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Subcritical solvothermal synthesis of condensed inorganic

materials

Richard I. Walton
School of Chemistry, University of Exeter, Stocker Road, Exeter, UK EX4 4QD.
E-mail: [email protected]

Received 22nd February 2002

First published as an Advance Article on the web 13th June 2002
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The solvothermal method has recently been extended from titanate capacitors found in most electronic devices. Fur-
zeolite synthesis to the formation of condensed inorganic thermore, the fine-chemical industry relies upon solid, in-
solids, which find uses in diverse areas due to properties organic catalysts; for example, the cracking of crude oil, the first
such as ionic-conductivity, solid-state magnetism, giant step in the production of organic chemicals from fossil fuels, is
magnetoresistance, low thermal expansion and ferroelec- almost exclusively performed using catalysts based on the
tricity. This offers specific advantages over the traditional microporous aluminium silicate zeolites. These examples
ceramic synthetic routes to inorganic solids and these are illustrate how research into the structures, properties and
highlighted with examples from the recent literature, and synthesis of inorganic solids is driven, to a certain extent, by
the efforts focussed on determining the formation mecha- commercial application and their value to the economy. The
fundamental physical aspects of their properties, however, also
nism of solids from the heterogeneous mixtures used in
continue to be the focus of much attention by chemists,
solvothermal procedures are discussed.
physicists, and materials scientists from an academic point of
view. Because of these reasons, solid-state chemistry continues
to be an area of great growth, and with the continued
1 Introduction: inorganic solids and their development of new advanced techniques for structural charac-
synthesis terisation (such as crystallographic studies of microcrystals, ab
initio structure determination from powder diffraction data, and
Solid inorganic materials supply the world with a diversity of new solid-state NMR techniques), huge advances have been
useful properties, ranging from electronic properties, such as made in understanding structure–property relationships of
conductivity, magnetism, and superconductivity, to properties materials. The number of new inorganic materials whose
which depend more directly on atomic arrangement, such as structure is now almost routinely determined continues to
porosity, negative thermal expansion, and elasticity.1 Examples increase dramatically year by year. This review will be
of how these properties are exploited include the latest concerned with one important part of inorganic solid-state
rechargeable and long-life batteries which rely on transition- chemistry, namely synthesis. This aspect of solid-state chem-
metal-containing oxides, the use of magnetic inorganic materi- istry is vital to study, since the development of new synthetic
als for data storage at the heart of computers, and miniaturised procedures has the great potential to allow the discovery of
novel solids, and offers the possibility of controlled synthesis of
desired materials with properties tuned for application.
We will be concerned with solids that have extended
structures, rather than molecular solids. Molecular solids, of
Richard Walton completed his BA degree in Chemistry at the course, exhibit many useful properties, and have been the focus
University of Oxford (Worcester College) in 1994 after of great attention because of this (for example, a number of
undergraduate research with Dr Ann Chippindale into the families of molecular superconductors are now known). The
synthesis and structures of new open-framework phosphates synthesis of molecular solids relies on crystallisation from a
which was awarded a University Part II thesis prize. He suitable solvent, usually at close to ambient temperature and
received his PhD from the University of Reading in 1997 pressure, and therefore, from the synthesis point of view, little
following research with Dr Simon Hibble into the structures of scope for adjusting reaction conditions presents itself. By
amorphous and poorly-crystalline transition-metal chalco- contrast, extended inorganic solids have been synthesised by a
genides. The same year he re- huge variety of methods for a good many years; these range
turned to Oxford to undertake from high temperature ‘ceramic methods’ to the use of sol–gel
post-doctoral research in the precursors, to solvent mediated crystallisations, to reactions
group of Professor Dermot performed in molten salts, to topotactic insertion and ion-
O’Hare into the development exchange processes.1
and use of in situ diffraction Traditionally, a high temperature ceramic approach would be
methods for following inor- used to form an inorganic solid, whereby solid starting materials
ganic solid-state reactions, in containing the desired chemical elements are intimately ground
particular focussing on hydro- in stoichiometric quantities, and heated at extreme temperature
thermal synthesis. In September (usually in excess of 1000 °C) for a period of between hours and
2000 Dr Walton took up his days. The method is often referred to as ‘shake and bake’ and
current post as Lecturer in the extreme temperature is necessary to enhance interdiffusion
Inorganic Chemistry at the Uni- of the solid reagents, and so allow chemical reaction to take
versity of Exeter. place. A classic example, and one we will consider in more
detail later, is the formation of ferroelectric BaTiO3 from

