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Solvothermal reactions: new trends in Materials Science
G. DEMAZEAU, G. GOGLIO, A. LARGETEAU Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB-UPR-CNRS 9048) 87 Avenue du Dr.A.Schweitzer-33608 PESSAC-Cedex (France) Ecole Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB) 16 Avenue Pey-Berland – 33607 PESSAC-Cedex (France) Université BORDEAUX 1 « Sciences et Technologies » 351 Cours de la Libération -33405 TALENCE-Cedex (France) Gérard DEMAZEAU demazeau@icmcb-bordeaux.cnrs.fr

Abstract

Solvothermal reaction can be described as a chemical reaction involving a solvent either in subcritical or supercritical conditions. Such a solvent can act as a chemical component or a fluid phase able through its physico-chemical properties to modify the reaction mechanisms. During these last twenty years solvothermal reactions have been developed in different areas involving basic or applied researches. Several aspects can be considered: - In Materials Chemistry: (i) the synthesis of novel materials, (ii) the development of nanochemistry, - In Materials Science (i) the development of new crystal growth processes, (ii) thin film deposition, (iii) new sintering processes in mild conditions. In all these domains solvothermal conditions induce an increase of the reactivity and consequently open both : a specific way to novel materials and the development of new processes either for preparing or shaping materials.

Introduction Solvothermal reaction can be defined as a chemical reaction involving a solvent either in subcritical or in supercritical conditions [1]. Such a solvent acts as a chemical component of the reaction or a fluid phase able, through its physico-chemical properties, to modify the reaction .solvothermal reaction can be considered as the generic term used for all solvents, hydrothermal reaction is the qualifying term when the solvent is water. Hydrothermal reactions were mainly used for oxides. The development of different solvents (H2S, NH3, C6H6…) has allowed to apply such chemical reactions for several classes of materials: sulfides, nitrides, carbides…

II. their reactivity… The thermodynamical parameters. .1 Synthesis of new original compositions In this domain two examples can be given.). (iii) the shaping of functional materials. In a first approach three main illustrations will be given: (i) the synthesis of new original compositions. ability to induce the formation of complexes…. are in the most cases optimized in order to obtain the mildest experimental conditions able to lead to the preparation of the final material or to get the appropriated shaping (nanocrystallites.the physico-chemical properties of this solvent. formation of complexes…) . thin film…). → the thermodynamical parameters: pressure. Considering the precursors.the chemical nature of the solvent. I. (critical temperature Tc. (ii) the preparation of hybride materials at the frontier between organic and inorganic chemistry. (dissolution.the nature of the precursors. the main interest of solvothermal reactions is to help the stabilization of novel materials or novel structures [2]. . The choice of the solvent is closely dependent on the chemical composition of the resulting material and also on its physico-chemical properties able to modify the reaction mechanism. thermal stability.the experimental conditions. the selection is mainly governed by their interaction with the solvent. single crystal. Main parameters governing the Solvothermal reactions Among the different parameters able to manage the chemical mechanisms of a solvothermal reaction . pressure and temperature.2 Different factors play an important role on solvothermal reaction: .it is possible to select: → the chemical parameters including the nature of the solvent and the precursors. . II. Schematically three main domains of applications for solvothermal reactions can be described: (i) the synthesis of novel materials. (ii) the development of new processes. . (iii) the stabilization of new solids possessing openstructure. Solvothermal synthesis of novel materials In Materials Chemistry . temperature.

in high pressure (3GPa) and medium temperature (800°C) conditions [13]. In order to reach such objective it was necessary to replace hydroxyl groups (OH-) for oxygen (O2-) and in parallel to induce cationic substitutions on Oh or/and Td sites of the micaphlogopite-type structure [Mg2+Oh→Al3+Oh.4].1 The preparation through “geomimetism” of a new class of material: the phyllosiloxides. The objective of this study was to prepare new layered structures derived from natural phyllosilicates with the mica-phlogopite-type structure. 8] many research works have been developed for stabilizing such a composition.3 II. Layer with Td sites Layer with Oh sites Figure : Schematic structure of a phyllosilicate with the mica-phlogopite type structure. Then .derived from the mica phlogopite: K(Mg3)(Si3Al)O10(OH)2.1. such a matrix has been used for preparing new layered oxides with transition cations as Fe3+ or Fe2+ in the octahedral sites [5.1.12].6]. II. .2 The preparation of carbonitrides Since the theoretical prediction that the hardness of different C3N4 forms could be higher than that of diamond [7. Al3+Td→Si4+Td] (Figure). In such an approach the first tentative was the preparation of the graphitic form -as macroscopic sample -using C3N3Cl3 as precursor and NH2NH2 as solvent . Different approaches have been investigated: high pressure solid state synthesis [9]. synthesis from organic precursors [10] and solvothermal reactions [11. was stabilized [3. Using a two-steps process: a sol-gel step followed by a solvothermal treatment of the resulting aerogel as precursor and 2-methoxy-ethanol as solvent – a novel material with the composition K(Mg2Al)Si4O12 .

