquerque et al. prepared spinel-structured an oxide by the simple coprecipitation of (Fe2+ + 2
Ni0.5Zn0.5Fe2O4 by precipitating a mixture of Fe, Ni, Fe3+) with NaOH at temperatures above 70 °C.165
and Zn nitrates with NaOH and calcining at 300 °C 5-25 nm particles of MnFe2O4 were similarly pre-
or higher.157 Particle sizes ranged from 9 to 90 nm, pared from aqueous Mn2+ and Fe2+ at temperatures
depending on the calcination temperature. MgFe2O4158 up to 100 °C.166 Pr3+-doped ceria has likewise been
and Sm1-xSrxFeO3-δ159 have been prepared by nearly precipitated by aging aqueous solutions of Ce(NO3)3
identical methods. and PrCl3 at 100 °C in the presence of a hexameth-
Table 3. Summary of Reactions for the Precipitation of Oxides from Aqueous Solutions
compd starting material ppt agent stabilizer conditions product size (nm) ref
VO2(B) NH4VO3 N2H4‚H2O none calcined 300 °C 35 44
Cr2O3 K2Cr2O7 N2H4‚H2O none calcined 500 °C 30 44
γ-Mn2O3 KMnO4 N2H4‚H2O none 8 44
MnFe2O4 MnCl2 NaOH none 100 °C 5-25 172
FeCl3
Fe3O4 FeCl2 NH4OH H+ N2 atm 8-50 173
FeCl3
NiO NiCl2 NH4OH CTAB annealed 500 °C 22-28 174
ZnO ZnCl2 NH4OH CTAB annealed 500 °C 40-60 174
SnO2 SnCl4 NH4OH CTAB annealed 500 °C 11-18 174
Sb2O3 SbCl3 NaOH PVA annealed 350 °C 10-80 175
ylenetetramine stabilizer to yield monodispersed 13 solution.177 The hydroxide mixture was then calcined
nm particles.167 In this case, the stabilizer indirectly at 400-700 °C in air to yield 12-41 nm LiCoO2.
serves as the precipitating agent by raising the pH Similar procedures have been adapted to the
high enough to induce precipitation of the metal hydroxide precipitation of other transition metals.
hydroxides. Amorphous RuO2-δ‚nH2O can be precipitated by
Chinnasamy et al. reported an extensive series of addition of tetramethylammonium hydroxide to
experiments for the spinel-structured CoFe2O4 de- RuNO(NO3)3 dissolved in alcohol at 90 °C.178 Subse-
signed to determine the influence of reaction tem- quent annealing of the product at 400 °C in air
perature, reactant concentration, and reactant addi- resulted in 14 nm crystalline RuO2. By contrast,
tion rate on the size of the products.168 In each case, precipitation of RuO2-δ‚nH2O from aqueous solution
aqueous solutions of Fe3+ and Co2+ were precipitated required over 2 weeks at 90 °C and ultimately
with dilute NaOH. The results were predominantly resulted in products containing about 5% metallic Ru.
in line with expectations based on the considerations There is at least one account of a nanoparticle oxide
outlined in section 2.1: Increasing the temperature synthesis in which the solvent also served as the
from 70 °C to 98 °C increased the average particle precipitating agent. Deb et al. prepared 5-20 nm
size from 14 to 18 nm. Increasing the NaOH concen- γ-Fe2O3 by melting a mixture of stearic acid (CH3-
tration from 0.73 to 1.13 M increased particle size (CH2)16COOH) and hydrated Fe(NO3)3 at 125 °C and
from 16 to 19 nm. NaOH concentrations of 1.5 M or calcining the product in air at 200 °C.179 The product
greater resulted in the formation of a secondary underwent the γ (maghemite) f R (hematite) phase
FeOOH phase, and slowing the NaOH addition rate transition on prolonged heating at 200 °C, well below
appeared to broaden the particle size distribution. the transition temperature of bulk γ-Fe2O3. The
Li et al. prepared 12 nm CoFe2O4 by a similar route results of Ennas et al., however, suggest that the
but stabilized the product by acidification with dilute phase transition temperature of γ-Fe2O3 is not strictly
nitric acid.169 The electrostatic repulsion of the par- a function of particle size, as they observed a transi-
ticles created by the adsorption of H+ at the particle tion starting at ∼250 °C for 5 nm γ-Fe2O3.180
surfaces resulted in an indefinitely stable colloid of In other cases, the use of aqueous solvents is
ferromagnetic particles (a ferrofluid). By contrast, avoided specifically to prevent the premature pre-
Fe3O4 ferrofluids, which tend to not be stable under cipitation of metal hydroxides/oxides. Premature
acidic solutions, have been sterically stabilized by precipitation tends to be problematic with high-
coating Fe3O4 nanoparticles with oleic acid, poly(vinyl valence, electropositive metals such as Ti4+, Zr4+, and
alcohol), or starch.170,171 so forth. This can, to some extent, be circumvented
A summary of oxides precipitated from aqueous by using metal chloride or metal alkoxide precursors
solutions, including the relevant reaction conditions, in nonaqueous solvents. The hydrolysis reactions can
is given in Table 3. consequently be controlled to limit particle growth
and prevent agglomeration. Ferroelectric BaTiO3, for
2.2.7. Precipitation of Oxides from Nonaqueous Solutions instance, has been prepared by precipitating a mixed-
metal alkoxide precursor, BaTi(O2C(CH3)6CH3)-
Simple precipitation reactions are sometimes car- [OCH(CH3)2]5 (that is highly susceptible to hydroly-
ried out in nonaqueous solvents. This method can be sis) with H2O2 in diphenyl ether solution with oleic
particularly advantageous when precipitating dis- acid as stabilizer.181 The addition of H2O2 effectively
similar metals that cannot be simultaneously pre- initiates an hydrolysis reaction. Condensation oc-
cipitated from aqueous solution due to large varia- curred as the solution was heated at 100 °C, resulting
tions in the pH values necessary to induce precipita- in Ba-O-Ti linkages, but with particle growth
tion of the constituent cations. Such is the case with constrained by the presence of the oleic acid stabi-
LiCoO2, a well-known cathode material for recharge- lizer. This method resulted in 6-12 nm monodis-
able lithium batteries.176 LiOH cannot be precipitated perse, crystalline particles that did not require cal-
from aqueous solution, but its solubility in alcohols cination. These reactions are similar in many re-
is greatly diminished. Hagenmuller et al. induced spects to the sol-gel reactions discussed in section 3.
nearly simultaneous coprecipitation of (LiOH + The method of Caruntu et al. for the synthesis of
Co(OH)2) by dripping a mixture of LiNO3 and Co(NO3)2 colloidal ferrites is similar in that a metal chelate
dissolved in ethanol into a stirred 3 M KOH ethanol precursor formed between a metal chloride and
diethylene glycol was subsequently subjected to position of metal-Cupferron complexes, M xCupx (Cup
controlled hydrolysis:182 ) C6H5N(NO)O-).184 The reactions involved injecting
a solution of FeCup3, MnCup2, or CuCup2 dissolved
in octylamine into a solution of trioctylamine under
inert atmosphere at 300 °C, well above the decom-
position temperatures of the Cupferron complexes.
The resulting precipitates were found to consist of
4-10 nm nanoparticles of either γ-Fe2O3, MnO, or
Cu and were easily dispersed in toluene.
Here, the diethylene glycol served as both solvent and 2.2.8. Coprecipitation of Metal Chalconides by Reactions
stabilizing agent, although the glycol was usually
of Molecular Precursors
exchanged for oleic or myristic acid to ensure growth Interest in chalcogenide nanoparticles has grown
termination. The authors have prepared a series of dramatically in recent years, primarily due to the
monodispersed MFe2O4 ferrites by this method, where potential applications of quantum dots (semiconduct-
M ) Mn, Fe, Co, Ni, or Zn, exhibiting sizes in the ing nanoparticles with band gaps that are particle-
3-7 nm range with the standard deviation of particle size dependent and therefore tunable).185-187 Because
sizes typically on the order of 15% (Figure 8). experimental and theoretical considerations for the
Using a somewhat more conventional route, Sun syntheses of nanoparticulate semiconductors have
et al. prepared 4 nm Fe3O4 by dissolving Fe(acac)3, recently been reviewed,188,189 we present only a brief
1,2-hexadecanediol, oleic acid, and oleylamine in overview here, with emphasis on the most recent
diphenyl ether and refluxing for 30 min.183 Precipita- developments.
tion was induced when ethanol was added under air Early studies on the physical and optical properties
atmosphere after the solution had cooled to room of quantum dots were severely hampered by a lack
temperature. It is uncertain in this method at what of synthetic routes to monodisperse products. De-
point or by what reagent Fe3+ is reduced to Fe2+. mand for nanocrystalline semiconductors with uni-
Rockenberger et al. developed a method for prepar- form size and shape stimulated research into syn-
ing surfactant-capped oxide nanoparticles by decom- thetic methods based on reactions with easily tunable
rates. Classic metathesis reactions between metal
and chalcogenide ions that occur instantaneously
upon mixing usually produce precipitates consisting
of agglomerated crystallites with widely disparate
sizes and shapes. A successful method of controlling
the precipitation process lies in performing the reac-
tions in heterogeneous media (reverse micelles, solid
templates, etc.; see section 4) where the rate is
controlled by diffusion restrictions.
Alternative methods may be based on nucleophilic
or other reactions between neutral molecules that are
readily kinetically controlled. The reaction between
metal- and chalcogen-containing covalent compounds
can have a significant potential energy barrier and
can be driven by thermal energy. Changing the
amount of supplied heat therefore allows tuning of
the reaction kinetics. This approach was systemati-
cally developed at AT&T Bell Labs by M. L. Steiger-
wald and L. E. Brus in the mid-1980s to mid-
1990s.190-196 Their novel strategy of using organic
chalcogenides, metal molecular carriers, and organic
coordinating solvents as the reaction media resulted
in the preparation and characterization of a variety
of nanoscale II-VI and III-V semiconductors.
The approach of temporal separation of nucleation
and crystal growth resulted in processable, highly
crystalline nanoparticles with unprecedentedly nar-
row size distributions. This method was developed
for cadmium chalcogenides,197-200 as well as for Ga
and In pnictides.201-203 For the synthesis of cadmium
chalcogenides, the Cd-precursor was Cd(CH3)2, and
the chalcogen source molecules were [(CH3)3Si]2S,
Figure 8. TEM images of MnFe2O4 nanoparticles pre-
[(CH3)3Si]2Se, R3PSe, and R3PTe (R ) C4-C8 n-alkyl).
pared by the hydrolysis and condensation of metal chelates Rapid injection of a room-temperature solution con-
in nonaqueous solutions. (Reprinted with permission from taining both precursors into the preheated (340-360
ref 182. Copyright 2002 American Chemical Society.) °C) solvents resulted in rapid nucleation, and ma-
nipulation of the temperature allowed the time-scale

separation of nucleation and growth of the nano-
crystals. Typically, the temperature was lowered to
280-300 °C and the relatively slow nanocrystal
growth takes place until the reactants are consumed.
Adding another portion of reagents allowed further
growth of the nanocrystals, thus expanding the size
tunability to 1.2-12 nm. The reaction medium was
a high-boiling mixture of trioctylphosphine (TOP) and
trioctylphosphine oxide (TOPO) that acts not only as
a solvent but also as a passivating agent and stabi-
lizer. Molecules of TOP and TOPO compounds readily
coordinate to metal and chalcogen intermediates and
bind to the surface of growing nanocrystals, thereby
reducing their surface energy. Nanocrystals grown
with their surfaces protected with these capping
ligands do not agglomerate but remain in reaction
solution as long as necessary in the experiments.
Detailed study of the evolution of nanocrystals’
sizes and size distributions revealed some key pro-
cesses.203 Depending on the concentration of mono-
nuclear species (reagents) and the sizes of the nano-
crystals, two distinct processes were found to be
occurring. When the concentration of the monomer
is higher than the solubility of the nanocrystals, the
“focusing” phase occurs when all nanocrystals grow,
and the smaller crystals grow faster than the larger
crystals. As a result, the size distribution of the
nanocrystals is narrowed. When the concentration of
the monomer becomes lower than the solubility of
nanocrystals at their critical size, the Ostwald ripen-
ing mechanism is engaged, whereby larger crystals
grow at the expense of smaller ones. This is a
“defocusing” phase when size distribution broadens.
Properly manipulating the kinetics of the reaction
while keeping the monomer concentration higher
than the critical threshold provides a versatile tool
for synthesizing monodispersed, variable-sized nano-
crystals of presumably the entire class of II-VI and Figure 9. (Top) CdSe dots formed in 13% tetradecylphos-
III-V semiconductors. phonic acid at 360 °C for injection and 250 °C for growth.
(Middle and bottom) Quantum rods grown from the dots
Further modification of this method led to the in the top image by a secondary injection and subsequent
development of a three-component coordinating sol- growth for 23 h. (Reprinted with permission from ref 207.
vent system containing TOP, TOPO, and hexadecyl- Copyright 2001 American Chemical Society).
amine for the synthesis of CdSe.204 Introducing the
additional complexing agent resulted in the elimina- centration higher than was used for spherical nano-
tion of the defocusing step from the nanocrystals’ crystals, nanorods were formed instead of nanopar-
growth phase. The resulting nanoparticles exhibited ticles (Figure 9). At these high concentrations, the
nearly spherical shapes with exceptionally narrow rate of reaction is very high and nanocrystals grow
size distributions without the need for size-selective in all directions, although faster along the c-axis.
fractionation. Substituting trialkylphosphine and Introducing an additional reagent that acts as a
trialkylphosphine oxide for the amine capping ligands strong ligand for Cd, such as alkylphosphonic acid
resulted in an increase in the photoluminescence (R ) C6 or C14), enables control of the reaction rate
quantum efficiency from 10-25% to 40-50%. Depos- and tuning of the morphology of the product. Soluble
iting a shell of ZnS around a CdSe core further and processable nanorods with a high aspect ratio
improved the room-temperature values of quantum (30:1) and arrow-, teardrop- and tetrapod-shaped
efficiency to 50-60%. CdSe nanocrystals have been reported.206
In addition to their hexagonal and cubic modifica- There are three distinctive diffusion-controlled
tions, cadmium chalcogenides can assume the highly phases of the process: one-dimensional growth,
anisotropic wurtzite structure with a unique c-axis. three-dimensional growth, and one-to-two-dimen-
Consequently, an uneven crystal growth under ki- sional ripening.207 The first phase occurs when the
netic conditions is expected. This was recently ob- monomer concentration at the beginning of the
served experimentally for the synthesis of CdSe by reaction is at its highest and results in nanorods with
the same organometallic reaction described above but high aspect ratios and uniform thicknesses. The
under modified conditions.205-207 At a monomer con- second phase occurs when the concentration of the
tion of the nucleation and growth processes, similar

to the cases of the systems described above for
cadmium chalcogenides.
Semiconductor quantum dots of CdSe and PbSe
doped with paramagnetic Mn2+ ions have been pre-
pared by modification of the above methods, in that
Mn2(µ-SeMe)2(CO)8 was added as a manganese-
containing precursor.211,212 Nanocrystals of these
diluted magnetic semiconductors may be useful as
materials for spin applications.
2.2.9. Microwave-Assisted Coprecipitation
The microwave processing of nanoparticles results
in rapid heating of the reaction mixtures, particularly
those containing water. As a consequence, the pre-
cipitation of particles from such solutions tends to
be rapid and nearly simultaneous. As outlined in
section 2.1, this leads to very small particle sizes and
narrow size distributions within the products. The
method offers the additional benefit of requiring very
short reaction times.
Pastoriza-Santos and Liz-Marzán were able to
make a direct comparison of colloidal Ag and Au
nanoparticles prepared by both reflux-induced pre-
cipitation and microwave-assisted precipitation. In
Figure 10. TEM micrographs of different sized wurtzite
CdSe nanocrystals (as-prepared) synthesized in stearic acid both cases, the metals were reduced by the solvent,
related solvents. (Reprinted with permission from ref 209. DMF.213 They found that, generally, the microwave
Copyright 2001 American Chemical Society.) method offered better control of particle size and
morphology.
monomer is intermediate and nanorods grow in all
three dimensions. Finally, the last phase of intra-
particle ripening at low monomer concentrations
results in mass transport from long to short dimen-
sions of nanorods that reduces their aspect ratio.
Evaluation of the possible pathways of the initial
reaction involving dimethylcadmium resulted in the
development of more practical methods of synthesiz-
ing nanocrystalline cadmium chalcogenides.208,209 In
this method, CdO was used instead of Cd(CH3)2 and
was predissolved in a solution of alkylphosphonic acid
(R ) C6H13 or C14H29) in TOPO. A solution of
chalcogen precursor [(CH3)3Si]2S, [(CH3)3Si]2Se, R3PSe,
or R3PTe (R ) C4-C8 n-alkyl) in TOPO was injected
into the hot Cd-containing solution, resulting in the
formation of colloidal nanoparticles. Cadmium car-
boxylates, such as acetate, laurate, and stearate have
been successfully substituted as cadmium precursors
that facilitate the nanocrystals’ growth (Figure 10).209
Tuning the concentrations of the reagents and reac-
tion temperature enabled the control of the nano-
crystals’ sizes and shapes, analogous with the sys-
tems where dimethylcadmium was employed. This
new one-pot method represents a significant step
toward the industrial-scale production of semicon-
ductor quantum dots, since the expensive, flammable,
and toxic dimethylcadmium has now been elimi-
nated.
The synthesis of monodispersed nanocrystals of
PbSe capped with oleic acid has been successfully
performed by combining lead oleate with trioctylphos-
phine selenide.210 Rapid injection of a solution of the Figure 11. TEM image (top) and size distribution (bottom)
precursors (in TOPO) into preheated (150 °C) di- of Ni nanoparticles prepared under microwave irradiation
phenyl ether, followed by controlled annealing of the and stabilized with PVP. (Reprinted with permission from
solutions at lower temperatures, allowed the separa- ref 216. Copyright 2002 Chemical Society of Japan.)
Figure 12. Schematic of a continuous-flow microwave reactor consisting of (a) a liquid column as a pressure regulator,
(b) a metal salt solution container, (c) a microwave oven cavity, (d) a metal cluster dispersion receiver, and (e) a spiral
tube reactor. (Reprinted with permission from ref 217. Copyright 2000 American Chemical Society.)
Table 4. Representative Sample of Nanoparticulate Compounds That Have Been Prepared by