230 Chem. Soc. Rev., 2002, 31, 230–238 DOI: 10.1039/b105762f

This journal is © The Royal Society of Chemistry 2002
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BaCO3 and TiO2 at temperatures in excess of 900 °C. The 2 The solvothermal method
method is widely applicable (conceivably, solid reagents
containing any chemical element can be reacted by this means) The historical use of hydrothermal synthesis in the production
and has the advantage in being stoichiometric and so the yield of inorganic solids has been reviewed previously; in particular
is 100%. Additionally, highly crystalline phases are produced an excellent article by Rabenau describes the development of
when the extreme temperatures of the ceramic route are the method from the nineteenth century to the mid 1980s.3
employed, which can greatly aid the structural characterisation Rabenau defined hydrothermal synthesis as the use of water as
necessary to understand their properties. These favourable a solvent in a sealed reaction container when the temperature is
features of the ceramic method of synthesis have been widely raised above 100 °C. Clearly the definition can be extended
exploited over the years to produce materials of increasing further to solvothermal chemistry being the use of a sealed
complexity; a good example is the synthesis of cuprate reaction vessel and temperature above the boiling point of the
superconductors in the 1980s, in which oxides containing up to solvent used. Under these conditions, autogeneous pressure (i.e.
six different metals, such as Tl1 2 yPbyY1 2 xCaxSr2Cu2O7,1 self-developing and not externally applied) is developed. The
were prepared from starting materials containing each of the pressure within the sealed reaction container is found to
elements required. The ceramic method, however, does present increase dramatically with temperature, but also will depend on
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a number of disadvantages: (i) the synthesis protocol is lengthy, other experimental factors, such as the percentage fill of the
often involving periods of heating of days with repeated vessel and any dissolved salts. The use of water as a solvent has
regrinding necessary to achieve the intimate mixing of reagents, been most widely investigated, specifically because of the rôle
(ii) control of particle size is very difficult to achieve, and in fact of hydrothermal processes in geological phenomena occurring
often irregularly sized and shaped crystallites are formed, and in the EarthAs crust. A number of fundamental properties of
(iii) since high temperatures and long heating times are used to water are greatly affected by pressure and temperature. For
bring about reactivity, only the most thermodynamically-stable example, the viscosity of water decreases with increasing
phases crystallise, and there is little scope for kinetic control and temperature, and at 500 °C and 10 bar is only 10% of its
isolation of metastable phases, materials which themselves magnitude under ambient conditions.3 Even under more mild
might have desirable physical and chemical properties. New conditions the viscosity is still lowered, and thus it may be
routes to the synthesis of inorganic solids have been developed envisaged that the mobility of dissolved ions and molecules is
in an attempt to overcome these shortcomings, and this article higher under hydrothermal conditions than at ambient pressure
will be concerned with recent developments in one of these and temperature. Similarly, the dielectric constant of water is
methods, namely the solvothermal method. affected by temperature and pressure, and is considerably
The sol–gel method and the molten-salt method are two reduced above the critical point; this can have major implica-
methods that have been employed in the synthesis of new solids tions on the solubility of solid reagents under reaction
in the quest for new low-temperature routes to inorganic solids,2 conditions.
and it is worth briefly considering these before moving on to In terms of practical considerations to consider when
discuss solvothermal synthesis. Both synthetic methods provide hydrothermal synthesis is employed, the most revealing data are
means to overcome the difficulties in achieving intimate mixing those describing the pressure developed inside a sealed reaction
of reagents during solid–solid reactions. The sol–gel method vessel as a function of percentage fill of the container and the
involves two steps. First, soluble metal reagents are mixed in temperature employed. Fig. 1 shows these data and demon-
solution, and an amorphous precipitate produced, in which the strates first the dramatic rise in pressure when high percentage
constituent metals are assumed to be mixed intimately. Second, fill of reaction vessel is used, and second how the pressure
calcination at high temperature is performed to drive off any by- inside the reaction container can be controlled by choice of
products and yield the desired crystalline product. The molten- temperature and/or the volume of solvent used.† Below the
salt method employs a liquid reaction medium, one effect of critical point of water, and even below 200 °C, a high
which is to enhance the rate of diffusion between reagents. percentage fill allows access to pressures of hundreds of
Often an alkali metal halide is used as the flux in the molten salt atmospheres. As an example of how the use of hydrothermal
method which will melt in excess of 500 °C, and the sol–gel conditions can affect the reactivity of inorganic solids, the
route uses high temperatures ( ~ 1000 °C) to burn off organic solubility of metal oxides under conditions of elevated pressure
components of the gel and to achieve high crystallinity in the and temperatures, a topic that has been studied because of its
product. Although both methods offer conditions milder than industrial and geological significance, provides useful insight.
those traditionally used, the problems of having little control For example, the solubility of TiO2 (rutile polymorph) at pH
over particle size and no kinetic control over the material
formed produced remain. Table 1 summarises the main † In the references cited, several different units of pressure are used,
synthetic methods available to the solid-state inorganic chemist, therefore as a guide for the reader some conversion factors are given. 1
with the advantages and disadvantages of each highlighted. atmosphere = 1.01 bar = 101 000 Pascal = 14.7 psi = 760 mm Hg.

Table 1 A summary of the characteristics, advantages and disadvantages of some of the common methods used in the preparation of condensed inorganic
solids

Method Typical temperature Advantages Disadvantages

Ceramic 800–1500 °C (1) Stoichiometric (1) Lengthy cycles of heating and grinding
(2) Crystalline products (2) No particle size control
(3) Only thermodynamic products are stable
Sol–gel Step 1: Room temperature (1) Mixing of reagents (1) Difficult to control particle size
Step 2: ~ 1000 °C (homogeneous product) (2) Impurities from gel precursor in product
Molten-salt < 1000 °C (1) Mixing of reagents (1) No particle size control
(2) Single step
Subcritical hydrothermal 100–250 °C (1) Mixing of reagents (1) Difficult to predict outcome of reaction
(2) Kinetic phases isolated
(3) Control of particle size
(4) Single step

