Hydrothermal Synthesis of Transition Metal Oxides Under Mild Conditions

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227

Hydrothermal synthesis of transition metal oxides under mild


conditions
M Stanley Whittingham

A notable development in mild (I 200-C) hydrothermal Traditional hydrothermal synthesis:


synthesis in the past few years has been the extension aluminosilicates and phosphates
of the synthesis technique from zeolites and metal Although hydrothermal synthesis has been the standard
phosphates to binary and ternary transition metal oxides. method for making synthetic (and probably naturally
This low-temperature technique is critical to the formation occurring) aluminosilicates for several decades, the report
of metastable phases not obtainable using traditional by the Mobil group in 1992 [3] on the formation of
high-temperature methods. New phases, as well as known the large mesoporous MCM-41 molecular sieves awoke
materials, of the oxides of tungsten, molybdenum, vanadium interest overnight. Preparations of MCM-41 use long-chain
and manganese have been formed, often in highly crystalline surfactants, such as CnHZn+t(CH3)3NBr (where 8 In I 16),
form. One enhancement of the technique is microwave as the templating or structure-directing molecule. At the
heating, which appears to accelerate nucleation, producing reaction temperature (1Oo’C) these molecules aggregate
very uniform particles in a few hours. into micelles and it is these micelles that are structure
directing. The presence of these liquid crystal templates
is necessary for the formation of mesoporous materials of
Address the MCM-41 type [SO]. At higher temperatures or for n 56,
State University of New York at Binghamton, Chemistry Department
and Materials Research Center, Vestal Parkway East, Binghamton,
individual molecules act as the templating agent and more
New York 13902-6000. USA; e-mail: stanwhit@binghamton.edu dense microporous materials are formed, such as ZSM-5

Current Opinion in Solid State 6 Materials Science 1996,


WI.
1:227-232

Q Current Science Ltd ISSN 1359-0266


The discovery of these mesoporous materials initiated
the investigation into whether similar transition metal
oxides could be synthesized [2*,6**,7]. Both hexagonal and
layer structures were formed for W, MO and V However,
Stein et a/. [6**], using transmission electron miscroscopy
Introduction
(TEM), showed that “despite the superficial similarity
The use of soft chemistry processes in solid state chem-
of TEM micrographs and powder X-ray patterns of this
istry has increased dramatically during the past decade
material to those of mesoporous silicates, the salt contains
[lo*]. These processes include intercalation, deinterca-
unconnected Keggin ions H2Wt20&“. The Keggin
lation, ion exchange, and mild thermal decomposition,
clusters form spherical cavities in which the surfactant
among others. More recently there has been a desire to
build structures with open crystalline lattices, or expand- resides, producing the salt (Ct9H42N)6(H2Wr@&, with
unit cell dimensions a -47.5& b-30.3& c-43.6& and
able layer structures, that can undergo redox reactions
B- 118’. For the Crz surfactant a similar salt is formed,
and therefore be used in electrochemical devices such as
with a = 50.6% b = 54.4& c = 13.1215, and B -99.2’ [2*,8*,9].
batteries, displays and sensors. Such structures are unlikely
Attempts to remove the templating ions result in the
to be thermally stable under traditional high temperature
formation of the normal metal oxides, and no new
solid state conditions, so new low-temperature approaches
structures. Stein et a/. [6**] also showed that when
need to be found. One of these is mild hydrothermal
NbxW6-x0,9(2+x)- c Iusters are formed they can react
synthesis, defined for this review as reactions occurring
with tetraethyl orthosilicate, forming Nb-O-Si linkages
between IOO’C and 200°C under autogenous pressure.
between the clusters. The layer structures are readily
A number of conditions are critical in determining what
formed by MO, Nb and Mn oxides and X-ray diffraction
solid phases, if any, are formed. These include the pH
clearly shows that MO and V oxides [9,10] and Mn chloride
of the reaction medium, its temperature (and therefore
readily form layer structures with the surfactant ions
the pressure), and the cations in solution. The last
CH,, za+tN(CH3)3 for lOSnll6 as indicated in Figure 1.
may act as the structure-directing species, or template,
and three will be covered here: small inorganic cations;
medium size, spherical organic cations, such as tetramethyl The 123 phosphates (the 123 refers to the chemical
ammonium [2*]; and large surfactants [3]. The older composition 1 Ag [or other monovalent cation], 2Ti and
classical hydrothermal literature has been covered by 3PO4) known to possess a tunnel structure, such as
Barrer [4]. This review will be restricted mainly to AgTiz(PO&, traditionally synthesized at high temper-
transition metal oxides, with a discussion of key recent atures, have been formed hydrothermally [ll]. Li and
relevant work on silicates and phosphates being included. colleagues [8’,12] also showed that a new layered titanium
228 Synthesis and reactivity of solids