Microwave-Assisted Coprecipitation
compd starting material solvent stabilizer microwave conditions product size (nm) ref
R-Fe2O3 Fe(NO3)3 H2O none reflux, 2.4 GHz, 850 W 50-100 224
Ni Ni(OH)2 EG PVP 2.5 GHz, 200 W 5-8 225
Ni Ni(OH)2 50% EG-H2O PVP 2.5 GHz, 200 W 3-9 216
H2SO4
Bi2S3 Bi(NO3)3 40% CHCO-H2O none reflux 10 × 300 rods 226
CS(NH2)2
Many colloidal metals can be prepared by micro- collapse of bubbles) that creates localized “hot spots”
waving mixtures of metal salts and polyalcohols. This with effective temperatures of 5000 K and lifetimes
method, originally developed by Fiévet et al.,214 is on the order of a few nanoseconds or less.227-229 As
now referred to as the microwave-polyol process. such, the chemical reactions largely take place inside
Recently, Yu et al. prepared 2-4 nm colloidal Pt the bubbles.230 The extremely rapid cooling rates
particles by irradiating a mixture of poly(N-vinyl-2- encountered in this process, however, strongly favor
pyrrolidone), aqueous H2PtCl6, ethylene glycol, and the formation of amorphous products.
NaOH with 2450 MHz microwaves in an open beaker Many of the methods reported in the literature for
for 30 s.215 Tsuji et al. have prepared PVP-stabilized, sonochemical syntheses of nanoparticles involve the
nanoparticulate Ni in ethylene glycol by a similar decomposition of carbonyl precursors, as discussed
method; a TEM image and size distribution chart for in section 2.2.5. Suslick et al., who have published
their products are presented in Figure 11.216 Tu et extensively on the use of ultrasound in chemical
al. adapted the method to a continuous-flow reactor; syntheses, have prepared amorphous, nanoparticu-
their apparatus is depicted in Figure 12.217 This late Fe, Co, and several Fe-Co alloys.231-233 Typi-
method can reportedly produce colloidal ∼1.5 nm Pt cally, the corresponding metal carbonyls were dis-
at 0.8 L/h. solved in decane and irradiated at 20 kHz for ∼3 h
Microwave methods have similarly been used for under an inert atmosphere to produce well-dispersed
the synthesis of chalcogenides. Gedanken et al. ∼8 nm particles (Figure 13). Others have reported
prepared CdSe, PbSe, and Cu2-xSe nanoparticles by the synthesis of 40 nm particles of M50 steel by a
microwave-refluxing218 solutions containing aqueous similar process.234
Cd2+, Pb2+, or Cu2+ and Na2SeSO3 in the presence of Oxides can be prepared by similar methods if the
an amine-based stabilizer.219 In the case of CdSe, sonication is performed under an oxygen atmosphere.
increased irradiation time influenced the structure Shafi et al. prepared amorphous nanoparticles of
of the product. Interestingly, as-prepared CdSe NiFe2O4 by sonicating a solution of Fe(CO)5 and
samples consisted of well-dispersed 4-5 nm particles, Ni(CO)4 in Decalin under a 1-1.5 atm pressure of
whereas the PbSe and Cu2-xSe formed aggregates. O2, although the products were agglomerated.235
Gedanken’s group has published extensively on vari-
ous oxides and chalcogenides prepared by microwave- In some cases, the use of carbonyl precursors is not
assisted irradiation.220-223 necessary. ZrO2, for instance, has been precipitated
by ultrasonic irradiation of an aqueous solution
A brief survey of compounds prepared by micro-
containing Zr(NO3)4 and NH4OH, followed by calci-
wave-assisted coprecipitation is given in Table 4.
nation at 300-1200 °C to improve the crystallinity
or, for temperatures of 800 °C and above, to induce
2.2.10. Sonication-Assisted Coprecipitation a tetragonal f monoclinic phase transition.236 Nano-
Like microwave-induced heating, sonication of a particulate, perovskite-structured La1-xSrxMnO3 has
liquid also results in rapid heating, although the been similarly prepared.237
mechanism is fundamentally different. The sonica- Zheng et al. have developed an interesting varia-
tion of a liquid results in cavitation (the implosive tion of this method, in which 100-200 nm hollow
The versatility and general usefulness of modern

sol-gel processing is reflected in the sheer volume of
available literature. Since this review is limited to
discussing those aspects of sol-gel processing relevant
only to the synthesis of nanoparticles, the reader is
referred to the literature for more detailed discus-
sions of the broader applications of the method.
Though somewhat dated, the review article by Hench
and West provides an excellent overview of the theory
concerning each step of the sol-gel process.241 Several
textbooks and reference works devoted entirely to the
application and theory of sol-gel science are also
available.242-249
Disregarding the nature of the precursors, which
are discussed in sections 3.1.1-3.1.4, the sol-gel
process can be characterized by a series of distinct
steps.
Step 1: Formation of stable solutions of the alkox-
ide or solvated metal precursor (the sol).
Step 2: Gelation resulting from the formation of
an oxide- or alcohol-bridged network (the gel) by a
Figure 13. TEM image of colloidal Fe particles prepared polycondensation or polyesterification reaction that
by the sonochemical decomposition of Fe(CO)5 in octanol. results in a dramatic increase in the viscosity of the
The particles are stabilized by oleic acid. (Reprinted with solution. If so desired, the gel may be cast into a mold
permission from ref 232. Copyright 1996 American Chemi- during this step.
cal Society.)
Step 3: Aging of the gel (syneresis), during which
the polycondensation reactions continue until the gel
transforms into a solid mass, accompanied by con-
traction of the gel network and expulsion of solvent
from the gel pores. Ostwald ripening and phase
transformations may occur concurrently with syner-
esis. The aging process of gels can exceed 7 days and
is critical to the prevention of cracks in gels that have
been cast.
Step 4: Drying of the gel, when water and other
volatile liquids are removed from the gel network.
This process is complicated due to fundamental
changes in the structure of the gel. The drying
process has itself been broken into four distinct steps:
241 (i) the constant rate period, (ii) the critical point,
(iii) the first falling rate period, and (iv) the second
falling rate period. If isolated by thermal evaporation,
Figure 14. TEM image of CdSe nanoparticles synthesized the resulting monolith is termed a xerogel. If the
in supramolecular vesicle templates. (Reprinted with per- solvent is extracted under supercritical or near-
mission from ref 238. Copyright 2002 Elsevier.) supercritical conditions, the product is an aerogel.
Step 5: Dehydration, during which surface-bound
spheres of CdSe have been precipitated by ultrasonic M-OH groups are removed, thereby stabilizing the
irradiation of a solution of Na2SeO3 and CdCl2 in the gel against rehydration. This is normally achieved
presence of sodium dodecyl sulfate (SDS), an anionic by calcining the monolith at temperatures up to 800
surfactant that serves as a vesicle template (Figure °C.
14).238 Step 6: Densification and decomposition of the gels
at high temperatures (T > 800 °C). The pores of the
3. Sol-Gel Processing gel network are collapsed, and remaining organic
species are volatilized. This step is normally reserved
3.1. Fundamentals of the Sol-Gel Process for the preparation of dense ceramics or glasses.
Traditionally, sol-gel processing refers to the hy-
3.1.1. Precursors and the Partial-Charge Model
drolysis and condensation of alkoxide-based precur-
sors such as Si(OEt)4 (tetraethyl orthosilicate, or While the above steps are common to most sol-gel
TEOS). The earliest examples of such reactions date processes, the natures of the specific reactions in-
to the work of Ebelmen in 1846.239 Sol-gel processing volved in hydrolysis and condensation differ substan-
did not garner wide attention until Geffcken and tially between the various types of possible precur-
Berger devised a method of preparing oxide films sors. The processing of metal alkoxides, solvated
from sol-gel precursors in the late 1930s, which metal cations, and organometallic precursors are
proved useful in the manufacturing of stained glass.240 discussed separately to avoid confusion.
Understanding of the formation, stability, and the Si/H2O ratio, more than one alkoxy group may
reactivity of alkoxides and solvated metal cations is be substituted:
greatly enhanced by a cursory understanding of the
partial-charge model of Livage et al., in which the Si(OR)4 + nH2O f Si(OR)4-n(OH)n + nROH (48)
partial charge, δ, on an atom, i, is given by
Variation and control of n has profound consequences
0
(χj - χi ) for the morphology and structure of the resulting
δi ) (43) gel.251
kxχi0 The relatively high electronegativity of Si weakens
the O-H bonds to the extent that condensation can
where χi0 is the electronegativity of the atom, k is a occur. Like hydrolysis, condensation of Si(OR)1-n(OH)n
constant (1.36 in the Pauling scale of electronegativ- can be catalyzed by either acid or base. Under acidic
ity) and χj is the mean electronegativity of the system. conditions
χj is given by
∑pixχi + kz
i
χj ) (44)
∑(pi/xχi) or
i
where pi is the stoichiometry of atom i, χi is the

electronegativity of atom i, and z is the net charge of
the ionic species. Though cumbersome to perform,
calculations of partial charge provide meaningful
insight into the chemistry of sol-gel precursors, and
the partial-charge model is frequently invoked in the And under basic conditions
literature.
3.1.2. Sol-Gel Chemistry of Metal Alkoxides
Ebelmen’s early work239 involving the hydrolysis
or
of SiCl4 complexed with alcohols formed the basis of
modern sol-gel processing. Although silicon alkoxide
chemistry exhibits a number of peculiarities, the
reaction mechanisms for the hydrolysis and conden-
sation of Si(OR)4, where R is an alkyl group, are followed by
analogous to those for many other metal alkoxides.
Si(OR)4 is discussed extensively here as an illustra-
tive example. Detailed descriptions of the alkoxide
chemistry of numerous elements are available else-
where.250 As noted previously, the degree of hydrolysis of the
Si(OR)4 is easily prepared from SiCl4 and the alkoxide precursor (n in Si(OR)4-n(OH)n) strongly
appropriate alcohol, as was reported in the original influences the structure of the Si-O-Si network.
work of Ebelmen:239 Because OH- is a marginally better leaving group
than -OR, the condensation process can be tailored
SiCl4 + ROH f Si(OR)4 + 4HCl (45)
to favor the formation of dimers, chains, or 3-D
agglomerates (Figure 15).
where R ) CH3, C2H5, or C3H7. The resulting prod- A similar effect has been demonstrated with tita-
ucts, in the absence of water, form a stable solution nium(IV) isopropoxide, Ti(OiPr)4, by substituting one
of Si(OR)4 particles. The introduction of water into or two of the OiPr- ligands with bidentate acetyl-
the system initiates hydrolysis. In acidic solution acetonate (acac) (Figure 16). Condensation of Ti-
(OiPr)4 resulted in 10-20 nm particles. In compari-
son, condensation of the precursor in Figure 16a
resulted in spherical, 5 nm particles, and condensa-
tion of the precursor in Figure 16b produced polymer
And in basic solution chains.
Whether the hydrolysis is acid or base catalyzed
also has important consequences for the structure of
the resulting gel network. For Si(OR)4-n(OH)n under
acidic conditions (pH < 4), the rate of hydrolysis will
always exhibit faster kinetics than the rate of con-
Note that eqs 46 and 47 are both nucleophilic densation due to the ability of -OR groups to better
substitution (SN2) reactions, characterized by the stabilize the transition states in eqs 46 and 47.
pentacoordinate transition state of Si. Depending on Moreover, the rate of condensation decreases with
Figure 17. Effects of pH on particle morphology in sol-

gel reactions. (Reprinted with permission from ref 252.
Copyright 1996 Swiss Chemical Society.)
complexes is rapid, to the extent that special han-

dling precautions must be taken to protect the
complexes from water and oxygen. Likewise, the
partial charges on the metals in alkali-metal alkox-
ides are so positive that their hydrolysis reactions
are notoriously violent.
The hydrolysis and condensation of alkali-metal
and alkaline-earth alkoxides in sol-gel type reactions
can be achieved provided that one or more hydroxo
ligands can be bound to the metal. For a transition
Figure 15. Precursors favoring the formation of dimers metal M of charge z+ in aqueous solution, water
and 2-D and 3-D structural moeities in sol-gel processing
of silicon alkoxides. molecules coordinate to the metal by transferring
electrons from their bonding orbitals to empty d-
orbitals on the metal:
Mz+ + hH2O f [M(OH2)h]z+ (56)
where h is the coordination number of the cation. The

electron-transfer weakens the O-H interactions of
Figure 16. Partial substitution of (TiOiPr)4 precursors.
Condensation of precursor A results in spherical particles. bound water, and depending on the pH of the
Condensation of B results in polymer-like chains. solution, various degrees of hydrolysis (deprotona-
tion) can be induced:
increasing n. As a result, Si-O-Si chains tend to
preferentially form in the early stages of the polym- [M(OH2)]z+ / [MsOH](z-1)+ + H+ /
erization process, followed by subsequent branching [MdO](z-2)+ + 2H+ (57)
and cross-linking of the chains during aging. Under
basic conditions, the stability of the transition states Any solvated metal may then be generally repre-
in eqs 46 and 47, and consequently the rate of sented as [MONH2N-h](2-h)+ where N is the coordina-
hydrolysis, increases with increasing n. Under these tion number of the metal and h represents the molar
conditions, the silica products tend to form large ratio of hydrolysis. In the case of highly reactive
agglomerates that eventually cross-link. The differ- compounds, controlling the hydrolysis ratio may
ences between acid and base catalyzed reactions and necessitate the use of nonaqueous solvents, where
the consequences for particle morphology are con- hydrolysis is controlled by strict control of water in
ceptually represented in Figure 17.252 the system rather than by pH. Diao et al. have
recently demonstrated the effectiveness of this ap-
3.1.3. Sol-Gel Chemistry of Aqueous Metal Cations proach in the preparation of gels from Mg(OEt)2 in
methanol and methanol-toluene solvents.253
The tendency of transition metals to exhibit sub- In reactions involving less-reactive metal alkoxides,
stantially lower electronegativities than Si greatly where aqueous solvents can be employed, the sig-
diminishes the stability of their alkoxide complexes nificance of pH in eq 57 is evident: acidic conditions
against hydrolysis. This is reflected in the partial- force the equilibria to the left and favor the formation
charge model: the partial charge, δ, on the metal of of hydroxo ligands, whereas basic conditions will force
a four-coordinate tetraethoxy complex (M(OEt)4) is the equilibria to the right and favor oxo ligands. The
+0.32 for Si, +0.63 for Ti, and +0.74 for Zr. High charge on the metal, however, also plays a significant
positive charges on the metal tend to stabilize the role in the above equilibria with respect to pH, given
transition state during hydrolysis. Consequently, the that highly positive charges on the metals tend to
rate of hydrolysis for the titanium and zirconium substantially weaken the O-H bonds and favor the
Figure 18. Relationship between charge, pH, and hy-

drolysis equilibrium of cations. (Reprinted with permission
from ref 254. Copyright 1972 David Kepert.)
formation of oxo ligands. The relationships between

