Ordered mesoporous metal oxides: synthesis and applications

Great progress has been made in the preparation and application of ordered mesoporous metal oxides during the past decade. However, the applications of these novel and interesting materials have not been reviewed comprehensively in the literature. In the current review we first describe different methods for the preparation of ordered mesoporous metal oxides; we then review their applications in energy conversion and storage, catalysis, sensing, adsorption and separation. The correlations between the textural properties of ordered mesoporous metal oxides and their specific performance are highlighted in different examples, including the rate of Li intercalation, sensing, and the magnetic properties. These results demonstrate that the mesoporosity has a direct impact on the properties and potential applications of such materials. Although the scope of the current review is limited to ordered mesoporous metal oxides, we believe that the information may be useful for those working in a number of fields.     

Container effect in nanocasting synthesis of mesoporous metal oxides

We report a general reaction container effect in the nanocasting synthesis of mesoporous metal oxides. The size and shape of the container body in conjunction with simply modifying the container opening accessibility can be used to control the escape rate of water and other gas-phase byproducts in the calcination process, and subsequently affect the nanocrystal growth of the materials inside the mesopore space of the template. In this way, the particle size, mesostructure ordering, and crystallinity of the final product can be systemically controlled. The container effect also explain some of the problems with reproducibility in previously reported results.     

Ordered mesoporous alumina-supported metal oxides

The one-pot synthesis of alumina-supported metal oxides via self-assembly of a metal precursor and aluminum isopropoxide in the presence of triblock copolymer (as a structure directing agent) is described in detail for nickel oxide. The resulting mesoporous mixed metal oxides possess p6 mm hexagonal symmetry, well-developed mesoporosity, relatively high BET surface area, large pore widths, and crystalline pore walls. In comparison to pure alumina, nickel aluminum oxide samples exhibited larger mesopores and improved thermal stability. Also, long-range ordering of the aforementioned samples was observed for nickel molar percentages as high as 20%. The generality of the recipe used for the synthesis of mesoporous nickel aluminum oxide was demonstrated by preparation of other alumina-supported metal oxides such as MgO, CaO, TiO 2, and Cr 2O 3. This method represents an important step toward the facile and reproducible synthesis of ordered mesoporous alumina-supported materials for various applications where large and accessible pores with high loading of catalytically active metal oxides are needed.     

Nanocast mesoporous mixed metal oxides for catalytic applications

Since the initial discovery of ordered mesoporous silica in early 1990s, considerable innovations were achieved regarding their synthesis, characterization and applications. One of the best outcomes of these intense research efforts is the development of a solid templating method called “nanocasting”, which is based on using mesoporous silica (or carbon) as a rigid template. This solid-to-solid replication method opened the pathway for synthesizing high surface area non-silica mesostructured materials that are challenging to obtain through conventional self-assembly processes which are based on amphiphilic soft structure-directing agents. In particular, the replicated metal oxide mesostructures obtained by this method were found to be highly versatile for a wide range of applications, especially in catalysis, owing to their large specific surface area. Furthermore, the nanocasting method is particularly suited for the synthesis of mixed metal compositions, favored by the possible confinement of mixed precursors in the nanopores of the template. In this account, we discuss some of the recent developments regarding the synthesis of nanocast mixed metal oxides and their perspectives of catalytic applications. It is here the choice of the authors to place emphasis on a few representative examples of compositions (e.g., non-noble metal-based catalysts, perovskites) and catalytic reactions (e.g., hydrogen production, gas-phase oxidation).     

Shape-controlled synthesis and characterization of cobalt oxides hollow spheres and octahedra

We demonstrated that single-crystalline cobalt monoxide (CoO) hollow spheres and octahedra could be selectively synthesized via thermal decomposition of cobalt(II) acetylacetonate in 1-octadecene solvent in the presence of oleic acid and oleylamine. The morphologies and sizes of as-prepared CoO nanocrystals could be controlled by adjusting the reaction parameters. Cobalt oxide (Co(3)O(4)) hollow spheres and octahedra could also be selectively obtained via calcination method using corresponding CoO hollow spheres and octahedra as precursors. The morphology, size and structure of the final products were investigated in detail by XRD, SEM, TEM, HRTEM, DSC, TG, and XPS. The results revealed that the electrochemical performance of cobalt oxide hollow spheres is much better than that of cobalt oxide octahedra, which may be related to the degree of crystallinity, size, and morphology of cobalt oxides.     