Chem. Soc. Rev., 2002, 31, 230–238 231

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bases). Such autoclaves can be used at up to 270 °C, and

depending on the engineering specification of the steel walls,
pressures of ~ 150 bar can be withheld.
The versatility of the solvothermal method has been well
demonstrated by the successful synthesis of zeolites and other
microporous phases.7 These solids find widespread application
in many areas (including catalysis, ion-exchange and sorption)
and hence have been the focus of much attention. In an effort to
extend the range of microporous solids away from the silicate
zeolites, an incredible range of ‘open-framework’ solids has
been reported in the literature in the past five years; and
presently in excess of one hundred new structures types are
described each year.7 These elegant structural architectures
have already been much reviewed and the existence of such a
range of possible structural types, indicates the versatility of the
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solvothermal synthesis method. In this current review I will

focus on the solvothermal synthesis of condensed inorganic
Fig. 1 Pressure as a function of temperature and percentage fill of water in solids. The definition condensed is not precise, but in this
a sealed vessel (after Rabenau3). context is taken to mean materials that do not possess the
characteristics of zeolites and other open-framework materials,
10.5 was found by Knauss et al. to increase by two orders of viz the presence of pores and channels, the incorporation of
magnitude on heating from 100 °C to 300 °C under hydro- ‘extra framework’, exchangeable cations, and loosely-bound,
thermal conditions.4 Such data, although rather limited due to zeolitic water. Essentially, I will focus on materials that are
the difficulties in acquiring them, demonstrate how the usually synthesised by ceramic routes, and this will include
chemical reactivity of usually insoluble reagents can be hugely some layered solids as well as materials with dense structures
modified by application of hydrothermal conditions. made up of structural units linked in three dimensions. The
It can be seen that the solvent properties of the water can be review will not be exhaustive; instead I will choose examples
vastly changed by use of hydrothermal conditions, and in effect that best illustrate the advantages of the use of solvothermal
a completely new solvent is found at high temperature and chemistry in solid-state synthesis over other preparative
elevated pressure, compared to at room temperature. Other approaches. The authors of references given, and the papers
solvent systems have been somewhat less studied, and water they cite, will provide the reader with many more examples of
still remains the most widely used solvent in solvothermal solvothermal synthesis.
synthesis; some examples of the uses of organic solvents will be
given below. Historically, hydrothermal synthesis utilised
temperatures above 300 °C and often took place in the
supercritical regime; until the 1980s this was geared largely 3 Solvothermal synthesis of condensed oxides
towards the production of large single crystals of inorganic
solids, by the use of the hydrothermal conditions to achieve 3.1 Ferroelectric titanates
controlled chemical transport.3 The vast majority of sol-
vothermal syntheses performed today in the synthesis of Although it well-established that binary transition-metal oxides,
inorganic materials utilise subcritical conditions, and I will such as iron oxides and chromium oxides for use in magnetic
focus on these much milder reactions conditions (temperature < recording devices, can readily be synthesised from soluble
250 °C), that are presently being used not only to provide a metal salts or via the hydrolysis of metal alkoxides using a
convenient low temperature route to materials with practical hydrothermal reaction,3 the considerable advantages of the
application, but also in the exploratory synthesis of new solvothermal method are best demonstrated by considering how
solids.5,6 This work has focussed largely on oxide-based mixed metal oxides can be produced, i.e. oxides that contain
materials, but some recent studies have extended the method- more than one metal. If the ceramic route is used in this case,
ology to allow the production of materials such as nitrides.5 repeated regrinding and heating are necessary to achieve sample
Subcritical solvothermal synthesis is commonly performed homogeneity. The enhanced interdiffusion of reagents in the
using TeflonTM-lined, stainless steel autoclaves, as shown in solution-mediated hydrothermal reactions, however, allows the
Fig. 2. The use of an autoclave is necessitated by the pressures rapid, direct crystallisation of a single-phase material. The most
well studied example is the ferroelectric material barium
titanate, BaTiO3, (whose synthesis I will consider in more detail
below). The tetragonal polymorph of BaTiO3 finds widespread
application in multilayer capacitors, thermistors, electro-optic
devices and dynamic random access memories, and these
important commercial uses have driven research into new
synthetic routes to its synthesis. The direct hydrothermal
crystallisation of BaTiO3 is found to occur at temperatures as
low as 80 °C from basic solutions containing a barium salt, and
solid TiO2. For comparison, the solid-state route to the same
material requires temperatures of greater than 900 °C. Dutta and
co-workers first made extensive studies of this reaction, and
showed conclusively that the ferroelectric tetragonal polymorph
Fig. 2 A schematic of a TeflonTM-lined, stainless autoclave typically used of BaTiO3 could be prepared from reaction mixtures of BaCl2,
in the laboratory to perform subcritical solvothermal synthesis. NaOH and TiO2 in water at 200 °C,8 and others have since
developed the method (see for example reference 9). The
developed in the solvothermal reactions, and the inert liner is tetragonal polymorph of BaTiO3 forms on cooling the product
used to protect the stainless steel outer shell from the corrosive through the Curie temperature of 120 °C where the cubic to
reagents typically used in synthesis (such as strong acids or tetragonal phase transition takes place. Interestingly, in the

