Metal sulfide mesostructures

Through a co-assembling route, mesostructured lamellar molybdenum sulfides are formed hydrothermally at about 85 °C using cationic surfactant molecules as the templates. The reaction temperature and the pH value of the reaction system are important factors that affect the formation of the mesostructured compounds. The amount of the template and that of the S source are less critical in the synthesis of the compounds. For the three as-synthesized mesostructured materials, the interlayer distance increases linearly with the chain length of the surfactant. Infrared and X-ray photoelectron spectroscopy reveals that the individual inorganic layers for the three compounds are essentially the same both in composition and in structure. The formal oxidation state of the molybdenum in the materials is +4 whereas there exist S2 anions and a small amount of (S-S)2 ligands in the mesostructures. The successful synthesis of MoS-L materials indicates that mesostructured compounds can be extended to transition metal sulfides which may exhibit physico-chemical properties more diverse than non-transition metal sulfides because of the ease of the valence variation for a transition metal. 

Three novel mesostructured tungsten sulfides, designated as MTS-W, MTS-M and MTS-C, were prepared by the condensation reaction of (NH4)2WS4 in the presence of octadecyltrimethylammonium bromide (OTAB) under refluxing conditions in water, methanol and carbon tetrachloride at 373 K, 338 K and 350 K, respectively. The three as-synthesized metal sulfides all have a layered structure with the d-spacing of 31 A, 30 A or 37 A. Partial removal of the organic surfactants from the layer galleries can be achieved by solvent extraction. 

Since the first synthesis of mesoporous materials MCM-41 at Mobile Coporation,1 most work carried out in this area has focused on the preparation, characterization and applications of silica-based compounds. Recently, the synthesis of metal oxide-based mesostructured materials has attracted research attention due to their catalytic, electric, magnetic and optical properties.2 5 Although metal sulfides have found widespread applications as semiconductors, electro-optical materials and catalysts, to just name a few, only a few attempts have been reported on the synthesis of metal sulfide-based mesostructured materials. Thus far, mesostructured tin sulfides have proven to be most synthetically accessible in aqueous solution at ambient temperatures.6-7 Physical property studies showed that such materials may have potential to be used as semiconducting liquid crystals in electro-optical displays and chemical sensing applications. In addition, mesostructured thiogermanates8-10 and zinc sulfide with textured mesoporosity after surfactant removal11 have been prepared under hydrothermal conditions. 

We have been interested in developing new routes to mesostructured metal sulfides. Our approach capitalizes on well-established solution condensation reactions that can transform discrete, soluble metal thiolate species into solid-state metal sulfide compounds. Here we wish to describe the use of (NH4)2WS4 as a precursor material in the synthesis of three mesostructured tungsten suldifes with the inorganic walls that consist of continuous WS3 chains and WS2. 

There have been only a few reports of mesostructured metal sulfides. Mesoporous cadmium sulfide was prepared from polyethylene oxide surfactants and cadmium salts exposed to hydrogen sulfide [35], A study of the effects of the counter-anion on the formation of CdS mesostructures led to the conclusion that the use of cadmium nitrate and perchlorate salts improved the degree of order of the mesostructure over the chloride, sulfate and acetate salts. This effect was attributed to the stronger acidity of conjugate acid by-products of the reaction in the case of nitrates that leads to the dissolution of high-energy defects and enhances structural order. 

Compared with metal oxides, less attention has been paid to the synthesis of mesostructured metal sulfides [61,205]. The only systematic work was reported by Anderson and Newcomer [205]. The liquid-crystal templating approach was applied to metal sulfides, such as Mo, W, Co, Fe, Zn, Ga, Sn and Sb sulfides. All of the products were lamellar and consisted of bilayers or interdigitated layers of surfactant molecules sandwiched between metal sulfide layers. 