charge, pH, and the position of the hydrolysis equi-
libria are represented in Figure 18.254
Figure 19. Structural relationship between a sol-gel
3.1.4. Condensation Reactions of Hydrolyzed Metals precursor, a xerogel, and an aerogel.
When the cation of a metal-alkoxide complex is ration, capillary forces induce stresses on the gel that
coordinatively unsaturated (when the coordination increase the coordination numbers of the particles
number N is equal to the cation’s charge, z), conden- and induce collapse of the network. The increase in
sation occurs via an SN2 reaction: particle coordination numbers results in the forma-
tion of additional linkages that strengthen the struc-
ture against further collapse and eventually lead to
the formation of a rigid pore structure. The structure
When, however, the metal is coordinatively saturated of the resulting xerogel can therefore be considered
(N - z > 0), nucleophilic addition occurs: a collapsed, highly distorted form of the original gel
network.
The supercritical extraction of solvent from a gel
does not induce capillary stresses due to the lack of
The three types of ligands that are possibly formed
solvent-vapor interfaces. As a result, the compres-
during hydrolysis differ significantly with respect to
sive forces exerted on the gel network are signifi-
their partial charges. As a consequence, the reactivity
of the metal cation will vary, as well. Because the cantly diminished relative to those created during
condensation of hydrolyzed metals occurs via nucleo- formation of a xerogel. Aerogels consequently retain
philic substitution and nucleophilic addition mech- a much stronger resemblance to their original gel
anisms, the most important characteristics of the network structure than do xerogels (Figure 19).
ligands are their nucleophilicity and leaving group Detailed investigations of the structural evolution of
behavior. As evident in eqs 58 and 59, the condensa- sol gels during aging and drying have been pub-
tion of hydrolyzed metals requires that the metal be lished.255
bound to at least one good nucleophile and one good
leaving group. High nucleophilicity requires that the 3.1.6. Gel Sintering
partial charge of the ligand be less than zero, and The sintering of gels, where the pore network is
the more negative the better. The partial charges of
collapsed and organic species are volatilized, is a
the ligands vary as δ(O2-) < δ(OH-) < δ(OH2),
critical factor in determining the size and morphology
irrespective of the metal they are bound to. Thus, in
of the sol-gel product. Due to the amorphous struc-
general, oxo ligands are good nucleophiles but poor
leaving groups, aquo ligands are good leaving groups ture of the gels, the sintering process is governed
but poor nucleophiles, and hydroxo ligands can serve primarily by viscous flow. The rate of contraction of
as either nucleophiles or leaving groups. Since at the gel networks, ∈, is given by256
least one hydroxo ligand is usually necessary for
3
condensation to occur, operation in the hydroxo γSVxN
region of Figure 18 becomes paramount. ∈) (60)
η
3.1.5. Xerogel and Aerogel Formation
where γSV is the gel’s surface energy, η is the
As a gel is evaporated to dryness, either by thermal viscosity, and N is the number of pores per unit
evaporation or supercritical solvent extraction, the volume. At least one topical review on the viscous
gel structure changessin some cases substantially. sintering of gels is available, although it pertains
During thermal drying or room-temperature evapo- primarily to the preparation of glasses.257
3.1.7. Controlling Particle Size and Morphology drying the product supercritically.263 Despite anneal-
ing at 500 °C, only slight agglomeration of the
As discussed in section 3.1.2, the gel network
nanoparticles was observed.
structure formed by acid- or base-catalyzed hydroly-
Neiderberger et al. have developed an interesting
sis of metal alkoxides can be tailored to favor the
variation of the sol-gel method that produces nano-
formation of polymeric chains with extensive cross-
crystalline products without a calcination step.264 The
linking and branching or the formation of discrete
method involves a nonhydrolytic sol-gel type reaction
spherical particles with minimal cross-linking. For
between a metal chloride and benzyl alcohol that
the purpose of preparing nanoparticles, base-cata-
presumably forms a MCl4-x(OCH2Ph)x or similar
lyzed hydrolysis is clearly preferred, though not
intermediate that undergoes acid-catalyzed hydroly-
always necessary. In any event, experimental evi-
sis by eqs 49 and 50. Particle size was controllable
dence suggests that precursor structure is at least
in the range 4-8 nm by variation of temperature and
as important as control of pH in directing the size
reactant concentrations. The process has since been
and morphology of sol-gel products.258
extended to vanadium and tungsten oxides.265
In the case of hydrolyzed cations, controlling the Other authors have demonstrated that titania
hydrolysis equilibrium can be particularly effective nanoparticles are easily prepared by controlled hy-
for directing the structure of the product. The sol- drolysis and condensation of Ti(OiPr) in an alcohol
gel processing of V2O5 is a vivid example. When solution acidified with HCl followed by supercritical
NaVO3 is solvated in water, cyclic [V4O13]4- results. drying.266,267 Recently, several groups have published
When passed through an ion exchange column, rather elaborate studies on the factors influencing
[V4O13]4- is converted to vanadic acid, H3VO4, which the particle sizes and particle size distributions
in aqueous solution coordinates two water molecules resulting from this reaction. Zhu et al. have detailed
to bring the coordination number of vanadium to the morphology of the products by electron micros-
six.259 Because the VdO and one of the V(OH2) groups copy and small-angle neutron scattering.268,269 Hsu
lie along the z-axis, condensation is restricted to two et al. studied the effects of varying the alkoxide/water
dimensions along the x-y direction. Condensation ratio, HCl concentration, reactant feed rate, and
(olation) along the y-axis, producing corner-sharing temperature.270 Their results indicate that the alkox-
octahedral chains, is fast due to the H2O ligand being ide/water (hydrolysis) ratio and HCl concentration
a good leaving group. Condensation along the x-axis are the most influential parameters governing both
(oxolation), resulting in edge-sharing octahedral mean size and size distribution. Liu et al. investi-
chains, is comparatively slow. Consequently, the gated the influence of UV radiation on the hydrolysis
resulting product consists of ribbonlike chains. and condensation of Ti(OiPr)4 in propyl alcohol.271
They found that UV radiation increased the oxygen
3.2. Sol-Gel Synthetic Methods defect concentration in the as-prepared amorphous
3.2.1. Sol-Gel Syntheses of Oxides TiO2, thereby allowing conversion to crystalline ana-
tase at temperatures as low as 100 °C.
Although the 1988 review by Livage et al. on the Oliveria et al. have adapted the sol-gel synthesis
sol-gel chemistry of transition metal oxides is some- route for titania nanoparticles described above to the
what dated and does not specifically address the synthesis of TixSn1-xO2 solid solutions.272 While rutile-
synthesis of nanoparticles, the paper still ranks as structured TixSn1-xO2 solid solutions are well docu-
one of the more comprehensive and authoritative mented, this appears to be the first report of an
articles written on sol-gel processing.260 The discus- anatase-structured TixSn1-xO2 solid solution.
sion here focuses on recent advances in the sol-gel In an excellent demonstration of the tailoring of
processing of nanoparticulate oxides. precursors to create a homogeneous network of
An important distinction should be made between mixed-metal cations, Yu et al. prepared 60 nm
processes in which a xerogel or aerogel is the end particles of phase-pure PbTiO3 by the hydrolysis and
product and those in which the xerogel or aerogel condensation of a precursor consisting of lead lactate
serves as a precursor that is subsequently calcined, (Pb(CH3CHOHCOO)2) and Ti(OBu)4 followed by cal-
sintered, and so forth. Despite supercritical drying, cinations of the product at 420 °C or higher.273
in the absence of a calcination step, many aerogel Similarly, Gun’ko et al. prepared precursors specif-
reactions will yield amorphous, although nanopar- ically tailored to the hydrolysis/condensation chem-
ticulate, products. Condensation and supercritical istry of the sol-gel process.274 The precursors, in this
drying of a Zr(NO3)4‚5H2O or ZrO(NO3)2‚2H2O pre- case, were substituted metal alkoxides, such as
cursor in alcohol, for instance, produced amorphous,
∼1 nm particles of ZrO2.261,262 Calcination of the FeBr2 + 2NaOtBu + THF (excess) f
product at 400 °C resulted in 2-3 nm agglomerated
particles with a mixed tetragonal/monoclinic phase Fe(OtBu)2(THF)2 (61)
composition.
Calcining an aerogel or xerogel will improve the The precursor formed in eq 61 was subsequently
crystallinity of the sample but normally leads to decomposed by ultrasonic irradiation, and the re-
agglomeration. This can be limited, however, if the sulting precipitate was dried at 300 °C to yield ∼15
calcination conditions are kept moderate. Hamdeh nm Fe3O4 (Figure 20). Starting from precursors of
et al. have prepared spinel-structured Ge0.5Fe2.5Oy Fe[NC(C6H4)C(NSiMe3)2]2Cl or Fe2(OSiPh2)3 resulted
nanoparticles by initiating hydrolysis of a mixture in nanoparticulate γ-Fe2O3 or Fe2O3-SiO2 compos-
containing Ge(OMe)4, Fe(OAc)2, and methanol and ites, respectively.
MoO3,279,281 and MnO2282,283 aerogels in batteries and

RuO2-TiO2284 nanocomposites in supercapacitors. A
recent review on the application of aerogels in
electrochemical energy conversion and storage has
been published by Rolison and Dunn285,286 and is also
covered in the review by Livage et al.260
3.2.2. Sol-Gel Syntheses of Other Inorganics

Though sol-gel methods are most commonly used
to synthesize oxides, the syntheses of carbides,
nitrides, and sulfides by sol-gel processes are also
known. In these instances, hydrolysis reactions,
which invariably produce hydroxides and oxides,
were avoided by performing the reactions in aprotic
solvents under inert atmospheres.
Kim et al. have recently reported the synthesis of
TiN by thermal decomposition of a titanium alkoxy
hydrazide precursor.287 The precursor was prepared
by addition of anhydrous hydrazine to titanium(IV)
isopropoxide in anhydrous acetonitrile to yield a
complex of composition Ti(OiPr)0.83(N2H3)1.17(NH)2‚
3CH3CN. Subsequent decomposition of the precursor
under nitrogen at 1000 °C resulted in 10-20 nm TiN.
The lack of oxides in the product is surprising, given
the presence of OiPr- in the precursor. The authors
attributed this to the presence of carbon (from
CH3CN) inhibiting the crystallization of an oxide
phase. The same authors have reported the syntheses
of ∼10 nm AlN288 and AlON289 powders by similar
routes.249
Nanoparticulate agglomerates of TiS2 and NbS2
have been prepared by reaction of Ti(OiPr)4 or
Nb(OEt)5 with H2S in benzene and acetonitrile solu-
tions, respectively, to yield metal alkoxysulfide in-
termediates.249,290 In these cases, the metal alkoxides
undergo thiolysis that is mechanistically similar to
hydrolysis in many respects. The alkoxysulfides were
decomposed at 600-800 °C under flowing H2S to
yield the metal sulfides.
3.2.3. Sol-Gel Processing of Nanocomposites

The sol-gel processing of silicon alkoxides allows
Figure 20. SEM (top), TEM (middle), and AFM (bottom)
images of Fe3O4 nanoparticles prepared by the hydrolysis/
the low-temperature preparation of amorphous phases.
condensation of a metallorganic precursor. (Reprinted with When metal oxides or metal chalcogenides are hy-
permission from ref 274. Copyright 2001 Kluwer Academic drolyzed and condensed simultaneously with silicon
Publishers.) alkoxides, the metal-containing nanoparticles become
dispersed in an amorphous silica matrix. The nano-
As an example of the variety of materials that can particles embedded in the silica tend to exhibit
be prepared by the condensation of hydrolyzed met- extremely narrow size distributions, and if the metal
als, Cerda et al. prepared 200-500 nm BaSnO3 by nanoparticle concentration is kept low, the particles
calcining a gel formed between Ba(OH)2 and K2SnO3 tend to be very well dispersed. Furthermore, the
at pH ∼ 11.275 The product contained a BaCO3 silica matrix tends to exhibit mesoporous structural
impurity unless calcined above 1000 °C, which led features, giving the composites high porosities and
to substantial aggregation of the particles. allowing for rapid mass exchange with liquids and
In recent years, the application of xerogels and gases. As such, nanoparticles dispersed in glass
aerogels in electrochemical energy storage has gained matrixes are very useful as heterogeneous cata-
increased attention. The high surface areas and lysts291-294 and chemical sensors.295-297 The highly
mesoporous structures of xerogels and aerogels ap- dispersed imbedded particles also greatly facilitate
pear to allow the storage of substantially more energy investigations of magnetic properties, since interpar-
than the same compounds prepared as dense, crys- ticle interactions can be minimized. Furthermore,
talline powders.276-278 Unfortunately, only a hand- imbedding nanoparticles in an amorphous matrix can
ful of elements exhibit metal-alkoxide chemistries have profound consequences for the nonlinear optical
amenable to sol-gel type syntheses. Investigations properties of materials, particularly when the nano-
have therefore been limited primarily to V2O5,279,280 composite is prepared as a thin film.298-300
Most sol-gel-based nanocomposite syntheses can be prior to addition to a TEOS solution at low pH. The
categorized as involving either (a) the mixing of a gels were aged and dried at room temperature to
preformed colloidal metal (or oxide) with a sol con- form xerogels. The photoluminescences of the com-
taining the matrix-forming species followed by gela- posites were found to vary significantly, depending
tion, (b) the direct precipitation of metal, metal oxide, primarily on the capping ligand.
and so forth nanoparticles within a prehydrolyzed With respect to the second approach, precipitation
silica sol, or (c) complexing the metal to a function- of metal or metal oxide particles from their precur-
alized silane and reducing the metal prior to hydroly- sors is carried out within the silica sol, usually by a
sis/condensation. Bronstein et al. have recently pub- low-temperature heat treatment. This in-situ nucle-
lished a comprehensive review of these techniques.301 ation/growth approach is generally used for the
With respect to the first approach described above, preparation of thin films,308 but solid monoliths may
the colloidal metal or metal oxide nanoparticles will also be prepared this way.
normally contain a stabilizing agent at the particles’ Liz-Marzán et al. developed a technique to apply
surfaces (see section 2.1.4). Consequently, the size SiO2 coatings to colloidal Au, forming an Au@SiO2
and size distribution of the individual colloidal par- core-shell arrangement.309 The Au sol was prepared
ticles are largely determined by their method of by the citrate method and a solution containing (3-
synthesis, before they are ever introduced into the aminopropyl)trimethoxysilane (3-APTMS) was added
sol. If the resulting gel is heated to even moderately to it, followed by a solution of sodium silicate. The
high temperatures, however, the stabilizing agent amino functional groups of the 3-APTMS were ef-
may decompose, leaving the colloidal particles subject fectively bound to the Au surfaces. The Si-O-Si
to aggregation unless the colloid concentration within network was formed by addition of the silicate ions
the sol is very low. Nanocomposites consisting of gold under basic conditions:
imbedded in silica matrixes are a common target with
this approach, which is not surprising given the well-
developed methods of preparing Au colloids and the
potential applications of gold nanoparticles in het-
erogeneous catalysis. Anderson et al. prepared such
a composite by adding a sol of colloidal Au (prepared
by the citrate method) to a silica sol, casting the sol
into a mold, and drying the composite supercritically After deposition of the initial SiO2 shell, the thickness
to form an aerogel.302 They were able to demonstrate of the SiO2 layer could be increased by mixing the
the porosity of the silica matrix by adsorbing methyl product with TEOS dissolved in an ethanol solution;
orange on the surfaces of the Au nanoparticles after SiO2 shells as thick as 83 nm have been successfully
the composite had been cast and dried. Others have grown (Figure 21). Lu et al. were able to prepare Au-
prepared similar composites starting from Au nano- SiO2 with shells as thick as 80 nm by a similar meth-
particles passivated with dodecanethiol.303 Wallace od in which the shells were deposited on Au colloids
et al. have adapted such Au-SiO2 composites to allow from TEOS solutions and the thickness was con-
the Au nanoparticles to act as nucleating agents for trolled by adjusting the reaction time.310 Ag@SiO2,311
self-organized protein superstructures that are sub- Fe2O3@SiO2,312 Fe3O4@SiO2,313 and CdTe@SiO2314 nano-
sequently encapsulated in the silica matrix after particles have been prepared by similar schemes.
supercritical drying.304 Cheng et al. prepared Au-SiO2 by combining
colloidal gold with a prehydrolyzed TEOS solution in
Morris et al. developed an intriguing variation of the presence of a dibenzoyltartaric acid stabilizer.315
this technique in which the colloidal solid is added After aging and drying, the resulting aerogel was
to a silica sol just prior to gelation.305 By minimizing calcined at 550 °C to produce 2-8 nm Au particles
the time of interaction between the colloidal particles homogeneously distributed in amorphous silica with
and the silica network, the colloids were not fully 3-4 nm pores. Others have achieved similar results
encapsulated by the silica network, which may be with Au imbedded in borosilicate glass.316
significant in terms of preserving the properties of Fonseca et al. prepared Ni-SiO2 nanocomposites
the guest species (catalytic activity, optical proper- by adding a mixture of Ni(NO3)2 and TEOS to a
ties, etc.). Colloidal particles of Pt, Au, carbon black, solution of citric acid dissolved in ethanol.317 Poly-
titania, and FeII(bpy) imbedded in zeolite have been esterification was induced by addition of ethylene
successfully incorporated into SiO2 matrixes in this glycol to the reaction mixture, and pyrolysis was
manner. carried out at 500 °C under inert atmosphere. The
Richard-Plouet et al. modified this technique such nickel ions were reduced by CO generated from
that Co2+ ions were complexed to PVA-based poly- pyrolysis of the organic matrix. The resulting Ni-
meric “microcapsules” prior to addition to a silica SiO2 nanocomposite contained 1.5-5 wt % of ∼3 nm
sol.306 Thermal treatments of the resulting gels under Ni particles dispersed in amorphous SiO2. The em-
a reducing atmosphere resulted in the formation of bedded Ni particles exhibited no signs of oxidation,
Co nanoparticles with an average diameter of ∼50 suggesting that the SiO2 matrix protects the embed-
nm. The silica matrix appeared to stabilize the Co ded particles.
particles against oxidation. Corrias et al. have reported FeCo-SiO2 composites
Zhang et al. have adapted this technique to the prepared in a similar manner.318,319 Interestingly, the
synthesis of luminescent Si-SiO2 nanocomposites.307 nature of the counterion in the metal salts was
The Si nanoparticles were stabilized with amino acids observed to influence the structure of the resulting
Figure 21. (A) TEM images of 15 nm Au particles coated with thin silica layers: (top) 18 h after addition of active silica;
(center) 42 h after addition; (bottom) 5 days after addition. (B) The silica shell keeps growing, but eventually small SiO2
particles nucleate from solution. (Reprinted with permission from ref 309. Copyright 1996 American Chemical Society.)
nanocomposite, in that metal nitrates favored the complexes are reduced to form metal nanoparticles
formation of low-density aerogels via a ferrihydrite prior to hydrolysis/condensation of the sol, Bharathi
+ Co3O4 intermediate,320 whereas metal acetates prepared Au-SiO2 by complexing an amino-function-
favored higher-density xerogels via a CoFe2O4 inter- alized silane to HAuCl4, inducing gelation, and re-
mediate.321 ducing the metal cations with sodium borohydride.327
The technique of precipitating a metal in a prehy- By binding to the gold surfaces, the aminosilane
drolyzed silica sol has also recently been employed groups ensured good homogeneity of the Au particles.
by Wu et al. for the preparation of Ag-SiO2 nano- Subsequent hydrolysis and condensation of the si-
composites.322 Aqueous AgNO3 solutions were added lanes resulted in the formation of the Si-O-Si
to prehydrolyzed TMOS sols prior to gelation. When network in which the Au particles were dispersed.
the condensation reaction was catalyzed by HCl, The resulting gels could be dried into monoliths or
reduction of Ag+ occurred via the photodecomposition deposited as thin films. An interesting variation of
of an AgCl intermediate. When catalyzed by HNO3, this experiment involves initiating hydrolysis/con-
the Ag+ reduction was explained as the likely result densation of the silane prior to reduction of the metal,
of photodecomposition of a complex formed between which yields 4-6 nm Au-SiO2, Pt-SiO2, or Pd-SiO2,
Ag+ and methanol radicals resulting from TMOS but 2-20 nm Ag-SiO2 particles.328
hydrolysis. Morley et al. have prepared similar Ag- Kobayashi et al. took a somewhat different ap-
SiO2 nanocomposites by thermal decomposition of proach to the synthesis of Au-SiO2 composites by
Ag+ complexes in silica sols in scCO2.323 first preparing Au@SiO2 core-shell particles and
Casas et al. have precipitated iron oxides in silica subsequently imbedding them in an amorphous SiO2
sols by combining Fe(NO3)3‚9H2O with TEOS in matrix.329 The Au@SiO2 was prepared by addition of
ethanol.324 The hydrated iron salt provided sufficient an aminosilane and sodium silicate to colloidal Au
water to induce hydrolysis of the orthosilicate. When prepared by the Turkevich method, resulting in Au
dried supercritically, their method resulted in ∼5 nm nanoparticles with 5-7 nm thick SiO2 shells in a
particles of Fe5HO8‚4H2O imbedded in a porous silica stable dispersion.309 The Au@SiO2 particles were
matrix. No phase change was observed when the imbedded in a SiO2 matrix by adding sodium silicate
samples were calcined. When prepared as a xerogel, or TMOS to the Au@SiO2 dispersion, lowering the
however, the iron nanoparticles were amorphous and pH, and inducing hydrolysis/condensation of the Si-
crystallized as a mixed γ/R-Fe2O3 phase when cal- O-Si network. As such, the possibility of the colloidal
cined at 400 °C or pure R-Fe2O3 when calcined at 600 particles agglomerating prior to gel formation was
°C. Others have prepared NiO-SiO2 and Ni-SiO2 greatly diminished and the Au@SiO2 exhibited excel-
nanocomposites by similar methods.325,326 lent dispersion in the silica matrix.
With respect to the third approach of preparing Nanocomposites formed by sol-gel processing are
metal-silica nanocomposites, where metal-silane not limited to metal nanoparticles or to silica ma-
trixes. Claus et al. developed a similar method for