232 Chem. Soc. Rev., 2002, 31, 230–238

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absence of chloride ions (for example if Ba(OH)2 was used as

the Ba2+ source), only the cubic BaTiO3 polymorph was
produced, and it was suggested that the cubic phase might be
stabilised at room temperature by the inclusion of hydroxy
groups in the solid. It was also noted that a degree of control of
particle size was possible, by varying temperature, time, and
choice of starting materials. This dependence of product
morphology and even crystal structure upon choice of synthesis
conditions illustrates how small changes in reaction conditions
can affect the outcome of a hydrothermal reaction. It is now
established that barium titanate fine powders (ranging in
diameters of 10’s of nanometers to microns) can be produced
with a narrow particle-size distribution by use of solvothermal
conditions; for instance, Pinceloup et al. investigated the use of
a water–isopropanol mixture as solvent and showed that by
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varying the composition of the solvent mixture it is possible to

adjust the average particle size of the product from 90 to 30 nm,
and thus to control surface area of the material produced, Fig.
3.10 Fig. 4 Stability and yield diagram in the Na–Bi–Ti–H2O system at 473 K as
a function of NaOH concentration, as determined by thermodynamic
modelling. The symbols denote the results of experimental syntheses: 5
Na0.5Bi0.5TiO3, 8 Bi4Ti3O12 + TiO2 and 1 Bi4Ti3O12 + TiO2 +
Na0.5Bi0.5TiO3. Reproduced from reference 13 with permission of the
American Chemical Society.

determined. Experimental verification of these data illustrated

the validity of the method, and demonstrates how computer
modelling might have an important rôle in aiding the future
development of the ‘rational synthesis’ of inorganic solids.

3.2 Vanadates

Although the ferroelectric titanates have attracted considerable

attention, the successful solvothermal synthesis of other
families of mixed-metal, transition-metal containing oxides has
Fig. 3 The dependence of particle size and surface area of barium titanate been reported in the past few years. The synthesis of some
powders as a function of isopropanol–water mixture used in their vanadates, of which the VIV-containing materials have exotic
solvothermal synthesis. Reproduced from reference 10 with permission of magnetic properties, illustrates other important aspects of the
Elsevier Science Limited.
solvothermal method. Oka and coworkers have studied the
formation of strontium vanadates and lanthanum vanadates
The concept of control of product form has been the focus of using solvothermal conditions.14,15 In the Sr–V–O system a new
much attention for hydrothermal barium titanate synthesis for a phase, SrV4O9, was produced by heating mixtures of SrCl2,
number of important practical reasons: fine powders can be NaVO3 and (CH3)4NCl solutions above 300 °C, Fig. 5. The
easily sintered to produce fine-grained ceramic samples with
improved electrical properties, the production of thin ( < 5 mm)
sheets for multilayer capacitors is possible and the fabrication of
miniaturised devices has also been postulated.11 Additional
chemical control of the nature of the products is possible via
partial substitution of barium or titanium (by Sr or Ca, and Zr or
Hf, respectively) and the use of hydrothermal conditions
produces highly homogeneous products, which may be attrib-
uted to the solvent permitting intimate mixing of the rea-
gents.11
Research into ferroelectric titanates is not just focussed on
those containing Group 2 metals, and hydrothermal chemistry
has also been employed in the synthesis of a number of phases
with useful properties. For example, Chen and Jiao have
recently described the direct hydrothermal formation of nano-
size particles of Bi4Ti3O12 at 240 °C.12 Alkali metal bismuth
titanates have similar properties and their hydrothermal synthe-
sis was part of an interesting study by Lencka et al. into the
possibility of predicting the outcome of new hydrothermal
reactions.13 The use of computer modelling, considering the
thermodynamics of the equilibria present in multicomponent
mixtures of solutions and solids, enabled the calculation of Fig. 5 Part of the crystal structure of the layered stronium vanadate, SrV4O9,
‘stability and yield’ diagrams as a function of pH and reagent a metastable phase prepared hydrothermally at 300 °C. Polyhedra are
{VO5} pyramidal units and circles represent strontium ions which sit
ratios and concentrations. For example in the synthesis of between the V4O9 layers in eight coordinate sites.
Na0.5Bi0.5TiO3, a stability plot, such as that shown in Fig. 4,
allowed the conditions for the formation of titanate in a pure synthesis is important in two respects: firstly, the material was
form, free of unwanted TiO2 (rutile) and Bi4Ti3O12 to be prepared as single crystals, which considerably eased structure