phosphate could be formed hydrothermally by reacting of tungsten oxides [15]. It showed how pH critically
N(CH&OH with phosphoric acid and the anatase form controlled the product formed. In this case, two hydrated
of Ti02 at 160°C for three days. The N(CH&+ ions tungsten oxides were formed, M,W03+x,2: at lower pH,
are readily ion exchanged for protons, producing the a hexagonal oxide and at higher pH, a pyrochlore form
composition TiO(OH)(HzPO4). 2H20 with a lattice repeat as indicated in Figure 2. Both of these have the same
distance of lO.OA. This acid readily reacts with bases, such basic building block: a hexagonal ring formed from corner
as long chain amines, expanding the layer structure in an sharing of Woo octahedra. The M ions in the tunnels
amount related directly to the length of the amine chain. are hydrated, and the water can be removed on heating.
The desired M ion can either be incorporated during the
synthesis or, in the case of the pyrochlore structure, it
Fiaure 1 can be ion exchanged in the previously formed structure.
Both these tungsten oxide structures also undergo redox
reactions, readily incorporating small ions such as lithium
and sodium [16]. In the case of the pyrochlore oxides
the conductivity is strongly dependent on the relative
humidity, and this makes these compounds potential
B humidity sensors [8’]. Thin films formed hydrothermally
2
by immersing the substrate in the reaction media in the
J
teflon reaction vessel [17] are being looked at for use
in electrochromic displays. Screen printed thin films are
being investigated for use as humidity sensors [18].

0 5 10 15 20 25 30
Figure 2
20

X-ray powder diffraction pattern of manganese chloride with


CtsHssN(CHs)s; a similar pattern with different intensities was
observed for the molybdenum oxide compound [lo]. The peaks
observed correspond to the 001 reflections for I=1 to I=5

Microwave heating of the hydrothermal reactor was found


[13*] in some cases to cut the reaction time significantly
and to produce some new phases as well as known
I Hexagonal PyrochlO~

ones. Thus, the 123 phosphates mentioned above were ‘zFic Hexagonal No FQI
formed when the sodium ion was present, whereas in the
presence of lithium ions the a- and y-titanium phosphates 1.5 2.0 4.5 PH
were produced (in two hours at 194°C). In addition, a
new titanium phosphate was also formed when lithium Effect of initial pH on the structure formed by the hydrothermal
was present. This new material had a layered structure reaction of sodium tungstate. Modified with permission from [15].

with an initial repeat distance of 13.2& which contracted


first to 11.4A and then 10.8A on heating. The chemical
composition of this compound was not reported, so it is not
known whether it is related to the layered structure formed The use of hydrothermal synthesis, at ZOO’C for four
using the N(CH$4+ ion. Girnus et a/. [ 14”] also found that days, has resulted in a number of new transition metal
microwave heating enhanced the hydrothermal process. selenates based on the hexagonal bronze (color of the
They produced aluminophosphate molecular sieves of tungsten oxides forming the hexagonal structure) structure
remarkable size uniformity and in a surprisingly short of Figure 2. In these compounds, the hexagonal sheets
time, up to 25 minutes, in contrast to the usual days are not joined together by W-O-W bonds, which result
or weeks. This process could revolutionize the use of in three-dimensional lattices, but form instead layer struc-
hydrothermal reactions if the price of the required ovens tures [ 19*,20]. In NH4(V02)3(SeO& [ 19.1, the hexagonal
becomes affordable. These small (30 l.trn long) crystals are net is made up of VO6 octahedra, reportedly the first
being considered for use as one-dimensional membranes. such arrangement of VO6 octahedra. The selenium atom
caps the small triangular site like a pseudotetrahedron
Tungsten, molybdenum and vanadium oxides with a lone pair of electrons occupying the fourth corner.
One of the first studies of the hydrothermal synthesis The ammonium ions are located between the hexagonal
of transition metal oxides was aimed at the formation sheets below the large six-membered rings of oxygen
Hydrothermal synthesis of transition metal oxides Whittingham 229

