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Titanium Dioxide Nanomaterials
Chapter · June 2015

DOI: 10.1002/9781119951438.eibc2335
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Titanium Dioxide foundation for a better understanding of the relationship be-
tween the structures and properties of TiO2 nanomaterials.
Nanomaterials Modification is an effective method to enhance the perfor-
mance of TiO2 materials. In general, the modification of TiO2
mainly focuses on bulk doping by (I) introducing alien atoms
Xiaodong Yan & Xiaobo Chen into the framework of TiO2 ,21,31,37–39 (II) surface decoration
University of Missouri–Kansas City, Kansas City, MO, USA with sensitizers (metal nanoparticles, inorganic semiconduc-
tors with narrow band gaps, and organic dyes),4,6,40–43 and (III)
self-structural modifications derived simply from tailoring the
normal valence states of Ti4+ and O2− in TiO2 .44–46
1 Introduction 1 In this article, we aim to summarize the widely used meth-
2 Synthesis of Titanium Dioxide Nanomaterials 1 ods to prepare TiO2 nanomaterials with different geometries
3 Properties and Modifications of Titanium Dioxide along with the modifications and applications of TiO2 nanoma-
Nanomaterials 22 terials. Typical synthetic examples are given in each method.
4 Applications of Titanium Dioxide Nanomaterials 27 It may be impossible to include all the research activities
5 Conclusion 32 of TiO2 nanomaterials in this article. Nevertheless, we try
6 Acknowledgments 32
our best to provide a comprehensive knowledge of the TiO2
7 Related Articles 32
8 Abbreviations 32
nanomaterials and the most updated development of TiO2
9 References 33 nanomaterials.
2 SYNTHESIS OF TITANIUM DIOXIDE

NANOMATERIALS
2.1 Titanium Dioxide Nanoparticles

1 INTRODUCTION
2.1.1 Sol–Gel Method
Titanium dioxide (TiO2 ) has been widely used in paints,
sunscreens, cosmetics, toothpastes, and foods, since its Sol–gel synthesis (see Sol-Gel Synthesis of Solids) is
first successful commercialization as white pigment.1 Since the most widely used method to prepare TiO2 nanomaterials
Fujishima et al.2 reported on the photocatalytic activity due to its simple operation, moderate reaction conditions,
of TiO2 in water splitting under ultraviolet (UV) light, and scalable production.47–54 In a typical sol–gel process,
intensive and extensive investigation has been attracted to monomers, which are usually inorganic metal salts or metal
its applications in photocatalysis and photovoltaics.3–9 Owing organic compounds such as metal alkoxides, will be converted
to its abundance, moderate cost, nontoxicity, biocompatibility, into a colloidal solution (or sol, which is formed from the
high chemical stability, and corrosion resistance,10,11 the hydrolysis and polymerization reactions of the monomers)
multifunctional TiO2 has greatly extended its applications that acts as the precursor for an integrated network (or gel)
in many other areas, such as sensors,12–14 lithium-ion of either discrete particles or network polymers. Complete
batteries,15–17 supercapacitors,18–20 catalyst support,21–23 polymerization and loss of solvent lead to the transition from
microwave absorbent,24,25 and biomedical applications.26–32 the liquid sol into a solid gel phase.34
These applications range from energy and environment to Sugimoto et al.47–50 have thoroughly investigated the
health, clearly demonstrating that TiO2 will surely play a hydroxo complex evolution of titanium(IV) ions in the sol–gel
more important role in serving human society and deserve process, and various factors affecting the yield, particle size,
more efforts in advancing its applications. and shape of TiO2 nanoparticles. In a typical synthesis, a
The production of TiO2 , especially those at the nanoscale, stock solution with Ti4+ of 0.5 mol L−1 was prepared by
is predicted to have great increase in the following decade.33 adding doubly distilled water into the mixture containing
Nanomaterials often exhibit unusual electronic (see Electronic titanium isopropoxide (TTIP) and triethanolamine (TEOA) at
Structure of Solids; Electronic Spectroscopy) and optical a molar ratio of [TTIP]:[TEOA] = 1:2; then, 10 mL of the
properties, which are the key factors deciding the perfor- stock solution was transferred into a Pyrex bottle, followed
mance of TiO2 in most of its applications. On the other by the addition of 10 mL doubly distilled water; the pH value
hand, various factors, such as shapes, size, and special facets, of the solution was adjusted by HClO4 or NaOH solution; the
will have significant influence on the properties of TiO2 final solution (pH ∼ 9.6) was aged in a screw-capped Pyrex
nanomaterials.34–36 Therefore, a variety of synthesis methods bottle at 100 ◦ C for 24 h to get the gelation (the first aging);
have been developed to fabricate TiO2 nanomaterials with finally, the as-prepared highly viscous gel was transferred
different morphologies and textures. These researches lay the into a Teflon-lined autoclave and aged at 140 ◦ C for 72 h
Encyclopedia of Inorganic and Bioinorganic Chemistry, Online © 2011–2015 John Wiley & Sons, Ltd.
This article is © 2015 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Inorganic and Bioinorganic Chemistry in 2015 by John Wiley & Sons, Ltd.
DOI: 10.1002/9781119951438.eibc2335
2 TITANIUM DIOXIDE NANOMATERIALS
(a) (b) (c)
(d) (e) (f)
200 nm
Figure 1 Transmission electron microscopy (TEM) images of TiO2 crystals obtained at different times during the second aging in a standard
preparation: (a) 0 h, (b) 2 h, (c) 3 h, (d) 4 h, (e) 8 h, and (f) 24 h [Reprinted from J. Colloid Interf. Sci., 259, T. Sugimoto, X. Zhou, and
A. Muramatsu, Synthesis of uniform anatase TiO2 nanoparticles by gel-sol method 3. Formation process and size control, 43-52, Copyright
(2003), with permission from Elsevier.]
(a) (b) (c)
200 nm
Figure 2 Effect of the initial pH on the particle size and shape of TiO2 crystals in a standard preparation: (a) pH 9.6, (b) pH 10.5, and
(c) pH 11.5 [Reprinted from J. Colloid Interf. Sci., 259, T. Sugimoto, X. Zhou, and A. Muramatsu, Synthesis of uniform anatase TiO2
nanoparticles by gel-sol method 4. Shape control, 53–61, Copyright (2003), with permission from Elsevier.]
to nucleate and grow TiO2 particles (the second aging).49,50 can be effectively controlled by the shape controllers, such
This above process was defined as a standard preparation. If as diethylenetriamine (DETA), sodium oleate, and sodium
a shape controller or surfactant was used, then the HClO4 stearate.50 For example, with increasing concentration of
or NaOH and the shape controller were added to the 10 mL DETA, the shape of the TiO2 particles was altered from
doubly distilled water before it was mixed with the 10 mL cuboids to ellipsoids (Figure 3a–c).50 However, excess DETA
stock solution; as sodium stearate has limited solubility at would inhibit the formation of TiO2 crystals (Figure 3d),
room temperature, it was added to the mixture of TTIP/TEOA owing to the inhibited nucleation of TiO2 by DETA strongly
to form a suspension.50 Figure 1 shows the time evolution of adsorbed to the embryos of TiO2 .50
the particle growth with the aging time. Very fine particles
are observed after 2 h, and then the particle size increases 2.1.2 Hydrothermal/Solvothermal Method
slowly to ca. 21 nm as the aging time is prolonged to 24 h.49
Also, the initial pH can greatly affect the particle size as well Hydrothermal and solvothermal processes are generally
as the shape of the TiO2 particles. As shown in Figure 2, carried out in Teflon-lined stainless steel autoclaves at a
on increasing the initial pH from 9.6 to 11.5, the particle temperature usually above the boiling temperature of the
size of TiO2 increases and the shape is transformed from solvent to create a high pressure. Often, the temperature and
cuboidal to ellipsoidal. In fact, the shape of the TiO2 particles pressure will be above the critical point of the solvents, leading
DOI: 10.1002/9781119951438.eibc2335
TITANIUM DIOXIDE NANOMATERIALS 3
Hierarchical structure is favored in certain applica-

tions.62–65 Yan et al.65 has developed a simple solvothermal
process to fabricate bicrystalline TiO2 spheres with a core-
shell structure (see scanning electron microscope (SEM) image
in Figure 5). Typically, a mixture of 15 mL alcohol and 5 mL
water was added dropwise into 20 mL acetone containing
polyvinyl pyrrolidone and 5 mL TB; after the solution was
(a) (b) stirred for 2 h, a white suspension was formed and subse-
quently 5 mL of 1.25 M NaOH solution was dropwise added to
it; the obtained mixture was stirred vigorously for another 3 h,
and then transferred to a 100 mL Teflon-lined stainless steel
autoclave; solvothermal treatment was carried out in an elec-
tric oven at 180 ◦ C for 6 h; the as-prepared sample was rinsed
with 0.1 M HCl and distilled water until pH value reached 7,
and then dried at 80 ◦ C for at least 1 day; finally, the sample was
sintered in a tubular furnace at 450 ◦ C for 4 h in air to obtain
(c) (d) anatase@TiO2 (B) core-shell spheres. Figure 5 schematically
illustrates the formation of anatase@TiO2 (B) spheres. 65
200 nm
Figure 3 Effect of the concentration of DETA on the shape of TiO2 2.1.3 Microemulsion and Micelle Methods
particles at pH 10.5: (a) no DETA, (b) 0.05 M, (c) 0.10 M, and (d)
0.25 M [Reprinted from J. Colloid Interf. Sci., 259, T. Sugimoto, Microemulsion and micelle-based methods have been
X. Zhou, and A. Muramatsu, Synthesis of uniform anatase TiO2 widely used in preparing TiO2 crystals.66–73 Microemulsions
nanoparticles by gel-sol method 4. Shape control, 53–61, Copyright are thermodynamically stable dispersions of oil, water, and
(2003), with permission from Elsevier.] amphiphilic surfactants (and frequently in combination with
co-surfactants), where the surfactants are used to stabilize
to the formation of supercritical fluids. This can significantly small droplets of one liquid that is immiscible with the second
increase the solubility of most solid precursors and allows the liquid but can dissolve precursors.66 There are three basic
precipitation of nanostructures from a wide range of inorganic types of microemulsions: oil dispersed in water (O/W), water
materials.55 According to the definition of hydrothermal and dispersed in oil (W/O, reversed), and bi-continuous. Similar
solvothermal methods, the solvents used differ. Generally, to microemulsions, micelle is an aggregate of surfactant
hydrothermal techniques employ water as solvent, while molecules dispersed in water, with the hydrophilic groups
solvothermal processes use nonaqueous solvents. However, in of the surfactants in contact with surrounding water molecules
effect, most of the hydrothermal and solvothermal processes and the hydrophobic regions oriented toward the interior of the
are carried out in a mixture of water and organic solvents.56–60 micelle. Micelles form under the condition that the surfactant
Dinh et al.61 have developed a versatile synthetic method concentration exceeds the critical micelle concentration.66
based on solvothermal technique for the fabrication of TiO2 The critical micelle concentration is the concentration of
nanocrystals with different shapes (Figure 4) by adjusting surfactants in free solution in equilibrium with surfactants in
the molar ratio of titanium butoxide (TB), oleic acid (OA), aggregated form. On the other hand, inverse micelles have the
and oleylamine (OM). Figure 4 schematically shows the hydrophilic groups at the center with the hydrophobic regions
preparation process and the evolution of the crystal shape extending out (water-in-oil micelle). In summary, in both
with the ratio of TB/OA/OM. In a typical process, TB was microemulsion and micelle methods, the reaction occurs in the
added to a mixture of X mmol OA, Y mmol OM, and 100 mmol small droplets or micelles that are stabilized by the surfactants.
absolute ethanol (X + Y = 50).61 For example, to synthesize Kim et al.67 have comprehensively studied the effects
TiO2 with truncated rhombic shape, 5 mmol of TB was added of H2 O/surfactant ratio, ammonia concentration, tetraethy-
to a 40 mL Teflon cup that contained 25 mmol OA, 25 mmol lorthotitanate (TEOT) feed rate, and reaction temperature
OM, and 100 mmol absolute ethanol; after the solution was on the particle size and particle size distribution of the TiO2
stirred for 10 min, the 40 mL Teflon cup was inserted (as nanoparticles in a W/O-type microemulsion-mediated method.
shown in Figure 4) into a 100 mL Teflon-lined stainless steel In a typical synthesis, surfactant was firstly dissolved in cy-
autoclave with 20 mL of mixture solution of ethanol and water clohexane, to which was added a required amount of distilled
(96% ethanol by volume, which is controlled at the azeotropic water with NH4 OH (while the concentration of H2 O was fixed
point to keep the water vapor stable during the crystallization at 4.0 M, the molar ratio of H2 O/surfactant was varied in the
process); then, the system was heated at 180 ◦ C for 18 h; the range of 10–25); then, TEOT was added to the microemulsion
obtained white precipitates were washed several times with with controlled feeding rate by a micro-feed pump under con-
ethanol and then dried at room temperature. 61 tinuous stirring for 24 h (The molar ratio of H2 O/TEOS varied
DOI: 10.1002/9781119951438.eibc2335
1:4:6 2:4:6
Titanium butoxide
Oleic acid
Oleyl amine
Ethanol
Fast hydrolysis
Ethanol and water
1:5:5 2:5:5
H2O vapor
Titanium butoxide Titanium butoxide
Oleic acid Oleic acid
M=
Oleyl amine Oleyl amine
A:O
h
Ethanol Ethanol
18
:O
C,
TB
0°
1:6:4 2:6:4
18
TB °C, 1
14
:O
Nuclei
A:O 8 h
M=
1:6:4 1:7:3 1:8:2
Controlled growth
Figure 4 Schematic illustration of the preparation and shape evolution of TiO2 nanocrystals at different conditions [Reprinted with
permission from C.-T. Dinh, T.-D. Nguyen, F. Kleitz, and T.-O. Do, ACS Nano, 2009, 3, 3737–3743. Copyright (2009) American Chemical
Society.]
Primary anatase
TiO2 particles
Alcohol and water