Chem. Soc. Rev., 2002, 31, 230–238 233

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solution, and secondly, the material is metastable with respect to day.18 This phase had previously only been made at high
other strontium vanadates, for example, if SrVO3 and VO2 are pressure and is metastable: on subsequent heating of the
heated in the correct ratio in a sealed tube, then a mixture of material in air, collapse of the structure took place resulting in
SrV3O7 and SrV5O11 is produced. The same authors were also an, as yet, unidentified bismuth lead oxide. Another important
able to isolate metastable LaV3O7 at temperatures as low as 220 feature of the study of Feng, was the demonstration of the effect
oC, and again single crystals were formed.15 of choice of reagents on outcome of reaction. For example,
Pb(NO3)2 could only be used as a reagent if NaBiO3 was the
bismuth source: if Bi(NO3)3 was used, then the desired product
3.3 Substituted ceria was not formed. It was suggested that the chemical reaction is a
redox process such as:
In tuning the electronic properties of mixed-metal oxides (to
2NaBiVO3 + 2PbII(NO3)2 + 2OH2 ? BiIII2Pb2IVO7 + H2O +
optimise conductivity or magnetic properties for example) a
2Na+ + 4NO32
common tactic is the partial substitution of one metal for
another of different valence or different ionic radius. An The formation of Bi2Pb2O7 thereby demonstrates how the
example of this approach was given in the Introduction when hydrothermal synthetic route offers the possibility of oxidation
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the synthesis of the superconducting cuprates was discussed. state control of constituent elements of a solid product by choice
The synthesis of such phases requires intimate mixing of the of appropriate starting materials. This is likely to be of great
reagents containing each individual element, and the ceramic future importance in the formation of transition-metal oxide for
route becomes increasing lengthy as more elements are which a variety of oxidation states of the metals are possible,
introduced and further cycles of heating and regrinding are and whose electronic properties depend crucially on the balance
necessary. A second aspect of the substitution of one element by of oxidation states present in the solid-state. Some recent results
another that must be considered is that structure required might by Henry et al. confirm this view; these workers investigated the
not be stable over the compositional range required: either formation of copper substituted bismuth lead oxides via
phase separation might take place or transformation into a solid hydrothermal chemistry, and were able to isolated two pre-
with completely different atomic arrangement. A good example viously unknown solids, Bi2.008Cu0.84O4 and Bi2Pb-
2+ and
of such substitution in solid-state chemistry is given by the 0.04Cu0.92O4, both of which contain a mixture of Cu
ternary Fe–Ce–O system, which Li et al. studied very Cu3+.19 Once again, the choice of starting materials was found
recently.16 By solid-state, ceramic means it was found to be to be crucial for synthesis of the desired single-phase product, in
impossible to partially substitute Ce4+ in ceria, CeO2, with Fe3+, particular the oxidation state of the reagents is important in
and all attempts led to the formation of either binary phases determining the ratio Cu2++Cu3+ in the product.
(CeO2 or Fe2O3) or unwanted ternary phases such as FeCeO3 or
FeCe2O4. Using a simple hydrothermal route, however, reaction
between alkali cerium nitrate and iron nitrate solutions was 3.5 Battery materials
achieved at 200 °C, and the products were highly crystalline
materials of composition Ce1 2 xFexO2. By varying the propor- The rechargeable lithium batteries which presently find wide-
tion of iron and cerium in the starting mixture, the composition spread use (for example in the ubiquitous mobile telephone),
of the product could be controlled precisely, and the maximum usually use LiCoO2 as the cathode material. This layered
Fe3+-substituted ceria was found to be Ce0.85Fe0.15O2 (if x > material is able to reversibly undergo intercalation and
0.15, then phase separation took place). It should be noted that deintercalation of Li+. On movement of the lithium ions from
on incorporation of Fe3+ into the fluorite structure of CeO2, an the cathode via an electrolyte to a graphite anode charging is
increase in oxide ion vacancies must be brought about to achieved and the reverse process, discharging, releases energy.
balance charge. Oxide ion vacancies in metal dioxides with the Cobalt is an expensive and toxic element, and so replacement
fluorite structure are responsible for their high solid-state ionic cathode materials are at the focus of much research attention.
conductivity, and this property finds important uses in solid One successful means of developing new battery materials
electrolytes, oxygen sensors, and gives rise to oxygen-storage has been via hydrothermal chemistry. The group of Tabuchi has
systems. A number of other workers have also concentrated on been at the forefront of this research.20,21 Firstly they demon-
the hydrothermal formation of cerium-containing oxides for strated that the direct hydrothermal synthesis of LiCoO2 from an
their properties associated with oxide ion vacancies; for aqueous Co3+ solution in the presence of excess LiOH was
example Greenblatt and co-workers have studied calcium and possible, using a temperature of 220 °C. Alternatively a Co2+
samarium substitution.17 reagent could be used and NaOH–NaClO3 used as an oxidising
agent in situ. For the formation of iron-doped samples, a
mixture of Fe(NO3)3 and Co(NO3)3 was utilised, and again
3.4 Lead oxides hydrothermal reaction performed at 220 °C in LiOH solution.
Battery cathode materials with composition LiCo1 2 xFexO2 (0
A study that is particularly worthy of mention is the hydro- 5 x 5 0.25) were successfully prepared by this means. The
thermal synthesis of the bismuth lead oxide Bi2Pb2O7 that was advantage of the hydrothermal route here is the homogeneity of
recently reported by Feng and coworkers.18 The solid has the the products formed; this subsequently allowed a survey of the
pyrochlore structure, a common structure type among ceramics electrochemical properties of a series of materials with a wide
with the A2B2O7 composition, and the family of bismuth oxides range of precisely-controlled compositions.21 The authors
have been widely studied for their potential use as solid proposed that the mixed metal species proceed via the formation
electrolytes. The ceramic synthesis of lead-containing oxides is of an amorphous Fe–Co oxide precipitate, Fig. 6.21
extremely difficult to achieve because of the volatility of PbO A number of other potential battery cathode materials have
(even if PbO2 or lead salts are used as a starting material these been synthesised using hydrothermal means, for example,
decompose into the monoxide) and this means that often ferrates and manganates. The case of LiMnO2 is particularly
inhomogeneous mixtures of solids are produced, and very high interesting. The material was first reported in 1996 by the group
pressures (3000 MPa) are necessary to avoid loss of the lead of Bruce and the material shown to have highly desirable
oxides during reaction. Remarkably, the group of Feng showed electrochemical characteristics.22 The synthetic route first used
that highly crystalline Bi2Pb2O7 is formed in quantitative yield involved two steps: the ceramic synthesis of NaMnO2 from
after heating an alkali aqueous mixture of Pb(NO3)2 and Na2CO3 and Mn2O3, followed by ion-exchange with a solution
NaBiO3 in a hydrothermal autoclave at 140 °C for a period of 1 of lithium bromide in alcohol. No direct high-temperature