imbedding gold nanoparticles in a TiO2 matrix by
substituting Ti(OBu)4 for TEOS, adding colloidal gold
by dropwise addition, and calcining the dried gel at
450 °C. The resulting Au-TiO2 composite contained
Au particles with a mean diameter of 1.1 nm. Others
have prepared Au@ZrO2 core-shell particles by a
similar method.330
Caizer et al. have reported a series of ZnxNi1-xFe2O4
(x ) 0.15, 0.35, 0.65) nanoparticles imbedded in SiO2
by simply adding TEOS to a water-ethanol solution
containing the proper stoichiometric ratios of dis-
solved metal nitrates.331 After drying, the gels were
annealed at 1100 °C. The products consisted of
amorphous silica containing a near-homogeneous
dispersion of 8-20 nm oxide particles. Ni-SiO2,
γ-Fe2O3-SiO2, and ZnO-SiO2 nanocomposites have
been prepared by almost identical methods, but
usually with lower calcinination temperatures, or
calcination under an H2 atmosphere in the case of
Ni.332
Figure 22. Conceptual representation of the condensa-
Xing et al. prepared ZnO-BN and TiO2-BN as- tion between a metal cation, citric acid, and a polyol: the
semblies by combining ZnO or TiO2 sols suspended early stages of the Pechini method. (Adapted from ref 338
in ethanol with a mixture of boric acid and urea, also with permission from the American Ceramic Society,
dissolved in ethanol.333 The BN is formed by www.ceramics.org. Copyright 1999. All rights reserved.)
H3BO3 + CO(NH2)2 f BN + H2O + COv (63) 3.3.1. Chelate Selection and Complex Formation
The literature contains numerous variations of the
and the resulting gels were calcined at 200-700 °C Pechini method, most involving alternative chelating
after drying. The products consisted of 10 nm agents. Ethylenediaminetetraacetic acid (EDTA) is
ZnO or 17 nm TiO2 encapsulated in concentric BN occasionally substituted for citric acid.340,341 EDTA is
sheets. widely used as a complexing agent for quantitative
complexometric titrations due to its ability to bind
almost any cation. The four carboxylate groups allow
3.3. The Pechini Method the molecule to behave as either a bi-, tri-, tetra-,
penta-, or hexadendate ligand, depending on the pH
In 1967, Pechini developed a modified sol-gel
of its solution. Although EDTA’s binding ability tends
process for metals that are not suitable for traditional
to increase with increasing pH, the polyesterification
sol-gel type reactions due to their unfavorable hy-
reaction between carboxylic acids and polyalcohols
drolysis equilibria.334 Although Pechini’s original
that is necessary for gelation is acid catalyzed.
method was developed specifically for the preparation
Fortunately, due to its zwitterionic character, EDTA
of thin films, it was later adapted to the synthesis of
will still bind many metals as a bidentate ligand,
powdered products.
even under highly acidic (pH < 4) conditions.
The Pechini method, as it is now referred to, relies Oxalic acid and polymeric alcohols such as poly-
on the formation of complexes of alkali metals, (vinyl alcohol) (PVA) have also been used as chelating
alkaline earths, transition metals, or even nonmetals agents for Pechini type syntheses.342,343 In the case
with bi- and tridendate organic chelating agents such of polymer alcohols, given the 3-D network provided
as citric acid. A polyalcohol such as ethylene glycol by the polymer, addition of a polyol and subsequent
is added to establish linkages between the chelates esterification are not necessary. The polymer is sim-
by a polyesterification reaction, resulting in gelation ply combined with the metal cations in solution to
of the reaction mixture. This process is represented form a precursor that is subsequently calcined to py-
schematically in Figure 22. 13C and 87Sr NMR studies rolyze the organic species. These reactions are some-
of some gelled precursors have recently been pub- times referred to as polymer combustion syntheses.
lished.335-337 After drying, the gel is heated to initiate There are a number of syntheses reported in the
pyrolysis of the organic species, resulting in ag- literature that, while similar to the Pechini method
glomerated submicron oxide particles. in their use of carboxylic acid-based chelating agents
The advantage of the Pechini method lies in the and pyrolysis of the resulting precursors, forego the
elimination of the requirement that the metals use of a polyol or similar reagent to induce polym-
involved form suitable hydroxo complexes. Chelating erization.344,345 As such, it is unclear whether these
agents tend to form stable complexes with a variety solutions are in fact forming gels or simply contain
of metals over fairly wide pH ranges, allowing for the precipitated metal-citrate complexes. We have noted
relatively easy synthesis of oxides of considerable that the products of such reactions tend to exhibit
complexity. Review articles covering the Pechini relatively large crystallite sizes with irregular mor-
process are available, although rare.338,339 phologies.346,347
Table 5. Representative Sampling of Oxides Prepared by the Pechini Method

starting chelating polymerization calcination product
compd material agent agent temp (°C) size (nm) ref
ZnTiO3 Zn(OAc)2 CA EG 500-1000 18-31 348
Ti(OBu)4
SrTiO3 Ti(OBu)4 CA + PAA EG 550-700 <500 349
YNi0.33Mn0.67O3 Y(NO3)3 CA EG 750-800 17 350
Ni(NO3)2
Mn(NO3)2
YBa2Cu3O7-δ Y(NO3)3 CA EG 920 not stated 351
BaCO3
CuCO3
YxZr1-xO2-x/2 Y(NO3)3 CA EG 600-1000 ∼20 352
ZrCl4
ZrxCe1-xO2 ZrOCl2 glycine none 600 13 353
(x ) 0.35) (NH4)2Ce(NO3)6
BaTiO3 BaCO3 CA EG 700-1100 50-340 354
Ti(OiPr)4
BaCeO3 BaCO3 CA EG 800-1000 ∼100 355
Ce(NO3)3
LaCoO3 La(NO3)3 glycine none 800 35 356
Co(NO3)2
RExLi1-xNbO3 Li2CO3 CA EG 500-900 40-60 357
(RE ) La, Pr, Sm, Er) Nb-ammonium complex
La2O3
Pr2(CO3)3
Sm2(CO3)3
Er2(CO3)3
La1.85Sr0.15CuO4 La(NO3)3 CA EG 900 <1 µm 351
SrCO3
Cu(NO3)2
Pb3MgNb2O9 PbCO3 CA EG 400-800 ∼50 358
MgCO3
Nb(OEt)5
Bi2Sr2Can-1CunO4+2n+δ Bi(NO3)3 EDTA none 700 not stated 359
(n ) 1, 2, 3)
3.3.2. Limitations of the Pechini Method sintered into dense ceramic pellets. This is particu-
larly useful for materials used as electrodes in devices
The primary disadvantage of the Pechini method such as the solid-oxide fuel cell (SOFC), where the
lies in the lack of control over particle size, shape, electrodes must be sufficiently dense as to not allow
and morphology. Unlike traditional sol-gel processes, permeation of gases through cracks or pores.
where the metal itself becomes an integral part of
the gel network, the gel network in the Pechini 3.3.3. Oxide Syntheses with the Pechini Method
method is formed by the esterification of the chelating The number of oxides prepared by the Pechini
agent and polyalcohol. The metal ions are essentially method now stretches into the hundreds. A repre-
trapped in the organic matrix, to which they are sentative sampling demonstrating the flexibility of
weakly bound. As such, the Pechini method cannot the method is given in Table 5. The discussion here
easily produce specific structural moieties such as should be considered an overview of recent develop-
2-D chains and ribbons. The particles obtained after ments and representative examples.
calcination are virtually always spherical or nearly Most syntheses involving the Pechini method still
spherical, and at least some aggregation from sin- use citric acid as the metal chelating agent and
tering should be expected. ethylene glycol as the polyol. Among the more recent
The Pechini method does afford some control over oxides prepared this way are 25 nm Y2O3,360 500 nm
particle size, but this is primarily achieved by varia- Bi2Ru2O7,361 sub-100 nm lanthanide-doped Y3Al5O12
tion of the calcination temperatures. If a pure product (YAG),362 LiMn2O4,363 BaFe12O19,364 and numerous
(free of organic contaminants) is to be obtained, perovskite-structured materials, such as LaCoO3365
calcination temperatures of at least 300 °C are and Ba(In0.67Mo0.33)O3.366
usually necessary, and some chelating agents require Oxides prepared using EDTA as chelating agent
substantially higher decomposition temperatures. include Ba2Ti9O20. The substitution of EDTA for citric
Furthermore, although the Pechini method could, in acid substantially reduced the amount of time the
theory, be adapted to the synthesis of sulfides, sample had to be calcined at 1200 °C in order to
carbides, or nitrides, to our knowledge, no such obtain a single-phase product.341 Similarly, Sen and
synthesis has ever been reported. The method should Pramanik prepared a series of nanocrystalline mo-
therefore be considered limited to the synthesis of lybdates by complexing the ions with EDTA in the
oxides. presence of PVA and sucrose and heat-treating the
Given the above limitations, it is not surprising precursor at 500 °C.367
that the Pechini method is frequently used to prepare Among the oxides prepared using oxalic acid as a
fine particles that are subsequently compacted and chelating agent are two (Tl0.6Pb0.2Bi0.2)Sr4-xCaxCu3Oy
Figure 24. Structure of cetyltrimethylammonium bromide

(CTAB), a common surfactant used in microemulsions.
Figure 25. Schulman’s model of the reverse micelle, as

published in 1943. (Reprinted with permission from Nature
(http://www.nature.com), ref 372. Copyright 1943 Nature
Publishing Group.)
Figure 23. TEM micrographs of LiMn1.9Cr0.1O4 powders
prepared by the Pechini method and calcined at (a) 500
°C, (b) 600 °C, (c) 700 °C, and (d) 800 °C. (Reprinted with ingly homogeneous solutions that Schulman termed
permission from ref 368. Copyright 2003 Kluwer Academic “micro emulsions.”372 The oil phases, in this case,
Publishers.) were simple long-chain hydrocarbons, and the surf-
actants were long-chain organic molecules with a
(x ) 2, 2.4) superconductors.342 The oxide gels were hydrophilic head (usually an ionic sulfate or quar-
prepared by dissolving the metal nitrates in water, ternary amine) and lipophilic tail. The surfactant in
adding an excess of oxalic acid, adjusting the pH to Schulman’s study was cetyltrimethylammonium bro-
∼7, and heating at 100-120 °C. The dried precursor mide (CTAB), which is still used extensively today
was subsequently annealed at temperatures up to (Figure 24).
940 °C under oxygen. Oxalic acid was substituted for The amphiphilic nature of the surfactants such as
citric acid in order to lower the decomposition tem- CTAB makes them miscible in both hydrocarbons
perature of the chelate and improve the purity of the and water, but when the surfactant is mixed with a
final product. hydrocarbon, the resulting mixture, although opti-
LiMn2-xCrxO4, which is of interest as a lithium-ion cally isotropic, cannot be properly described as a
battery cathode material, has been prepared by a solution. As noted by Schulman, the orientation of
modified Pechini method using PVA as a chelating the surfactant molecules is not random.373 Instead,
agent.368 The metal nitrates were dissolved in aque- the surfactant, through ion-dipole interactions with
ous solution to which PVA was added. After drying the polar cosurfactant, forms spherical aggregates in
at 80 °C, the precursors were calcined at 500-900 which the polar (ionic) ends of the surfactant mol-
°C. Agglomerates ranged from 25 to 90 nm in ecules orient toward the center. The cosurfactant acts
diameter depending on the calcination temperature as an electronegative “spacer” that minimizes repul-
(Figure 23). 33 nm average diameter Co3O4 particles sions between the positively charged surfactant
were prepared by a similar route with decomposition heads. The addition of water to the system will cause
at 350 °C,369 and 5-30 nm NiFe2O4 has been pre- the aggregates to expand from the center as the
pared using poly(acrylic acid) (PAA) as the complex- water molecules (again as a result of ion-dipole and
ing agent, followed by heating at 300 °C.370 dipole-dipole interactions) situate at the center of
Very recently, Tan et al. prepared LaCoxMn1-xO3 the sphere (Figure 25).
perovskites with average diameters of 14 nm (x ) Later, Friberg demonstrated through a series of
0.4) and 18 nm (x ) 0.3) by complexing mixtures of NMR and IR experiments that the orientation of the
the metal cations (preprecipitated as hydroxides) molecules in the microemulsions minimizes inter-
with diethylenetriaminepentaacetic acid (H5DTPA).371 facial tension between aggregates, and as such,
The complex was calcined at 500 °C with relatively microemulsions are thermodynamically stable.374
little sintering observed. This stability distinguishes microemulsions from
traditional macroemulsions, which are, by definition,
thermodynamically unstable.
4. Microemulsions
The following discussion will be brief, given the
4.1. Fundamentals of Microemulsions abundance of review articles both on the general
characteristics of microemulsions375-382 and on their
Hoar and Schulman noted in 1943 that certain extensive use as micro- and nanoreactors.380,383-388
combinations of water, oil, surfactant, and an alcohol- The review article by Winsor, though outdated,
or amine-based cosurfactant produced clear, seem- stands out among the review papers concerning
Figure 26. Structure of AOT (sodium bis(2-ethylhexyl)-

sulfosuccinate).
microemulsion phase behavior, and much of the

theory discussed therein is still valid.389 The more
recent paper by Silber et al., that comprehensively
reviews the methodologies for probing the physical
and chemical properties of microemulsions, is also
noteworthy.390
4.1.1. Common Surfactants

Figure 27. Phase diagram for the H2O-AOT-isooctane
The CTAB surfactant investigated by Schulman in microemulsion system at 15 °C. Om denotes the reverse
micellar region. (Reprinted with permission from ref 393.
1943 has since been more thoroughly investigated.391 Copyright 1979 Elsevier.)
More recently, other surfactants have emerged, most
notably sodium bis(2-ethylhexyl)sulfosuccinate (gen-
erally referred to by its trade name, Aerosol OT or surfactant, then
AOT) (Figure 26).392 Like CTAB, AOT is ionic, but
in this case the amphiphile is an anion. The funda- ΣM ) 4πRM2 ) nsΣs (67)
mental properties of AOT and AOT-based micro-
emulsions have been investigated rather exten- where Σs is the molar interfacial area at the surfac-
sively.393-410 Somewhat less commonly used are tant-oil boundary. Since the volume in this model
nonionic surfactants, most based on polyethylene is fixed, then
ethers such as pentaethylene glycol dodecyl ether
(PEGDE), CH3(CH2)11-O-(CH2-CH2-O-)5-H,50 or [H2O] nw
Triton-X:411,412 ω0 ) ) (68)
[S] ns
Combining eqs 66-68 gives
3Vs 3Vwω0
RM ) + (69)
where n ≈ 10. Reviews detailing the phase behav- Σs Σs
iors of numerous nonionic surfactants are avail-
able.413,414 Experimentally, RM has been shown to vary lin-
early with water content in various AOT and CTAB
4.1.2. Reverse Micelle Formation and Phase Equilibria reverse micellar systems above a critical ω0 of about
10, below which Vs, Vw, and Σs also increase with
The spherical aggregates described by Schulman increasing ω0.391,392 As such, the size of the water pool
and represented in Figure 25 are commonly referred at the reverse micelle core can be carefully controlled
to as reverse micelles and are generally characterized by adjusting the [H2O]/[S] ratio, provided ω0 g 10.
by ω0, the molar ratio of water to surfactant, S: However, controlling the size of the reverse micelles
does not address the issue of micelle formation. As a
ω0 ) [H2O]/[S] (65) four-component mixture of oil-water-surfactant-
cosurfactant, the phase equilibria of reverse micelle
To establish the relationship between ω0 and the systems are inherently complex.415,416 Friberg noted
micellar radius, RM, we first consider the micellar early on that microemulsions tend to form over fairly
molar volume, VM, given by limited oil/water/surfactant ratios.374 Such phase
relationships are normally depicted with Gibbs tri-
4πRM3 angles; a representative example is given in Figure
VM ) ) nsVs + nwVw (66) 27, where Om (oil-continuous micelle phase) repre-
3
sents the region of interest.393 Note that solutions
where ns and nw are the moles of surfactant and containing low volume fractions of oil form liquid
water per micelle, respectively, and Vw is the volume crystalline (LC) phases and that solutions containing
of water in the micelle.380 Assuming that the surface more than 50% H2O versus AOT tend to contain both
area of a micelle, ΣM, is determined solely by the an Om and a water phase.
Experiments focusing on the interfacial water of