atoms. In a related compound, (NH4)2(MoO$$e03, the of hydration can be removed on heating to 17o’C, and
planes of MOO, octahedra are capped on only one side is readily reabsorbed from air on cooling. This structure
by selenium atoms [ZO]. On the other side the oxygens reacts readily and reversibly with lithium ions, both
project into the interlayer region. The ammonium ions chemically and in electrochemical cells [32].
reside in the interlayer region in two different sites, one
of which is above the hexagonal cavity with no bonding Single crystals of the high-temperature phase Ko.sV205
to the adjacent layer, and the other bonds to six oxygens [33] have been prepared [34] by the hydrothermal reaction
in a hexagonal ring below and to three oxygens above of VO(OH)z with aqueous KC1 at 28OC, and their struc-
the interlayer region. Cesium forms a related compound, ture determined. This is an example of a low-temperature
the major difference being that the first cesium ion is reaction providing the quality of sample necessary for
in a trigonal prismatic site. Tungsten forms compounds structure determination. Ko5V205 can undergo oxidative
isostructural with the molybdenum ones, and Rietveld hydration as indicated in the following equation:
analysis has been used to elucidate the hydrogen bonding
in the ammonium compound [21]. In all these compounds,
in contrast to the simple hexagonal tungsten oxides, the
transition metal ion is off-center in the octahedron, leading These oxidative hydration reactions are analogous to
to a range of metal-oxygen bond distances. No interesting those reported for the alkali manganates and the layered
redox or ion-exchange chemistry is reported for either dichalcogenides.
class of compound, in contrast to the related antimony
compounds K#bO&(XO& (where X =P, As), in which A new vanadium phenanthroline oxide layer compound
the sheet oxygens are capped on both sides by phosphate has been reported [35]. It was formed hydrothermally at
or arsenate groups [22,23]. 18o’C for two days, and contains three different sorts
of vanadium atoms: a VO4 tetrahedron (four vanadium
A number of new molybdenum oxides have also recently oxygen single bonds), a VOs,=O tetrahedron (three single
been reported. The well known hexagonal molybdates, and one double bond), and a VO3Nz,=O octahedron (five
(Na * ~H~O)MO~O~$H)~ for which M -NH4, Ag and Na, single and one double bond), all distorted from ideal
have been successfully synthesized. hydrothermally in high symmetry.
crystallinity [24]. The monovalent cations can be removed
from the central tunnel to give hexagonal Moo3 [25]. By In addition to this phenanthroline complex and the
using the larger tetramethyl ammonium cation (rather than (N[CH&)V40lo phase mentioned above (8’,30], two
NH$ in the reaction a new layer structured molybdate, new layer structure vanadium oxides containing organic
(N(CH&)Mo-012, was synthesized [26]. This structure cations have recently been reported [36,37]. In one of
has Moe012 sheets between which reside the N(CH& these [36] 1,3-diaminopropane is found between vanadium
ions, which appear not to be ion exchangeable in oxide sheets, made up from vanadyl and vanadate groups:
contrast to the titanium phosphate described above. (V~VO)[VVO~][C~N~H~~]~.J. In the other [37] l,Cdiazo-
A new barium molybdate, BaMoqOt3-2Hz0, has also bicyclo(2.2.2)octane (DABCO) is found between highly
been formed hydrothermally by heating an HCl-acidified puckered layers of vanadium oxide: (C,jHl4N2)V6014H20.
mixture of BaC03 and Moo3 at 2OO’C for three days
[27]. This has a layered structure, composed of Mo4013 Manganese oxides
sheets between which reside the barium ions and water In recent years there has been increasing interest in
molecules. Strontium forms an isostructural compound. manganese oxides for application as battery cathodes or
Water loss occurs at 25&35o’C, and the structure in both ion exchangers. Many approaches have been used to
cases is destroyed, suggesting that water plays a critical synthesize new structures and to more easily prepare
role. known compounds. Hydrothermal approaches are part of
this increased effort.
Although there have been extensive reports of the
hydrothermal synthesis of phosphates of vanadium and Lithium and sodium manganese oxides have been pre-
molybdenum [28,29], very little has been published until pared by the hydrothermal reaction between yMn02
recently on the preparation of vanadium oxides. The and LiOH and NaOH respectively at 17o’C [38*]. The
known compounds NaVzOs and LiVzO5 can be formed degree of incorporation of lithium or sodium in the
hydrothermally [8’], and two new layered compounds, final product increased with length of reaction, and
(N[CH&)V40lo [8’,30] and Li,Vz4OaHzO [8’,31] after 24 days of reaction the products had the formu-
have been reported. The (N[CH&)+ ion is critical in lae Li1.27Mn1.7304.0.4H20 and Nau.~Mn02.15.0.6H20.
the formation of both phases: even though it is not The oxidation numbers of the manganese are 3.89 and
incorporated into the structure of the latter, its absence 3.99, which is the same as the 3.90 oxidation number of
precludes the formation of the corresponding phase. The the starting material y-MnOz. Acid treatment with 1 M
lithium compound has a tetragonal structure, a-3.705A HN03 removed 98% of the Li+ and 85% of the Na+,
and c- 15.80411, with space group I 4lmmm. Its water and leached out Mn(I1) raising the oxidation state of
230 Synthesis and reactivity of solids