234 Chem. Soc. Rev., 2002, 31, 230–238

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ethylenediamine or ethylenetriamine were used as solvents,

particles of CdS with rod-like morphology were produced with
widths of 30–90 nm and lengths of up to 900 nm.26 In contrast,
when water, pyridine, or a number of different alcohols were
used as solvent, spherical particles with diameters of typically
80–200 nm were produced, the precise size of which depended
on the conditions used. The choice of solvent was also found to
affect the polymorph of CdS produced: the use of solvents with
the lowest dielectric constant (ethanol or THF) led to the
formation of pure hexagonal CdS, whereas if solvents such as
pyridine or ethylenediamine were used, mixtures of cubic and
hexagonal CdS were produced. Yu et al. have thus demon-
Fig. 6 A scheme for the proposed hydrothermal formation of LiCoO2 and
strated the versatility of the solvothermal route to CdS, and
isostructural iron-substituted materials under hydrothermal conditions (after although at present the processes taking place within the
Tabuchi et al.20). solvothermal autoclave are not understood, the empirical data
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relating choice of reagents, conditions and reaction outcome

suggest that the method could be used for the preparation of
ceramic route could be found. Hydrothermal chemistry, how- solids of precisely required properties. This is particularly
ever, has since allowed the direct one-step preparation of because the electronic properties of semiconductors are highly
LiMnO2 using mild temperatures ( ~ 220 °C).23 Tabucchi et al. dependent on the particle size, especially when nanometer-sized
used a similar methodology to their previous work to achieve particles are studied.
this, i.e. the reaction of metal salts in a solution of excess LiOH The same workers have more recently extended the sol-
and high pH. The hydrothermal synthesis of layered manganese vothermal route to CdS to allow the preparation of ordered
oxides has now become a focus of great attention, and large macroporous forms of the solid.27 The importance of such
number of alkali-metal containing, mixed-metal materials have morphologies of CdS lies in their application in photonic band
now been prepared for electrochemical testing; examples gap technology, a current focus of materials research. By using
include potassium manganese oxides24 and manganese–vana- SiO2 spherical particles as templates, the solvothermal treat-
dium oxides.25 ment of a CdS, CdCl2 and thiourea mixture in CS2 at 160 °C led
to the formation of a composite from which the SiO2 could be
removed by HF treatment. This is the first successful demon-
4 Solvothermal synthesis of chalcogenides stration of the formation of ordered macroporous CdS, and the
synthetic route employed avoids the problems which plague
4.1 General considerations high temperature routes to sulfides, in particular aerial oxida-
tion.
Metal sulfides, selenides, and tellurides are families of solids
that all have diverse properties in the solid-state, and, as with the
oxides discussed above, studies of their synthesis and structures
is very much application driven. Their use in catalysis (e.g. 4.3 Ternary chalcogenides
MoS2 in hydrotreating catalyst) and in semiconducting devices
(e.g. Zn(S,Se)) are among the most widely-studied uses of the A good example of a ternary chalcogenide that has been studied
chalcogenides. Synthesis of solid chalcogenides (in this case the by solvothermal means is that of CdIn2S4, a material that has
chalcogenides are taken to be compounds of elements in Group photoelectric applications. Hu et al. have demonstrated that
16 heavier than oxygen) is often more difficult than the reaction at 180 °C between CdS and InCl3·4H2O in the presence
synthesis of oxides; although at room temperature most sulfides of thiourea and using water as a solvent allows the formation of
and selenides are kinetically stable with respect to the oxide, at CdIn2S4 in a single step.28 The distinct advantage of this
the elevated temperatures used in solid-solid reactions, the solvothermal approach over traditional solid–solid reactions is
formation of either SO2 or SeO2 is entropically very favourable, in the control of particle morphology; for cadmium indium
and aids the formation of the metal oxide rather than the desired sulfide, the particle morphology of the CdS starting material
chalcogenide. Thus the solid-state, ceramic formation of directly affects the morphology of the product. For example
sulfides and selenides tends to be performed in sealed ‘nanorods’ with diameter 10–30 nm and length of up to 1000 nm
containers and under inert atmospheres. Solvothermal ap- could be formed from rod-like CdS particles, or ‘nanospheres’
proaches for the synthesis of chalcogenides will clearly already from spherical CdS particles.
use sealed reaction containers, but as with the oxides described The use of solvothermal synthesis of chalcogenides is not just
above, the use of solvent allows much more control of the nature limited to sulfides; selenides and tellurides have similar
of the product to be achieved than with traditional solid–solid desirable properties and have been successfully synthesised
reactions. In the case of the chalcogenides, a further advantage using solvothermal routes. Similar advantages to the systems
of solvothermal routes is the low level of oxide impurities in the discussed above are noted, particularly in the advantage of
products. isolating metastable phases not seen at high temperatures. For
example, Li et al. described the isolation of the phase
Rb2Hg3Te4 from a mixture of Rb2Te, Hg2Cl2, Te, and FeCl2,
using ethylenediamine as a solvent and a temperature of 180°
4.2 Cadmium sulfide C.29 In this case, an inert atmosphere within the sealed reaction
container was necessary to avoid oxidation of the product . In
The synthesis of cadmium sulfide, CdS, has recently been the addition, FeCl2 was found to be vital for the successful synthesis
focus of much attention and a solvothermal synthesis route of the desired phase, and it was suggested that it might play the
allows the formation of the solid directly from a variety of rôle of a reducing agent, since Hg(II) in the starting material
cadmium salts and thiourea in organic solvents.26 Yu and must be reduced to Hg(I) to produce the desired product. Li et al.
coworkers investigated the effect of choice of solvent and give reference to the solvothermal synthesis of a number of
reaction conditions on CdS formation at 180 °C and demon- other tellurides, and the reader is directed to these for further
strated a remarkable control of product morphology. When information.29

