Facile synthesis for ordered mesoporous gamma-aluminas with high thermal stability

The facile synthesis of highly ordered mesoporous aluminas with high thermal stability and tunable pore sizes is systematically investigated. The general synthesis strategy is based on a sol-gel process associated with nonionic block copolymer as templates in ethanol solvent. Small-angle XRD, TEM, and nitrogen adsorption and desorption results show that these mesoporous aluminas possess a highly ordered 2D hexagonal mesostructure, which is resistant to high temperature up to 1000 degrees C. Ordered mesoporous structures with tunable pore sizes are obtained with various precursors, different acids as pH adjustors, and different block copolymers as templates. These mesoporous aluminas have large surface areas (ca. 400 m2/g), pore volumes (ca. 0.70 cm3/g), and narrow pore-size distributions. The influence of the complexation ability of anions and hydro-carboxylic acid, acid volatility, and other important synthesis conditions are discussed in detail. Utilizing this simple strategy, we also obtained partly ordered mesoporous alumina with hydrous aluminum nitrate as the precursor. FTIR pyridine adsorption measurements indicate that a large amount of Lewis acid sites exist in these mesoporous aluminas. These materials are expected to be good candidates in catalysis due to the uniform pore structures, large surface areas, tunable pore sizes, and large amounts of surface Lewis acid sites. Loaded with ruthenium, the representative mesoporous alumina exhibits reactant size selectivity in hydrogenation of acetone, D-glucose, and D-(+)-cellobiose as a test reaction, indicating the potential applications in shape-selective catalysis.     

Ordered mesoporous Fe2O3 with crystalline walls

Alpha-Fe(2)O(3) has been synthesized with an ordered mesoporous structure and crystalline walls that exhibit a near-single crystal-like order. The unique magnetic behavior of the material, distinct from bulk nanoparticles of alpha-Fe(2)O(3) or mesoporous Fe(2)O(3) with disordered walls, has been established. Magnetic susceptibility, M?ssbauer, and neutron diffraction data show that the material possesses the same long-range magnetic order as bulk alpha-Fe(2)O(3), despite the wall thickness being less than the 8 nm limit below which magnetic ordering breaks down in nanoparticulate alpha-Fe(2)O(3), yet the Morin transition of bulk alpha-Fe(2)O(3) is absent. It is also shown by TEM, PXRD, and EXAFS that alpha-Fe(2)O(3) with the same ordered mesoporous structure but disordered walls contains small crystalline domains. M?ssbauer and magnetic susceptibility data demonstrate that this material exhibits no long-range magnetic order but superparamagnetic behavior.     

Synthesis of ordered mesoporous NiO with crystalline walls and a bimodal pore size distribution

A mesoporous solid with crystalline walls and an ordered pore structure exhibiting a bimodal pore size distribution (3.3 and 11 nm diameter pores) has been synthesized. Previous attempts to synthesize solids with large ordered mesopores by hard templating focused on the preparation of templates with thick walls (the thick walls become the pores in the target materials), something that has proved difficult to achieve. Here the large pores (11 nm) do not depend on the synthesis of a template with thick walls but instead on controlling the microporous bridging between the two sets of mesopores in the KIT-6 template. Such control determines the relative proportion of the two pore sizes. The wall thickness of the 3D cubic NiO mesopore has also been varied. Preliminary magnetic characterization indicates the freezing of uncompensated moments or blocking of superparamagnetism.     

Facile synthesis of ordered mesoporous carbons with high thermal stability by self-assembly of resorcinol-formaldehyde and block copolymers under highly acidic conditions

The effect of phenols reactivity with formaldehyde on the formation of ordered mesoporous carbons has been investigated. A strategy to accelerate the polymerization of phenolic resins by using strongly acidic conditions is proposed. The self-assembly of resorcinol-formaldehyde and block copolymers (e.g., F127) under highly acidic concentrations (e.g., 1.5 M HCl) is probably driven by the I+X-S+ mechanism and hydrogen bonding and affords a highly reproducible approach for synthesis of ordered mesoporous carbons. The synthesis can be readily scaled up with no change in sample quality. The carbon material obtained (denoted as C-ORNL-1) exhibits highly ordered hexagonal mesostructure, with a typical BET surface area of approximately 600 m2/g, pore size of 6.3 nm, and pore volume of approximately 0.60 cm3/g. One of the unique structural features of C-ORNL-1 is its high thermal stability; it can be graphitized at 2600 degrees C while considerable mesoporosity is maintained.     