3. Solvothermal reactions have improved the development of such a class of materials [19]. Mo(CO)6. . . III. Ni) with en=ethylenediamine were synthesized at 150°C and autogeneous pressure using GeO2 and S8 as reactants and ethylenediamine as solvent [17]. new mixed-metal carbonyl telluride clusters [(Ph4P)2(Fe2MTe3(CO)11] with M = Mo and W were prepared at 80°C and autogeneous pressure .Using CCl4 and NH4Cl as precursors ( in such a case an excess of the liquid phase CCl4 can be used as solvent) in a temperature domain close to 400°C and with autogeneous pressure (few MPa) the formation of the graphitic form was announced [15]. host-guest assemblies… These structures are in many cases thermally unstable and consequently solvothermal processes in mild conditions appear a fruitful route. Two illustrations can be given: the solvothermal synthesis of two new zinc phosphates (C8N4H26)[Zn2(HPO4)4] and (C8N4H26)[Zn6(PO4)4(HPO4)2] [20]. with experimental conditions :350°C. 5 MPa. the solvothermal synthesis of new mixed-valence iron alumino-phosphate [FeII(H2O)2FeIII0. Na2Te2 and Ph4PBr as reagents and CH3OH as solvent [16]. New organic-inorganic hybrid materials constructed from copper-organo-imine subunits and molybdoarsenate clusters have been recently described through hydrothermal reactions at medium temperature (180°) [18].3 The synthesis of materials with open framework Inorganic open framework with regular pore architectures are an important class of functional materials because of their large domains of applications: catalysis.4 Then in order to reduce the preparation conditions different solvothermal reactions have been developed: . II. the preparation of the β form of C3N4 was claimed [14].using Fe3(CO)12. 5 trichlorotriazine (C3N3Cl3) and lithium nitride (Li3N) as precursors with benzene as solvent. solvent and thermodynamical conditions can lead to original processes for preparing functional materials. At the beginning of the solvothermal processes. One of the most illustrative example is the synthesis of cubic boron nitride c-BN.8Al1. the synthesis of such materials required mild conditions. II.Using 1. The development of new processes The induction of new reaction mechanisms through the selection of appropriated precursors.2(PO4)3] H3O [21].2 The preparation of new organic-inorganic hybride materials Due to their specific composition. Thiogermanates (enH)4Ge2S6 and [M(en)3]2Ge2S6 (M = Mn.

7 GPa. . using boron halides (BCl3. . in size and morphologies.1 Elaboration of small crystallites Concerning the synthesis of well-defined nanocrystallites.different solvothermal processes have been investigated at different temperatures. In some cases. selenides [35] (* due to the large development of such research domain only some examples are quoted). A specific hydrothermal reaction called “phase selective process” has been also used with H3BO3 and NaN3 as reagents and N2H4. During these last ten years solvothermal reactions have been developed in these different axis. phosphides [33].the preparation of nanocrystallites.H2O as solvent [29]. solvothermal reactions – due to the wide spread of solvent composition – have allowed to developed borides [30]. T≈600°C) compared to the conventional ones (5<P<7 GPa. IV. such a process requires high pressures – high temperatures conditions [22]. 1000<T<1700°C) [25]. . presents the same structures that carbon (graphite-like (h-BN). During these last five years . IV. the formation of c-BN was claimed. sulfides [34].using a nitriding solvent (NH2NH2) as flux and h-BN as precursor.the elaboration of single crystals. BBr3) and nitrides (Li3N) as precursors and an organic solvent (C6H6) [26-28]. IV.led to a strong reduction of the pressure – temperature conditions (P=1. isoelectronic of two carbons.the deposition of thin films. The elaboration process for c-BN is also based on a flux assisted conversion of h-BN using mainly nitrides as flux-precursors . opening a new route to the synthesis of superhard materials. zinc-blende (c-BN) and hexagonal lonsdaleite-type). Solvothermal reactions and the shaping of functional materials In order to improve the functionality of materials three different ways have been developed: . The first solvothermal process . During these last ten years different thermodynamical calculations [23] or experimental approaches (involving the c-BN→h-BN transformation [24]) suggested that c-BN could be thermodynamically stable in normal pressure conditions in mild temperatures conditions. carbides [31].2 Crystal growth in solvothermal conditions The main characteristic of these processes is the low or medium temperature used compared to the conventional processes.5 Due to the position of the elements B and N in the periodic table BN. nitrides [32].

Conclusions Solvothermal reactions appear a fruitful tool in different domains involving Materials Chemistry and Materials Science. hydrothermal sintering as been developed [43]. Single crystals of different materials as ZnS. opto-electronic.3 Solvothermal deposition of thin films Such a process has been tested in few cases: carbon deposition on SiC as substrate [41]. SnS2…– due to their physical properties – will be required for different applications leading to the development of new crystal-growth processes. Such reactions open the development of new processes either for preparing and shaping materials with different compositions (borides. The main advantage of such a sintering process is to be efficient at medium temperature compared to the conventional sintering processes . 685. C. under high pressure and medium temperature ..4 Solvothermal sintering Due to the reactions induced .such developments will be closely associated to different applications concerning in particular semi-conductors. chromium oxides on whiskers of aluminium borate [42]. PbS. . Such processes require an evaluation versus the conventional ones (CVD. spintronic… References [1] DEMAZEAU G.for obtaining single crystals with a low-temperature form [36]. The main illustration concerning the first domain of application is the hydrothermal crystal growth of α-quartz [36] In the near future the third domain of applications will be intensively developed using nonaqueous solvents. IV.for developing new crystal-growth processes of non-oxides (nitrides. Acad. PVD) in order to be developed. recently the crystal growth of GaN using NH3 as solvent and Li3GaN2 as precursor has been evaluated [40]. 1999. sulfides. nitrides.6 The hydro. . selenides…. Sci.R. between the solid and the fluid phases at the interface between the grains. sulfides…) [39]. In the future .).Consequently this sintering process open a new route to the preparation of dense ceramics in mild conditions. t. Paris.38]. IV.2(Série IIc). For example. optics.for preparing single crystals with a low density of defects (increasing temperature being able in many cases to favor it ) [37.or solvothermal crystal growth is developed mainly in three directions: . .

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