reverse micelles have confirmed that the water
molecules in close proximity to the surfactant are
greatly influenced by dipole-dipole and ion-dipole
interactions with the ionic surfactants and polar
cosurfactants, and are largely immobilized.397,404 The
water at the reverse micelle core is affected to a lesser
extent, but the immobilization of the interfacial water
reduces the effective radius, RE, of the core water pool
(that which is available for solvation, transport, etc.
of dissolved salts) to RE ≈ 1/2ω0.
Last, the presence of the surfactant molecules in
the reverse micelles, which to some extent act as
capping agents, may serve to prevent flocculation of
the products but does not alleviate the issue of
Ostwald ripening (section 2.1.3).420
Figure 28. Schematic of a collision between two reverse 4.1.4. Factors Influencing Surfactant Selection
micelles with dissimilar cores. The micelles form a short-
lived dimer, as some surfactant molecules are released into Careful consideration of a number of factors is
the oil phase and the contents of the micellar cores are advisable when selecting a suitable surfactant, start-
exchanged. ing with the reactants and reaction conditions. The
surfactant should be chemically inert with respect
4.1.3. Reaction Dynamics in Reverse Micelles to all other components of the microemulsion. This
The small size of reverse micelles subjects them to is particularly relevant when the system contains
continuous Brownian motion, even at room temper- oxidizing or reducing agents. On this matter, both
ature. Collisions between micelles are frequent, and CTAB and AOT are stable against mild oxidizers, like
approximately one collision in every thousand results dilute H2O2, and mild reducing agents, such as
in the formation of a short-lived dimer, formed by the hydrazine. However, stronger reducing agents such
expulsion of some surfactant molecules into the bulk as borohydride ions can be problematic.421
oil phase (Figure 28).400,417 During the ∼100 ns The possible interference of the counterions of ionic
lifetime of the dimer, two reverse micelles will surfactants should likewise be carefully considered.
exchange the contents of their aqueous cores before In a reaction involving Ag+, for instance, the dissoci-
decoalescing, resulting in the eventual equilibrium ated Br- ions of CTAB would cause immediate
distribution of all contents.396 precipitation of AgBr. The Na+ ions of AOT could
Given the above model of reverse micelle interac- similarly interfere with an intended precipitation
tion, the suitability of reverse micelles as nanoreac- reaction, that is, resulting in NaMnF3 instead of
tors becomes evident. Since the size of the water pools KMnF3.422 Fortunately, at least in the case of AOT,
in reverse micelles can be controlled by adjusting ω0, Na+ can be exchanged for ions more compatible with
and the Brownian motion of the particles allows the the synthesis prior to incorporation into reverse
distribution of reactants, then not only can reactions micelles.423
be performed inside the micellar cores, but also the
products will have nearly uniform size and shape. 4.2. Microemulsion Synthetic Methods
The earliest reports of syntheses inside reverse 4.2.1. Synthesis of Metals by Reduction
micelle cores involved the preparation of colloidal
metals in the early 1980s,50 although the reaction When a reverse micelle solution contains a dis-
dynamics of microemulsions were still not fully solved metal salt and a second reverse micelle solu-
understood at the time. tion containing a suitable reducing agent is added,
The complexity of reverse micelle systems should the metal cations can be reduced to the metallic state.
not be underestimated, especially after ionic salts Such reactions are, for all practical purposes, identi-
have been dissociated in the aqueous cores. Equilib- cal to those discussed in section 2.1 for the precipita-
rium constants and reaction rates frequently vary by tion of metals from aqueous solutions. Although the
more than an order of magnitude compared to the number of metals that can be prepared this way is
cases of similar systems in bulk aqueous solution.407 somewhat limited by the aqueous nature of the
Solvated ions tend to affect both the stability of reactions, this approach has garnered much attention
reverse micelles and the phase equilibria.401,418 In due to the potential application of the products as
particular, solvated ions in reverse micelles formed catalysts.50 Table 6 provides a partial list of the
from ionic surfactants cause a contraction of RM, due metals prepared by this method.
to interactions with the charged surfactant heads, The reducing agent must be stable in an aqueous
and tend to make the micelles more spherical.399 environment and not react with the other compo-
Moreover, the influence of solvated ions on RM nents of the reverse micelle system. This immediately
tends to increase with increasing concentration and excludes all nonaqueous reducing agents, such as
charge.394 Predictably, interactions with the surfac- those discussed in section 2.2.2. Since bubbled H2 gas
tant also change the physicochemical properties of results in slow reduction kinetics for many metals,
the solvated ions.408,419 particularly at room temperature,50 sodium borohy-
Table 6. Representative Examples of Nanoparticulate Metals Prepared by Reduction in Microemulsions

metal starting material surfactant reducing agent reaction conditions product size (nm) ref
Co CoCl2 AOT NaBH4 <1 424
Ni NiCl2 CTAB N2H4‚H2O pH ∼ 13 4 370
Cu Cu(AOT)2 AOT N2H4 2-10 425, 426
Cu(AOT)2 AOT NaBH4 20-28 425, 426
Se H2SeO3 AOT N2H4‚2HCl 4-300 427
Rh RhCl3 PEGDE H2 3 50
Pd PdCl2 PEGDE N2H4‚H2O pH ∼ 7 4 50
Ag AgNO3 PEGDE NaBH4 3-9 421
Ir IrCl3 PEGDE H2 70 °C 3 50
Pt H2PtCl6 PEGDE N2H4‚H2O 3 50
Bi BiOClO4 AOT NaBH4 Ar atm 2-10 428
Figure 29. Absorption spectra, size-distribution histograms, and TEM images of Cu nanoparticles reduced with NaBH4
at various ω ) [H2O]/[AOT] ratios. (Reprinted with permission from ref 425. Copyright 1993 American Chemical Society.)
dride and hydrazine (usually in the form of water- 2PtCl42- + N2H5+ / Pt + N2v + 5H+ + 8Cl- (71)
soluble N2H4‚2HCl or N2H4‚H2O) are most commonly
employed in such reactions. This reaction, performed in a PEGDE-hexane-
The reduction of most metals is straightforward. water microemulsion, resulted in stable suspensions
One of the earliest reported reduction reactions in of 3 nm Pt particles.
reverse micelles was that of H2PtCl6 with hydrazine Lisiecki and Pileni adapted the technique to the
via a PtCl42- intermediate:50 reduction of Cu2+ with hydrazine and NaBH4, but
they started from a Cu(AOT)2 precursor:425,426
2PtCl62- + N2H5+ /
2- + -
Cu(NO3)2 + 2Na+AOT / Cu(AOT)2 + 2NaNO3
4PtCl4 + N2v + 5H + 4Cl (70) (72)
This technique is advantageous in that the NO3- are presented in Figure 30 and are typical for
counterions can be removed from the precursor, products of these types of reactions.
thereby avoiding any potential interferences, as
discussed in section 4.1.3. Using hydrazine as the 4.2.2. Synthesis of Alloys by Reduction
reducing agent, Lisiecki and Pileni obtained 2-10 nm Substitutional alloys can similarly be prepared if
Cu particles, whereas borohydride resulted in par- salts of different metals are dissolved in the reverse
ticles of 20-28 nm (Figure 29). micelle solution prior to reduction, provided the two
The reduction of oxo ions is somewhat more com- metals are miscible in the metallic state. Reverse
plicated and provides an example of where the control micelle solutions containing both Fe2+ and Pt2+, for
of pH is particularly important. In the case of example, have been reported as being simultaneously
H2SeO3, for example:427 reduced with BH4-.429 Variation of the Fe/Pt ratio
resulted in FePt, Fe2Pt, disordered FePt3, or ordered
FePt3.429,430
4.2.3. Synthesis of Metal Oxides
The synthesis of oxides from reverse micelles relies
Both BH4- and N2H4‚H2O would have failed in the on the coprecipitation of one or more metal ions and
above example barring the addition of acid, since the is similar in most respects to the precipitation of
presence of H+ is required to initiate the reduction oxides from aqueous solutions (section 2.2.5). Typi-
process. cally, precipitation of hydroxides is induced by addi-
The dispersities and size distributions of metal tion of a reverse micelle solution containing dilute
nanoparticles precipitated in microemulsions are NH4OH to a reverse micelle solution containing
typically very good. The TEM image and size distri- aqueous metal ions at the micellar cores. Alterna-
bution chart for Ni nanoparticles precipitated from tively, dilute NH4OH can simply be added directly
a water-CTAB-n-hexanol system by Chen et al.370 to a micelle solution of the metal ions. The precipita-
tion of the metal hydroxides is typically followed by
centrifugation and heating to remove water and/or
improve crystallinity. This technique has proven par-
ticularly useful in preparing mixed-metal ferrites:431
∆, O2
M2+ + 2Fe2+ + OH- (excess) 98
MFe2O4 + xH2Ov (74)
where M ) Fe, Mn, or Co. The oxidation of Fe2+ f

Fe3+ results from the reaction being performed under
air, although other authors prefer to use Fe3+ as a
starting material.432 The products were typically on
the order of 10-20 nm in diameter. Zhang et al. have
recently demonstrated that, at least in the case of
MnFe2O4, the cation distribution within the spinel
structure of oxides prepared this way exhibits a
strong temperature dependence.433
In cases where a transition metal cation is either
not soluble or not stable in aqueous solution, nano-
particles may be prepared by hydrolysis of a suitable
precursor, very similar to the reactions used in the
sol-gel method (section 3.1). TiO2, for example, has
been prepared from tetraisopropyl titanate:434
Ti(OiPr)4 + 2H2O f TiO2 + 4(iPr-OH) (75)
In this case, the reverse micelles containing the

precursor were prepared in the absence of water;
hydrolysis occurred when a second water-containing
reverse micelle solution was added. Proper adjust-
ment of the reactant concentrations resulted in either
amorphous TiO2 ([H2O]/[AOT] e 6) or anatase ([H2O]/
[AOT] g 10).
In some instances, as with coprecipitation reac-
Figure 30. TEM micrograph and size distribution of nickel
nanoparticles prepared in a water-in-oil microemulsion.
tions, microemulsions are used to prepare precursors
[NiCl2] ) 0.05 M; [N2H4OH] ) 1.0 M; water/CTAB/n- that are decomposed to the desired phase by subse-
hexanol ) 22/33/45; 73 °C. (Reprinted with permission from quent calcination, although this will inevitably result
ref 370. Copyright 2000 American Chemical Society.) in some degree of agglomeration. Yener and Giesche
Figure 31. TEM images of Fe2O3 (hematite) particles prepared in an AOT microemulsion: (A) as-prepared (bar ) 100
nm), (B) calcined at 450 °C (bar ) 50 nm); (C) calcined at 600 °C (bar ) 50 nm). The evolution of the crystalline hematite
phase can be traced by powder X-ray diffraction (D). (Reprinted from ref 435 with permission from American Ceramic
Society, www.ceramics.org. Copyright 1999. All rights reserved.)
prepared a series of mixed-metal ferrites by precipi- by similar processes. The BaFe12O19 prepared in this
tating the precursors in a H2O-AOT-isooctane way is noteworthy in that it exhibits a higher
system and calcining the products at 300-600 °C; the coercivity and saturation magnetization than samples
TEM images and powder X-ray patterns of one of prepared by a traditional coprecipitation route.442 A
their samples are reproduced in Figure 31.435 Kumar representative sampling of various oxides pre-
et al. prepared 10 nm particles of the YBa2Cu3O7-δ pared by coprecipitation in microemulsions is given
superconductor by combining a micellar solution of in Table 7.
Y3+, Ba2+, and Cu2+ prepared in an Igepal CO-430-
cyclohexane system with a second micellar solution 4.2.4. Syntheses of Other Inorganics
containing oxalic acid in the aqueous cores.436 The
precipitate was collected by centrifugation and cal- Many of the earliest microemulsion-based synthe-
cined at 800 °C to decompose the oxalate precursors. ses reported in the literature involved the coprecipi-
Nanoparticulate Al2O3,437 LaMnO3,438 BaFe12O19,439 tation of transition-metal halides or sulfides. Similar
Cu2L2O5 (L ) Ho, Er),440 and LiNi0.8Co0.2O2441 are to the precipitation of hydroxides, two micelle solu-
among the oxides that have recently been prepared tions containing the desired ions are prepared sepa-
Table 7. Survey from the Literature of Oxides Prepared from Microemulsions

oxide starting material surfactant precipitating agent reaction conditions product size (nm) ref
LiNi0.8Co0.2O2 LiNO3 NP-10 kerosene calcined 400-800 °C 19-100 441
Ni(NO3)2
Co(NO3)2
Al2O3 AlCl3 Triton X-114 NH4OH calcined 600-900 °C 50-60 437
TiO2 Ti(OiPr)4 AOT H2O 20-200 434
Mn1-xZnxFe2O4 Mn(NO3)2 AOT NH4OH calcined 300-600 °C 5-37 435
Zn(NO3)2
Fe(NO3)3
Fe3O4 FeCl2 AOT NH4OH ∼2 443
FeCl3
Fe3O4 FeSO4 AOT NH4OH 10 431
CoCrFeO4 CoCl2 SDS CH3NH2 calcined 600 °C 6-16 444
CrCl3
Fe(NO3)3
CoFe2O4 CoCl2 SDS CH3NH2 dried 100 °C 6-9 445
FeCl3
Ni1-xZnxFe2O4 Ni(NO3)2 AOT NH4OH calcined 300-600 °C 5-30 435
Zn(NO3)2
Fe(NO3)3
CuM2O5 Cu(NO3)2 CTAB (NH4)2CO3 calcined 900 °C 25-30 440
(M ) Ho, Er) NO(NO3)3
Er(NO3)3
Y3Fe5O12 Y(NO3)3 Igepal NH4OH + calcined 600-1000 °C 3 446
Fe(NO3)3 CA-520 (NH4)2CO3
YBa2Cu3O7-δ Y(OAc)3 Igepal oxalic acid 3-12 436
BaCO3 CA-430
Cu(OAc)2
SnO2 SnCl4 AOT NH4OH calcined 600 °C 30-70 447
BaFe12O19 Ba(NO3)2 CTAB (NH4)2CO3 calcined 950 °C 5-25 439, 442
Fe(NO3)3
CeO2 Ce(NO3)3 CTAB NH4OH calcined 500-700 °C 6-10 448
Na2S, Na2Se, or similar salts as the precipitating

agent. Hirai et al., for example, recently prepared
2-4 nm diameter PbS particles from micellar solu-
tions of Pb(NO3)2 and Na2S.450 Due to the high
solubility of PbS relative to those of most metal
chalcogenides, the authors found that using a large
excess of one of the reactants tended to reduce the
particle size of the products; the excess of either Pb2+
or S2- is thought to minimize the effects of Ostwald
ripening.
Similarly, Gan et al. have prepared ∼5 nm par-
ticles of Mn-doped ZnS in a microemulsion system
consisting of NP-5 and NP-9 surfactants and petro-
leum ether as the oil phase.451 Precipitation was
Figure 32. TEM image of nanocrystalline KMnF3. (Re- induced by adding a micellar solution of Na2S to a
printed with permission from ref 422. Copyright 1999 micellar solution of MnCl2 and ZnCl2. Subsequent
Everett E. Carpenter.) hydrothermal treatment of the products increased
the average diameter to ∼12 nm but substantially
rately and then rapidly mixed. Initially used to broadened the size distribution.
prepare simple binary halides such as AgCl,449 the Vaucher et al. recently reported a microemulsion-
method was later adapted to more complicated based route to nanocrystalline Prussian blue,
ternary systems, like the cubic, perovskite-structured [AFeIII{FeII(CN)6}] (A ) Li+, Na+, K+, NH4+).452
nanocrystals of KMnF3 depicted in Figure 32, pre- AOT-isooctane microemulsions containing aqueous
pared by422 (NH4)3[Fe(C2O4)3] and (NH4)3[Fe(CN)6] with ω )
5-20 were combined and exposed to UV light. Stable
MnCl2(aq) + KF(aq) f KMnF3(s) + 2KCl(aq) suspensions of Prussian blue particles appeared after
(76) a few days. The cubic 16 nm particles with very
narrow size distributions (σ ) 2.5 nm) self-assembled
This is an example of a reaction in which both the into highly ordered 2-D (or 3-D) superlattices con-
starting materials and the surfactant must be care- taining 60-100 nanoparticles. The same authors
fully chosen; when attempted in AOT, the above have reported the synthesis of Co3[Fe(CN)6]2.453 Oth-
reaction produced NaMnF3. ers have reported Cu2[Fe(CN)6] nanoparticles pre-
Metal chalcogenides can likewise be precipitated pared by a similar route, though no self-assembly was
using a reverse micelle solution containing dissolved observed in this system.454
4.2.5. Synthesis of Core−Shell and Onion-Structured

Nanoparticles
Many metallic nanoparticles, particularly Fe, are
susceptible to rapid oxidation to the point of pyro-
phoricity. This problem can be largely circumvented,
however, by coating the nanoparticles with gold or
other inert metals. Gold coatings are of particular
interest because the nanoparticles’ surfaces can be
subsequently functionalized with various organic
species by taking advantage of the very strong Au-S
bond, as described in section 2.1.4.
The technique for applying gold coatings on metal
nanoparticles is reasonably straightforward and sim-
ply adds an additional step to the reverse micelle
synthesis. A water-soluble gold salt (HAuCl4) is
dissolved and dispersed in a separate reverse micelle
solution that is then added to the metal-containing
reverse micelle solution that has already been re-
duced with an excess of BH4-. The aqueous AuCl4-
ions encapsulate the metal particles and are subse-
quently reduced by
8AuCl4- + 3BH4- + 9H2O /