the manganese to 4.00 and 3.96, respectively. The X-ray formed when NaBi03. nHz0 was heated hydrothermally
powder diffraction peaks are rather broad and indicate that between 120°C and 170°C. At higher temperatures Bi407
the lithium compounds have the spine1 structure, with was formed. If alkaline solutions are used, then the
8.18A and 8.058, lattice parameters for the lithium and pyrochlore Nao.39Bi3.4507 was formed. The Biz04 phase
hydrogen forms. A monoclinic phase, LiMnO3, was formed loses oxygen at 300°C producing Bi407, emphasizing the
when > 1 M LiOH was used. The sodium compounds have need for low-temperature synthesis methods for many
a layered structure with layer repeat distances of 7.19A and materials.
7.25A for the Na+ and H+ forms, respectively.
Chen et al. [48] studied the effect of additives on the
A second route to the formation of these manganese phase formed (i.e. anatase or rutile) and its morphology
compounds is by the hydrothermal decomposition of when titanium oxide gels are hydrothermally treated at
aqueous potassium or sodium permanganate solutions at 140°C or 200°C for 12 hours. The gels were formed
170°C for four days [32,39]. This decomposition reaction by the Hz02 oxidation of titanium in the presence of
is accelerated by the addition of one or two drops of ammonia. Reaction in nitric acid resulted in rutile, with
nitric acid to drop the pH to around 3.5; in the case of the morphology depending on the acid concentration and
sodium, nitric acid is apparently required to drive the length of heating. Fluoride ion additives gave square
reaction to completion. The ratio of Mn to protons is plate-like anatase; the absence of nitric acid also resulted
around 100 so the acid does not act as a direct reactant in anatase.
as in other acid based syntheses of manganates [40,411.
Layered manganates, of formula Ko.zsMnOz. 0.6HzO and
Calcium titanate coatings were formed on TiAl by
Nao.35MnOz. 0.7&o, that are isostructural with the well
the ZOO’C hydrothermal treatment of NaOH/Ca(OH)z
known layered transition metal disulfides, MxTiSz . yHz0,
solutions whilst a current of lO-30mAcm-2 was applied,
are formed by this approach. The rhombohedral lattices
with the TiAl as anode. Thicker and more adhesive films
have hexagonal parameters a = 2.856& c = 21.01 A and
were formed when a current was passed [49*].
a = 2.852 A, c -21.85 A for the potassium and sodium com-
pounds respectively. On gently heating to 200°C the water
is reversibly lost, leading to compounds similar to those There has not been much effort to hydrothermally form
formed at high temperatures (42,431; the hydrothermal layer or open structure titanates, such as the interest-
compounds also lose oxygen, leading to increased levels ing lepidocrocite layer structure [SO]. This solid acid,
of both Mn(II1) and manganese vacancies just as with HxTiz_x/404. HzO, has a charge: unit area comparable to
compounds formed at high temperatures. These layered that of smectite clays, and readily partakes in acid-base and
manganates readily and reversibly intercalate lithium ion-exchange reactions. It represents another interesting
ions, just as reported for compounds prepared by other chemically active layer oxide like the manganates.
methods [41,44*,45]. The precise structure (in particular
the vacancy concentration and position of the manganese Recently, effort has been placed on synthesizing layer
ions) of the manganates formed by different routes is not structure ternary iron oxides analogous to the sulfides and
clear, nor is it clear how these affect the long-term use of manganates. Attempts to form ternary lithium iron oxides
such materials in rechargeable batteries. It is likely that appear to result in a mixture of phases including layer and
the lithium containing manganese oxides will be just as spine1 structures (511. The sodium compound a-NaFeOz
complex as the hydrogen containing manganese oxides was formed by hydrothermal treatment of FeOOH with a
used in aqueous cells [46*]. large excess of NaOH (Na: Fe=ZSO) at 22O’C; however,
no characterization data is given. This sodium compound
The first example of an all-manganese alluaudite was was then partially converted to the lithium compound
formed hydrothermally by the reaction of manganic acid, by ion exchange under hydrothermal conditions [52], for
phosphoric acid and DABCO at 180°C for one week [47]. example, 80% conversion in four hours at 140°C.
Thin colorless crystals of composition AgMn3(P04)(HPO&
were produced. A sodium compound of essentially the
same structure was also formed, with only the Ag and Na
having different sites. In both of these, hydrogen bonds Conclusions
play a key role in the structure, which contains tunnels in Hydrothermal synthesis has been substantially extended
which the monovalent cations reside. Larger cations, such beyond its traditional domain of aluminosilicate and
as K or Tl, could not be incorporated into the structure, phosphate synthesis to form new transition metal oxides,
possibly because of the limited size of the tunnels. many of which are not obtainable using other methods.
This is just the beginning of the exploration of the
new frontiers being opened up by this low-temperature
Bismuth, titanium and iron oxides technique. Extensions such as microwave heating and
Binary oxides can be formed hydrothermally. Thus, mon- electrochemical enhancement can be expected to see more
oclinic Biz04 with mixed valence (i.e. Bi(III)Bi(V)04) was applications.
Hydrothermal synthesis of transition metal oxides Whittingham 231

