Hydrothermal Synthesis of Transition Metal Oxides Under Mild Conditions
Hydrothermal Synthesis of Transition Metal Oxides Under Mild Conditions
Hydrothermal Synthesis of Transition Metal Oxides Under Mild Conditions
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
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].
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
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