Hydrolyzation
Acetone, PVP and

tetrabutoxytitanium
t
s
en
es
m
oc
at
pr
tre
al
OH
rm
Na
the
Calcination
vo
l
So
500 nm
Anatase sphere core Hydrogen titanate layer

TiO2(B) nanosheet shell
Precursor
Anatase@TiO2(B) hierarchical spheres
Figure 5 Schematic illustration of the formation of the anatase@TiO2 (B) spheres [Reprinted from J. Power Source, 269, Z. Yan, L. Liu, J.
Tan, Q. Zhou, Z. Huang, D. Xia, H. Shu, X. Yang, and X. Wan, One-pot synthesis of bicrystalline titanium dioxide spheres with a core-shell
structure as anode materials for lithium and sodium ion batteries, 37–45, Copyright (2014), with permission from Elsevier.]
DOI: 10.1002/9781119951438.eibc2335
from 10 to 28.); TiO2 particles were separated by centrifuge ethanol and 10 mL deionized water, then 1.0 mL 25% ammonia
and then washed with acetone to remove organics and surfac- solution was added; the mixtures were sealed in a Teflon-lined
tants; the sample was dried at 100 ◦ C for 24 h and calcinated autoclave (50 mL) and heated at 160 ◦ C for 16 h to obtain
at 400–1000 ◦ C for 2 h.67 H2 O/surfactant ratio and feed rate highly crystalline TiO2 crystals; the as-prepared product was
were found to be key parameters affecting the particle size collected by centrifuge, washed with excess ethanol, and
of TiO2 nanoparticles.67 On the other hand, H2 O/surfactant dried naturally.70 With only increasing the amount of TB
ratio, ammonia concentration, and feed rate were proved to be from 0.5 to 3.0 g, the average size of the microspheres
able to significantly affect the particle size distribution. 67 increases from 200 nm and 400 nm to uncontrollably over
Chen et al.70 have reported on the surfactant-directed 1 μm (Figure 6a–c).70 Figure 6(d) schematically displays the
particle growth of the mesoporous TiO2 microspheres in the
self-assembly of size-tunable mesoporous titanium dioxide
presence of DA as a surfactant.
microspheres. A typical procedure for microsphere synthesis
is as follows. A stock solution of 45 mL ethanol, 1 g TB, and
1 g decylamine (DA) was prepared; then, 15 mL of water was 2.1.4 Pulsed Laser Deposition
added dropwise into the stock solution under vigorous stirring
for 2 h; the white precipitate was collected by centrifuge, Pulsed laser deposition (PLD), a type of physical vapor
washed with excess ethanol, and dried naturally; 1.6 g of the deposition, is a much faster method to fabricate nanoparticles
TiO2 microspheres were dispersed into a mixture of 20 mL and nanoparticle films directly from bulk targets74 and
1 μm 1 μm
(a) (b)
I II III
Monomer Homogeneous Diffusion controlled growth

accumulation nucleation
c
b
Supersaturation
a
Sc
Hybrid micelle
=
Cluster seed
Sm
Hybrid chain
1 μm
(c)
(d) Time
Figure 6 SEM images of mesoporous TiO2 microspheres (particle size vs TB content): (a) 0.5 g TB, (b) 1.0 g TB, and (c) 3.0 g TB with a
constant DA/H2 O/TB ratio of 1:1:15; (d) schematic illustration of the formation and size variation of the mesoporous TiO2 microspheres (the
microsphere growth can be roughly divided into three stages: stage I witnesses the monomer accumulation, stage II comes the homogenous
nucleation, and stage III represents the diffusion-controlled growth). Sc is critical supersaturation, the minimum supersaturation level for
homogenous nucleation of the smallest cluster seeds; Sm is the critical supersaturation level for hybrid micelle formation [Reprinted from
Power Sources, 196, W. Chen, Y. Qiu, K. Yan, and S. Yang, Surfactant directed self-assembly of size-tunable mesoporous titanium dioxide
microspheres and their application in quasi-solid state dye-sensitized solar cells, 10806–10816, Copyright (2011), with permission from
Elsevier.]
DOI: 10.1002/9781119951438.eibc2335
Computer UV laser pulse

Substrate holder
Polymer Pure polymer (PLD) or

Mask Lens Plasma frozen target (MAPLE)
Solvent
Target Liquid nitrogen

reservoir
Pump system
Volatile solvent is
pumped away
(MAPLE)
(a) (b)
Figure 7 (a) Experimental setup of a MAPLE deposition system [Reproduced from Nanoparticle Thin Films for Gas Sensors Prepared
by Matrix Assisted Pulsed Laser Evaporation as published in Sensors, 9, 2682–2696, 2009, http://www.mdpi.com/1424-8220/9/4/2682. ©
A. P. Caricato, A. Luches, and R. Rella 2009. Distributed under the Creative Commons Attribution 3.0 License.]. (b) Difference between
conventional PLD and MAPLE in fabricating thin films [Reproduced from Ref. 77. With kind permission of Springer Science+Business
Media.]
has been employed to fabricate TiO2 thin films.75,76 The

mechanisms involved in PLD are very complex, but the
process of PLD can be simplified into four stages: (I) creation
of partially ionized atomic vapor (plasma) from a target
(usually a solid target); (II) spatial diffusion and distribution
of the plasma; (III) deposition of the plasma onto a heated
substrate; and (IV) nucleation and growth of the nanoparticles
or film on the substrate surface. On the other hand, matrix-
assisted pulsed laser evaporation (MAPLE), a technique based
on PLD, was initially developed for functional organic thin
films for chemical sensor applications.77 Figure 7(a) shows
the schematic diagram of a MAPLE deposition system.
Currently, it has attracted much interest in TiO2 nanoparticle
film fabrication,74,78–80 because MAPLE demonstrates some
advantages, such as more controllable nanoparticles film
CNR-IMM TOPO 5.0 kV ×5000 1μm WD 10.0 mm
morphology and uniformity. The main difference between
PLD and MAPLE is shown in Figure 7(b), that is, the precursor
in PLD is in solid state while it is solution based in MAPLE. Figure 8 SEM image of TiO2 nanoparticle thin film on an alumina
Rella et al. have thoroughly investigated the TiO2 substrate deposited by MAPLE technique. The dark and bright zones
nanoparticle thin film deposited by MAPLE.78–80 Figure 8 correspond to the regions of the substrate uncovered and covered by
shows the SEM image of the TiO2 nanoparticle thin the thin sensing layer, respectively [Reprinted from Sens. Actuators,
film deposited by the MAPLE technique onto an alumina 127, R. Rella, J. Spadavecchia, M.G. Manera, S. Capone, A. Taurino,
M. Martino, A.P. Caricato, and T. Tunn, Acetone and ethanol solid-
substrate.78 In a typical preparation process, a stock solution state gas sensors based on TiO2 nanoparticles thin film deposited by
of 1 mL TB in 5 mL alcohol in a Pyrex tube was heated in matrix assisted pulsed laser evaporation, 426–431, Copyright (2007),
a furnace at 220 ◦ C for 2 days; the precipitate was separated with permission from Elsevier.]
by centrifuge, then thoroughly washed with ethanol and
dichloromethane, and finally dried in air at 60 ◦ C; then,
the as-prepared nanoparticles were dispersed in deionized at 5 × 10−4 Pa by a pump system (the pressure increased to
water with a concentration of 0.2 wt.% accompanied by 4 × 10−3 Pa during the laser-induced evaporation process of
sonication for 10 min; the solution was gradually immersed the solvent); the frozen solution was irradiated with an ArF
into liquid nitrogen (−196 ◦ C), then the frozen solution was (λ = 193 nm) excimer laser (a laser beam with an energy
quickly mounted onto a rotating target holder cooled with density of 550 mJ cm−2 ); the evaporated solvent was pumped
liquid nitrogen to guarantee a low and constant temperature away from the vacuum chamber while the nanoparticles were
(−160 ◦ C); the pressure in the vacuum chamber was controlled deposited on the fixed substrate.78
DOI: 10.1002/9781119951438.eibc2335
2.2 Titanium Dioxide Nanorods tailoring the ratio between acetic acid (HAc) and TTIP.89 In a
typical synthesis, 3.36 mmol TTIP was added to benzyl alcohol
2.2.1 Hydrothermal/Solvothermal Method in a glass vessel being vigorously stirred for several minutes
at room temperature, then to which HAc was added (the total
Hydrothermal treatment is widely used to synthesize TiO2 volume of the solution was kept constant at 5 mL by controlling
nanorods. Often, a substrate, such as fluorine-doped tin volume of the benzyl alcohol); the reaction vessel with a pale
oxide (FTO),3,81–84 Ti foil,85–87 and even carbon fibers,88 yellow solution was sealed with a Teflon cap and kept at 200 ◦ C
is needed for the growth of TiO2 nanorods. Specially, the for 12 h; the precipitate was centrifuged, washed twice with
small lattice mismatch between the FTO substrate and rutile ethanol and dichloromethane, and subsequently dried in air at
TiO2 plays a key role in driving the nucleation and growth 60 ◦ C.89 Figure 10 shows the transmission electron microscopy
of the rutile TiO2 nanorods on FTO.81 Therefore, the FTO (TEM; see Transmission Electron Microscopy) images of the
substrate may be the most widely used one for the growth samples prepared under different HAc/TTIP ratios. Nanorods
of TiO2 nanorods. Liu et al.81 have thoroughly studied can only be obtained at the HAc/TTIP ratio of 4:1.
the growth parameters (growth time, growth temperature, Microwave-assisted hydrothermal or solvothermal method
initial reactant concentration, acidity, and additives) of TiO2 is becoming more and more popular,90–93 because microwave
nanorods on FTO substrate. In a typical synthesis, a certain irradiation will directly activate most molecules that possess
amount of deionized water and concentrated hydrochloric a dipole or are ionic. As energy transfer occurs in less than
acid (36.5–38.0 wt.%) was mixed to reach a total volume of a nanosecond, microwave-assisted method can remarkably
60 mL in a Teflon-lined stainless steel autoclave (125 mL); reduce the reaction time for synthesis of organic and inorganic
after stirring for 5 min, 1 mL of TB was added to the solution; materials (see Figure 11). Yang et al.90 has examined the
after stirring for another 5 min, two pieces of FTO substrates effects of reaction temperature and time on the morphology
(that were ultrasonically cleaned for 60 min in a mixture of the TiO2 nanorods in a microwave-assisted hydrothermal
of deionized water, acetone, and 2-propanol with a volume reaction. The typical preparation process is similar to that
ratio of 1:1:1) were immersed into the precursor solution; the of hydrothermal reaction, except for using microwave as the
hydrothermal synthesis was carried out at 150 ◦ C for 18 h in heating source.
an electric oven.81 Figure 9 shows the field emission scanning
electron microscopy (FESEM) images of the oriented rutile
TiO2 nanorods prepared with different amounts of TB. The 2.2.2 Surfactant-Assisted Method
density and diameter of the TiO2 nanorods increases with the
increase in the initial concentration of TB. In general, the reduction in surface energy is the primary
Surfactant- and substrate-free solvothermal method has driving force for simple particle growth, and morphology
been developed to synthesize pure anatase TiO2 nanorods by evolution is driven by minimizing the area of crystal faces
of high surface energy. Therefore, with the assistance of
surfactants that can serve as surface-capping agents, the shapes
of TiO2 nanostructures can be well tailored by affecting the
relative growth rates of certain facets.55 The most commonly
used surfactants are amines, OA, decanoic acid, 1-octa-decene,
trimethylamine-N-oxide dehydrate, and so forth.94–100
Surfactant-assisted method is often combined with hy-
drothermal or solvothermal treatment.94–97 Yun et al.94 have
(a) 500 nm (b) 400 nm synthesized TiO2 nanorods with different aspect ratios using
different surfactants. In a typical synthesis, deionized water
was added to a mixture of 0.1 mol TTIP and 0.2 mol TEOA
to achieve 200 mL aqueous solution; 20 mL of the precursor
solution was mixed with 20 mL of 0.02 M OA, 0.2 M diethy-
lamine, or 0.1 M DETA aqueous solution; the mixtures were
placed in Pyrex bottles and heated at 100 ◦ C for 24 h; then,
the as-prepared gel was transferred to a Teflon-lined autoclave
(c) 500 nm (d) 500 nm and kept for 72 h at 250 ◦ C.94 The TEM images show the
aspect ratio changes with the surfactants (Figure 12).
Nonhydrolytic sol–gel reaction can get rid of hydrother-
Figure 9 FESEM images of TiO2 nanorods grown at 150 ◦ C for mal/solvothermal treatment.98–100 For example, Buonsanti
18 h with different amounts of TB in a mixture of 30 mL of deionized
water and 30 mL of hydrochloric acid: (a) 0.5 mL, (b) 0.75 mL, (c) et al.98 have developed a surfactant-assisted nonaqueous strat-
0.85 mL, and (d) 1 mL of TB [Reprinted with permission from B. egy combined with high-temperature aminolysis of titanium
Liu and E. S. Aydil, J. Am. Chem. Soc., 2009, 131, 3985–3990. carboxylate complexes to prepare TiO2 nanocrystals. In a typ-
Copyright (2009) American Chemical Society.] ical synthesis, a stock solution containing 3 g 1-octa-decene,
DOI: 10.1002/9781119951438.eibc2335
(a) 100 nm (b) 100 nm (c) 100 nm
(d) 100 nm (e) 100 nm (f) 100 nm
Figure 10 TEM images of the samples prepared under different HAc/TTIP ratios: (a) 0:1, (b) 0.1:1, (c) 1:1, (d) 2:1, (e) 3:1, and (f) 4:1
[Reproduced from Ref. 89 with permission of The Royal Society of Chemistry (http://dx.doi.org/10.1039/C0JM01167C).]
anisotropic growth of TiO2 nanocrystals as well as benefit

5 the formation of regular nanorods.98 As expected, the size
of the as-prepared TiO2 nanorods increases on increasing the
continuous addition of stock solution (Figure 13).
4 M-W assisted reaction
Hydrothermal (Ref. 81)
Length (µm)
6 Hydrothermal (Ref. 80) 2.2.3 Direct Oxidation