Acknowledgements new layered titanium phosphate. Solid State lonics 1993,


63:391-395,
Thanks are due to the National Science Foundation and the Department
of Energy (rhrough Lawrence Berkeley Laboratory) for support of this work 13. Komameni S, Li GH, Roy R: Microwave-hydrothermal
over the “ears. I also thank A Ramanan for manv fruitful discussions in the . processing for synthesis of layered and network phosphates. J
early stages, and Peter Zavalij and my students Kenneth Reis, James Li, Mater Chem 1994,4:1903-l 906.
Jindong Guo, Rongji Chen, Tom Chirayil, Gerald Janauer and Art Dobley This paper notes the advantages of using microwave heating in hydrothermal
for their contributions. synthesisto cause more rapid nucleationand possibly the formationof new
phases.
14. Gimus I, Pohl M-M, Richter-Mendau J, Schneider M, Noack M,
References and recommended reading .. Venzke D, Caro J: Synthesis of AIP04-5 aluminophosphate
molecular sieve crystals for membrane applications by
Papers ot particular interest, publishedwithin the annual period of review,
microwave heating. Advan Mater 1996,7:711-714.
have been highlightedas: Again, microwave heating is shown to have some specitic advantages, such
as very rapid crystallizationand extremely uniform crystallite size. Clearly a
. of special interest method to be followed.
.. of outstanding interest
15. Reis KP, Rsmsnan A, Whittingham MS: Hydrothermal synthesis
of sodium tunpstates. Chem Mater 1990,2:21 Q-221.
1. RouxelJ, ToumouxM, Brec. R (Eds): Soft Chemistry Routes to
.. New Materials - Chimie Deuce. In Mater Sci Forum, vd 152-l 53. 16. Reis KP, Ramanan A, Whittingham MS: Synthesis of novel
Switzerland:Trsns Tech Publications;1QQ4. compounds with the pyrochlom and hexclgonal tungsten
An excellent review of soft chemistryapproaches to the synthesisof solids, bronze structures. J Solid State Chem 1992, Q&31 -47.
covering a timely conference (Nsntes, 1993). 17. Guo J, Li YJ, Whiiingham MS: Hydrothermal synthesis of
2. Whittingham MS, Li J, Guo J-D, Zavslij P: Hydrothermal synthesis electrode rnaterlals: pyrochlore tungsten trioxlde WO, film J
. of new oxide matarlals using the tetramethyl ammonium ion. Power Sources 1995,54:461-464.
Mater Sci Forum 1994,152-l 5399-l 08. 18. Li YJ, Tsai PP: Lacunar pyrochlore-typa tungsten oxides
This paper covers the critical role that the tetrsmethyl ammonium ion plays as humtditv senslna materials. In Proceedinos of the 70th
in controllingthe structureformed, leading predominantlyto layer structures. lnternationaj ConferGtce on Solid State Ion&: 1995 LX&ember
3. Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, 3-8; SingaporeSolid State lonics 1996, in press.
Schmitt KD, Chu CT-W, Olson DH. Sheppsrd EW, McCullen 19. Vaughey JT, Harrison WTA, Dusseck LL. Jacobson Al: A new
SB et aL: ri new family of mesop&oui inolecular sieves . Iaye-md-selenium oxide with a structum relatad to hexagonal
prepared wtth liquid crystal templates J Amer Chem Sot 1992, tungsten oxide: NH&/O&SeO&. lnorg Chem 1995,
114:10034-t 0043. 33:4370-4375.