Chem. Soc. Rev., 2002, 31, 230–238 235

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5 Barium titanate: a model system for

understanding hydrothermal crystallisation
mechanism of metal oxides?
5.1 The kinetics and mechanism of hydrothermal BaTiO3
growth
In this section I return again to the of barium titanate system and
consider the large amount of data relating to the hydrothermal
synthesis of this material with a view to understanding how
inorganic solids form from heterogeneous mixtures (i.e. of
solids and fluids) in a solvothermal autoclave. Owing to the
commercial value of tetragonal BaTiO3, and the highly
favourable control over particle morphology for device fabrica-
tion offered by the solvothermal method, the synthesis of this
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solid has been more widely studied than the other systems
mentioned above (in fact as long ago as 1945 a hydrothermal
route to BaTiO3 was described in a patent).30 In recent years,
research has focussed not simply on documenting the effect of
reaction conditions on the form, purity and crystalline poly-
morph formed, but also on understanding the chemical
processes taking place within the hydrothermal autoclave that
lead to the crystallisation of the inorganic solid. This mecha- Fig. 7 Schematic of two crystallisation models proposed for the hydro-
nistic insight would be extremely valuable: fine control of the thermal formation of BaTiO3 from Ba salts and TiO2. (a) The heterogeous
form of the product could be achieved by precise adjustment of in situ transformation mechanism, (b) the homogeneous dissolution-
the reaction conditions known to affect the nature of the precipitation mechanism.
product, and new syntheses developed rationally without
suggested from these data that two distinct regions of crystal
lengthy ‘trial and error’ experiments to determine the effect of
growth are present: one corresponding to dissolution-precipita-
reaction conditions on the product. Understanding the hydro-
tion and a second stage involving heterogeneous transforma-
thermal formation mechanisms of inorganic solids is un-
tion. Additional information on particle morphology from
fortunately very difficult and this is largely because experi-
transmission electron microscopy showed that there was no
mental data are difficult to obtain under real reaction conditions
observable particle size growth with time once BaTiO3 had
since sealed steel pressure containers are used. Thus not even
formed, suggesting that nucleation was extremely rapid. In
accurate ‘extent of reaction’ curves have been determined for
other studies of quenched materials, further qualitative results
many solid-forming reactions.
have been obtained. For example, Pinceloup et al. used high-
The kinetics and mechanism of hydrothermal barium titanate
resolution transmission electron microscopy to show that at all
crystallisation were reviewed in 1996 by Eckert et al. who also
stages of reaction, materials isolated were BaTiO3, with no
presented new experimental data obtained by analysing sample
evidence for any Ti-rich particles that might be expected if
quenched from hydrothermal autoclaves after different periods
heterogeneous nucleation were taking place, and furthermore
of heating.30 For the synthesis of BaTiO3 from TiO2 (usually the
showed that there was no relationship between BaTiO3 particle-
anatase polymorph) and barium salts (such as BaCl2 or
size distribution, and the initial TiO2 particle-size distribu-
Ba(OH)2) in alkaline solutions, two distinct reactions mecha-
tion.10
nisms were put forward, Fig. 7. The first, the ‘in situ reaction
mechanism’, envisages the complete dissolution of the barium
salt followed by a heterogeneous reaction between the dissolved 5.2 Time-resolved studies of BaTiO3 formation
ions and solid TiO2 particles. The formation of a continuous
barium titanate layer on the TiO2 particles means that at later There are considerable assumptions made when quenching a
stages of reaction Ba2+ ions must diffuse through this barrier to sample from elevated temperature and pressure to study extent
react with remaining TiO2. The second, alternative, mechanism of reaction: in particular that the solid recovered is the same as
is the so called ‘dissolution precipitation mechanism’. This that present under reaction conditions, and no changes in the
homogeneous mechanism involves the dissolution of both Ba- material have taken place on cooling. By developing a means of
and Ti-containing reagents, followed by crystallisation from observing hydrothermal crystallisation in situ, however, it is
solution of BaTiO3. Both models are considered to be extreme possible to study materials under reaction conditions, and thus
types of reaction mechanism, and in reality it is likely that each to track physical and chemical changes in real time, to obtain
process might be occurring simultaneously, or at different extent of reaction curves.32 Recent work by the author and the
stages of reaction; for example, dissolution of reagents might group of OAHare in Oxford has provided new insights into
occur followed by formation of BaTiO3 from solution on the barium titanate formation mechanism by using time-resolved
surface of any undissolved TiO2. The simple models, never- neutron diffraction to follow chemical reactions within a
theless, provide a starting point for considering how mixed- hydrothermal reaction vessel.33–35 This avoids the problems of
metal oxides might form from hydrothermal solutions. the quenching studies, and, since reactions are continually
The acquisition of experimental data to distinguish the two monitored, crystallisation curves can be produced that contain
crystallisation models for hydrothermal barium titanate forma- far more points than those determined by a lengthy series of
tion have largely been accumulated by study of samples quenching experiments. We have used two of the most recently
quenched from the elevated temperatures and pressures present constructed neutron diffractometers to study hydrothermal
in the hydrothermal autoclave. For example, Kerchner et al. barium titanate crystal growth; the GEM diffractometer at ISIS,
examined quenched materials by powder X-ray diffraction, the UK spallation neutron source, which offers an extremely
elemental analysis, and transmission electron microscopy.31 By large detector coverage, and high counting rate, and the D20
comparing the amount of barium remaining in solution, and diffractometer at the ILL, Grenoble, which has a large position-
using diffraction to determine the fractional crystallinity of each sensitive detector.33,34 Fig. 8 shows typical time-resolved
sample, an extent of crystallisation curve was obtained. It was diffraction data measured during the formation of BaTiO3 from