3
Direct oxidation of titanium foils by hydrogen peroxide
Length (µm)
2 can easily produce TiO2 nanorod arrays at a low temperature

2 of 80 ◦ C.101–103 More importantly, the preparation process is
easy to operate. As a typical synthesis reported by Mu et al.103 ,
1 0 Ti foil was degreased by sonication in acetone, 2-propanol,
0 300 600 900 1200 and ethanol, subsequently rinsed with ultrapure water, and
Time (min) finally dried in a nitrogen stream; Ti foil was immersed in
0
0 20 40 60 80 100 a 30 mL H2 O2 (30 wt.%) solution, and the mixture was kept
Time (min) at 80 ◦ C for 72 h; finally, the sample was rinsed with plenty
of ultrapure water followed by thermal treatment in a muffle
furnace at 300–500 ◦ C.
Figure 11 Growth rate of TiO2 nanorods during a microwave- Oxygen-containing organic molecules, such as acetone,
assisted hydrothermal reaction. The inset indicates the growth rate of
ethanol, and acetaldehyde, can also be used as oxygen
a conventional hydrothermal reaction in literature [Reprinted with
permission from M. Yang, B. Ding, S. Lee, and J-K. Lee, J. Phys. sources to oxidize the Ti foils at high temperatures to
Chem. C, 2011, 115, 14534–14541. Copyright (2011) American produce TiO2 nanorods.104,105 Peng et al.105 have devel-
Chemical Society.] oped a high-temperature-driven oxidation of Ti foils using
oxygen-containing organic molecules to directly synthesize
TiO2 nanorods on the Ti foils. Briefly, titanium plates
13 or 52 mmol OM, and 0.5 mmol OA in a three-neck flask (30 × 15 × 0.8 mm−3 ) were degreased with acetone, washed
was degassed at 120 ◦ C for 30 min; after it was cooled down with distilled water, then immersed in 30 wt.% HCl at 80 ◦ C
to 50 ◦ C under N2 flow, 0.5 mmol of TiCl4 was added to the for 10 min, washed with distilled water, and finally dried in
stock solution; then, the flask was kept for 30 min at 290 ◦ C a vacuum oven at 40 ◦ C; the pretreated Ti plates were placed
with a ramp rate of ∼25 ◦ C min−1 ; subsequently, the reac- in a horizontal tube furnace, and then an argon (99.999%)
tion could be either halted by removing the heating mantle flow at a flow rate of 200 sccm was kept for 4 h to purge the
and allowing rapid cooling or continued upon addition of a system; after the furnace was heated up to 850 ◦ C at a rate
room-temperature feedstock precursor solution (an equimo- of 30 ◦ C min−1 , a mixture of argon (200 sccm) with selected
lar TiCl4 /OA mixture in 1-octa-decene) at a constant rate oxygen source was introduced into the system and kept for
of 0.1 mL min−1 which was controlled by a syringe pump.98 1.5 h; finally, the system was cooled down to room tempera-
High OM/OA ratio is found to be favorable for inducing the ture under a argon flow.105 The morphology of TiO2 nanorods
DOI: 10.1002/9781119951438.eibc2335
Longitudinal
direction
d101 Longitudinal
direction
d101
2 nm 200 nm 2 nm d101
200 nm 2 nm 200 nm
(a) (b) (c)
Figure 12 TEM images of TiO2 nanocrystals with controlled aspect ratio by (a) 0.02 M OA, (b) 0.2 M diethylamine, and (c) 0.1 M DETA
aqueous solution [Reprinted with permission from H. J. Yun, H. Lee, J. B. Joo, W. Kim, and J. Yi, J. Phys. Chem. C, 2009, 113, 3050–3055.
Copyright (2009) American Chemical Society.]
Slow heterogeneous
Delayed nucleation—
nucleation of brookite
fast growth of anatase seeds
onto anatase seeds
Slow heating
TiCl4:OA:OM
(I) (II) (III)
(b) 30 nm (c) 30 nm
Fast anatase-to-brookite Fast growth
conversion of brookite nanorods
Slow Continued
TiCl4:OA TiCl4:OA
addition addition
(IV) (V) (VI) (d) 30 nm (e) 30 nm
Anatase
(a) Brookite
Figure 13 (a) Schematic illustration of the formation pathway to brookite nanorods.98 The formation pathway of brookite nanorods is as
follows: brookite could originate through direct solid-state phase transformation of the initially formed c-axis-elongated anatase seeds (stage
III), followed by further exclusive growth in the orthorhombic phase (stages IV–VI).98 TEM images of TiO2 nanorods obtained at different
OM/OA ratios of 26 (b and c) and 104 (d and e).98 (b) and (d) were obtained after continuously adding another 2 mmol stock solution while
(c) and (e) were obtained after continuously adding another 20 mmol stock solution [Reprinted with permission from R. Buonsanti, V. Grillo,
E. Carlino, C. Giannini, T. Kipp, R. Cingolani, and P. D. Cozzoli, J. Am. Chem. Soc., 2008, 130, 11223–11233. Copyright (2008) American
Chemical Society.]
varies with oxygen sources. As shown in Figure 14, O2 and are introduced into a reaction chamber at near ambient temper-
HCOOH cannot lead to the generation of TiO2 nanorods, H2 O atures and directed toward a heated substrate in order to induce
just brings about large and long microcrystalline fibers, and controlled chemical reactions, resulting in the deposition of
oriented and aligned TiO2 nanorod arrays can only be obtained a solid thin film on the surface of the substrate. Metal-organic
using CH3 CH2 OH, CH3 CHO. or CH3 COCH3 .105 chemical vapor deposition (MOCVD) and surface-reaction-
limited pulsed chemical vapor deposition (SPCVD) methods
have been used to prepare TiO2 nanorods.106–111
2.2.4 Chemical/Physical Vapor Deposition Well-aligned densely packed rutile TiO2 nanorods have
grown on sapphire substrates by MOCVD method.108
Chemical vapor deposition (CVD; see Chemical Vapor Figure 15 schematically shows the cold-wall MOCVD ap-
Deposition) is a chemical process, in which precursor gases paratus. The by-pass flow path is designed for controlling the
DOI: 10.1002/9781119951438.eibc2335
55, and 60 ◦ C, respectively; oxygen gas with a flow rate of 30

sccm was used to convey the source vapor and to invoke the
chemical reaction; the substrate temperature (Ts ) and cham-
ber pressure (Pc ) were controlled at 550 ◦ C and 1.5–5 mbar,
respectively, during deposition.108 Pc and Ts are the variables
affecting compositions and morphologies of the samples.108
The deposition rate can be controlled by directly adjusting the
(a) 1 μm (b) 1 μm temperature of the precursor reservoir, which will change the
partial pressure of the source vapor under the mass-transport-
limited condition.108 Figure 15(b) shows the typical SEM
images of TiO2 nanorods prepared by MOCVD method.
2.3 Titanium Dioxide Nanowires
2.3.1 Hydrothermal/Solvothermal Method

(c) 1 μm (d) 1 μm
Well-aligned TiO2 nanowire arrays can be prepared by

hydrothermal112–120 or solvothermal method121–124 . The syn-
thesis of TiO2 nanowires on FTO substrates and carbon fibers
follows a similar process.114–116 First, TiO2 nanoparticle-
seeded substrates are achieved by spin coating or directly
immersing the substrates into the Ti-containing solution; sec-
ond, the growth of TiO2 nanowires on substrates is carried
out by hydrothermal or solvothermal treatment. In a typical
(e) 1 μm (f) 1 μm
synthesis, the carbon fibers were immersed in 0.2 M TiCl4
aqueous solution for 10 min followed by being heated on a
Figure 14 SEM images of the TiO2 nanorods prepared by oxidizing hotplate at 350 ◦ C in air for 10 min; 0.6 mL TB was added to a
Ti using (a) O2 , (b) HCOOH, (c) H2 O, (d) CH3 CH2 OH, (e) CH3 CHO, mixture solution containing 20 mL concentrated hydrochloric
and (f) CH3 COCH3 as oxygen sources [Reproduced with permission acid (37%) and 20 mL deionized water; this clear solution
from Ref. 105. © IOP Publishing. Reproduced by permission of IOP with the seeded carbon fibers was transferred to a Teflon-lined
Publishing. All rights reserved.] stainless steel autoclave (50 mL); the hydrothermal treatment
was carried out in an electric oven at 160 ◦ C for 5 h, and
steady-state chamber pressure before the deposition.108 The then cooled down slowly; finally, the as-prepared sample was
precursor evaporator is heated to a designated temperature annealed in air or H2 at 550 ◦ C for 1 h.116 Figure 16 shows the
to facilitate the transport of the source vapor to the growth SEM images of TiO2 nanowires on carbon nanofibers.
chamber.108 Three independent thermal couples are mounted Que et al.118 has prepared ultra-long single crystalline
on the transport line to control and monitor the temperature of TiO2 nanowires on Ti foil by a three-step synthesis process.
the shower head (Tsh ), gas transfer line (Ttl ), and the precursor Firstly, after the Ti foil was degreased by sonication in
reservoir (Tpr ).108 Typically, Tsh , Ttl , and Tpr were set at 50, acetone, 2-propanol, and ethanol for 15 min, respectively,
Growth
Shower head
chamber
Hot passage
Tsh Ttl
O2
Bypass Tpr
Substrate
or O2 Precursor
and holder
evaporator
200 nm 200 nm
To pumping unit
(a) (b)
Figure 15 (a) Schematic diagram of the cold-wall MOCVD apparatus; (b) FESEM images of the TiO2 nanorods grown on sapphire (100)
substrate [Reproduced with permission from Ref. 108. © IOP Publishing. Reproduced by permission of IOP Publishing. All rights reserved.]
DOI: 10.1002/9781119951438.eibc2335
increases gradually with prolonging hydrothermal duration,