This paper, and others discussingphosphate groups ([22,231), show that the
4. Barrer RM: Hydrothermal Chemistry of Zeolites. London:
Academic Press; 1962. hexegonelbronze sheets can be separated and the smaller sites capped by
a variety of groups.
5. Beck JS, Vartuli JC, Kennedy GJ, Kresge CT, Roth WJ, Schramm
. 20. Harrison WTA, Duesack LL, Jacobson AJ: Synthesis, crystal
SE: Mdwular or supmmoleculrr ternplating: deflninQ the
structuras, and properttes of new layerad molybdenum (VI)
role of suffactant chemistry In the formation of microporous
selenttes: (NH&$MoO3)sSeO~ and Cs#oO&Se03. lnorg
and mesoporous molecular sieves. Chem Mater 1994,
Cham 1995,33:6043-6049.
6:1816-1821.
The critical and essential rde that surfectants play in defining the structure 21. Harrison WTA, Dusasck LL, Vogt T, Jacobson AJ: Synthesis,
of the aluminosiliie formed wes ascertained. High temperatures (>l OOC) crystal structums and propartlas of new layered tungsten (VI)-
or short carbon chains lead to single chsin templates which give the more containing materials based on the hexclQOna)-WOgstructure:
dense microporoussolids, whereas longer chains and temperatures around @&WO@eO~ (M =NH,, Rb, Cs). J Solid State Chem 1995,
100% leed to the aggregation of the amines and MCM mesoporous mate- 120:112-l 20.
riels.
22. Piiard Y, Lachgar A, ToumouxM: Structum crlstalline du
0. Stein A, Fendorl M, Jtie T, Mueller KT, Benesi Al, Mallwk TE: phosphatoantimonata K3Sb3P2014. J So/id State Chem
.. Salt-gel synthesis of porous transition metal oxides. Chem 1985, 58:253-256. mle translation:Crystalline structure of the
Mater 1995,7:304-3 13. phosphatoantimonateKsSbsP20t 4.1
This paper clearly shows that the transition metal oxide materials formed
23. Lachgar A, Deniard-Courant S, Pifferd Y: Adsorption and
using liquid crystal templates are not extended three-dimensionelstructures
structural studies of water In the layered compounds
like the aluminosilicates.Rather, the metal oxide forms clusters, akin to the
K3SbxMZO,., xHl0 (M=P,As). J Solid State Chem 1988,
well known Keggin clusters.
7%5r2-376: -
7. Ciesia U, Demuth D, Leon R, Petroff P, Stucky G, Unger Y 24. Guo J-D, Zavelij P, Whittingham MS: Metestable hexagonal
Schtlth F: Sutfactant controlled preparation of mesostructurad molybdates: hydrothermal preparation, structure and reactivity.
transltton-metal oxlde compounds. J Chem Sot Chem Commun J Solid State Chem 1995, 117~323-332.
1994,1387-l 388.
25. Guo J, Zavelij P, Whittingham MS: Preparation and
8. Whittingham MS, Guo J-D, Chen R, Chirayil T, Jsnauer G, Zavslij characterlxatlon of a MOOI with hexagonal structure. Eur J
. P: The hydrothcrmsl synthesis of new oxide materials. Solid Solid State Chem 1994, 31~033-042.
State Ion& 1995, 75:257-260.
A timely report of the usa of hydrothermalmethods for the synthesisof tran- 26. Guo J, Zavslij P, Whittinghsm MS: Hydrothermal synthesis of
sition metal oxides, particularlyfor spplicetion in the electrochemical srea a new molybdata with a layered structure, (NMe,)Mo,dOtF
Describes several new vanadiumand molybdenumcompounds. Chem Mater 1994, 6~357-359.