8Au + 3B(OH)3 + 21H+ + 32Cl- (77)
forming a metallic gold shell around the metal

particles.455,456 AuCl4- is sufficiently oxidizing for Figure 33. TEM image and schematic of an onion
N2H5+ to achieve the same result. Probability dic- structure. (Reprinted with permission from ref 458. Copy-
tates, however, that some gold-containing reverse right 1999 Materials Research Society.)
micelles will be reduced before coalescing with a
metal-containing nanoparticle. As a result, the final
product will typically contain some gold particles and
possibly some uncoated transition metal particles. In
any event, it should be noted that recent results by
Ravel et al., who performed X-ray absorption spec-
troscopy (XAS) on gold-coated iron particles, indicate
that the iron cores of such particles are still suscep-
tible to oxidation.457
Taking the above process one step further, the
synthesis can begin with Au nanoparticles, followed
by a coating with Fe and followed again with a
coating of Au, creating an Au-Fe-Au onion type
structure (Figure 33).430,458
The preparation of core-shell type structures is not
limited to metals as the core or shell materials.
Combinations of precipitation, reduction, and hy- Figure 34. TEM images of SiO2-coated Fe3O4 nanopar-
drolysis reactions can be performed sequentially to ticles prepared in water-in-oil microemulsions. (Reprinted
produce oxides coated with metals, oxides coated with from ref 460 with permission from the American Ceramic
oxides, and so forth. Fe3O4, for example, can be coated Society, www.ceramics.org. Copyright 1999. All rights
reserved.)
with another oxide, such as MnO, with strict control
of shell thickness.431 In this case, reverse micelles nm Fe2O3 or Fe3O4 by combining a reverse micelle
containing 10 nm diameter Fe3O4 core particles, solution containing Fe2+ and Fe3+ with one containing
formed by precipitation and auto-oxidation of Fe2+, NH4OH. Silica coatings with thicknesses as low as 1
were combined with a reverse micelle solution con- nm were applied by adding tetraethyl orthosilicate
taining aqueous KMnO4 with ω ) 15. The perman- (TEOS) to the NH4OH reverse micelles prior to
ganate was subsequently reduced by addition of mixing. In this case, NH4OH plays a dual role as both
another 15 nm reverse micelle solution containing precipitating agent for the iron ions and catalyst for
hydrazine. The product thus consisted of nanopar- the hydrolysis of TEOS. Tago et al. prepared SiO2-
ticles with 10 nm diameter Fe3O4 cores and 2.5 nm coated CoxFe3-xO4 by a similar method (Figure 34).460
thick MnO shells. Gan et al. used nonionic surfactant micellar sys-
Santra et al. recently reported a similar method tems to coat BaSO4 particles with polyaniline.461 A
for producing SiO2-coated iron oxides in a nonionic micellar solution containing BaCl2, HCl, and aniline
surfactant system.459 The authors precipitated 1-2 was combined with a second solution containing
Figure 36. TEM images of Ag nanoparticles synthesized

in microemulsions containing (a) liquid CO2 (25 °C and 300
bar) and (b) supercritical CO2 (35 °C and 367 bar).
(Reprinted with permission from ref 464. Copyright 1999
Figure 35. TEM image of Au clusters embedded in a silica American Chemical Society.)
matrix. The particles are 5.7 nm in diameter and highly
dispersed. Particle size is independent of gel precursor type, cussed in section 2, adapted to a microemulsion to
drying procedure, and the H2O/Si ratio. (Reprinted with help restrict the size distribution of the particles. The
permission from ref 462. Copyright 1997 American Chemi- method was developed specifically for the preparation
cal Society.) of nanoparticulate Co, which tends to form Co2B
when reduced with borohydride in the presence of
K2S2O8 and H2SO4. Precipitation of BaSO4 within the
high concentrations of water.39 In this modified
micelles was immediate whereas the formation of the
method, the [water]/[surfactant] ratio was kept low
polyaniline required up to 24 h.
and constant. After small Co seeds were precipated
Martino et al. combined the reverse micelle method
in the reverse micelle cores, additional microemul-
with sol-gel processing to encapsulate Au nanoclus-
sions containing aqueous Co2+ or BH4- were added
ters in silica matrixes.462 The Au was precipitated by
sequentially, and the process could be repeated
injecting a solution of LiBH4 into a micellar solution
several times. With each addition of reactant, the Co
containing HAuCl4 and TEOS. Gelation of the TEOS
was preferentially precipated on the existing Co seeds
was induced by raising the pH, and the gel was
rather than nucleating as new crystallites. The size
transformed into a xerogel by drying or into an
of the resulting nanocrystals could be controlled in
aerogel by supercritical CO2 extraction. The product
the range 3.8-8.8 nm with a relatively narrow size
consisted of 5-7 nm Au particles imbedded in a
distribution. This method should be adaptable to
porous silica matrix (Figure 35).
other metals.
4.2.6. Microemulsion Syntheses in Supercritical CO2
Recently, a number of researchers have reported
5. Hydrothermal/Solvothermal Processing of
syntheses of nanoparticulate metals and chalco- Nanoparticles and Nanocomposites
genides using microemulsions in which supercritical
CO2 (scCO2) serves as the solvent (oil phase).463 The 5.1. Principles of Hydrothermal and Solvothermal
surfactant systems discussed in section 4.1 are not, Processing
by themselves, suitable for use in scCO2 because the In a sealed vessel (bomb, autoclave, etc.), solvents
intermicellar van der Waals attractions are too can be brought to temperatures well above their
strong. Ji et al. recently reported the synthesis of Ag boiling points by the increase in autogenous pres-
nanoparticles in a system consisting of water, AOT, sures resulting from heating. Performing a chemical
and perfluoropolyether-phosphate ether (PFPE-PO4) reaction under such conditions is referred to as
as a cosurfactant in scCO2 at 35 °C and 367 bar.464 solvothermal processing or, in the case of water as
Two micellar solutions, one containing AgNO3 and solvent, hydrothermal processing. Review articles
the other containing NaBH(OAc)3 as the reducing devoted specifically to these methods appear fre-
agent, were prepared and mixed. The 5-15 nm quently in the literature.469-474
products were polydispersed with slight agglomera- The critical point for water lies at 374 °C and 218
tion (Figure 36). The method was later adapted to atm. Above this temperature and pressure, water is
the synthesis of Cu, CdS, and ZnS nanoparticles.465,466 said to be supercritical. Supercritical fluids exhibit
Others have used this method to prepare nanopar- characteristics of both a liquid and a gas: the
ticulate silver halides.467 interfaces of solids and supercritical fluids lack
surface tension, yet supercritical fluids exhibit high
4.2.7. The Germ-Growth Method viscosities and easily dissolve chemical compounds
Lin et al. have developed a variation of the micro- that would otherwise exhibit very low solubilities
emulsion process in which seed crystals are first under ambient conditions.
precipitated in the micellar cores and subsequently Some solvothermal processes indeed involve super-
grown by further addition of reactant.468 This is critical solvents. Most, however, simply take advan-
essentially the seed-mediated growth method dis- tage of the increased solubility and reactivity of metal
salts and complexes at elevated temperatures and

pressures without bringing the solvent to its critical
point. In any event, solvothermal processing allows
many inorganic materials to be prepared at temper-
atures substantially below those required by tradi-
tional solid-state reactions. Unlike the cases of
coprecipitation and sol-gel methods, which also allow
for substantially reduced reaction temperatures, the
products of solvothermal reactions are usually crys-
talline and do not require postannealing treatments.
As a matter of safety, the pressures generated in
a sealed vessel should always be estimated before-
hand. The equations necessary for doing so go far
beyond the ideal gas law and are outlined in the
review by Rajamathi and Seshadri.471
5.2. Hydrothermal and Solvothermal Methods Figure 37. (top) TEM image of CeO2 nanoparticles coated
with turbostratic boron nitride and (bottom) the size
5.2.1. Solvothermal Processing of Nanocrystalline Oxides distribution of the sample. (Reprinted with permission from
The synthesis of nanocrystalline TiO2, which is an ref 481. Copyright 2003 Royal Society of Chemistry.)
important photocatalyst for the decomposition of toxic
Inoue et al. were able to reduce the particle size of
chemicals, is one of the more thoroughly investigated
hydrothermally prepared colloidal CeO2 to 2 nm by
solvothermal/hydrothermal reactions. Oguri et al.
autoclaving a mixture of cerium metal and 2-meth-
reported in 1988 the preparation of anatase by
oxyethanol at 250 °C.482 In this case, the autoclave
hydrothermally processing hydrous titania prepared
was purged with nitrogen prior to heating and the
by the controlled hydrolysis of Ti(OEt)4 in ethanol.475
colloidal particles were coagulated after heating with
The reaction conditions leading to monodispersed
methanol and ammonia. The authors noted that
anatase nanoparticles by this approach were eluci-
higher reaction temperatures tended to increase
dated by others.476 The extension of the method to
particle size.
the preparation of lanthanide-doped titania particles
The solvothermal syntheses of some transition
has also been reported.477
metal oxides can be achieved by the decomposition
More recently, Cheng et al. developed a method for of metal-Cupferron complexes, MxCupx (Cup )
preparing nanoparticulate, phase-pure rutile and C6H5N(NO)O-), based on the method of Rockenberger
anatase from aqueous TiCl4 by a hydrothermal et al.184 discussed in section 2.2.9. Thimmaiah et al.
process.478 They found that acidic conditions favored were able to replace the amine-based solvents used
rutile while basic conditions favored anatase. Inter- by Rockenberger with toluene and prepared ∼10 nm
estingly, they discovered that higher temperatures diameter γ-Fe2O3 and ∼7 nm CoFe2O4 by hydrother-
favor more highly dispersed products and that min- mal heating of the reaction mixtures.483 The authors
eralizers such as SnCl4 and NaCl tended to reduce noted, however, that the presence of at least trace
the average grain size, while NH4Cl led to ag- quantities of a strongly coordinating amine was
glomeration. necessary to act as a capping agent and prevent
Research on the synthesis of nanophase TiO2 still aggregation and that longer-chain amines tended to
continues. Expanding the work of Cheng et al., others reduce the average particle size of γ-Fe2O3. The same
have determined that the phase purity of the prod- group has reported the synthesis of nanoparticulate
ucts from hydrothermally processed aqueous TiCl4 ZnFe2O4 by an identical method.472
depends primarily on concentration, with higher con- In many cases, anhydrous metal oxides have been
centrations of TiCl4 favoring the rutile phase, while prepared by solvothermal treatments of sol-gel or
particle size depends primarily on reaction time.479 microemulsion-based precursors. Wu et al. prepared
Yin et al. modified the process to produce 2-10 nm anatase and rutile TiO2 by hydrothermal treatment
crystallites of monodispersed, phase-pure anatase by of acidified Ti(OBu)4 in a Triton X-100-n-hexanol-
adding citric acid to stabilize the TiO2 nanoparticles cyclohexane microemulsion.484 The microemulsion
and hydrothermally heating the precursors in the was heated to 120-200 °C in a stainless steel
presence of KCl or NaCl mineralizers.480 autoclave. Microemulsions acidified with HNO3 pro-
The hydrothermal synthesis of nanocrystalline, duced monodispersed anatase nanoparticles while
monodispersed CeO2 with a very narrow size distri- those acidified with HCl produced rutile nanorods.
bution was recently reported by Masui et al.481 The Rutile-structured TiO2 prepared this way has been
authors combined CeCl3‚6H2O and aqueous ammonia shown to be active toward the photocatalytic oxida-
with a citric acid stabilizer and heated the solution tion of phenol.485
in a sealed Teflon container at 80 °C. The CeO2 nano-
particles exhibited a 3.1 nm average diameter. The 5.2.2. Synthesis of Nanocrystalline Nitrides and
ceria particles were subsequently coated with BN by Chalcogenides
combining them with a mixture of boric acid and 2,2′- Yang et al. prepared a series of MSe2 (M ) Ni, Co,
iminodiethanol, evaporating the solvent, and heating Fe) nanoparticles by a solvothermal reduction pro-
at 800 °C under flowing ammonia (Figure 37). cess.486 The starting materials in this case were the
appropriate metal chloride, elemental Se, hydrazine,

and a strongly coordinating solvent such as pyridine,
DMF, or ethylenediamine. The reaction was initiated
under ambient conditions before the mixture was
transferred to an autoclave and heated to 80-200 °C.
By varying the solvent and reaction temperatures,
the authors were able to vary the sizes and morphol-
ogies of the products from filament-like to octahedral
to spherical.
Although the presence of water can sometimes
cause problems with the synthesis of non-oxidic
species in hydrothermal reactions, the literature Figure 38. Schematic of a continuous-flow hydrothermal
nonetheless contains numerous examples of suc- reactor for the production of nanoparticles. See text for a
cessful syntheses of nanoparticulate metal chalco- detailed description of the apparatus. (Reprinted with
permission from ref 497. Copyright 2000 Royal Society of
genides.487 Peng et al. developed a method for the Chemistry.)
hydrothermal synthesis of ZnSe and CdSe.488 The
starting materials in this case were powdered Zn or
Cd metal and Se powder that were heated to 180 °C
in an autoclave filled to 70% capacity with water. The
products, while nanoparticulate, were agglomerated
due to the absence of a stabilizer or capping agent.
Gautam et al. were able to solvothermally prepare
monodispersed ∼3 nm CdSe particles using trioctyl
phosphine oxide (TOPO) as a capping agent.489
Chen et al. prepared a series of MS2 (M ) Ni, Co,
Fe, Ni, Mo) sulfides and MSe2 (M ) Ni, Mo) selenides
hydrothermally using metal chlorides and Na2S2O3
or Na2SeSO3 as starting materials, or in the case of
the molybdenum-containing products, Na2MoO4 was
used and hydrazine was added.490 The average crys-
Figure 39. TEM micrographs showing the decomposition
tallite size of the agglomerated products ranged from product of Fe(OAc)2 in a hydrothermal flow reactor at 300
∼4 nm for MoS2 to ∼85 nm for FeS2. °C and 25 MPa. (Reprinted with permission from ref 504.
While most hydrothermal syntheses of chalco- Copyright 2001 Royal Society of Chemistry.)
genides involve the preparation of binary systems,
more complicated ternary compounds have also been
reported. A series of MIMIIIS2 (MI ) Ag+, Cu+; MIII ) namely the design and operation of “continuous flow”
Ga3+, In3+) semiconductors have been prepared by hydrothermal reactors and microwave-assisted solvo-
Liu et al. from the combination of MCl salts with thermal processing. Continuous flow reactors are
elemental Ga or In (M′) and S:491,492 particularly relevant given their suitability to large-
scale production.496
3MCl + 4M′ + 6S f 3MM′S2 + M′Cl3 (78) Continuous flow reactors, such as that depicted in
Figure 38 for the synthesis of Ce1-xZrxO2 nanopar-
The reactions were carried out in autoclaves heated ticles in near-critical water,497,498 should be distin-
to 180-230 °C with ethylenediamine as solvent. The guished from the aerosol- and vapor-phase flow
products ranged from 5 to 12 nm but exhibited some reactors that have been used for some time for the
signs of agglomeration. synthesis of nanoparticles,499-503 and from the mi-
Xiao et al. were able to take the previously men- crowave flow reactors discussed previously (section
tioned process one step further, preparing the CuIn- 2.2.8). From the diagram in Figure 35, a mixture of
(SexS1-x)2 quaternary semiconductors over the full 0 aqueous (NH4)2Ce(NO3)6 and Zr(OAc)4 was combined
e x e 1 compositional range.493 In this case, the start- at the mixing point (X) with a stream of near-critical
ing materials were InCl3‚4H2O, CuCl2‚2H2O, Se, and water heated to 400 °C in a preheater (PH); the
S, and ethylenediamine was the preferred solvent. liquids were transported with pumps (P). The mix-
Particle sizes were typically on the order of 15 nm. ture was then cooled immediately with a water cooler
Metal nitrides such as GaN can be prepared by (C) and passed through a filter (F). The final product
similar reactions involving Li3N:494,495 was collected as a colloidal suspension. The pressure
in the system was controlled with the back-pressure
GaCl3 + Li3N f GaN + 3LiCl (79) regulator (BPR). This arrangement produced 5 nm
colloidal particles at rates up to 10 g/h. The composi-
The reactions were typically carried out in nonpolar, tion of the Ce1-xZrxO2 nanoparticles could be varied
aprotic solvents such as benzene at ∼280 °C. over the entire 0 e x e 1 compositional range by
adjusting the ratios of Ce4+ and Zr4+ in the starting
5.2.3. New Developments in Hydrothermal/Solvothermal solution.498 The same authors have reported the
Methods syntheses of a series of ferrite nanoparticles by a
In the past few years, two new developments have similar method, including the Fe3O4 particles de-
emerged in solvothermal/hydrothermal syntheses, picted in Figure 39, produced by decomposition of
Fe(OAc)2.504 Others have successfully adapted the

