Mesostructured solid template

For many oxides, including mixed metal oxides, of catalytic interest, preparing a high-surface-area solid with thermally stable porous structure was extremely difficult until recentiy. The hard templating procedure provides a systematic solution to this problem. Nanocasting that makes use of a mesostructured solid template is a special case. Both mesostructured silica and mesostructured carbon have been demonstrated so fer as hard templates. Rather precise replicas of these nanomolds have been obtained for a variety of oxide-type perovskites. Unprecedented specific surface areas in the 150-200 m /g were reached. 

Ordered mesoporous silica seems to be an ideal hard template, which can be used as a mold for other mesostructures with various compositions, such as ordered mesoporous carbon and metal oxides. Mesoporous silicas with various different structures are available, and silica is relatively easily dissolved in HF or NaOH. Alternatively, mesoporous carbons with a solid skeleton structure are also suitable choices as hard templates due to their excellent structural stability on thermal or hydrothermal and chemical treatment. A pronounced advantage of carbon is the fact that it is much easier to remove than silica by simple combustion. The nanocasting synthesis of mesoporous carbon by using mesoporous silica as template will be discussed in detail in the section on mesoporous carbon. In many cases, silica is unsuitable for synthesizing framework compositions other than carbon, since the leaching of the silica typically affects the material which is filled into the silica pore system. 

AG), NaAlOa or Al2(S04)3 x 18 H2O as silica or aluminum source, respectively, and tetraethylammonium bromide (TEABr) or phosphoric acid as template or promoter. The gel composition and the aging and mesostructuration-crystallization conditions are indicated in Table 1. The obtained solids were dried and the occluded surfactant molecules extracted with 50 mL of ethanol at 60 °C. Subsequently, the samples were washed with distilled water, dried overnight at 60 °C and calcined in air at 350 °C for 18 h (samples 1 and 2) or at 550 °C for 6 h (samples 3, 4 and 5). 

Besides cooperative pathways, also tme liquid crystal templating (TLCT) and the hard template route (Section 9.3.7) have been developed for the synthesis of ordered mesoporous materials. In the case of the TLCT, a preformed surfactant liquid crystalline mesophase is loaded with the precursor for the inorganic materials (140). The nanocasting route, on the other hand, is a clearly distinct method (141). Here, no soft surfactant template is used but, instead, the pore system of an ordered mesoporous solid is used as the hard template serving as a mold for preparing varieties of new mesostructured materials, for example, metals, carbons, or transition metal oxides. 

Oxides Compared to silica-based networks, nonsiliceous ordered meso-poious materials have attracted less attention, due to the relative difficulty of applying the same synthesis principles to non-sihcate species and their lower stability (227). Nonsiliceous framework compositions are more susceptible to redox reactions, hydrolysis, or phase transformations to the thermodynamically preferred denser crystalline phases. Template removal has been a major issue and calcination often resulted in the collapse of the mesostracture. This was the case for mesostractured surfactant composites of mngsten oxide, molybdenum oxide, and antimony oxide, and meso-structured materials based on vanadia that were obtained at early stages. Because of their poor thermal stability, none of these mesostructures were obtained as template-free mesoporous solids (85, 228, 229). 

True Liquid Crystal Templating and Eyaporation-induced Mesostructure Formation Non-silica Mesoporous Solids... 

Liquid crystalline mesophases can also be prepared in non-aqueous solution. Using ethanolic solutions of non-ionic block copolymers as a medium, Zhao et for example, have developed a route by which mesoporous metal phosphates and borates can readily be prepared. A mixture of the metal alkoxide and the acidic chloride is used to give a complex in ethanolic solution. This acid-base pair reacts in one component of the liquid crystalline assembly to give a mesophase solid of uniform composition. Evaporation of the ethanol leaves the mesostructure. This appears to be one of the most promising routes to the formation of non-silica mesoporous solids. Many reports of these solids have appeared, particularly of metal oxides such as titanium dioxide, but loss of ordering on the mesoscale frequently occurs upon template removal. The route of Sanchez, which involves the use of titanate precursor species in the sol-gel, is a promising approach to stable mesostructured titania that retains its porosity. 

Mesostructured inorganic solids, originated from self-assembling of supramolec-ular structures, represent a class of suitable templates for the achievement of nanostructured materials. Ordered mesoporous polymers and carbonaceous frameworks... 

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