9. Janauer GG, Dobley A, Guo J, Zavelij F’,Whittingham MS: 27. Harrison WTA, Dussack LL, Jacobson AJ: Hydrothermal
Hydrothermal synthesis of novel tungsten and molybdenum svntheses and orooarttes of new lavered alkaline-earth
oxides by use of surfactant templates. Abstract 0742 of the ~olybdat&l) iydiates - sinQle-cry&l structure of
Meeting of the Materials Research Society, 1995 November BaMo&32H20. J Solid State Chem 1995, 116:95-l 02.
27-December 1, Boston. Pittsburgh:Materials Research Society; 20. JohnsonJW, Jacobson At, Brody JF, Rich SM: Coordination
1995. intercalation reactions of the layered compounds VOPO, and
10. Guo J: Novel tungsten oxides and molybdenum oxides: low VOAsO, with pyrldlne. Inorg Chem 1982, 21:3820-3825.
temperature synthesis, characterlxation and thelr appllcattons 29. Haushalter RC, Mundi LA: Reduwd molybdenum phosphates:
In the energy area CPhD ThesIsI. Binghamton:State Universityof octahedml-tetmhedml fmmawork solids with tunnels, c.a~es,
New York; 1994. and mlcropores. Chem Mater 1992, 4~31-48.
11. Li YJ, Monteith J, Whittingham MS: Crystalllzatlon of A~TI@O& 30. Zavslij P, Whittingham MS, Boyian EA, Pechsrsky VK, Jacobson
and related compounds close to amblent conditions. Solid RA: New structum TMAV,O,e Z Kristaliogr 1996, in press.
State lonics 1991, 46:337-340.
31. Chirayil T, Zavalij P, Whittinghem MS: Hydrothermal synthesis
12. Li YJ, Whtinghsfn MS: Hydrothemml synthesis of new and characterixatton of LI,V~~O~H20. Solid State lonics 1996,
me&&able phases: preparation and Intercalatton of a in press.
232 Synthesis and reactivity of solids