Formation of highly ordered mesoporous titania films consisting of crystalline nanopillars with inverse mesospace by structural transformation

Highly ordered mesoporous titania films consisting of crystalline nanopillars with open-spaced, perpendicular, and continuous porosity have been prepared via structural transformation from a 3D hexagonal mesostructure during the thermal treatment. The mechanism of the structural transformation is explained by the crystallization of the titania framework and the large contraction of the initial 3D hexagonal mesostructured film upon calcination. This structural transformation provides a new approach to generate mesoporous thin-film materials with unique structures.     

Synthesis of ordered mesoporous Fe3O4 and gamma-Fe2O3 with crystalline walls using post-template reduction/oxidation

Ordered mesoporous Fe(3)O(4) with crystalline walls (inverse spinel structure) has been synthesized for the first time, representing to the best of our knowledge, the first synthesis of a reduced mesoporous iron oxide. Synthesis was achieved by reducing ordered mesoporous alpha-Fe(2)O(3) (corundum structure) to Fe(3)O(4) spinel then to gamma-Fe(2)O(3) by oxidation, while preserving the ordered mesostructure and crystalline walls throughout. Such solid/solid transformations demonstrate the stability of the mesostructure to structural phase transitions from the hexagonal close packed oxide subarray of alpha-Fe(2)O(3) (corundum structure) to the cubic close packed subarray of Fe(3)O(4) spinel and gamma-Fe(2)O(3). Preliminary magnetic measurements reveal that the spins in both Fe(3)O(4) and gamma-Fe(2)O(3) are frozen at 295 K, despite the wall thickness (7 nm) being less than the lower limit for such freezing in corresponding nanoparticles (>8 nm).     

Facile synthesis of ordered magnetic mesoporous gamma-Fe2O3/SiO2 nanocomposites with diverse mesostructures

On the basis of a sol–gel process, a facile, low cost, and one-step approach for preparing ordered magnetic mesoporous γ-Fe₂O₃/SiO₂ nanocomposites by an evaporation-induced self-assembly (EISA) approach is presented. Various mesostructured silica materials (P6mm or Im3m) incorporated with different amounts of iron oxide (n_Si/n_Fe=9/1, 8/2, 7/3, respectively) were synthesized and characterized by XRD, TEM, N₂-sorption analyses, and superconducting quantum interference device (SQUID) magnetometer. The HCl-leaching experiments together with TEM micrographs and nitrogen sorption analysis suggested that most of the γ-Fe₂O₃ domains of several nanometers were embedded in the silica walls, rather than dispersed in the mesopores, which could cause the significant pore clogging reported in some studies. The release behaviors of lysozyme from these magnetic porous nanocomposites were investigated for the possible application of drug targeting and control release. The influence of iron precursors was also studied and a possible mechanism was proposed. The hydrolysis of Fe³⁺ ions under weakly acidic conditions and the induced formation of SiOFe bonds may account for the synthesis of this kind of nanocomposite. These multifunctional nanostructured materials would have a wide range of applications in toxin removal, catalysis, waste remediation, and biological separation as well as novel drug-carrier technologies.     

Controlled synthesis of highly dispersed platinum nanoparticles in ordered mesoporous carbons

A novel route has been developed to fabricate ordered carbon mesoporous materials with well-dispersed, highly stable Pt nanoparticles of ca. 2-3 nm on the pore walls using platinum acetylacetonate as the co-feeding carbon and Pt precursor.     

Synthesis and microwave absorbing properties of highly ordered mesoporous crystalline NiFe2O4

Highly ordered mesoporous NiFe(2)O(4) with excellent microwave absorption properties has been synthesized by using mesoporous silica (KIT-6) as a hard template.     

Synthesis and photocatalytic properties of highly crystalline and ordered mesoporous TiO2 thin films

Highly crystalline and ordered mesoporous TiO2 thin films have been synthesized by stabilization of the mesostructure with confined carbon; the films exhibit 2.5% photoconversion efficiency for the water photolysis at zero-bias and Xe lamp illumination of 40 mW cm(-2).     