method to the synthesis of TiO2505 and BaTiO3.506
Microwave-assisted solvothermal methods are some-
what less commonly encountered in the literature.
Nonetheless, microwave-hydrothermal processing has
been used since 1992 for the synthesis of various
oxides507 and zeolites,508 although these methods were
originally developed in the interest of reducing reac-
tion times rather than particle sizes. Komarneni et
al., in particular, made extensive use of this method
to synthesize a wide variety of compounds and
composite materials.507,509-514 More recently, they
have adapted their method specifically toward the
synthesis of nanoparticles, including the MFe2O4 (M
) Zn, Ni, Mn, Co) ferrites,515 BaTiO3,516 and mono-
dispersed R-Fe2O3.517 Komarneni and Katsuki have Figure 40. (a) High-resolution TEM image of Au@Pt
recently reviewed this work.518 Other recently re- particles prepared from a seed-mediated growth process.
ported nanophase compounds prepared by the mi- The EDX spectra of the circled areas are presented in part
crowave-hydrothermal technique include Fe3O4,519,520 b. (Reprinted with permission from ref 532. Copyright 1991
colloidal, anatase-structured TiO2,521 ZrO2,522 and Wiley-VCH.)
Ce0.75Zr0.25O2.523
One of the primary uses of the microwave-hydro- Au0, the reduction kinetics of this process are greatly
thermal method is in the preparation of nanostruc- enhanced in the presence of the colloidal Au seed
tured mesoporous materials.524-526 This is, however, particles, in which the Au surfaces serve as catalysts.
an extremely broad topic and is beyond the scope of The reduction of AuCl4- therefore preferentially
this review. The interested reader is referred to any occurs at the Au surfaces, as opposed to leading to
of several excellent review articles addressing the the nucleation of new, smaller Au particles from
synthesis of mesoporous materials.527-529 solution. This process can therefore be described as
electroless plating.543 Taking the process one step
6. Templated Syntheses further, Schmid et al. deposited ∼9 nm thick Pt and
Pd shells on 18 nm colloidal Au particles from
The synthesis of nanoparticles on templates has solutions of HtPtCl2 or H2PdCl4 using hydroxylamine
garnered an increasing amount of attention in the hydrochloride (NH2OH‚HCl) as the reducing agent
past few years. As will be discussed here, this and p-H2NC6H5SO3-Na+ as a stabilizer (Figure 40).532
approach encompasses a broad array of synthetic In recent years, a great deal of interest has
strategies and frequently involves methods that are developed in the synthesis of metal and metal oxide
best described as hybrids between previously dis- nanoparticles on polymer templates. Initially, these
cussed techniques. reactions consisted simply of the reduction of transi-
The technique of heterogeneous nucleation dis- tion metals, the decomposition of metal carbonyls, or
cussed in section 2, in which “seed” crystals serve as precipitation of metal oxides in polymer matrixes.
nucleation sites for further deposition and growth of Platonova et al. prepared 1 nm Co in a polystyrene
crystallites, can essentially be considered one of the (PS)-PVP copolymer this way.544 The syntheses of
simpler forms of a templated synthesis. This tech- nanoparticulate CoFe2O4545 and Fe3O4546 have re-
nique can be used to increase the average particle cently been achieved by similar methods. In recent
size of nanoparticles, such as when aqueous Au3+ is years, various researchers have developed increas-
deposited on colloidal Au, or Ag+ is deposited on ingly complex variations of these syntheses. Bron-
colloidal Ag.530,531 The method can also be used for stein et al. prepared 1-2 nm Au, Pd, and Pt using
the synthesis of core-shell and onion structures, such poly(octadecylsiloxane), which formed a bilayer struc-
as the deposition Pd, Bi, Sn, or In on colloidal ture of opposing Si-O-Si chains with water inter-
Au,532,533 Au on TiO2,534 CeO2 on carbon nanotubes,535 calated between the layers.547 Metal cations were in-
Ni on Al2O3 particles,536 ZnO on Al2O3,537 Ni on Pd serted into the aqueous layers prior to reduction with
or Pt,538 or CdS on HgTe.539 Pileni has recently borohydride ion. Liang et al. have reported a process
reviewed these methods.540 Pradhan et al. have by which Au was deposited on spherical particles of
written a more general review of seed-mediated polystyrene (PS) by first coating the PS with a pos-
methods for nanoparticle syntheses.541 itively charged polymer like poly(allylamine hydro-
To maintain the narrow size distribution of the chloride) and combining it with colloidal Au stabilized
nanoparticles, care must be taken to ensure that with 4-(dimethylamino)pyridine (DMAP).548 The cap-
smaller particles do not nucleate from solution during ping ligands of the colloidal Au particles were con-
the deposition process. Several new techniques have sequently electrostatically attached to the coated PS
recently emerged to prevent this occurrence. Brown particles. The gold particles could then be enlarged
et al. used hydroxylamine (NH2OH) for the seed- by the hydroxylamine method described previously.
mediated growth of colloidal Au, increasing the The polymers were subsequently removed either by
average diameter from 12 nm up to 50 nm.542 The calcination of the products at 310 °C under oxygen
use of hydroxylamine is critical to this process. While or by washing with THF, resulting in the formation
hydroxylamine can theoretically reduce AuCl4- to of 500 nm diameter hollow gold spheres.
In an inverse approach to the above process,

Marinakos et al. used colloidal Au particles as
templates for the formation of hollow polymer
spheres.549 They deposited the colloidal Au (prepared
by the citrate method discussed in section 2.2.1) into
the spheres of a porous alumina membrane and
applied one or more layers of a polymer, such as
polypyrrole, to the Au by diffusing pyrrole vapor
through the membrane in the presence of a polym-
erization initiator. Au was subsequently dissolved by
washing with a cyanide solution, and the alumina
membrane could be removed by treatment with dilute
KOH. The polymer coating could be varied from 5 to
100 nm thick, depending on the time allowed for
vapor deposition. The sizes of the cores were con-
trolled by varying the diameters of Au particles in
the colloids from 5 to 200 nm. Nair et al. have
similarly prepared hollow ZrO2 nanoparticles by
leaching Ag from Ag@ZrO2 particles with CCl4.550
Crooks et al. have encapsulated Pd and Pt nano-
particles as small as 1 nm with dendrimers such as
poly(amidoamine) by absorbing the respective metal
cations into the dendrimer structure prior to chemical Figure 41. TEM image of <1 nm Pd nanoparticles in a
reduction.551 The authors have extended this process silica monolith. (Reprinted with permission from ref 563.
to the encapsulation of Cu, Ni, Fe, Au, and Ru and Copyright 2001 Wiley-VCH.)
have recently reviewed this work in detail.552
which Al2O3 membranes were dipped in the ap-
The synthesis and deposition of nanoparticles propriate sols and heated to 400 °C.565 Others have
inside the pores of mesoporous materials, such as similarly deposited 30 nm Eu2O3 particles in amor-
MCM-41, have become rather commonplace, and the phous alumina.566
topic has been extensively reviewed.553-556 Meso- In a rather unique approach, Hoh et al. were able
porous alumina exhibits rather unusual surface to precipitate 1-7 nm CoFe2O4 within the pores of
properties and has been shown to be an effective Dowex, a common ion exchange resin with sulfonic
adsorbent for ions from aqueous solutions.557 The acid functional groups.567 In this case, aqueous solu-
ions, once adsorbed into the pores, can be subse- tions containing Co2+ and Fe3+ were combined with
quently oxidized or reduced to nanoparticulate oxides the resin, followed by addition of NaOH to initiate
or metals. Such composite materials are particularly precipitation. Ding and Gin, in contrast, prepared
attractive as supported catalysts.558-560 The methods 4-7 nm Pd in the channels of a lyotropic liquid
of preparing these composite materials extend well crystal polymer by an ion exchange reaction, followed
beyond simple adsorption and include vapor phase by reduction under hydrogen, although the ordered
methods561 as well as electrodeposition.554,562 The pore structure appears to collapse during the reduc-
discussion here, however, will be limited to wet- tion process.568
chemical methods. Kim et al. prepared Au nanoparticles in meso-
The synthesis of metal-SiO2 composites discussion porous carbon by first encapsulating colloidal Au with
in section 3.2.3 can be viewed as a primitive version SiO2 shells formed by the hydrolysis of aminopropyl-
of this template approach, but in the case of the sol- trimethoxysilane in the presence of sodium silicate.569
gel methods, the metal or metal oxide nanoparticles The Au@SiO2 particles were subsequently encapsu-
are not necessarily contained within the SiO2 pores. lated in mesoporous silica by initiating a second
Bronstein et al., however, were able to incorporate hydrolysis reaction of TEOS and octadecyltrimeth-
Pd and Pt into the pores of SiO2 monoliths by oxysilane. After calcination, the particles containing
submerging the preprepared monoliths in solutions Au@SiO2 cores and porous silica shells were satu-
of PdCl42-, PtCl42-, or PtCl62- for periods up to 72 h rated with phenol and a polymerization initiator and
followed by reduction with either aqueous NaBH4 or heated under vacuum, resulting in the formation of
gaseous H2.563 The Pd and Pt particles so-prepared an amorphous carbon-silica composite. The silica
appear to have diameters below 1 nm (Figure 41). could be subsequently removed by etching with an
Lensveld et al. similarly deposited <10 nm par- HF solution. The final product consisted of 13 nm Au
ticles of NiO inside the pore structure MCM-41 by cores surrounded by 15-25 nm thick carbon shells
impregnating the mesoporous material with aqueous with hollow cores. Because the interiors of the carbon
solutions of a nickel citrate complex followed by shells are larger than the 13 nm Au particles, the
calcination of the composites at 450 °C in air.564 This, resulting product is referred to as a nanorattle
in effect, can be viewed as the synthesis of NiO by (Figure 42). The subject of carbon-encapsulated metal
the Pechini method (section 3.3) inside a mesoporous nanoparticles, including their various methods of
material. Lakshmi et al. have likewise reported the syntheses, has recently been reviewed.570
synthesis of nanostructured TiO2, WO3, and ZnO in Morley et al. deposited 10-100 nm Ag particles
porous alumina using a modified sol-gel process in within the pores of poly(styrene-divinylbenzene) beads
Figure 42. TEM images of Au@HCMS polymer capsules

(left) and Au@HCMS carbon capsules. (Reprinted with
permission from ref 569. Copyright 2002 American Chemi-
cal Society.)
and silica aerogels by solvothermal treatment in

supercritical CO2.323 The silver precursor, in the form
of Ag(hfpd)(tetraamine) or Ag(hfpd)(tetraglyme) (hfpd
) 1,1,1,5,5,5-hexafluoropentane-2,4-dione), was com-
bined with the host material and CO2 in an autoclave
and heated to 40 °C (4000 psi). Subsequent decom-
position of the complexes to Ag metal was performed
in a second step, in which the autoclave was filled
with H2 and heated to 60 °C (1000 psi).
Last, although carbon nanotubes cannot be clas-
sified as a mesoporous material, Wu et al. were able
to deposit CuO and Fe-Ni alloy nanorods inside
carbon nanotubes with 3-10 nm interior diameters
by combining acid-washed nanotubes with saturated
solutions of the appropriate metal nitrates and
calcining at 450 °C under inert atmosphere or
H2.571,572 In the case of CuO, the nanotube templates
could subsequently be removed by calcination at 750
°C in air. Others have deposited Ni and CoNiFe alloy
nanoparticles on the surfaces of carbon nanotubes
electrochemically.573
7. Biomimetic Syntheses
Interest in biotemplated nanoparticle syntheses
was spurred dramatically when Meldrum et al.
reported the synthesis of nanometric iron sulfide and
amorphous manganese and uranyl oxides within
protein cages.574 The ferritin-containing protein cages
Figure 43. Scanning force microscopy (SFM) images of
were, in effect, serving as nanoreactors to constrain the different routes of cluster synthesis in the presence of
particle growth. Douglas and Young later reported DNA: (a) DNA was added 5 min after clusters were
the similar host-guest encapsulation of paratung- prepared; (b) clusters were prepared in the presence of
state and decavanadate inside the protein cage of a nonactivated native DNAsthat is, the reducing agent and
virus.575 Research along these lines continues, now DNA were added to the [PtCl4]2- solution at the same time;
involving the protein engineering of viral cages as and (c) clusters were prepared in the presence of activated
tailored nanoreactors.576 DNA. (Reprinted with permission from ref 585. Copyright
2002 Wiley Europe.)
Much of the recent interest in biological nano-
particle syntheses is based on the molecular self- methylammine borane as a reducing agent. The DNA
assembly of nanoparticles. Most of this work stems molecules effectively served as a heterogeneous nucle-
from the 1996 report by Mirkin et al., who demon- ating agent and template for the formation of nano-
strated that functionalized DNA is capable of direct- particulate Pt chains. Through an impressive appli-
ing the self-assembly of Au nanostructures into cation of scanning force microscopy (SFM), the
regularly spaced 2-D arrays.577 This line of research researchers were able to observe the formation of the
continues at a rapid pace,578-581 and review articles Pt particles on the biomolecules in situ (Figure 43).
appear frequently.582-584 Similarly, Dujardin et al. used the tobacco mosaic
Seidel et al. were recently able to induce the virus as a template for the growth of <10 nm Pt, Au,
nucleation and growth of Pt nanoparticles at single and Ag nanoparticles into cylindrical aggregates.586
DNA molecules.585 In this case, λ-DNA was aged in At the cutting edge of these types of syntheses,
a K2PtCl4 solution, followed by the addition of di- nanoparticles have recently been encapsulated in
engineered viral cages. Douglas et al. have recently

engineered a cowpea chlorotic mottle virus devoid of
nucleic acid and with a functionality mimicking that
of ferritin.576 Approximately 8 nm diameter γ-FeOOH
particles were subsequently grown inside the 18-24
nm viral cages by the addition of aqueous Fe2+
solutions in the presence of air. A detailed description
of the fundamentals of such processes is available in
an excellent review by Douglas.584
Some microorganisms exhibit the ability to reduce
metals, particularly those exhibiting high reduction
potentials, such as Fe(III), Cr(VI), Mn(IV), and
Co(III).587-590 Roh et al. have recently published
reports detailing the microbial synthesis of magne-
tites in which suspensions of FeOOH, solvated metal
cations, and appropriate buffers were combined with
glucose or lactate in the presence of Thermoanaero-
bacter ethanolicus, an iron(III)-reducing bacterium,
and incubated at 65 °C.591,592 Although the reduction
and mineralization mechanisms are not well under-
stood,587,593 this method resulted in nanocrystalline
(FeII1-xMIIx)FeIII2O4 (MII ) Mn2+, Ni2+, Co2+) and
FeII(FeIII2-xCrIIIx)O4 ferrites in large yields.
The ability of some plants to uptake gold from soil
is well-known, as mining companies take advantage
of this phenomenon to aid in the exploration pro-
cess.594 Gardea-Torresday et al. were able to induce
the uptake of gold into live alfalfa plants by adding
aqueous KAuCl4 to the nutrient solution used to grow
the plants.595 The gold was apparently reduced to
Figure 44. Low-magnification TEM image of an alfalfa metallic Au prior to uptake. Transport of the Au
shoot showing aggregates of gold nanoparticles and
the particle size distribution in a typical sample. The particles through the roots to the shoots resulted in
plant actively uptakes metallic Au from solid media, aggregation of the 4-5 nm Au particles into clusters
after which nucleation and growth of the Au particles (Figure 44). While this technique is not practical as
continues inside the roots and shoots. (Reprinted with a synthetic method, the potential applications for the
permission from ref 595. Copyright 2002 American Chemi- reclamation (bioremediation) of former mining sites
cal Society.)
are obvious.
Table 8. Colloidal Nanoparticles Stabilized by Solvated Ions
nanocrystalline core core size (nm) stabilizing ions, solvent ref
ScOOH 2-ethoxyethanol, acetylacetone 597
TiO2 10-20 Cl-, H3O+, H2O, poly(vinyl alcohol), eosin 598
TiO2 CH3CO2-, ClO4-, Br-, NO3-, OH-, propanol 28
MnOx 2-8 NMe4+, OH-, H2O 599
MnFe2O4 Cl-, H3O+, H2O 600
R-Fe2O3 4-5 Cl-, H3O+, H2O 601
γ-Fe2O3 2-15 (broad) (1) NMe4+, OH-, H2O; (2) oleic acid + 602
sodium dodecylbenzene sulfonate; (3) polystyrene
γ-Fe2O3 (4-6) × (20-50) (rods) H3O+, H2O, Cl- 603
Fe2O3, Fe3O4 5-15 NMe4+, OH-, H2O 604
Fe3O4 5.7 NMe4+, OH-, H2O 605
Fe3O4 6, 12 H3O+, H2O, Cl- 606
Fe3O4 7 citrate, OH-, H2O 607
Fe3O4 8.5 H3O+, H2O, Cl- 603
NiFe2O4 NO3-, H3O+, H2O 608
CuFe2O4 NO3-, H3O+, H2O 608
ZnO CH3CO2-, ClO4-, Br-, NO3-, OH-, propanol 28
ZnO <7 ethanol 609
ZnFe2O4 NO3-, H3O+, H2O 608
ZrO2 10-20 Cl-, H3O+, H2O, poly(vinyl alcohol), eosin 598
Pd, Pd-Au, Pd-Au-Ag citrate, H2O 114
CdSe, CdSe/CdS citrate, OH-, H2O 610
SnO2 Cl-, H2O, ethanol, acetylacetone 611
Au 17 × (39-730) citrate, H2O, poly(vinylpyrrolidone) 612
(spheres, rods)
CeO2 7 NO3-, H3O+, H2O 613
Table 9. Capping Ligands and Coordinating Polymers