32. Chen R, Chirayil T, Whittingham MS: The hydrothermal synthesis 43. Parant J-P Olazcuaaa R. Delalette M. Fouassier C. Haaenmuller
of sodium manganese oxide and a lithium vanadium oxide. In P: Sur quelques n&veiles phases’de formule Na,finOs (xc1 1.
Proceedings of the 70th lntemational Conference on Solid State J Solid State Chem 1971, 3:1-l 1. fTitle translation: Concerning
lonics: 1995 December 3-8; SingaporeSolid State lonics 1996, new phases of the formula N%MnOs (x<l).l
in press.
44. Leroux F. Guvomard D. Piffard Y: The 2D Ranclete-tvoe
33. Pouchard M, Hagenmuller P: Le systeme KxVsOs - sur quelques . mangantc acid and its alkali-exchanged derivatlve:‘Part II -
nouvelles familles de bronzes oxygenes de vanadium. Mater electrochemical behavior. So/id State lonics 1995, 88307-316.
Res Bull 1967, 2:799-808. [Title translation: The KxVsOs The beginnings of the building of a thorough understanding of the electro-
system-concerning a new family of bronze oxides of vanadium.] chemical reduction of manganates.
34. Oka Y, Yao T, Yamamoto N: Layered structures of hydrated
45. Gras FL, Rahs S, Anne M, Strobe1 P: Reversibility of lithium
vanadium oxides. Part 4. Single crystal structure and phase
intercalation in lithium and sodium phyllomanganates. J Power
conversion of the unhydreted potassium intercelate K&sOs. J
Sources 1995, 54:319-322.
Mater Chem 1995, 5:1423-t 426.
35. Duan CY, Tian VP, Lu ZL, You XZ, Huang XY: A novel 46. Chabre Y, Pannetier J: structural and electrochemical properties
layered mixed-valence vanadium phenanthroiine . of the proton/yMnOs system. Prog So/id State Chem 1995,
complex-hydrothermal synthesis and crystal-structure of 23:1-130.
V(IV)VfV)sOr(phen). lnorg Chem 1995, 34:1-2. An extensive and thorough review of the interaction of pratonic species with
manganese oxides, which will provide a good basis for the understanding of
36. Riou D, Ferey G: Intercalated vanadyl vanadate the interaction of lithium ions with the manganates.
(VtvO)[Vv0410.5[CsN2Ht~l: hydrothermal synthesis, cryfsal
structure, and structural considerations with VsOs and other 47. Leroux F, Mar A, Guyomard D, Piiard Y: Cation substitution
vanadyl compounds. J Solid State Chem 1995, 120:137-l 45 in the alluaudite structure type - synthesis and structure of
AgMns(P04)(HPO&. J So/id State Chem 1995, 117:206-212.
37 Nazar LF, Koane BE, Britten JF: Hydrothermal synthesls
and crystal structure of a novel layered vanadate with 1,4- 48. Chen QW, Gian YT, Chen ZY, Zhou GI, Zhang YH: Preparation
diazobicyclof2.2.2loctane as the structure-dire&g agent: of TiOs powders with different morphologies by an oxidation
(CaH14N&Ot4HsO. Chem Mater 1996, 6:327-329. hydrothermal combination method. Mater Lett 1995, 22:77-80.
38. Fang Q, Kanoh H, Miyai Y, Ooi K: Hydrothermel synthesis of
. 49. Yoshimura M, Urushihara W, Yaahima M, Kakihana M: CaTIOs
lithium and sodium manganese oxides and their metal ion
. coating on TiAl by hydrothermal electrochemicel technique.
extraction/insertion reactlons. Chem Mater 1995, 7:1226-l 232.
. . . . . ..I
An tnteresttng paper mat proposes a mecnantsm to expten me rote ot
I, Intermetallics 1995, 3:125-l 28.
the interlayer manganese in ion-exchange reactions of manganates formed Another enhanced hydrothermal method in which the adhesion of thin films
to metals is enhanced by a hydrothermal deposition in the presence of an
hydrothermally. Suggests that both ion-exchange and redox reactions occur
electrical field.
simultaneously.
39. Chen R, Zavalij P, Whittingham MS: Hydrothermal synthesis and 50. Saaaki T. Watanabe M. Michiue Y. Komatsu Y. lzumi F. Yakenouchi
characterization of KxMnOsyHxO. Chem Marer 1996, in press. S: Preparation and acid/base properties of a protdnated
titanate with the lepidocrocite-like layer structure. Chem Mater
40. Leroux F. Guvomard D. Piiard Y: The 2D Rancfete-tvpe 1995, 7:1001-1007.
manganfc acid and its alkali-exchanged derlvatlvei.Part I -
chemical characterization and thermal behavior. Solid State 51. Tabuchi M, Ado K, Sakaebe H, Maaquelier C, Kageyama H,
lonics 1995, 89:299-306. Nakamura 0: Preparation of AFeOx (A=Li, Na) by hydrothermal
41. Bach S, Pereiraramos JP, Cachet C, Bode M, Yu LT: Effect of method. Solid State lonics 1995, 79:220-226.
Bl-doping on the electrochemicel behavior of tayered MnOs
52. Tabuchi M, Maaquelier C, Takeuchi T, Ado K Matsubara I,
as lithium intercalation compound. Electrochim Acta 1995,
Shirana T, Kanno R, Naau S, Sakaebe H, Okuyama H, Nakamura
49785-789.
0: LI+/Na+ exchange from a-NaFeOa using hydrothermal
42. Delmaa C, Fouaaaier C: Les phases K,Mn02 (xl1 ). Z Anorg Al/g reaction. In Proceedings of the 10th International Conference on
Chem 1976, 420:184-l 92. fTitle translation: The K&tnOs (x<l) Solid State lonics: 1995 December 3-8; Singapore. Solid State
phases.] lonica 1996, in press.

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