and then decreases, but the average diameters of these TiO2
nanowires exhibit no obvious change.
Gonzalo-Juan et al.95 have reported the synthesis of TiO2
nanowires by ligand-mediated shape control in a solvothermal
process. Their research shows that an excess of OA (the ratio
of OA to OM is 100:0) generates preferential growth along the
[001] plane, suppressing the growth of the nanostructure along
2 μm 300 nm the [101] plane and leading to the formation of nanowires,
whereas higher concentration of OM (the ratio of OA to OM
(a) (b)
is 50:50) contributes to the onset of anisotropic growth along
the [101] plane, assisting the formation of nanorods.95
Figure 16 SEM image of hydrogenated TiO2 nanowire arrays Recently, Wu et al.125 have developed a substrate- and
at (a) a low resolution and (b) a high resolution [Reproduced surfactant-free solvothermal method to synthesize anatase
from Ref. 116 with permission of The Royal Society of Chemistry
TiO2 nanowires. In a typical synthesis, 0.2 g lithium acetate
(http://dx.doi.org/10.1039/C4TA03495C).]
dehydrate was dissolved in a mixture (10 mL) of N,N-
dimethylformamide (DMF) and HAc, and then 0.2 mL TB
it was immersed in 1 M NaOH aqueous solution (40 mL) in was added to the solution; after the solution was transferred
an Teflon-lined stainless steel autoclave (80 mL); then, the into a Teflon-lined stainless steel autoclave, the hydrothermal
hydrothermal treatment was carried out in an electric oven at treatment was conducted in an oven at 200 ◦ C for 20 h;
220 ◦ C for 24 h; after cooling down to room temperature, the the product was washed thoroughly with ethanol for several
sample was washed with enough deionized water and dried times, and then dried in a vacuum oven at 60 ◦ C overnight.125
naturally.118 Secondly, the sample was immersed in 0.5 M HCl The Li+ ions are believed to be crucial for the formation
aqueous solution for 2.5 h to replace Na+ with H+ .118 Finally, of 1D nanostructure, but the exact mechanism is still
the sample was calcinated at 450 ◦ C in air for 30 min.118 As unclear.125 Furthermore, the morphology and structure of
shown in Figure 17, the thickness of the TiO2 nanowire arrays the TiO2 nanowires are greatly affected by the volumetric
13.8 μm
7.1 μm
72 nm
78 nm 48 nm 66 nm
70 nm
80 nm 76 nm
2 μm
72 nm
1 μm
(a) (b)
15.9 μm
10.1 μm 72 nm
100 nm
68 nm 80 nm
70 nm
76 nm 2 μm
2 μm 70 nm 80 nm
(c) (d)
Figure 17 Cross-sectional FESEM images of TiO2 nanowire arrays with different hydrothermal duration: (a) 16 h, (b) 20 h, (c) 24 h, and (d)
28 h [Reprinted from J. Power Sources, 266, L. Que, Z. Lan, W. Wu, J. Wu, J. Lin, and M. Huang, High-efficiency dye-sensitized solar cells
based on ultra-long single crystalline titanium dioxide nanowires, 440–447, Copyright (2014), with permission from Elsevier.]
DOI: 10.1002/9781119951438.eibc2335
200 nm
1 μm 100 nm
(a) (b)
200 nm
1 μm 100 nm
(c) (d)
200 nm
1 μm 100 nm
(e) (f)
Figure 18 FESEM and TEM images of TiO2 nanowires prepared with different volumetric ratios of DMF/HAc: (a, b) 4/6, (c, d) 5/5, and (e,
f) 6/4 [Reproduced from Ref. 125. © WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2012.]
ratio of DMF/HAc. As shown in Figure 18(a–d), flower-like In a typical synthesis, Ti foils (5 × 5 × 0.01 cm3 ) were etched
assemblies were obtained with the DMF/HAc ratio of 4/6 and for 2 min in a mixture of 55 wt.% hydrofluoric acid, 63 wt.%
5/5 maybe due to limited crystal growth. However, when the nitric acid, and distilled water (volume ratio was 1:3:6),
ratio of DMF/HAc reached 6:4, freestanding nanowires were and then rinsed in an ultrasonic bath; one piece of Ti foil
achieved (Figure 18e and f). These phenomena indicate that was immersed in 50 mL 30 wt.% H2 O2 aqueous solution that
DMF also plays an important role in the preferential growth contained 15 mg melamine and 0–5.0 mL 63 wt.% HNO3 ;
of the TiO2 crystals along the [101] direction.125 heat treatment was performed in an oven at 80 ◦ C for 72 h;
finally, the sample was rinsed with distilled water, dried at
2.3.2 Direct Oxidation 80 ◦ C, and annealed at 450 ◦ C for 1 h in air.126,128 Figure 19
shows the SEM images of the sample prepared via the above
Similar to the preparation of TiO2 nanorods, direct process. Obviously, the HNO3 concentration is crucial for the
oxidation of Ti foils assisted with aqueous hydrogen peroxide formation of TiO2 nanowires. It seems that the concentration
solution can also be used to prepare TiO2 nanowires.126–128 of HNO3 at 0.174–0.580 M is more preferred.126
DOI: 10.1002/9781119951438.eibc2335
ZJU 5.0 kV 4.0 mm ×50.0 k SE(M) 12/24/2008 17:23 1.00 um ZJU 5.0 kV 4.0 mm ×50.0 k SE(M) 12/24/2008 17:27 1.00 um
(a) (b)
ZJU 5.0 kV 3.8 mm ×50.0 k SE(M) 12/24/2008 17:32 1.00 um ZJU 5.0 kV 3.6 mm ×50.0 k SE(M) 12/24/2009 15:52 1.00 um
(c) (d)
Figure 19 FESEM images of TiO2 nanowires prepared at different concentrations of HNO3 : 0 M (a), 0.174 M (b), 0.725 M (c), and 1.45 M
(d) [Reproduced from Ref. 126 © The American Ceramic Society, 2009.]
High-temperature oxidation of Ti foils by oxygen- nanowire three-dimensional architecture, that is, the TiO2
containing organic molecules provides another way to synthe- nanowires were grown on Si nanowire backbones by SPCVD.
size TiO2 nanowires.129,130 Daothong et al.129 have reported In a typical synthesis, an atomic layer deposition system was
on the size-controlled growth of TiO2 nanowires by oxida- applied to conduct the SPCVD growth of TiO2 nanowires.134
tion of titanium substrates in the presence of ethanol vapor Si nanowire substrate was put in the tube chamber with
at 700–850 ◦ C for 30 min. The preparation process is similar its front side 2.5 cm away from the precursor nozzles; the
to that of preparation of TiO2 nanorods by direct oxidation chamber temperature was quickly heated up 600 ◦ C with a
of titanium foils in the presence of oxygen-containing or- constant N2 flow of 40 sccm; deionized water and TiCl4
ganic molecules. Figure 20 shows the SEM images of TiO2 were introduced as growth precursors sequentially with puls-
nanowires by oxidation of titanium substrates in the presence ing and purging durations of 2 and 60 s, respectively; the
of ethanol vapor at different temperatures. It is clear that the chamber pressure difference before and after TiCl4 puls-
diameter of the as-prepared TiO2 nanowires can be controlled ing stage was controlled to be 20 millitorr by adjusting the
by temperature. The minimum diameter is observed at 750 ◦ C. temperature of TiCl4 reservoir; after a 400-cycle SPCVD
growth, the chamber was cooled down to room temper-
ature naturally.134 Figure 21 shows the SEM images of
2.3.3 Chemical Vapor Deposition the as-prepared TiO2 /Si nanowire three-dimensional archi-
tecture. As shown in Figure 21(d), each single TiO2 nanowire
CVD method is an important technique to prepare TiO2 demonstrates necklace structure composed of coherent
nanowires.131–134 Shi and Wang134 have prepared TiO2 /Si nanocrystals.134
DOI: 10.1002/9781119951438.eibc2335
100 nm 100 nm
(a) (b)
100 nm 100 nm
(c) (d)
Figure 20 SEM images of TiO2 nanowires by oxidation of titanium substrates in the presence of ethanol vapor at temperatures of (a) 700 ◦ C,
(b) 750 ◦ C, (c) 800 ◦ C, and (d) 850 ◦ C for 30 min [Reprinted from Scripta Mater., 57, S. Daothong, N. Songmee, S. Thongtem and P. Singjai,
Size-controlled growth of TiO2 nanowires by oxidation of titanium substrates in the presence of ethanol vapor, 567-570, Copyright (2007),
with permission from Elsevier.]
2 μm 300 nm
(a) (b)
200 nm 50 nm
(c) (d)
Figure 21 Morphology of TiO2 –Si nanowire 3D architecture: (a) planar view (the inset is a digital photo of the as-prepared sample);
(b) closer view; (c) highly packed TiO2 nanowires filled the narrow space between adjacent Si nanowires; and (d) single TiO2 nanowire
[Reproduced from Ref. 134 with permission of The Royal Society of Chemistry (http://dx.doi.org/10.1039/C2EE22113F).]
DOI: 10.1002/9781119951438.eibc2335
2.4 Titanium Dioxide Nanotubes the growth of TiO2 nanotubes will go through three stages
(Figure 24a): (I) the Mn+ ions are solvated in the electrolyte,
2.4.1 Hydrothermal Method that is, the Ti foil is continuously dissolved (and corrosion, or
electropolishing of the metal, is observed); (II) the Mn+ ions
Hydrothermal method is one of the main approaches formed react with O2− (provided by H2 O in the electrolyte)
to produce TiO2 nanotubes.135–141 In most cases, TiO2 and form a compact oxide layer if compact oxide is not soluble
nanotubes are transformed from TiO2 particles by being in the electrolyte; (III) under some electrochemical conditions,
autoclaved in concentrated (usually ≥ 10 M) NaOH aqueous competition between solvation and oxide formation is estab-
solutions,135–140 during which the TiO2 particles are converted lished (leading to porous compact oxide).154 Figure 24(b–e)
to titanate units in the form of nanosheets and then the shows the SEM images of the TiO2 grown on Ti foil corre-
nanosheets reassemble into the shape of tube.142 As a sponding to the three stages. Under some specific conditions,
common synthesis process, 2 g of TiO2 nanoparticles was disorganized rapid growth of TiO2 nanotube bundles (IV in
added to 50 mL of 10 M NaOH solution and kept for 24 h Figure 24) or formation of thick self-organized mesoporous
at 130 ◦ C in a Teflon-lined stainless steel autoclave; after layers (V in Figure 24) can be observed.154
being cooled down naturally, the precipitates were collected, Schmuki’s group has thoroughly investigated the growth
washed with water and then 0.1 M HCl aqueous solution until and morphologies of TiO2 nanotube arrays under various
the pH value of the washing solution reached 7, and dried conditions.144–151 As shown in Figure 25, the tube diameter
at temperatures below 100 ◦ C.135,136,138 The concentration of and bottom layer thickness increase with increasing the
NaOH is a crucial factor for the successful transformation anodization potential. However, the top layer thickness firstly
of TiO2 nanoparticles to nanotubes. As the concentration of increases, then almost keeps constant at high anodization
NaOH increases from 5 to 7 M, more nanosheets are observed potential of above 20 V, which could be ascribed to significant
(Figure 22a and b), indicating that the reaction kinetics is thinning of the tube walls due to chemical dissolution of
proportional to the concentration of NaOH. When it reaches the oxide with time149 and as well may be related to the
10 M, the transformation is fully completed (Figure 22c). On increase in the tube diameter. The solvent in the electrolyte is
the other hand, the reaction time influences the morphology another crucial factor significantly affecting the growth of the
and size of the TiO2 nanotubes. With increasing reaction time, TiO2 nanotubes. As is depicted by Figure 26, TiO2 nanotubes
the TiO2 nanotubes become longer but have smaller diameters prepared in organic solutions (Figure 26b) show much better
(Figure 23). regularity and homogeneity in comparison to the nanotubes
prepared in aqueous solutions (Figure 26a); also, nanotubes
2.4.2 Electrochemical Anodization prepared in organic electrolytes exhibit ultrahigh aspect ratio
and smooth surface, while thinning of the tube wall toward
Electrochemical anodization of Ti substrates in ade- the mouth and ripples on the tube walls were observed for
quate electrolytes under specific electrochemical conditions the ones prepared in aqueous electrolytes.146,147,150,151 In a
is a simple, cost-effective approach to fabricate TiO2 typical synthesis, Ti foils (99.6% purity) were degreased by
nanotubes.143–153 Figure 24(a) schematically shows the for- sonication in acetone, ethanol, and deionized water and then
mation of TiO2 nanotube arrays on the Ti foil during the dried in a nitrogen stream; anodization was conducted in a
electrochemical anodization process. When Ti foil is exposed two-electrode system in a hot (80 ◦ C) H3 PO4 /HF electrolyte
to a sufficiently anodic voltage, it will undergo an oxidation (3 M HF) at 15 V (a DC power supply) for 2 h with a Ti
reaction (M → Mn+ + ne− ).154 Depending mainly on the elec- foil and a Pt foil as the working and counterelectrodes; after
trolyte and the particular anodization parameters, essentially anodization, the sample was rinsed with ethanol and dried in
500 nm 100 nm 100 nm
(a) (b) (c)
Figure 22 TEM images of samples synthesized at 130 ◦ C for 3 h in NaOH solutions with different concentrations: (a) 5 M, (b) 7 M, and (c)
10 M [Reproduced from Ref. 139. With kind permission of Springer Science+Business Media.]
DOI: 10.1002/9781119951438.eibc2335
100 nm 100 nm
(a) (b)
100 nm 100 nm
(c) (d)
100 nm
(e)
Figure 23 TEM images of samples synthesized at 130 ◦ C under 10 M NaOH with different reaction times: (a) 0 h, (b) 1 h, (c) 3 h, (d) 5 h, and
(e) 7 h [Reproduced from Ref. 139. With kind permission of Springer Science+Business Media.]
a nitrogen stream.152 It should be noted that the morphology followed by a thermal treatment to form TiO2 , and finally the
and texture are greatly dependent on the solutes and solvents removal of the template to leave behind TiO2 nanotubes. Na
in the electrolytes, anodization voltage and time, and even et al.159 have prepared the TiO2 nanotubes using ZnO nanorods
impurity in the Ti foil. as templates, as shown in Figure 27. Typically, indium-doped
tin oxide (ITO)-coated glass substrate was rinsed by sonication
in acetone and isopropyl alcohol successively for 20 min and
2.4.3 Template Method dried a nitrogen stream; the ZnO nanorods were then generated
on ITO substrate (working electrode) by electrodeposition at
Template method offers another effective way to produce −0.9 V vs Ag/AgCl (reference electrode) in a three-electrode
TiO2 nanotubes with well-controlled diameter and length. In system in 5 × 10−3 M ZnCl2 and 0.1 M KCl solution that was
general, the preparation procedure of template TiO2 nanotubes saturated with bubbling oxygen at 80 ◦ C; a Pt wire was used
is deposition of a Ti precursor onto the surface of the template as the counterelectrode; TiO2 -covered ZnO nanorod arrays
(such as anodic aluminum oxide and ZnO nanorods155–162 ), were achieved by dropping the precursor solution (which was
DOI: 10.1002/9781119951438.eibc2335
composed of 2 mL TTIP, 150 mL 2-propanol, and 0.75 mL

HCl) on the ZnO-covered ITO substrates; then, the substrates
(a) were spun at room temperature, followed by heat treatment
I
Cathode Anode
e−
at 450 ◦ C for 30 min in a furnace to form the TiO2 crystals;
+
II finally, the ZnO nanorod template was removed by 0.75 M
M HCl.159
III
Nanopores Nanotubes 2.4.4 Electrospinning Technique
IV Ultrahigh-aspect-ratio TiO2 nanotubes can be readily
prepared by electrospinning technology, where polymer is
V
often used as the medium to form nanofibers. One way
to prepare TiO2 nanotubes by electrospinning technology
is to coat the electrospun polymer nanofibers with titanate
(b) (b*) precursors, which then will undergo thermal treated in air to
condense the TiO2 particles and meanwhile the template will
TiO2 be burnt off.162–164 Another way to obtain TiO2 nanotubes is
Stage I
to use a coaxial spinneret system, which only undergoes a two-
Ti substrate step process to obtain TiO2 nanotubes.161,165,166 Figure 28(a)
100 nm 200 nm schematically demonstrates the coaxial electrospinning setup
(c) (c*) and preparation process. In a typical synthesis, TTIP was
dissolved in HAc (2 mL) and ethanol (2 mL) to form a mixture
solution, which was then mixed with ethanol (3 mL) that
Stage II contained 0.3 g polyvinylpyrrolidone (PVP, Mw ≈ 1 300 000);
the mixture was stirred for 20 min and immediately transferred
100 nm 200 nm into a plastic syringe connected to the outer needle while heavy
mineral oil was added to another syringe that was connected
(d) (d*) to the inner needle; the feeding rates of PVP solution and
mineral oil were fixed at 0.6 and 0.3 mL h−1 , respectively; a
high voltage was applied to the dual nozzle, and the nanofibers
Stage II–III
were collected on the aluminum foil 15 cm below the tip of
the needle; the obtained nanofibers were left in air for 5 h to
100 nm 200 nm
allow the complete hydrolysis of TTIP; the mineral oil was
(e) (e*) extracted by immersing the fibers in octane overnight; finally,
hollow TiO2 nanofibers are obtained by calcining the precursor
nanofibers in air at 500 ◦ C for 1 h.165 Figure 28(b) shows
Stage III the typical SEM images of the ultra-long TiO2 nanotubes
from coaxial electrospinning. Obviously, the TiO2 nanotubes
100 nm 200 nm exhibit fibrous morphology, but hollow structure (the inset in
Figure 28b).
Figure 24 (a) The electrochemical anodization process: (I) metal

electropolishing, (II) formation of compact anodic oxides, (III) self- 2.5 Titanium Dioxide Nanosheets
ordered oxides (nanotubes or nanopores), (IV) rapid (disorganized)
oxide nanotube formation, and (V) ordered nanoporous layers Hydrothermal and solvothermal methods are the dominant
[Reproduced with permission from Ref. 154. © WILEY-VCH Verlag routes to prepare nanosheets. Often, TiO2 nanosheets are
GmbH & Co. KGaA, Weinheim, 2011.]; (b–e) SEM cross-sectional dominated by {001} facets.167–172 Hydrofluoric acid is often
(b–e) and top-view (b*–e*) images of TiO2 formed at 20 V in
glycerol/0.35 M NH4 F with anodization time of (b, b*) 60 s, (c, c*) used as the F− donor for stabilizing the {001} high-
75 s, (d, d*) 100 s, and (e, e*) 110 s (in the top-view images, the border energy facet, facilitating the growth of the corresponding
separates the anodized from the nonanodized region) [Reprinted from surface.167–169,172,173 Wen et al.173 have synthesized micro-
Electrochim. Acta, 54, S. Berger, J. Kunze, P. Schmuki, D. LeClere, sized TiO2 nanosheets with high-reactive {001} and {100}
A. T. Valota, P. Skeldon, and G. E. Thompso, A lithographic approach facets, corresponding to percentages of 98.7% and 1.3%. In
to determine volume expansion factors during anodization: Using the
example of initiation and growth of TiO2 -nanotubes, 5942–5948, a typical synthesis, a suspension of 0.45 g TiF4 in 20 mL
Copyright (2009), with permission from Elsevier.] 1-butanol powder was prepared in a 50 mL Teflon reactor
after being stirred for a few seconds; subsequently, 0.2 mL
DOI: 10.1002/9781119951438.eibc2335
1800
2V 5V 1600
300
250
Layer thickness (nm)