The key property required of the inorganic species is ability to build up (polymerize) around the template molecules into a stable framework. As is already evident in this article, the most commonly used inorganic species are silicate ions, which yield a silica framework. The silica can be doped with a wide variety of other elements (heteroatoms), which are able to occupy positions within the framework. For example, addition of an aluminium source to the synthesis gel provides aluminosilicate ions and ultimately an aluminosilicate mesoporous molecular sieve. Other nonsilica metal oxides can also be used to construct stable mesoporous materials. These include alumina, zirconia, and titania. Metal oxide mesophases, of varying stability, have also been obtained from metals such as antimony (Sb), iron (Fe), zinc (Zn), lead (Pb), tungsten (W), molybdenum (M), niobium (Nb), tantalum (Ta), and manganese (Mn). The thermal stability, after template removal, and structural ordering of these mesostructured metal oxides, is far lower, however, than that of mesoporous silica. Other compositions that are possible include mesostructured metal sulfides (though these are unstable to template removal) and mesoporous metals (e.g., platinum, Pt). 

Ordered mesoporous materials of compositions other than silica or silica-alumina are also accessible. Employing the micelle templating route, several oxidic mesostructures have been made. Unfortunately, the pores of many such materials collapse upon template removal by calcination. The oxides in the pore walls are often not very well condensed or suffer from reciystallization of the oxides. In some cases, even changes of the oxidation state of the metals may play a role. Stabilization of the pore walls in post-synthesis results in a material that is rather stable toward calcination. By post-synthetic treatment with phosphoric acid, stable alumina, titania, and zirconia mesophases were obtained (see [27] and references therein). The phosphoric acid results in further condensation of the pore walls and the materials can be calcined with preservation of the pore system. Not only mesoporous oxidic materials but also phosphates, sulfides, and selenides can be obtained by surfactant templating. These materials have pore systems similar to OMS materials. 

Non-aqueous synthetic methods have recently been used to assemble mesoporous transition metal oxides and sulfides. This approach may afford greater control over the condensation-polymerization chemistry of precursor species and lead to enhanced surface area materials and well ordered structures [38, 39], For the first time, a rational synthesis of mesostructured metal germanium sulfides from the co-assembly of adamantanoid [Ge4S ()]4 cluster precursors was reported [38], Formamide was used as a solvent to co-assemble surfactant and adamantanoid clusters, while M2+/1+ transition metal ions were used to link the clusters (see Fig. 2.2). This produced exceptionally well-ordered mesostructured metal germanium sulfide materials, which could find application in detoxification of heavy metals, sensing of sulfurous vapors and the formation of semiconductor quantum anti-dot devices. 

The change of composition of mesoporous materials can be done by direct synthesis and post-synthesis modification. Now, the composition of mesoporous materials can be extended to nonsilica oxides, phosphates, sulfides, even metals. The study of nonsilica mesoporous materials started much later than that for silica-based materials. The main reasons include the hydrolysis and condensation reactions of transition metal precursors is difficult to control the inorganic wall easily crystallizes and results in the loss of mesostructures the synthetic procedure is difficult to repeat. 

Ozin etal. subsequently prepared hexagonal mesostructured germanium sulfides by using low-valent metal cations such as Co +, Ni +, Cu+, and Zn + to connect [Ge4Sio] clus-... 

Stupp and coworkers first prepared mesostructured sulfides with oligomeric alkyl ethylene oxides [89, 90]. Lyotropic surfactant liquid-crystal phases are generated with the addition of appropriate metal ions, for example, Cd +. Hydrogen sulfide or hydrogen selenide gas is then fed into the solution to solidify the mesostructured organic-inorganic composites. The difficulty in this process remains the removal of the surfactants. A family of mesostructured solids, such as CdS, ZnS, and CdSe, have been successfully synthesized. 

Maclachlan MJ, Coombs N, Ozin GA (1999) Ntm-aqueous supramolecular assembly of mesostructured metal germanium sulfides from (Ge4Sio) clusters. Nature 397 681 84... 

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