donor
atom neutral anionic polymeric
C RNC
N R3N, R2HN, RH2N, [-CH2CH2NH-]n
aromatic amines polyvinylpyridine
O ROH, R2O, RCO2 -, RSO3-, RPO3 2-, [-CH(OH)CH2-]n
RC(O)NR2, RO- [-CH2CH2O-]n
R3PO [-CH(CO2H)CH2-]n
poly(vinylpyrrolidone)
starch (dextran)
cyclodextrine
alginic acid
P PR3
S R 2S RS-, RCS2-, RCOS- polythiophene
Table 10. Nanoparticles Stabilized with Lipophilic Capping Ligands with O-Donor Atoms
nanocrystalline core core size (nm) capping ligand ref
TiO2 5.5-10 trioctylphosphine oxide 614
MnFe2O4 5.3, 6.6 oleic acid, myristic acid 182
FePt 3, ..., 10 oleic acid 91
Fe-Co oleic acid 183
Fe-FeOx oleic acid 183
Fe2O3 5-16 octylphosphonic acid 615
11-undecenoic acid
dodecylphosphonic acid
γ-Fe2O3 4, ..., 16 oleic acid 616
γ-Fe2O3 4 caprylic acid 617
γ-Fe2O3 10 (1) 2-bromo-2-methylpropionic acid; (2) styrene; 618
(3) polymerization
γ-Fe2O3 4-10 dodecanol, 619
2,2′-didodecyl-1,3-dihydroxypropane,
2-dodecyl-1,3-dihydroxypropane,
tridodecylcarbinol,
didodecylcarbinol
Fe3O4 4, 8-16 oleic acid 181
Fe3O4 6, 12 oleic acid 620
Fe3O4 4.2, 6.6 oleic acid, myristic acid 182
Co 3-13 oleic acid 89, 91
Co 2.2-6.4 oleic acid 129
Co 4 × (25-75) disks oleic acid 126, 108
8 (spheres)
CoFe2O4 3.3, 4.2 oleic acid, myristic acid 182
Co-Ni oleic acid 183
CoPt 1.9 oleic acid 129
CoPt3 1.8 oleic acid 129
Ni oleic acid 183
NiFe2O4 3.6, 5.1 oleic acid, myristic acid 182
ZnO octadecylphosphonic acid 621
ZnFe2O4 5.1, 5.6 oleic acid, myristic acid 182
CdS 1.2, ..., 11.5 trioctylphosphine oxide 197, 199
CdS various sizes hexylphosphonic, tetradecylphosphonic acid 208
CdSe 1.5, ..., 10 trioctylphosphine oxide 203
CdSe 1.5, ..., 10 tributylphosphine oxide 199
CdSe various sizes and shapes hexylphosphonic acid 206, 207
CdSe various sizes hexylphosphonic, tetradecylphosphonic acid 208
CdSe 1.5, ..., 10 hexadecyl phosphate 199
CdSe 1.5, ..., 25 stearic acid or dodecylamine 209, 622
CdSe 4 penta(3-hexylthiophene) phosphonic acid, 623
tri(3-hexylthiophene) phosphonic acid
CdSe‚ZnS ZnS shell various sizes trioctylphosphine oxide + trioctylphosphine + 204
hexadecylamine
CdTe various sizes hexylphosphonic, tetradecylphosphonic acid 208
CdTe 1.2, ..., 11.5 trioctylphosphine oxide 197, 199
InP 20-50 trioctylphosphine oxide 202
BaTiO3 4-12 oleic acid 606
Pb1-xMnxSe 10.5 oleic acid 212
PbSe 3.5, ..., 15 oleic acid 210
Eu2O3 2-40 trioctylphosphine oxide 624
Gd2O3 lauric acid-liposome 625
Table 11. Nanoparticles Stabilized with Lipophilic Capping Ligands with C-Donor Atoms
Co@Pt core-shell 6.27 dodecylisocyanide 129
Table 12. Nanoparticles Stabilized with Lipophilic Capping Ligands with N-Donor Atoms
Mn3O4 trioctylamine 184
γ-Fe2O3 trioctylamine 184
γ-Fe2O3 5 octylamine 626
γ-Fe2O3 7.2, 10.4 octylamine, dodecylamine 483
CoFe2O4 7.3 octylamine, dodecylamine 483
Ni 3.7 hexadecylamine 80
Cu2O 4-10 hexadecylamine 184
Ru 2-3 rnh2 (r ) octyl, dodecyl, hexadecyl) 146
CdS 1.2, ..., 11.5 pyridine 197
CdSe 1.2, ..., 11.5 pyridine 197
CdSe various sizes hexadecylamine (trioctylphosphine + trioctylphosphine oxide) 204
CdSe@ZnS (core-shell) various sizes hexadecylamine (trioctylphosphine + trioctylphosphine oxide) 204
CdTe 1.2, ..., 11.5 pyridine 197
In2O3 4, 6, 8 oleylamine 627
Table 13. Nanoparticles Stabilized with Lipophilic Capping Ligands with S-Donor Atoms
ZnO octanethiol, dodecanethiol 621
Ru 2-3 RSH (R ) octyl, dodecyl, hexadecyl) 146
Ru 1.6, ..., 6 dodecanethiol 78
Pd 1-5 hexanethiol 628
Pd 1.8, ..., 6.0 RSH (R ) C4-C16 n-alkyls) 629
Cd32S14(SC6H5)36(DMF)4 thiophenol 630
Au 2 RSH (R ) butyl, decyl, dodecyl, octadecyl) 631, 632
Au 1-3 dodecanethiol 57
Au@Ag RSH (R ) butyl, decyl, dodecyl, octadecyl) 631, 632
Au@Pt 3.5 RSH (R ) butyl, decyl, dodecyl, octadecyl) 631, 632
Table 14. Nanoparticles Capped with P-Donor Atoms

Cu146Se73(PPh3)30 triphenylphosphine 633
CdS 3-4 tributylphosphine 634
CdS 1.2, ..., 11.5 trioctylphosphine 197
CdSe 1.2, ..., 11.5 trioctylphosphine 197
CdTe 1.2, ..., 11.5 trioctylphosphine 197
CdTe@CdS tributylphosphine 634
8. Surface-Derivatized Nanoparticles metal oxides, sulfides, and so forth. Stability of these

colloids is optimized as the interaction of the nano-
This section focuses on the basic issues related to crystals with the solvent and solvated ions is main-
nanoparticles with chemically modified surfaces; tained to overcome the van der Waals interaction
however, topics dealing with design and application between the nanocrystals that otherwise leads to
of the specific functional nanocomposites are not agglomeration. The mechanism of sol stabilization
considered here. As was outlined in the previous involves the adsorption of multiple layers of solvent
sections, the most common methods of synthesizing molecules and solvated ions on the nanocrystals’
nanocrystalline inorganic substances are based on surfaces, forming electric double layers (EDLs). The
reactions performed in solutions. Solution techniques resulting highly dynamic assemblies possess exces-
allow maintainance of the desired composition of the sive electrical charges at their peripherals that cause
reaction mixtures while eliminating the diffusion electrostatic repulsion between them. Details of
restrictions; such methods therefore permit accurate modern DLVO theory that explain the dynamics in
control of the stoichiometry. Solution techniques also such systems are beyond the scope of this article, and
allow management of the reaction kinetics and the the interested reader is referred to the literature.596
course of crystallization of the insoluble target prod- Application of the EDL-stabilization method to the
uct. Solution reactions facilitate tuning the equilib- synthesis of colloidal inorganics is limited primarily
rium between the reagents, products, and solvent to aqueous solutions, although it may be used with
and, therefore, provide the opportunity for controlling other polar protic solvents as well. The dynamic
the interaction of growing crystals with the environ- nature of EDLs and their sensitivity to their environ-
ment. One of the familiar examples of a system where ment impose a significant limitation to the stability
these interactions are tuned to the desired extent is of the corresponding colloids, but they also open up
the synthesis of aqueous colloids (sols) of metals, exceptional possibilities for further chemical steps
Table 15. Nanoparticles Stabilized with Functionalized Polymers

nanocrystalline core core size (nm) polymeric molecule ref
FeOOH alginic acid 635-637
γ-Fe2O3 alginic acid 638-640
Fe3O4 10 poly(vinyl alcohol) 641, 642
Fe3O4 6, 12 poly(ethylene oxide) (glycol) 114
Fe3O4 5.7 poly(meth)acrylic acid 605
Fe3O4 5.7 poly(hydroxymethyl)methacrylate 605
Fe3O4 6, 12 starch (dextran) 606
Fe3O4 starch (dextran) 643, 644, 645
Co 5 poly(dimethylphenylene oxide) 141
Co 1.4 poly(vinylpyrrolidone) 144
Co 1.6 poly(vinylpyrrolidone) 141
Co 4.2 polyphenylene oxide 646
Co‚CoO 7.5 poly(dimethylphenylene oxide) 141
CoO poly(vinylpyrrolidone) 141
CoPt0.9 1 poly(vinylpyrrolidone) 143
CoPt2.7 1.5 poly(vinylpyrrolidone) 143
Co3O4 2 poly(vinylpyrrolidone) 141
Co3.2Pt poly(vinylpyrrolidone) 143
Ni 3-5, 20-30 nm agglomerates poly(vinylpyrrolidone) 143
ZnO 3.7 poly(vinylpyrrolidone) 647
ZnO 2.6, 2.8, 3.6, 4.0 poly(vinylpyrrolidone) 648
Ru 1.7 cellulose acetate 146
Ru 1.1 poly(vinylpyrrolidone) 646
Ru 1.1 poly(vinylpyrrolidone) 146
Pd 2.5 poly(vinylpyrrolidone) 649
Pd‚Ni poly(vinylpyrrolidone) 649
CdTe alginic acid 650
CdxHg1-xTe alginic acid 650
Pt 1.6 poly(vinylpyrrolidone) 646
Pt‚Ru fcc f hcp poly(vinylpyrrolidone) 646
HgTe alginic acid 650
toward the modification of the nanoparticles’ sur- the polar group (“head”) of these compounds adsorbs
faces, such as depositing a layer of another inorganic on the surfaces of nanocrystals and the organic
substance (inorganic core-inorganic shell compos- nonpolar “tail” faces the peripherals of the resulting
ites), attaching certain organic capping ligands (in- assembly, thereby providing steric repulsion. In the
organic core-organic shell composites), depositing/ case of quarternary ammonium halides (CTAB,
assembling the surfactant-free nanoparticles on the DDAB, DPB, TOAB, etc.), halide anions surround the
preferred substrate, covalent binding to the desired nanoparticle surface while their bulky cationic part-
(bio)molecular systems, and so forth. The most recent ners form the external protecting shell. The nano-
developments that utilize colloidal inorganic nanoparticle-surfactant assemblies can be viewed as
particles stabilized by solvated ions are summarized water-free surfactant micelles bodied with the nano-
in Table 8. crystals. Details of the application of surfactant-
According to an alternative method, van der Waals stabilized microemulsions for the synthesis of nano-
interparticle attractions that lead to agglomeration crystalline materials are described in section 4.1 of
are compensated by surrounding the nanocrystals this review.
with bulky organic shells that help keep them apart The term “capping ligand” is used for organic
from each other. This organic interface possessing molecules that contain a donor group with substit-
either hydrophilic or lipophilic properties efficiently uents of varying steric bulk. The main distinction
stabilizes colloids in aqueous or nonpolar solvent between capping ligands and surfactants lies in the
media. There are different types of substances used differences of the strength of their binding to metal
as components of organic shells, the most common atoms at the nanocrystal surface, which is greater
being ionic surfactants, coordinating polymers, and in the case of capping ligands. These molecules
capping ligands. All these compounds possess polar usually closely relate to complexing agents, whose
groups that can be attached to the nanoparticle binding to metal atoms or ions has a pronounced
surface and a bulky component within the molecule covalent character. Generally, colloids containing
that provides spatial isolation of the nanocrystal from surfactants have only limited stability, while nano-
the environment and provides the solubility proper- crystals surrounded by capping ligands are similar
ties. to giant metal-cluster complexes that are described
The term “surfactant” is used here for the sub- as individual substances. To reach the same stability,
stances commonly used for preparation of water-oil a smaller mass of capping ligand per unit mass of
microemulsions, such as AOT, sodium dodecyl sul- nanocrystals is required than if surfactant (or poly-
fate, CTAB, DDAB, DPB, and TOAB, and for other meric) stabilizer is used. In many cases a monolayer
similar compounds with amphiphilic properties. The of the molecules of capping ligand around the nano-
AOT and sodium dodecyl sulfate surfactants have an crystal is sufficient to attain stability against ag-
anionic sulfate ester group with a bulky lipophilic glomeration with the possibility of isolating and
substituent. Stabilization of colloids is achieved when redissolving the solute. The borderline between cap-
Table 16. Nanoparticles Stabilized with Tetraalkylammonium Salts

nanocryst core core size (nm) tetraalkylammonium salt ref
Co 2.5 +
Oc4N Cl -
651
Ni 4.5 Oc4N+: glycolate, lactate, tartrate, gluconate, 652
acetate, dichloroacetate, pivalate, pyruvate,
formate, nitrate, bromide
Cu 5-10 Oc4N+, Br- 653
Pd 3.6 Oc4N+: glycolate, lactate, tartrate, gluconate, 652
acetate, dichloroacetate, pivalate, pyruvate,
formate, nitrate, bromide
Pd 2.75, 2.0 Oc4N+, Bu4N+, Cl- 654
PtRu 1.2 Oc4N+, Cl- 655
Pt3Sn 1.3 Oc4N+, Cl- 656
Table 17. Nanoparticles Stabilized with Hydrophilic Capping Ligands with O-Donor Atoms
nanocryst core core size (nm) capping ligand ref
FeOx 5 phosphorylcholine 657, 658
FeOx bis- and trisphosphonates, carboxylates, sulfonates 658
γ-Fe2O3 4 betaine chloride, 2,5-dihydroxybenzoic acid 659
Fe3O4 8.5-11 carboxylated poly(aminoamide) dendrimer 660
Table 18. Nanoparticles Stabilized with Functionalized and Hydrophilic S-Donor Capping Ligands
Cd17S4(SCH2CH2OH)26 mercaptoethanol 661
Cd32S14(SCH2CH(OH)CH3)36‚4H2O mercapto-2-propanol 662
CdSe 1-mercapto-2,3-propanediol, 610
3-mercaptopropyltrimethoxysilane
CdSe@CdS 1-mercapto-2,3-propanediol, 610
3-mercaptopropyltrimethoxysilane
CdTe nanocrystals, nanowires mercaptoacetic acid 663
Pt 1.2 1,3-propanedithiol, 1,8-octanedithiol, 147
p-hydroxythiophenol, p-aminothiophenol,
p-mercaptobenzoic acid
Au 4.6 nm; 30 nm spherical mercaptoacetic acid 664
aggregates
Au 2.8 ( 1 mercaptopoly(ethylene glycol) 665
Au 1.8 HS(CH2CH2O)xCH3; x ) 2, 3, 4 666
Au 5 4-mercaptophenol 667
Au 1.02, 1.08, 1.28, 1.94, 3.36 mercaptosuccinic acid 74
Au ∼145 atoms 3-Br(CH2)3SH, 8-Br(CH2)8SH, 12-Br(CH2)12SH 668
ping ligands and surfactants, however, is not always O- and S-donor type carboxylates, phosphonates,
clearly defined. sulfonates, alkoxides, and thiolates. Among common
In some methods of synthesizing nanoparticles, the neutral ligands are amines (aliphatic and aromatic),
passivating agents are introduced into the reaction phosphines, phosphine oxides, alcohols, amides, ethers,
solution at the initial step. If capping ligands are and sulfides. The nature of the substituents in
used, they interact with metal ions in solution and capping ligands is variable, depending on the specific
therefore affect the reaction equilibrium and the application of the nanocomposite. Hydrocarbon chains
rates of crystal nucleation and growth, thus influenc- are used for oil-soluble particles, but polar functional
ing the entire course of the precipitation reaction. groups are preferred when an application requires
Adjustment of the complexing properties of reaction solubility in water or other polar solvents and a
solutions allows tuning not only of the nanocrystal certain reactivity is required for obtaining more
size but also of the shapesfrom spheres to polygons, complex molecular assemblies. The classification of
rods, and wires (see sections 2.2.5 and 2.2.8 of this the recently studied systems on the basis of type of
review). donor groups and type of substituent (determining
The importance of capping ligands is not only in hydrophilic or lipophilic properties) is given in Tables
providing suitable synthesis conditions and the abil- 10-18.
ity to tune the nanocrystals’ sizes and shapes. Due
to differences in electronic and binding properties,
capping ligands influence the optoelectronic and 9. Acknowledgments
magnetic properties of functional nanocrystalline
inorganic materials. For this reason, it seems useful We wish to extend our thanks to those authors
to classify capping ligands on the basis of their donor cited in this work who graciously provided us with
group. This general classification is shown in Table TEM, SEM, and AFM images and so forth. Financial
9. support from the Defense Advanced Research Projects
Typical capping ligands can be classified as anionic Agency (Grant No. MDA972-03-C-0100) is also grate-
and neutral. The most common anionic ligands are fully acknowledged.
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Chem. Rev.

2004, 104, 3893−3946 3893

Recent Advances in the Liquid-Phase Syntheses of Inorganic Nanoparticles

Received October 28, 2003

Contents 3.3.1. Chelate Selection and Complex 3919

at the Bottom” speech,1 if only for its historical

xAy+(aq) + yBx-(aq) / AxBy(s) (1)

Combining eqs 6 and 7 exception to various approximations and assumptions

dr 1 1 where K is the coarsening rate, given by 4RD/9, and

where γ is the interfacial tension, RG is the universal

Table 1. Representative Sampling of Nanoparticulate Metals Precipitated from Aqueous Solutions

recently reported the synthesis of Au, Pt, Pd, and Ag

2.2.2. Precipitation of Metals by Reduction from

In instances where the strong reducing power of eaq-

Figure 5. Mechanism of Au nanoparticle enlargement

a fixed concentration of oleic acid, the length of the

saturation magnetization of Co and Ni nanoparticles The coprecipitation of metal cations as carbonates,

nipulation of the temperature allowed the time-scale

tion of the nucleation and growth processes, similar

Table 4. Representative Sample of Nanoparticulate Compounds That Have Been Prepared by

The versatility and general usefulness of modern

where pi is the stoichiometry of atom i, χi is the

Figure 17. Effects of pH on particle morphology in sol-

complexes is rapid, to the extent that special han-

Mz+ + hH2O f [M(OH2)h]z+ (56)

where h is the coordination number of the cation. The

Figure 18. Relationship between charge, pH, and hy-

formation of oxo ligands. The relationships between

MoO3,279,281 and MnO2282,283 aerogels in batteries and

3.2.2. Sol-Gel Syntheses of Other Inorganics

3.2.3. Sol-Gel Processing of Nanocomposites

trixes. Claus et al. developed a similar method for

Table 5. Representative Sampling of Oxides Prepared by the Pechini Method

Figure 24. Structure of cetyltrimethylammonium bromide

Figure 25. Schulman’s model of the reverse micelle, as

Figure 26. Structure of AOT (sodium bis(2-ethylhexyl)-

microemulsion phase behavior, and much of the

4.1.1. Common Surfactants

Combining eqs 66-68 gives

Experiments focusing on the interfacial water of

Table 6. Representative Examples of Nanoparticulate Metals Prepared by Reduction in Microemulsions

where M ) Fe, Mn, or Co. The oxidation of Fe2+ f

Ti(OiPr)4 + 2H2O f TiO2 + 4(iPr-OH) (75)

In this case, the reverse micelles containing the

Table 7. Survey from the Literature of Oxides Prepared from Microemulsions

Na2S, Na2Se, or similar salts as the precipitating

4.2.5. Synthesis of Core−Shell and Onion-Structured

8AuCl4- + 3BH4- + 9H2O /

forming a metallic gold shell around the metal

Figure 36. TEM images of Ag nanoparticles synthesized

salts and complexes at elevated temperatures and

appropriate metal chloride, elemental Se, hydrazine,

Fe(OAc)2.504 Others have successfully adapted the

In an inverse approach to the above process,

Figure 42. TEM images of Au@HCMS polymer capsules

and silica aerogels by solvothermal treatment in

engineered viral cages. Douglas et al. have recently

Table 9. Capping Ligands and Coordinating Polymers

Table 14. Nanoparticles Capped with P-Donor Atoms