1400
Tube diameter (nm)

100 nm 100 nm 1200 200
1000
200 nm 200 nm 200 nm 300 nm 150
800
600 100
10 V 15 V
400 50
200
0
0
0 5 10 15 20 25 30 35 40 45
200 nm 500 nm 200 nm 500 nm (b) U (V)
20 V 25 V 100
90
80
Layer thickness (nm)

67 nm
70
200 nm 500 nm 200 nm 500 nm 60
50 21 nm
30 V 35 V 40
85 nm
30
20
45 nm
10
200 nm 500 nm 0
200 nm 500 nm 10 15 20 25 30 35 40
(a) (c) U (V)
Figure 25 (a) SEM top and cross-sectional images of the TiO2 nanotubes obtained at various anodization voltages, (b) tube diameter and top
layer thickness, and (c) the bottom layer thickness in dependence of the anodization voltage [Reprinted from J. Electroanal. Chem., 621, J.M.
Macak, H. Hildebrand, U. Marten-Jahns, and P. Schmuki, Mechanistic aspects and growth of large diameter self-organized TiO2 nanotubes,
254–266, Copyright (2008), with permission from Elsevier.]
7 μm 100 nm
2.5 μm
(a) (b)
Figure 26 The cross-sectional SEM images of TiO2 nanotubes: (a) in 1 M (NH4 )2 SO4 + 0.5 wt.% NH4 F using a potential sweep from
open-circuit potential to 20 V with sweep rate 0.1 V s−1 [Reproduced with permission from Ref. 146. © WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim, 2005.]; (b) in glycerol electrolyte with 0.5 wt.% NH4 F using a potential sweep from open-circuit potential to 20 V with
sweep rate 1 V s−1 [Reproduced with permission from Ref. 147. © WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2005.]
48% HF was added to the suspension, and immediately, surfaces. The mechanism of these anatase TiO2 nanosheets
the solvothermal treatment was conducted in the Teflon-lined wholly dominated with {001} and {100} facets might be
autoclave at 210 ◦ C for 24 h in an oven; finally, the as-prepared attributed to the extremely small lattice mismatch between
product was collected by centrifugation and washed with the (100) planes of cubic TiOF2 and tetragonal anatase TiO2 ,
ethanol three times.173 The FESEM images of the as-prepared which means that the solid TiOF2 acts as a ‘‘hard template’’
TiO2 nanosheets are shown in Figure 29. The micro-size to generate the thermodynamically unfavorable crystal facets
paper-like anatase TiO2 nanosheets exhibit flat and smooth of anatase TiO2 .173
DOI: 10.1002/9781119951438.eibc2335
Growth of ZnO nanorods on ITO TiO2 formation on ZnO nanorods Removal of ZnO nanorods by wet etching
ZnO nanorods ZnO nanorods
TiO2 nanotubes
500 nm
TiO2
ITO ITO ITO

Glass Glass Glass
5 μm
(a) (b)
Figure 27 (a) Schematic process for the fabrication of the TiO2 nanotubes using ZnO nanorods as templates and (b) SEM image of the
as-prepared TiO2 nanotubes [Reprinted from Electrochim. Acta, 53, S.-I. Na, S.-S. Kim, W.-K. Hong, J.-W. Park, J. Jo, Y.-C. Hah, T. Lee,
and D.-Y. K, Fabrication of TiO2 nanotubes by using electrodeposited ZnO nanorod template and their application to hybrid solar cells,
2560–2566, Copyright (2008), with permission from Elsevier.]
Syringe pump
Syringe pump
Outer tube
50 nm
Inner capillary
High-voltage
V Power supply
Collector 2.00 μm
(a) (b)
Figure 28 (a) Schematic illustration of coaxial electrospinning setup for the preparation of core–shell TiO2 nanofibers and (b) SEM images
of hollow TiO2 nanofibers prepared by electrospinning technology (the inset is cross section of the hollow TiO2 nanofiber) [Reprinted from
Mater. Res. Bull., 48, W. Chang, F. Xu, X. Mu, L. Ji, G. Ma, and J. Nie, Fabrication of nanostructured hollow TiO2 nanofibers with enhanced
photocatalytic activity by coaxial electrospinning, 2661–2668, Copyright (2013), with permission from Elsevier.]
Using organic molecules as the capping agents can avoid 2.6 Faceted Crystals
the use of highly corrosive hydrofluoric acid. Chen et al.170
have prepared large ultrathin anatase TiO2 nanosheet spheres Many synthesis methods have been developed to prepare
using DETA as the capping agent. In a typical synthesis, a faceted TiO2 crystals, including hydrothermal/solvothermal
solution was prepared by adding 0.03 mL of DETA to 42 mL method, gas oxidation method, topotactic transformation,
isopropyl alcohol, to which 1.5 mL TTIP was added; the and epitaxial growth. Among them, hydrothermal and
mixture solution was then transferred to a 60 mL Teflon-lined solvothermal methods are most widely used due to the versatile
stainless steel autoclave and kept in an electric oven at 200 ◦ C ability in manipulating the nucleation and growth behaviors
for 24 h; the white precipitate was separated by centrifugation, (particularly growth rates along different orientations) of
washed thoroughly with ethanol, and dried at 60 ◦ C overnight; crystals.36 Surface energy is the primary driving force for
finally, the samples were annealed at 400 ◦ C for 2 h with a simple particle growth; meanwhile, the high-energy surfaces
heating rate of 1 ◦ C min−1 .170 Figure 30 shows the as-prepared diminish rapidly during the crystal growth process as a result
anatase TiO2 spheres, which is assembled by ultrathin TiO2 of the minimization of surface energy. Therefore, lowering
nanosheets with nearly 100% exposed {001} facets.170 the surface energy of the high-energy surface is the strategy to
DOI: 10.1002/9781119951438.eibc2335
5.0 mm 2.0 mm
(a) (b)
1 μm
(001) Figure 31 SEM image of the as-prepared anatase TiO2 single

(100) crystals with a large percentage of reactive {001} facets [Reprinted
by permission from Macmillan Publishers Ltd: Nature, H. G. Yang,
27.9 nm C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith, H. M. Cheng, and
4140 nm
G. Q. Lu, Nature, 2008, 453, 638–641, copyright 2008.]
300 nm
(100)
(c) (d)
Faceted anatase is the most widely investigated

Figure 29 (a–c) FESEM images of anatase TiO2 nanosheets phase.175–193 Among them, {001}, {010}, and {101} faceted
synthesized at 210 ◦ C for 24 h and (d) schematic structure of anatase TiO2 crystals have been widely reported,175–179,181–188
the as-obtained anatase TiO2 nanosheets [Reproduced from Ref. while only limited reports have focused on the synthesis of
173 with permission of The Royal Society of Chemistry (http://
dx.doi.org/10.1039/C0CC05798C).] TiO2 crystals with {110} facet180 and high-index facets189–193 .
Yang et al.177 first reported the anatase TiO2 single crystals
with a high percentage (47%) of {001} facet using hydrofluoric
acid as the morphology controlling agent. Typically, 5.33 mM
TiF4 aqueous solution containing 10 wt.% hydrofluoric acid
was used as the precursor solution, and then the reaction
was performed in a Teflon-lined stainless steel autoclave
at 180 ◦ C for 14 h.177 Figure 31 shows the SEM image of
the as-prepared anatase TiO2 crystals in the shape of highly
truncated bipyramids with two square {001} surfaces and
eight isosceles trapezoidal {101} surfaces.36
On the other hand, Ye et al.188 have synthesized anatase
TiO2 nanocrystals with highly exposed {101}, {001}, or
{010} single facets from potassium titanate by hydrothermal
method without using fluorine and organic capping surfactants.
400 nm
Typically, 1 g TiO2 nanoparticles (P25) was dispersed in
40 mL of 10 M KOH under magnetic stirring; then, the
reaction was conducted in a Teflon-lined stainless steel
autoclave (50 mL) at 200 ◦ C for 24 h; after cooling down
Figure 30 TEM images of as-prepared anatase TiO2 nanosheet to room temperature, the white precipitate was collected by
spheres [Reprinted with permission from J. S. Chen, Y. L. Tan, centrifugation, divided into two parts (one part was washed
C. M. Li, Y. L.Cheah, D. Luan, S. Madhavi, F. Y. C. Boey, L. A. with ethanol (E-precursor) and the other was washed with
distilled water (W-precursor)), and dried at 80 ◦ C.188 To
Archer, and X. W. Lou, J. Am. Chem. Soc., 2010, 132, 6124–6130.
Copyright (2010) American Chemical Society.]
prepare {101} faceted TiO2 (TiO2 -101), 0.1 g of E-precursor
was dispersed in 90 mL distilled water under sonication; then,
hydrothermal treatment was carried out in a Teflon-lined
favor the growth of the corresponding surface. Capping agents stainless steel autoclave (100 mL) at 200 ◦ C for 24 h, and it
can play such roles in lowering the surface energy by physical was cooled down naturally; the white precipitate was separated
interaction with the high-energy surface. Thus, an appropriate by centrifugation and washed successively with HCl solution
capping agent is the key to tunable percentages of different (pH = 5) and distilled water until pH = 7.0; finally, the as-
facets. To date, fluorine ions are still the dominant adsorbed prepared sample was dried at 80 ◦ C.188 The route to {001}
species in fabricating faceted TiO2 crystals.174 faceted TiO2 is similar to that of the TiO2 -101 except the
DOI: 10.1002/9781119951438.eibc2335
NONE SEI 15.0 kV ×60,000 100 nm WD 8.3 mm NONE SEI 15.0 kV ×50,000 100 nm WD 8.1 mm
(a) (b)
[001]
90*
44*
[010]
NONE SEI 15.0 kV ×50,000 100 nm WD 7.7 mm
(c)
Figure 32 FESEM images of TiO2 with highly exposed (a) {101}, (b) {001}, and (c) {010} facets [Reproduced from Ref. 188 with permission
of The Royal Society of Chemistry (http://dx.doi.org/10.1039/C3TA11791J).]
addition of 0.3 mol (NH4 )2 CO3 .188 The preparation process faceted TiO2 nanorods with diameters of 50–100 nm.196 The
of TiO2 -010 is similar to that of the TiO2 -101 except that spherical surface or the top facets of the TiO2 nanorods are all
PT-E is replaced by PT-W.188 As shown in Figure 32, TiO2 occupied by the {111} facets, while the side facets of the TiO2
nanocrystals with highly exposed (a) {101}, (b) {001}, and (c) nanorods correspond to the {110} facets (Figure 33c).
{010} facets appear as bipyramids, sheets, and rods, which Lai et al.197 have reported on the fabrication of rutile TiO2
result from the preferential growth of the specified facets. single crystals with adjustable ratios of {110}, {111}, and
Faceted rutile crystals with {001}, {110}, and {111} {001} facets. In a typical synthesis, a 0.015 M TiCl4 solution
facets also have attracted much attention.194–201 Chorine- was prepared by dissolving TiCl4 into a 3.5 M hydrochloric
containing Ti sources and concentrated hydrochloric acid or acid solution under vigorous stirring in an ice water bath;
chloride solutions are often used in the preparation of faceted then, 60 mL of the solution was transferred to a Teflon-lined
rutile.194,196–198 Sun et al.196 have synthesized faceted rutile autoclave with various amount of NaF; hydrothermal reaction
TiO2 microspheres with 100% exposed {111} facets on the was carried out at 220 ◦ C for 12 h in an oven, and then
spherical surface. In a typical synthesis, an aqueous solution it was cooled down naturally; the sample was collected by
(50 mL) containing titanium trichloride (0.15 M) and sodium centrifugation, washed with deionized water for 4–5 times,
chloride (3 M) was initially sealed in a p-polyphenylene-lined and dried in a vacuum oven at 80 ◦ C for 24 h; finally, the sample
autoclave, and then heated at 200 ◦ C in an oven for 16 h; was heated in air at 600 ◦ C for 2 h.197 Figure 34 schematically
the obtained precipitation was filtered, washed, and dried at shows the morphology evolution of the rutile TiO2 single
110 ◦ C overnight, followed by calcination at 400 ◦ C in air crystal particles with different ratios of titanium precursor to
for 4 h.196 As shown in Figure 33(a) and (b), the as-prepared NaF as well as their actual SEM images. With increasing the
TiO2 microsphere with a diameter of ∼2 mm is constructed by content of NaF, the {110} facet gradually diminishes, but the
DOI: 10.1002/9781119951438.eibc2335
{110}
{111} I l=m
I I
(n = 0)
{110} m
{111} II l=m−n
{111}
II l
1 μm (n ≠ 0)
200 nm n
m
(a) (b) (c)
Figure 33 FESEM images of (a) a typical well-crystallized microsphere and (b) its magnified spherical surface.196 Two kinds
of top-facet structure models in panel (c) [Reproduced from Ref. 196 with permission of The Royal Society of Chemistry
(http://dx.doi.org/10.1039/CC15350A).]
Ti:F
1:0.5 1:1 1:2 1:2.5 1:3