General, spontaneous ion replacement reaction for the synthesis of micro- and nanostructured metal oxides

A novel spontaneous ion replacement route based on the solubility difference as the driving force to synthesize a number of metal oxides has been established. We present a comprehensive study on the ion replacement reaction for chemical synthesis of micro- and nanostructured Mn2O3, ZnO, CuO, CdO, Al2O3, and CaO samples. This novel approach described herein is derived from the solubility difference between two carbonate salts, in which a metal cation can be driven from one liquid phase into another solid phase in the solution system. The resulting metal carbonate salts are initially formed and subsequently calcined to form highly crystallined metal oxides. The variation of pH values, reaction temperature, and reagent shapes can vary the solubility of these two carbonate salts, which thus changes the final morphology of metal oxides. The present work makes a progress to simply and mildly synthesize metal oxides with various morphologies, due to the fact that materials with a desired morphology are a key engineering step toward their shape-dependent chemical and physical properties.     

Highly stable mesoporous metal oxides using nano-propping hybrid gemini surfactants

Noble Gemini surfactants containing a siloxane moiety have been designed and successfully synthesized in the present study and are utilized as structure-directing agents for mesoporous metal oxides such as zirconia, titania, and vanadia. The siloxane moiety is believed to play an important nano-propping role during the surfactant removal by direct calcination, yielding thermally stable mesoporous metal oxides. It is also believed that the synthesis strategy described here can be applied to the synthesis of robust nanostructured materials such as nanoparticles and nanorods in addition to mesoporous materials.     

Ultrasound-assisted synthesis of nanostructured transition metal oxides

Ultrasound pretreatment of aqueous solutions of cetyltrimethylammonium bromide as a structure- directing agent has been applied to prepare nanostructured mesoporous Mn, Fe, and Ni oxides. After removal of the template by triple extraction with a water–ethanol solution of sodium acetate or ammonium chloride, air-calcined samples of oxide materials prepared in such a way possess surface areas of about 300–450 m²/g and are thermally stable up to 300°C.     

SBA-15固载金属氧化物介孔材料的研究进展

介孔分子筛SBA-15具有独特的物理化学性质和广阔的应用前景,成为目前众多研究领域的一个研究热点。本文结合我们自己的工作和国内外相关研究,较全面地阐述了近年来几种SBA-15固载金属氧化物介孔材料的研究状况,并展望了今后其研究、发展方向和应用前景。     

One-step synthesis of ordered mesoporous carbonaceous spheres by an aerosol-assisted self-assembly

Ordered mesoporous carbonaceous spheres with variable structures have been successfully prepared by using phenolic oligomers as a carbon precursor and amphiphilic triblock copolymers as a template via a one-step aerosol-assisted organic-organic self-assembly method.     

Aerosol assisted synthesis of silica/phenolic resin composite mesoporous hollow spheres

Hollow spheres of phenolic resin/silica composite are synthesized by macroscopic phase separation of a sorbitan monooleate surfactant Span 80 during aerosol-assisted spraying. The cavity can be evolved from multiple compartments to single hollow cavity with the increase of Span 80 content. The composite shell becomes mesoporous due to the release of small molecules after thermal treatment above 350 °C. After further thermal treatment at a higher temperature for example 900 °C in nitrogen or 1,450 °C in argon, the carbon/silica composite hollow spheres or crystalline silicon carbide hollow spheres are derived, respectively. Compared to the pure phenolic resin-based carbon spheres, thermal stability of the carbon-based composite spheres in air is essentially improved by the introduction of inorganic component silica. The carbon-based composite hollow spheres combine both performances of easy mass transportation through macropores and high specific surface area of mesopores, which will be promising to support catalysts for fuel cells. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

New families of supermicroporous metal oxides: the link between zeolites and mesoporous materials

Sol-gel hydrolysis reactions in propanol of two or more metal acetates or alkoxides in n-alkylamines have been found to yield porous mixed oxides with the presence of pores largely in the 10-20 A region.     

Block copolymer-templated mesoporous oxides

Block copolymers (BC) are indeed suitable and versatile templates for the creation of mesostructured and mesoporous materials. Great advances have been achieved in the last 3 years. Nowadays, it is possible to obtain highly controlled large-pore and highly stable mesostructured and mesoporous materials (silica, non-silica oxides, carbons,…) shaped as powders, films, monoliths or aerosols. This paper reviews mainly the synthesis of BC-templated mesostructured oxides, stressing in the physical, chemical and processing parameters, which have to be thoroughly controlled to reproducibly obtain mesoporous materials.     