Facile synthesis of ordered mesoporous molybdenum carbide electrocatalysts for high-performance hydrogen evolution reaction

In this study, a simple method was designed to prepare ordered mesoporous carbons embedded with molybdenum without any extreme conditions. We prepared three different ordered molybdenum carbide materials with mesoporous structures to explore the influence of the structure of molybdenum-based materials on the HER catalytic efficiency. The ordered mesoporous molybdenum carbide catalysts (CMK-3-MoCx, fCMK-3-MoCx, CMK-8-MoCx) were characterized by SEM, TEM, XRD, nitrogen adsorption-desorption and XPS. The HER is catalyzed efficiently on the three electrocatalysts, fCMK-3-MoCx shows the best HER electro-catalytic performance with a small onset potential of −0.06 V vs. RHE, a low tafel slope of 66 mV dec⁻¹ and a small over-potential value of 89 mV at 10 mA cm⁻². This excellent performance on HER is due to its high specific surface area and highly ordered mesoporous structure that resulted in excellent proton transport efficiency and high electron transfer rate. Our results provide a new research direction for the application of flat ordered mesoporous structures in catalysis.     

Facile method to synthesize platelet SBA-15 silica with highly ordered large mesopores

Highly ordered mesoporous SBA-15 silica with large pore diameter of 18 nm (nominal BJH pore diameter ~22 nm) and short pore length (~500 nm) was synthesized using a micelle expander 1,3,5-triisopropylbenzene in the absence of ammonium fluoride by employing short initial stirring time at 17 °C followed by static aging at low temperature. Scanning and transmission electron microscopies revealed that the material comprised of platelet particles in which large mesopores were nearly flawlessly arranged within uniform domains up to 3 μm in size. The platelet SBA-15 had the (100) interplanar spacing of 17 nm, high surface area (~470 m(2) g(-1)) and large pore volume (~1.6 cm(3) g(-1)). The hydrothermal treatment at 130 °C for 2 days was employed to eliminate constrictions from the pore channels. The control experiment showed that a sample prepared with prolonged stirring had very similar mesoporous properties, but the particle size was smaller and the domains were irregular, proving that the static conditions facilitate the formation of SBA-15 with platelet particle morphology. The absence of ammonium fluoride was also critical in attaining the platelet particle shape.     

One-pot synthesis of highly crystalline mesoporous TiO2 nanoparticle assemblies with enhanced photocatalytic activity

We report an unprecedented formation of mesoporous titania via a surfactant-assisted aggregating assembly of TiO(2) nanoparticles. These mesostructures possess a highly crystalline anatase phase, large and accessible pore surface area, and exhibit superior photocatalytic performance.     

Facile synthesis of thick ordered mesoporous TiO2 film for dye-sensitized solar cell use

Crack-free thick ordered mesoporous TiO₂ films with excellent optical quality have been synthesized by combination of “Doctor Blade” technique and a two-step evaporation induced self-assembly (EISA) method. By employing the as-synthesized mesoporous film with the thickness of 7 μm as the photoanode in dye-sensitized solar cell (DSC), a solar conversion efficiency of 6.53% has been obtained at 30 mW cm⁻² light intensity.     

An ordered mesoporous aluminosilicate with completely crystalline zeolite wall structure

An ordered mesoporous aluminosilicate with completely crystalline zeolite pore wall structure, denoted as OMZ-1, was successfully synthesized by recrystallization of SBA-15 using in situ formed CMK-5 as the hard template. The role of carbon material not only serves as a hard template to preserve ordered mesoporous structure but also kinetically controls the crystallization process to form large crystals.     

Helical periodic mesoporous 1,4-phenylene-silica nanorods with chiral crystalline walls

Helical periodic mesoporous 1,4-phenylene-silica nanorods with chiral crystalline walls were prepared using the self-assembly of a pair of enantiomers as templates.     

Synthesis of ordered mesoporous crystalline carbon-anatase composites with high titania contents

A direct-triblock-copolymer templating method is demonstrated to synthesize ordered mesoporous crystalline C-TiO(2) (MCT) composites using phenolic resins and acid-base pairs [acidic TiCl(4) and basic counterpart Ti(OC(4)H(7))(4)] as carbon and titanium sources, respectively. The composites possess highly crystalline anatase pore walls that are "glued" by amorphous carbon, ordered mesostructure, high surface areas (approximately 200 m(2)/g), and large pore volumes (approximately 0.15 cm(3)/g). The titania content is as high as 87 wt%. MCT composite favors the immobilization of proteins and enhances the electrocatalytic properties in relation to the reduction of hydrogen peroxide.     

Sol-gel synthesis of ordered mesoporous alumina

Well-ordered mesoporous alumina materials with high surface area and a narrow pore size distribution were synthesized using a sol-gel based self assembly technique.