(001)
(110)
(111)
(111)
Figure 34 Schematic drawings and morphology (SEM images) {210}

[001]
evolution of the rutile TiO2 single crystal particles with different ratios
of Ti/F [Reproduced from Ref. 197 with permission of The Royal 100 nm
Society of Chemistry (http://dx.doi.org/10.1039/C3TA00188A).]
Figure 35 TEM image of phase-pure brookite nanospindles [Re-

{001} facet seems to keep unchanged. Interestingly, the {001} produced from Ref. 203 with permission of The Royal Society of
facets appear when the Ti/F ratio reaches 1/3. Of course, the Chemistry (http://dx.doi.org/10.1039/C3CC43416H).]
shape of the faceted TiO2 crystals changes with the facet
evolution, that is, from nanorods to nanobipyramids.
Compared to anatase and rutile TiO2 crystals, brookite TiO2 3 PROPERTIES AND MODIFICATIONS OF
has drawn much less interest because of the extreme difficulty TITANIUM DIOXIDE NANOMATERIALS
in synthesizing pure-phase brookite.36 Still, brookite TiO2
with a preferential lattice extension in the c-axis direction have
3.1 General Properties of Titanium Dioxide
been synthesized.98,200–203 Zhao et al.203 have synthesized
Nanomaterials
phase-pure brookite TiO2 nanospindles preferentially grown
along the {001} direction. Typically, 100 mL of 0.22 M Titanium dioxide frequently exists in four mineral forms:
TiOSO4 · 2H2 O was prepared and hydrolyzed for 6 h to yield anatase, rutile, brookite, and TiO2 (B). The first three types are
transparent solution; 50 mL of 2.5 M NaOH solution was the main crystal types. As shown in Figure 36, the structures of
added with continuous stirring to form a white suspension; anatase, rutile, and brookite are all built upon the connection of
the precipitate was filtered, washed with deionized water slightly distorted TiO6 octahedron building blocks. Unlike the
thoroughly, and re-dispersed in 70 mL 1 M NaOH solution; anatase (tetragonal, I41 /amd) and rutile (tetragonal, P42 /mnm)
hydrothermal reaction was carried out in a 100 mL Teflon-line that have good symmetry, brookite (orthorhombic, Pbca) is in
stainless steel autoclave at 220 ◦ C for 48 h, and it was cool low symmetry. Rutile and brookite exhibit corner- and edge-
downed naturally; finally, the white precipitate was collected, sharing TiO6 units, while anatase is built by sharing the edges
washed with excess distilled water, and dried at 60 ◦ C for of TiO6 units in all three directions.204,205 The key physical
6 h.203 Figure 35 shows the TEM image of as-prepared parameters are shown in in Table 1.204–212 Among various
brookite nanospindles that have a length of ∼280 nm and polymorphs, rutile is the most stable phase for particles having
a width of ∼50 nm.203
DOI: 10.1002/9781119951438.eibc2335
a size above 35 nm, while anatase is considered to be the most

thermodynamically stable for the nanoparticles with a size
below 10–20 nm.213
Titanium dioxide is an n-type semiconductor (see
Semiconductors) due to oxygen vacancies in the TiO2 lat-
tice, but with a large band gap (>3 eV). Most of its important
applications, such as photocatalysis and photovoltaics, are
c b
related to its light adsorption ability. The main mechanism of
b a light absorption in pure semiconductors is interband electron
a c
(a) transitions. The absorption is especially small in TiO2 , where
the direct electron transitions between the band centers are
depressed by the crystal symmetry.34 The photocatalytic effi-
ciency is mainly decided by the light adsorption and charge
transfer (see Charge Transfer). However, TiO2 suffers from
rapid recombination of photo-excited charge carriers (see
Charge Carrier), and limited light adsorption only to UV
light (which makes up less than 5% of solar radiation) due to
its large band gap.45,206
3.2 Modifications of Titanium Dioxide Nanomaterials

c c
Modifications of the electronic structure of TiO2 have been
b a a b introduced to shift the onset of the response from the UV to the
(b) visible as well as effective strategies to separate the photon-
induced charge carriers. The schematic working principles
of these modifications have been schematically summarized
in Figure 37.7 Figure 37(a) schematically shows the wide
band gap of the pristine TiO2 . The band gap is the differ-
ence between the minimum energy of conduction band (CB;
see Conduction Band) and the maximum energy of valence
band (VB; see Valence Band). EF represents the Fermi level.
c b
There are two ways to narrow the bang gap of TiO2 and
thus to extend the light absorption of TiO2 toward visible
a a
b c wavelength range: one way is to incorporate alien elements
(c) to the framework of the TiO2 crystals; another way is to en-
hance the surface defects, Ti3+ , and oxygen vacancies, by, for
Figure 36 Polyhedral representation of the (a) rutile, (b) anatase, example, high-temperature hydrogenation17,18,24,46,84 and vac-
and (c) brookite [Reproduced with permission from Ref. 204. © IOP uum treatment15,16 . However, underlying these modification
Publishing. Reproduced by permission of IOP Publishing. All rights strategies are the different mechanisms that drive red-shift of
reserved.] this onset to the visible range. The corporation of alien metal
ions could raise the VB by forming a solid solution of two
Table 1 Physical properties of anatase, rutile, and brookite204–212

Anatase Rutile Brookite
Crystal structure Tetragonal Tetragonal Orthorhombic
Lattice constant (Å) a = 3.79 a = 4.59 a = 9.17
c = 9.51 c = 2.96 b = 5.46
c = 5.14
Density (g cm−3 ) 3.79 4.13 3.99
Mohr’s hardness 5.5–6.0 6.0–6.5 5.5–6.0
Refractive index 2.561, 2.488 2.605–2.616, 2.890–2.903 2.583, 2.700
Band gap (eV) 3.2 ± 0.1 3.0 ± 0.1 3.4 ± 0.1
Light absorption (nm) <390 <415 —
Bulk conductivity (S cm−1 ) 5 × 10−8 10−2 –10−7(a) 3 × 10−7
(a) The electrical conductivity of rutile varies with the heat-treatment conditions.212
DOI: 10.1002/9781119951438.eibc2335
No doping Metal incorporation Nitrogen doping Oxygen vacancies
min min min min

ECB ECB ECB ECB
Eg Eg Eg Eg
EF EF EF EF
Oxygen vacancy states
E max
VB
Hybridized orbitals
max Nitrogen 2p states
E max
VB E VB max
E VB
(a) (b) (c) (d)
min − −
ECB − min
ELUMO − min
ECB ECB
EgSensitizer Sensitizer
Eg
hn Eg hn Eg
max EF EF
E VB + EHOMO +
E max
VB E max
VB
(e) (f)
−
min −
ECB EFmetal
−
hn
Co-catalyst
max
E VB
+
(g)
Figure 37 (a) Pristine TiO2 with a wide band gap; (b) hybridization with other orbitals to raise the VB; (c) creation of dopant states above
the VB level; (d) creation of impurity states from oxygen vacancies below Fermi level; (e) sensitization with a narrow-band semiconductor
with aligned CB minima; (f) sensitization with a dye that absorbs in the visible region; and (g) surface decoration with metal nanoparticles to
facilitate the electron transfer [Reproduced with permission from Ref. 7. © WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2013.]
or more semiconductors (Figure 37b); the doping of nitro- from the excited sensitizers into the CB of TiO2 (Figure 37e
gen could create intraband states above the VB (Figure 37c); and f). As TiO2 acts only as a mediator for transferring
oxygen vacancy could bring about intraband impurity states electrons from the sensitizers to the substrate,206 the CB of
(Figure 37d).7 Also, these two electronic modification methods the narrow-band semiconductors or the lowest unoccupied
can improve the electrical and ionic conductivities of TiO2 , molecular orbital (LUMO; see Molecular Orbitals) of the
which are beneficial to the enhancement of its anodic per- dyes has to be higher in energy than the CB of TiO2 for the
formance in lithium-ion batteries.16,39 Sensitizing TiO2 with electron transfer to occur, and the energy level of the VB of
narrow-band semiconductors or visible-light-active organic narrow-band semiconductors or the highest occupied molecu-
molecules provides another way to extend the light adsorp- lar orbital (HOMO; see HOMO) of the dyes should lie above
tion of TiO2 toward the visible light region. This process is the VB of TiO2 to ensure activity under visible light. Sur-
known as sensitization, which involves the electron transfer face decoration of TiO2 by metal nanoparticles can promote
DOI: 10.1002/9781119951438.eibc2335
the separation of the photo-excited electrons and holes. As 5 5

O 2p
shown in Figure 37(g), the photo-excited electron can easily 4 4
Ti 3d
transfer to the metal co-catalyst, which could enhance the 3 3 Total
photocatalytic efficiency. 2 2
Energy (eV)
Energy (eV)
1 Eg = 2.14 eV 1
Since the 1980s, numerous studies have been dedicated
0 0
to the transition metal doping.21,31,39,91,92,136,194,211 However,
−1 −1
metal-doped TiO2 often suffer from thermal instability, in- −2
−2
creased recombination centers of photo-excited charge carri- −3 −3
ers, and in some cases poor reproducibility in improvement −4 −4
of activity.36,206,214 Since N-doped TiO2 was found to ex- −5 −5
hibit photocatalytic activities under visible light,215 nonmetal (a) G F Q Z G (b) DOS (a.u.)
doping has become an alternative way to modify the elec-
4 5
tronic structure of TiO2 , and seems to be more promising. Ti 3d
3 4
Although various nonmetal elements (such as B, C, N, F, and 2 3
O 2p
S) have been used as dopants,19,37,38,198,215–217 nitrogen still 2
N 2p
Energy (eV)
1 Eg = 1.85 eV
Energy (eV)
Total
is the most attractive one. The introduction of nitrogen into 0 1
the framework of TiO2 crystals can be achieved mainly by −1
0
following three approaches. (i) In situ doping using nitrogen- −1
−2
−2
containing titanium sources.172,217–219 Xiang et al.217 reported −3 −3
on the self-doped nanosized TiO2 sheets using titanium ni- −4 −4
tride as bifunctional raw materials. The first-principle DFT −5 −5
calculations (see Figure 38a–d) demonstrated that the in- (c) G F Q Z G (d) DOS (a.u.)
terstitial N dopant can induce the local states near the VB
1.4
edge and narrow the band gap, which results in the visible-
light response of N-doped TiO2 (Figure 38f). Obviously, 1.2
the digital images show that N-doped TiO2 is light yellow
1.0
Absorbance (a.u.)
(Figure 38f). Typically, 0.2 g TiN powder, 30 mL absolute

ethanol, 3 mL nitric acid (65 wt.%), and 1.0 mL hydrofluoric 0.8
acid (40 wt.%) were added to a 50 mL Teflon-lined autoclave
0.6 (e) (f)
at room temperature, and then hydrothermal reaction was
conducted at 180 ◦ C for 24 h; finally, a yellow precipitate 0.4
was collected, washed with ethanol and distilled water three (f)
0.2
times, and dried in an oven at 100 ◦ C for 8 h. (ii) Posttreat- (e)
ment in an ammonia gas flow at high temperatures.59,220–222 0.0
For example, TiO2 nanowires were annealed in an NH3 flow
300 400 500 600 700 800
(100 mL min−1 ) at a high temperature of 500 ◦ C, and their
Wavelength (nm)
color changed from white to bright yellow, indicating success-
ful N incorporation.221 The nitrogen content can be controlled
by the annealing time. For instance, TiO1.988 N0.012 and Figure 38 Band structure plots (a, c) and total density of states (b,
TiO1.957 N0.043 nanowires are obtained by annealing in NH3 d) for pure TiO2 (a, b) and N-doped TiO2 at 2.08 at.% doping levels
at 500 ◦ C for 1 and 2 h, respectively.221 (iii) Doping through (c, d). The energy is measured from the top of the VB of pure anatase
TiO2 .217 UV–visible absorption spectra of (e) P25 titania and (f)
nitrogen-containing (such as ammonium fluoride/chloride and N-doped TiO2 ; the inset shows digital photos of the corresponding
urea) solution.37,223–227 Often, nitrogen-containing molecules titania [Reproduced from Ref. 217 with permission of The Royal
are directly added to the precursor solutions of TiO2 nanoma- Society of Chemistry (http://dx.doi.org/10.1039/C1CC11740H).]
terials. For example, urea was dissolved in deionized water
and then added to the TTIP-HAc mixture to form a sol; upon
drying, the white power was annealed at 600 ◦ C, and became which inhibits its wide application. Thus, other metals, such
slight yellow.224 as Cu228 and Ni229 , have been adopted to replace Pt. Yu and
Metal nanoparticles on the surface of TiO2 crystals can Ran228 have prepared Cu(OH)2 cluster modified TiO2 , and part
retard the recombination of photo-excited electrons and holes of the Cu(OH)2 clusters was reduced to Cu clusters during
in TiO2 because metal nanoparticles promote the separation the illumination that greatly facilitated the electron transfer.
and transfer of photo-excited electrons from TiO2 to metal Typically, 0.4 g of P25 was dispersed in 50 mL of 0.25 M
(e.g., Pt) clusters.4,154 To date, Pt decoration is still the most NaOH aqueous solution, and then the 0.0077 M Cu(NO3 )2
effective way to promote the photocatalytic efficiency of TiO2 . aqueous solution (the nominal molar ratios of Cu(OH)2 to
However, Pt is a rare noble metal and extremely expensive, (TiO2 + Cu(OH)2 ) were 0, 0.05, 0.25, 1, 2, and 7) was added
DOI: 10.1002/9781119951438.eibc2335
TiO2
200 nm
Cu(OH)2 cluster
20 nm
Figure 39 High-magnification TEM images of Cu(OH)2 clus- Figure 40 Typical TEM image of P25-graphene composite
ter modified TiO2 with nominal molar ratios of Cu(OH)2 to [Reprinted with permission from H. Zhang, X. Lv, Y. Li, Y. Wang,
(TiO2 + Cu(OH)2 ) was 1% [Reproduced from Ref. 228 with and J. Li, ACS Nano, 2010, 4, 380–386. Copyright (2010) American
permission of The Royal Society of Chemistry (http://dx.doi. Chemical Society.]
org/10.1039/C0EE00729C).]
dropwise to the mixture under stirring; the mixed solution was