Nonequilibrium plasma-chemical synthesis of nanosized particles of metal oxides

The results of investigation into the synthesis conditions and basic characteristics of nanoparticles of titanium dioxide and the mixed oxide (TiO₂)_x(SiO₂)_1?x from a gaseous mixture of oxygen, hydrogen, and titanium tetrachloride (or a mixture of titanium and silicon tetrachlorides) are reported. The synthesis was initiated by a pulsed electron beam and was a chain process in character. The geometric dimensions of oxide particles were measured and their X-ray diffraction, X-ray fluorescence, and IR spectrometric studies were performed. It was shown that the nonequilibrium character of the synthesis process induced by a pulsed electron beam allowed the temperature threshold for the formation of the crystalline structure of particles to be lowered.     

General routes to porous metal oxides via inorganic and organic templates

The generation of porous metal oxides by removal of template molecules from inorganic polymers formed by sol-gel type hydrolysis and condensation of metal alkoxides is described. The template molecules include organic polymers, copper (II) ions in hybrid copper oxide/silica sols and copper (II) bis(hexafluorocetylacetonate) (hfac). Neutron scattering experiments on the system in which polyacrylic acid (Mw=2,000 Daltons) is used as an organic template to generate microporous tin oxide show that removal of the template generates skeletal voids. In a second series of experiments, mixed copper/silicon oxide xerogels were prepared by hydrolysis of mixtures of Si(OEt)₄ and Cu(OCH₂CH(CH₃)N(CH₃)H)₂ in the ratios of Si:Cu=2:1, 4:1, 9:1. Selective removal (etching) of the copper component generates porous silica. Neutron scattering data and BET surface area measurements are consistent with the creation of pores with molecular dimensions (micropores, 10 Å or less). In the third strategy, Si(OEt)₄ is hydrolyzed in the presence of Cu(hfac)₂, a volatile, inert inorganic template, in a 4 to 1 molar ratio. Removal of the template from the xerogel at 100°C in vacuo affords microporous silica.     

Facile synthesis and characterization of novel mesoporous and mesorelief oxides with gyroidal structures.

In this paper, we bring forward an effective strategy, solvothermal postsynthesis, to prepare ordered mesoporous silica materials with highly branched channels. Structural characterizations indicate that the titled mesoporous materials basically have the cubic double gyroidal (space group Ia-3d) structure with small fraction of distortions. The mesopore sizes and surface areas can be up to 8.8 nm and 540 m2/g, respectively, when microwave digestion is employed to remove the organic templates. A phase transition model is proposed, and possible explanations for the successful phase transition are elucidated. The results show that the flexible inorganic framework, high content of organic matrix, and nonpenetration of poly(ethylene oxide) segments may facilitate the structural evolution. This new synthetic strategy can also be extended to the preparation of other double gyroidal silica-based mesoporous materials, such as metal and nonmetal ions doped silica and organo-functionalized silica materials. The prepared 3D mesoporous silica can be further utilized to fabricate various ordered crystalline gyroidal metal oxide "negatives". The mesorelief "negatives" (Co3O4 and In2O3 are detailed here) prepared by impregnation and thermolysis procedures exhibit undisplaced, displaced, and uncoupled enantiomeric gyroidal subframeworks. It has been found that the amount of metal oxide precursors (hydrated metal nitrates) greatly influence the (sub)framework structure and single crystallinity of the mesorelief metal oxide particles. The single crystalline gyroidal metal oxides are ordered both at mesoscale and atomic scale. However, these orders are not commensurate with each other.     

Uptake of curcumin by supported metal oxides (CaO and MgO) mesoporous silica materials

A series of LaMnO₃ perovskites as catalysts for selective reduction of NO by CO were synthesized using microwave and ultrasound assisted sol-gel method. The catalysts were characterized by BET area measurements, Scanning Electron Microscopy (SEM), X-Ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) techniques. XRD results showed revealed the orthorhobic crystalline structure and with very high purity. SEM analyses proved lower particle size for ultrasound (US) assisted synthesized LaMnO₃. In addition, US assisted synthesized LaMnO₃ presented higher surface area respect to other catalysts, synthesized by the other methods. Results revealed that the ultrasound assisted synthesized catalyst determines the lowest crystallite size, the highest surface area and the highest concentration of O-vacancies and, as a consequence, the highest catalytic activity.

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Synthesis of crystallized mesoporous transition metal oxides by silicone treatment of the oxide precursor

Ordered mesoporous transition metal oxides were successfully crystallized after strengthening the amorphous framework by a silica layer, which efficiently protected the original mesoporous structure against crystallization and resulting mass transfer.