236 Chem. Soc. Rev., 2002, 31, 230–238

 View Article Online

not just applicable to the well-known microporous, zeotype

materials. The advantageous aspects of the solvothermal
synthesis route, in particular the formation of homogeneous
sample of complex mixed-metal solids, the isolation of
metastable phases not seen at high temperature, and the control
of crystal form, make the method particularly attractive for
future study.
The vast majority of materials discussed has been reported
only in the past five years and the rate of publication of new
examples of the solvothermal synthesis of new materials
continues to increase. There is clearly very much scope for
exploratory synthesis in the field described in this article. The
use of solvents other than water has been rather limited so far,
and this is an obvious direction in which to extend the ideas
discussed here. The use of solvothermal chemistry has almost
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exclusively concentrated on the formation of oxides, and other

chalcogenides, and rather less work has so far focussed on the
possibility of the formation of nitrides, borides or carbides,5
Fig. 8 Time-resolved neutron diffraction data measured during the
crystallisation of BaTiO3 from BaCl2 and TiO2 in an alkaline aqueous
families of materials that all are of interest for their particular
solution at 200 °C. Selected peaks of the three crystalline phases present are technological applications. There are literally thousands of
indicated. possible combinations of metals that could conceivably be
combined to formed mixed chalcogenides or pnictides, for
TiO2 (anatase) and BaCl2 in a NaOD solution (deuterated example, with the additional choice of solvent, reagents and
reagents are used to eliminate the incoherent scattering of reaction conditions adding other dimensions to the scope of
protons and reduced background in the data). discovery of new materials. As well as this ‘trial and error’
These are among the first data available in which the approach to synthesis that this last statement suggests, there is
hydrothermal crystallisation of a metal oxide is ‘seen’ in real considerable research effort taking place into the formation
time. Integration of characteristic Bragg reflections of the mechanisms of inorganic solids under solvothermal conditions,
crystalline starting material and product allows quantitative and the development of new technology for following reactions
crystallisation curves to be calculated such as those shown on in situ using time-resolved probes to achieve this. The
Fig. 9. These data are particularly informative since we can development of in situ probes is not only focussed on diffraction
methods, that probe changing long-range order with time,32 but
also spectroscopic techniques such as NMR spectroscopy that
allow local atomic order to be monitored.36 Clearly a full
description of hydrothermal crystallisation mechanism requires
much more information to be gathered, even for a single system
like barium titanate for which a variety of starting material and
reaction conditions can be employed. The studies that so far
have been performed provide the first reliable evidence of the
processes taking place within a sealed solvothermal autoclave,
and will provide a firm foundation to begin understanding
mechanistic detail of the formation of other metal oxides, and
then other inorganic solids. An understanding of how materials
form will allow new synthesis to be performed with some
confidence of the outcome of reaction, and thus solid materials
produced with desired properties.

Fig. 9 Crystallisation curves derived from the in situ neutron diffraction

experiment showing rapid decay of TiO2, and growth of BaTiO3.
7 Acknowledgements
observe directly the decay of a significant amount of TiO2
before the onset of crystallisation of BaTiO3. This strongly I thank my previous and present co-workers in the field of
suggests dissolution of TiO2 is taking place, and thus, at least at solvothermal synthesis, particularly the group of Professor
the early stages of reaction, a dissolution–crystallisation O’Hare in Oxford, who exposed me to their widespread
mechanism predominates. Kinetic analysis of these data was chemical interests. I am grateful to Jeroen Spooren for proof-
also performed and we were able to successfully model the data reading, and the EPSRC for currently funding my research in
by using a nucleation growth model, a model that may be this area of chemistry.
interpreted as resulting from a situation where crystal growth
occurs from nucleation sites in a uniform mixture of reactive
species formed from the starting materials.34 This model is
consistent with the dissolution–precipitation model for crystal
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