was added and stirred for another 2 h; then, the suspension
stirred for 6 h at room temperature, and then the precipitate
was transferred into a 40 mL Teflon-lined autoclave and
was collected and washed with deionized water and ethanol
maintained at 120 ◦ C for 3 h to simultaneously achieve the
five times; finally, the obtained sample was dried at 80 ◦ C for
reduction of graphene oxide and the deposition of P25 on
12 h. 228 Figure 39 clearly shows the excellent combination of
the carbon substrate; finally, the resulting composite was
Cu(OH)2 cluster and TiO2 crystal.
collected by filtration, rinsed with deionized water several
Surface decoration with organic dyes (usually transition
times, and dried at room temperature. Figure 40 shows the
metal complexes) or narrow band gap semiconductors (CdS,
TEM image of the as-prepared TiO2 -graphene composite.
Bi2 S3 , etc.) is found to effectively extend the photoresponse
of TiO2 into the visible region as well. While dye/complex Visible-light activity can be triggered by intrinsic defects
catalysis systems show a large visible-light response and as well, such as oxygen vacancies and Ti3+ species.240,241
unique selectivity in photocatalysis, they have low stability There are quite a few practical approaches to prepare
under light irradiation,230–232 limiting their commercial use. self-modified TiO2 nanomaterials, such as high-temperature
CdS is an important visible-light-sensitive semiconductor hydrogenation,17,18,24,46,84,242–244 plasma treatment (includ-
with band gap energy of 2.42 eV,233 which has been widely ing plasma-assisted hydrogenation),245–247 and vacuum
investigated in photosensitizing TiO2 .40,137,233–235 However, activation.15,16,248 In 2011, Chen et al.242 made breakthrough
CdS is not stable in aqueous media during the photocatalytic by achieving black titanium dioxide nanocrystals through hy-
reactions where the Cd2+ will be reduced by the photo-excited drogenation. As shown in Figure 41(a) and (b), the white
electrons and the S2− will be oxidized by the photo-excited TiO2 nanocrystals become black after hydrogenation, which
holes.234,235 is caused by the disordered out layer as verified by the
Recently, graphene (see Graphene) oxide/graphene–TiO2 high-resolution transmission electron microscopy (HRTEM)
heterostructures have attracted much interest mainly (Figure 41b). The bulk structure of the anatase TiO2 exhibits no
due to the greatly enhanced performance of TiO2 in obvious change after hydrogenation, but the surface structure
photocatalysis.226,236–239 Gao et al. reported on the sulfonated displays great difference. In a typical synthesis, a precursor
graphene oxide–TiO2 composites with highly efficient solution consisting of TTIP, ethanol, hydrochloric acid, deion-
hydrogen production.239 On the other hand, the study by ized water, and an organic template, Pluronic F127 (the molar
Zhang et al.237 shows that graphene oxide–TiO2 composites ratios of TTIP/F127/HCl/H2 O/ethanol is 1:0.005:0.5:15:40)
are the same as other TiO2 -carbon (carbon nanotubes, was heated at 40 ◦ C for 24 h and then evaporated and dried
fullerenes, and activated carbon) composite materials on at 110 ◦ C for 24 h; the dried powders were then calcinated at
enhancement of photocatalytic activity of TiO2. In a typical 500 ◦ C for 6 h to remove the organic template and enhance the
synthesis for TiO2 -graphene composite,238 a suspension crystallization of TiO2 (both the temperature ramp rate and
containing 2 mg graphene oxide, 20 mL distilled H2 O, and the cooling rate are approximately 0.3 ◦ C min−1 ); the resulting
10 mL ethanol was sonicated for 1 h, to which 0.2 g P25 white-colored powders were first maintained in a vacuum for
DOI: 10.1002/9781119951438.eibc2335
5 nm 5 nm CB −
hn
n
e atio
r fac bin hn VB +
Su com
re −++
3
− + D+
2
+ Oxidation
(a) (b) 1 4 3
4
D
Figure 41 HRTEM images of TiO2 nanocrystals (a) before and (b)

−++ −++
n
after hydrogenation (the insets in (a) and (b) are the digital images
tio
ina
A− −
co e
of the corresponding samples) [From X. Chen, L. Liu, P. Y. Yu, and Volume
re rfac
mb
recombination
S. S. Mao, Science, 2011, 331, 746–750. Reprinted with permission
Su
Reduction
from AAAS (http://www.sciencemag.org/content/331/6018/746).]
A
1 h and then hydrogenated in a 20.0-bar H2 atmosphere at

Figure 42 Schematic demonstration of the photocatalytic mech-
about 200 ◦ C for 5 days.242 anism of TiO2 . A is electron acceptor and D is electron donor
[Reproduced with permission from Ref. 7. © John Wiley & Sons,
Ltd., 2013.]
4 APPLICATIONS OF TITANIUM DIOXIDE
NANOMATERIALS
during the UV light irradiation, where C is the concentration
of methylene blue at the corresponding sampling time and C0
4.1 Photocatalysis is the initial concentration of methylene blue). In detail, under
UV light illumination, 85% and 70% of the given methylene
The general process of photocatalysis is shown in
blue molecules were decomposed by P25-GR and P25-CNTs
Figure 42.7 Light with energy greater than the band gap
within 1 h, respectively.238 In comparison, only ∼25% of the
of the TiO2 nanocrystals excites an electron from the VB
initial molecules were degraded by pure P25 after 55 min.
to the CB; meanwhile, a positive hole will be generated in
Remarkably, even under visible light illumination, 65% of the
the VB. The electrons and holes that have been transferred
molecules were decomposed by P25-GR after 55 min.238
onto the surface of TiO2 can act as redox active sites, leading
to the desired redox reactions. For example, the electrons
scavenged by O2 can yield superoxide radical anions, while 4.2 Solar Cells
the holes that react with H2 O can produce hydroxyl radicals.
These radicals can oxidize organic species, such as phenol6 The types of TiO2 -based photovoltaic cells include
and cancer cells27 . Thus, photocatalysis can be applied dye-sensitized solar cells70,88–90,118 (see Dye-Sensitized So-
in degradation of pollutants,4–6 photodynamic therapy,27,28 lar Cells: An Overview), polymer-inorganic hybrid solar
reduction of CO2 ,7,8,178 and water splitting.112,114,143 However, cells,249–251 quantum dot (see Quantum Dots) sensitized
the charge carriers with opposite charges will recombine on solar cells,252,253 inorganic solid-state solar cells,254,255 and
the surface (surface recombination) or even in the bulk of the perovskite-sensitized solar cells.91,256,257 Their working prin-
semiconductor (volume recombination),7 which will compete ciples are similar. Dye-sensitized solar cells are mainly
with the desired redox reactions and thus greatly decrease the composed of dye-sensitized TiO2 photoelectrode, counter-
efficiency of the photocatalytic process. Therefore, various electrode, and electrolyte, as shown in Figure 44. At the heart
modification methods as mentioned above have been widely of the system is a nanocrystalline mesoporous TiO2 film with
used to reduce the charge recombination and thus enhance the a monolayer of the dye attached to its surface. The film is
photocatalytic performance of the TiO2 nanomaterials. fully wetted with the electrolyte. As mentioned in Section 3.2,
For instance, the photodegradation rate of methylene blue photo-excited dye molecule will transfer its excited electron
could be speeded up using carbon nanotubes and graphene as into the CB of TiO2 , and the electrons will be collected at
surface modifiers of TiO2 . As shown in Figure 43, the P25- the conductive substrate and conducted to the outer circuit to
carbon nanotubes (P25-CNTs) and P25-graphene (P25-GR) generate current. The original state of the dye is subsequently
nanocomposites exhibited greatly enhanced photocatalytic restored by electron donation from the electrolyte, an organic
performance either under UV or visible light (C/C0 is the solvent with a redox system (usually the iodide/triiodide cou-
normalized temporal concentration changes of methylene blue ple). The regeneration of the sensitizer by iodide prevents
DOI: 10.1002/9781119951438.eibc2335
UV light (1) P25 Visible light (1) P25

1.0 1.0 (2) P25-CNTs
(2) P25-CNTs
(3) P25-GR (1) (3) P25-GR
(1)
0.8
0.8
C/C0
C/C0
0.6
0.6
(2) (2)
0.4
(3) 0.4 (3)

0.2
0 10 20 30 40 50 60 0 10 20 30 40 50 60 70
(a) t (min) (b) t (min)
Figure 43 Photodegradation of methylene blue under (a) UV light and (b) visible light (λ > 400 nm) over (1) P25, (2) P25-CNTs, and (3)
P25-GR photocatalysts [Reprinted with permission from H. Zhang, X. Lv, Y. Li, Y. Wang, and J. Li, ACS Nano, 2010, 4, 380–386. Copyright
(2010) American Chemical Society.]
Light
TiO2 S*/S*
e
Photoelectrode
CB EF,n
e
Maximum
voltage
e Electrolyte
l− l3− l−/l3−
e
EF,redox
S*/S
Counter electrode
Figure 44 Schematic representation, operating principle, and energy level scheme of dye-sensitized solar cells [Reprinted with permission
from Y. Bai, I. Mora-Seró, F. D. Angelis, J. bisquert, and P. Wang, Chem. Rev., 2014, 114, 10095–10130. Copyright (2014) American
Chemical Society.]
the recapture of the CB electron by the oxidized dye. The 5

iodide is regenerated in turn by the reduction of triiodide at the
Current density (mA cm−2)
counterelectrode, with the circuit being completed via electron 4

migration through the external load. The voltage generated 500 nm
under illumination corresponds to the difference between the 3

Fermi level of TiO2 and the redox potential of the electrolyte.
2
The electrons can be conducted to the outer circuit to drive
the load and make electric power.
1
A set of factors affect the overall performance of the
500 nm
dye-sensitized solar cells, such as the energy gaps and molar 0
absorption coefficients of the dyes,258 anchoring conformation 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
of dye molecules on the surface of titanium dioxide,259 Voltage (V)
and shape, size, and porosity of titanium dioxide.70,88,118
Guo et al.88 prepared rectangular bunched rutile TiO2
nanorod arrays on carbon fibers for dye-sensitized solar cells. Figure 45 Photocurrent–voltage characteristics (J − V curve) of
the dye-sensitized solar cells based on TiO2 nanorod arrays and
Figure 45 shows the photocurrent-voltage characteristics for bunched TiO2 nanorod arrays on carbon fibers [Reprinted with
dye-sensitized solar cells based on TiO2 nanorod arrays and permission from W. Guo, C. Xu, X. Wang, S. Wang, C. Pan, C.
bunched TiO2 nanorod arrays on carbon fibers.88 The TiO2 Lin, and Z. L. Wang, J. Am. Chem. Soc., 2012, 134, 4437–4441.
nanorod arrays gave a conversion efficiency of 0.76%, but a Copyright (2012) American Chemical Society.]
DOI: 10.1002/9781119951438.eibc2335
Discharge to increase the conductivity of the pristine TiO2 nanoparticles,

surface or bulk modification has been widely adopted to
overcome the drawbacks and thus increase its capacity and
e− e−
Separator rate performance.15–17,39 Figure 47(b) clearly shows that
the surface-amorphized anatase TiO2 nanoparticles present
Li+ Li+ Li+ Li+ a smaller hysteresis. This indicates that the charge diffusion
Li+
is greatly enhanced by the amorphized layer coupled with the
Li+ Li+ Li+
oxygen vacancy.16 More importantly, the discharge capacity
+
Li+
Li
Li+ of the surface-amorphize TiO2 (206 mAh g−1 at C/5) is 27.2%
higher than that of the pristine TiO2 (162 mAh g−1 at C/5),
Cathode Electrolyte Anode (TiO2) and its rate performance is also much better.16
Figure 46 Schematic illustration of a lithium-ion battery in a

discharge process
4.4 Sensors
remarkable increase to 1.28% was observed in bunched TiO2 TiO2 nanomaterials have been widely investigated in
nanorod arrays.88 This could be attributed to the larger surface various sensors.14,74,78,84,86 Herein, we just briefly introduce
area of the bunched nanorods, leading to more dye molecules the gas sensor, chemical oxygen demand sensor, and
adsorbed onto the surface of the TiO2 .88 biosensor, as classified by Bai and Zhou12 in an excellent
review. Figure 48 schematically shows the electrodes, setups,
and sensing processes of the three types of sensors.12
4.3 Lithium-Ion Batteries Different types of sensors have different working principles,
but all the sensing processes could be simplified into four
Owing to the stability over multiple cycles, safer lithiation
steps: (i) contact of TiO2 -based electrode with analyte; (ii)
potential relative to graphite, reasonable capacity, high-rate
undergoing a specific chemical or biochemical reaction on the
capability, nontoxicity, and low cost,260 TiO2 has been
electrode–analyte interface and giving rise to a signal received
intensively and extensively studied as lithium-ion battery
by transducer; (iii) signal being converted to electronic signal
anode material.15–17,39,63,93 Importantly, TiO2 has a working
and amplified by detector circuit; and (iv) signal being sent to
potential higher than 1 V, which can greatly limit the reduction
computers for data processing and resulting quantity presented
of the electrolytes or the formation of the solid–electrolyte
interface layer.36,261 through an interface to operator.12 A gas sensor is a device that
Figure 46 schematically displays the simplified lithium-ion detects the presence of targeted gases, such carbon monoxide,
battery model as well as the discharge process of the lithium- ethanol, and acetone.14,74,78 In a gas sensor, when a gas
ion batteries. Lithium-ion batteries consist of cathode, anode, flow passes through the TiO2 electrode (Figure 48a), the
separator, and electrolyte. The cathode and anode electrodes resistance of TiO2 electrode will decrease or increase with
are separated by the separation, and both cathode and anode the absorbing of gas molecules onto the surface of the
materials are fully wetted with electrolyte. The discharge TiO2 nanomaterials and subsequently undergoing electron
process of lithium-ion batteries corresponds to the transfer transfer from gas molecules to TiO2 .12 A chemical oxygen
of lithium ions from anode materials, across the electrolyte demand sensor is built to detect the total number of oxygen
and separator inserting into the framework of the cathode equivalents consumed in the oxidation of organic compounds,
materials. In addition, the charge process just undergoes a especially in water by photo-excited holes, which can act as
reversible reaction. oxidant agent. A chemical oxygen demand sensor as well as
Figure 47(a) shows the typical charge–discharge profiles a biosensor is usually assembled as a typical three-electrode
of the anatase TiO2 in half cells where the cathode material system (Figure 48b). Recently, biosensors have been of high
is replaced by lithium metal (counterelectrode). Generally, interest for their widespread applications such as in drug
the operating voltage of TiO2 nanomaterials is in the discovery, disease diagnosis, environmental monitoring, and
range 1.0–2.5/3.0 V.15–17,39,63,93 The flat plateau region at food safety.213 In a biosensor, specified biomolecules, such
about 1.75 V vs Li/Li+ corresponding to the insertion of as deoxyribonucleic acid, antibodies, enzyme, and protein,
Li+ into the framework of TiO2 (discharge process). It is are immobilized on the surface of the TiO2 materials. In
worth noting that the large hysteresis between the charge addition, these biomolecules will interact with the analyte (e.g.,
and discharge voltage is caused by the inconsistency of H2 O2 86 ), and then the transducer will transform the biological
equilibrium for every individual nanocrystal in the many- response into readable or quantified signal. Figure 48(c, I–III)
particle electrode as a whole,262 which is partially caused by displays the typical responses of the three typical sensors
the poor Li+ conductivity of the electrode materials. In order toward target analytes.
DOI: 10.1002/9781119951438.eibc2335
3 3
2 2
Voltage (V)
Voltage (V)
1 1
cycle 100 cycle 35 cycle 1 cycle 100 cycle 35 cycle 1
0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
(a) Capacity (mAh g−1) (b) Capacity (mAh g−1)
Figure 47 Galvanostatic charge/discharge profiles with first cycle at C/25 rate, 35th cycle at 1C rate, and 100th cycle at 1C rate for the
electrodes made of (C) the pristine TiO2 nanoparticles and (D) surface-amorphized anatase TiO2 nanoparticles. The rate 1C (335 mA g−1 ) was
calculated from the theoretical specific capacity value of 335 mAh g−1 [Reprinted with permission from T. Xia, W. Zhang, J. Murowchick,
G. Liu, and X. Chen, Nano Lett., 2013, 13, 5289–5296. Copyright (2013) American Chemical Society.]
Target sample: gas Gas sensor 200 300 400 500 400 300 200 100
Type 1
Ω
Resistance
Gas
Gas
Titania matrix Type 2

Gas
Ω 0 104 1 104 2 104 3 104 4 104 5 104
Substrate I Time
Gas
Target sample: chemicals in water COD sensor

Current
W R C
Light
0 20 40 60
Electrolyte
Titania matrix
II Time
Substrate
Electrochemical biosensor
W R C
Current
Target samples: biological materials
Titania matrix with biomolecule
Electrolyte
DNA Antibodies Enzyme Protein
1.0 −0.8 −0.6 −0.4 −0.2 0.0
Substrate
III Potential
(a) (b) (c)
Figure 48 Electrodes, setups, and sensing processes of the typical TiO2 -based gas sensor, chemical oxygen demand sensor, and biosensor
[Reprinted with permission from J. Bai and B. Zhou, Chem. Rev., 2014, 114, 10131–10176. Copyright (2014) American Chemical Society.]
DOI: 10.1002/9781119951438.eibc2335
Formation of Ca-rich Ca-P Formation of amorphous

Formation of −OH− groups compound Ca-P compound
SBF SBF Ca2+ SO42− Ca2+ SBF CO32− SO42−
SO42− PO43− K+
Cl− Na+ CO 2−
Cl− Cl−
3 + +
CO3 2−
Mg 2+ K Mg2+ Na
K+ Na+ Ca2+ PO43−
2+ PO43− PO43− 2+ PO43−
Mg PO43− PO43− PO43− Ca
PO43− Ca2+ Ca2+
2+ 2+
2+
Ca Ca 2+ Ca
Ca
+ + + + + + + + + − − − − − − −
− − − − − − − 2+ 2+ 2+
Ca2+ Ca Ca Ca Ca
2+
Ca-P
OH O
OH OH OH
O OH OH OH OH OH OH OH OH
Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti Ti
O O O O O O O O O
O O O O O O O O O O O O
R-TiO2 R-TiO2 R-TiO2
PEEK PEEK PEEK
3.5
3 Formation of HA
SBF K+ Cl−
2−
Na+ CO3 SO42−
2.5 Mg2+
Ca/P molar ratio
PO43− 3− Ca
2+
2+ Ca2+ PO4
2 Ca
1.5
Ca/P molar ratio of HA
1 HA
O O OH OH OH OH
Ti Ti Ti Ti Ti Ti Ti Ti
O O O 0.5 O O O
O O O O O O O O
R-TiO2 0 R-TiO2
PEEK 0 5 10 15 20 25 30 PEEK
Immersion period (day)
Figure 49 A suggested mechanism of hydroxyapatite layer growth on rutile TiO2 with corresponding Ca/P molar ratio. PEEK represents
polyetheretherketone [Reprinted from Thin Solid Films, 549, M.-H. Chi, H.-K. Tsou, C.-J. Chung, and J.-L. H, Biomimetic hydroxyapatite
grown on biomedical polymer coated with titanium dioxide interlayer to assist osteocompatible performance, 98–102, Copyright (2013), with
permission from Elsevier.]
4.5 Biomedical Applications Design and application of drug delivery systems have
received much attention owing to their high value in medical
Bone tissue engineering offers an alternative approach for treatments. A desired drug delivery system should maximize
the repair and regeneration of lost bones,263 which is expected the therapeutic activity and meanwhile avoid or minimize
to play an important role in modern biomedical treatment. the side effects.213,263 TiO2 nanomaterials have been widely
Biocompatibility, osteoconductivity and osteoinductivity, studied as the drug carriers, and the geometry of TiO2
biodegradability, mechanical properties, and interconnected material to some extent determines the controllability of the
porosity are considered to be the most important characteris- drug release.29,268–271 Among various types of nanostructured
tics for bone implant materials.263 TiO2 is such a material that TiO2 , tubular structure seems to be a promising one for drug
possesses many of the characteristics and exhibits good per- storage and subsequent controlled release owing to its large
formance in inducing the growth of bone tissues.26,263–267 Fur- pore volume and easy modification.29,268,271 Several strategies
thermore, the negatively charged hydroxyl groups, which can have been employed to control the release kinetics of drugs in
be easily formed on the surface of TiO2 materials, are believed TiO2 nanotubes.29,268,271 Figure 50(a) shows the commonly
to be highly favorable for the growth of hydroxyapatite.26,35 used strategies to confine the drugs into the TiO2 nanotubes.
Figure 49 shows the possible mechanism of the enhanced As can be seen from Figure 50(b), the drug release can be
growth of hydroxyapatite on the surface of TiO2 owing to the very fast by just physisorption (Figure 50a, I), and only shows
rich negatively charged hydroxyl groups.26 limited improvement even with cap (Figure 50a, II). However,
DOI: 10.1002/9781119951438.eibc2335
Drug loading methods

HRP 0.6
OPDA I
Relative reflected intensity changes

APTES n) 0.5
HRP attached by APTES tio
sorp
ysi
(ph
ling 0.4
Fil ) II
rption UV illuminate
ysiso
g (ph
Fillin c a p Without UV
with 0.3
Cova
lent li
nked
III 0.2
Co
val
TiO2 nanotubes en
wit t link
hc e
ap d 0.1
IV 0.0
(a) (b) I II III IV
Figure 50 (a) Methods for drug loading using horseradish peroxide (HRP) as a hydrophilic model drug: (I) immersion without any TiO2
surface modification, (II) immersion after octadecylphosphonic acid (OPDA) modification in the upper nanotube layer (hydrophobic cap),
(III) covalently attached HRP over the entire nanotube layers, (IV) OPDA cap in the upper nanotube layer and covalently attached HRP in
the lower nanotube layer; (b) relative reflected intensity changes for the four different types of nanotubes used in this study with and without
UV illumination [Reprinted with permission from Y.-Y. Song, F. Schmidt-Stein, S. Bauer, and P. Schmuki, J. Am. Chem. Soc., 2009, 131,
4230–4232. Copyright (2009) American Chemical Society.]
drug release kinetics become satisfactory when the drugs are There is no doubt that TiO2 nanomaterials will greatly change
covalently linked onto the pore surface of the TiO2 nanotubes our life if continuous and exciting progress can be made.
(Figure 50a, III). In that case, the introduction of cap is capable We sincerely hope this article will help the novices readily
of further slowing the drug release (Figure 50a, IV). Drugs that enter into this field and inspire more researchers to make
can be activated with UV light provide a more smart approach contribution to the development of TiO2 nanomaterials.
to control the release rate of drugs by just controlling the UV
illumination, which is based on the fact that the photo-excited
holes in the VB of the TiO2 will lead to chain-scission of a 6 ACKNOWLEDGMENTS
monolayer attached to TiO2 .271 As expressed by Figure 50(b,
III and IV), the release rates of drugs with and without UV X.C. thanks the support from College of Arts and
illumination exhibit big difference. Sciences, University of Missouri – Kansas City, and the
Interdisciplinary Intercampus (IDIC) Research Program at the
University of Missouri System.
5 CONCLUSION
The diverse applications of TiO2 cover important global 7 RELATED ARTICLES

issues, especially the energy and environment issues, making
it a star material and spurring tremendous interest. To date, Defects in Solids; Semiconductor Interfaces; Lithium–Ion
huge progress has been made in rational design and fabrication Batteries: Li–6 MAS NMR Studies on Materials;
of TiO2 nanomaterials with different structures, textures, and Lithium–Ion Batteries; Crystal Structures; Photochemistry;
geometries as well as in the fundamental understanding of UV-Visible Spectroscopy; Vacant Site; Valence Band Edge;
the relationship between the properties and structures. What’s Crystallographic Radius; Quantum-Size Effect; Nanoparticle
more, various modification strategies have been developed
to move the development of TiO2 nanomaterials a big
step forward. Despite those remarkable achievements, the
performance of the TiO2 nanomaterials still cannot meet 8 ABBREVIATIONS
the demand for practical applications. While a lot of work
still needs to be done following the past researches, new CB conduction band
technology and new concept in design and fabrication of TiO2 CVD chemical vapor deposition
nanomaterials are needed to ultimately achieve the actual DA decylamine
applications of TiO2 nanomaterials in many important areas. DETA diethylenetriamine
DOI: 10.1002/9781119951438.eibc2335
DMF N,N-dimethylformamide 14. Z. M. Seeley, A. Bandyopadhyay, and S. Bose, Thin Solid

FESEM field emission scanning electron microscopy Films, 2010, 519, 434.
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Titanium Dioxide Nanomaterials

Chapter · June 2015

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2 SYNTHESIS OF TITANIUM DIOXIDE

2.1 Titanium Dioxide Nanoparticles

(a) (b) (c)

(d) (e) (f)

(a) (b) (c)

Hierarchical structure is favored in certain applica-

Alcohol and water

Acetone, PVP and

Anatase sphere core Hydrogen titanate layer

Monomer Homogeneous Diffusion controlled growth

Computer UV laser pulse

Polymer Pure polymer (PLD) or

Target Liquid nitrogen

has been employed to fabricate TiO2 thin films.75,76 The

(a) 100 nm (b) 100 nm (c) 100 nm

(d) 100 nm (e) 100 nm (f) 100 nm

anisotropic growth of TiO2 nanocrystals as well as benefit

6 Hydrothermal (Ref. 80) 2.2.3 Direct Oxidation

2 can easily produce TiO2 nanorod arrays at a low temperature

(a) (b) (c)

55, and 60 ◦ C, respectively; oxygen gas with a flow rate of 30

2.3 Titanium Dioxide Nanowires

2.3.1 Hydrothermal/Solvothermal Method

Well-aligned TiO2 nanowire arrays can be prepared by

increases gradually with prolonging hydrothermal duration,

500 nm 100 nm 100 nm

(a) (b) (c)

composed of 2 mL TTIP, 150 mL 2-propanol, and 0.75 mL

Figure 24 (a) The electrochemical anodization process: (I) metal

Layer thickness (nm)

Tube diameter (nm)

Layer thickness (nm)

ITO ITO ITO

(001) Figure 31 SEM image of the as-prepared anatase TiO2 single

Faceted anatase is the most widely investigated

1:0.5 1:1 1:2 1:2.5 1:3

Figure 34 Schematic drawings and morphology (SEM images) {210}

Figure 35 TEM image of phase-pure brookite nanospindles [Re-

a size above 35 nm, while anatase is considered to be the most

3.2 Modifications of Titanium Dioxide Nanomaterials

Table 1 Physical properties of anatase, rutile, and brookite204–212

No doping Metal incorporation Nitrogen doping Oxygen vacancies

min min min min

(a) (b) (c) (d)

the separation of the photo-excited electrons and holes. As 5 5

(Figure 38f). Typically, 0.2 g TiN powder, 30 mL absolute

dropwise to the mixture under stirring; the mixed solution was

Figure 41 HRTEM images of TiO2 nanocrystals (a) before and (b)

1 h and then hydrogenated in a 20.0-bar H2 atmosphere at

UV light (1) P25 Visible light (1) P25

(3) 0.4 (3)

the recapture of the CB electron by the oxidized dye. The 5

counterelectrode, with the circuit being completed via electron 4

under illumination corresponds to the difference between the 3

Discharge to increase the conductivity of the pristine TiO2 nanoparticles,