Enhancing Methane Aromatization Performance by Reducing the Particle Size of Molybdenum Oxide.

Efficient use of natural gas to produce aromatics is an attractive subject; the process requires catalysts that possess high-performance active sites to activate stable C-H bonds. Here, we report a facile synthetic strategy to modify HMCM-49 with small molybdenum oxide nanoparticles. Due to the higher sublimability of nano-MoO3 particles than commercial MoO3, they more easily enter into the channels of HMCM-49 and associate with Brønsted acid sites to form active MoCx-type species under calcination and reaction conditions. Compared with commercial MoO3 modified MCM-49, nano-MoO3 modified MCM-49 exhibits higher methane conversion (13.2%), higher aromatics yield (9.1%), and better stability for the methane aromatization reaction.

Recent Advancements in Graphene-Based Supports of Metal Complexes/Oxides for Epoxidation of Alkenes.

In the past decade, there has been great progress in the preparation and catalytic applications of graphene-supported metal complexes/oxide catalysts. Graphene-based materials have attracted tremendous research interest owing to special physicochemical properties, for example, unique two-dimensional structure, high theoretical specific surface area, high electrical conductivity, and outstanding acid-base resistance properties. Graphene-supported metal complexes/oxides have been extensively investigated, and exhibit good catalytic activity and stability in water splitting (H2 generation or oxygen evolution), oxidation/epoxidation of alkenes, C-C bond formation, and so forth. Herein, recent developments in graphene-supported metal complexes/oxides for the catalytic epoxidation of different alkenes are summarized. Site isolation and synergistic interactions between metal complexes/oxides and graphene are the two key roles for enhancing the catalytic activity, whereas the hydrophobicity of the support can efficiently improve epoxide selectivity. In addition, the possible mechanisms of catalytic epoxidation are summarized. This review provides a feasible scheme for the potential application of graphene-based materials and guidance for the rational design of heterogeneous catalysts for catalytic applications.

Assembling photoluminescent tri(8-quinolinolato)aluminum into periodic mesoporous organosilicas.

Mesostructured and mesoporous materials are emerging as a new class of optical materials. However, their synthesis is nontrivial. In this work, periodic mesostructured metal complex-containing silicas of MCM- and SBA-type bearing homogeneously distributed photoluminescent tri(8-quinolinolato)aluminum inside the channel walls (denoted as Alq3@PMO-MCM and Alq3@PMO-SBA, respectively) have been achieved via one-pot co-assembling of inorganic/surfactant/optically active species. A comprehensive multianalytical characterization of the structural and optical properties demonstrates that both Alq3@PMO-MCM and Alq3@PMO-SBA series gainfully combine the photoluminescent properties of Alq3 with the porous features of PMOs. Regularly arranged pores provide high surface area to disperse optically active components well and render Alq3-containing PMOs promising materials for optoelectronic applications.

Hemoglobin immobilized with modified "fish-in-net" approach for the catalytic removal of aniline.

Blood is a waste product of the slaughter industry, while its main component hemoglobin (Hb) is a pseudo-peroxidase which is able to oxidize polycyclic aromatic hydrocarbons (PAHs) in the presence of H(2)O(2). In order to use Hb for wastewater treatment, we encapsulated it in silica-based matrix by modified "fish-in-net" approach. The as-synthesized catalysts were characterized by SEM, TEM, BET and solid-state UV-vis spectroscopy. It was found that Hb was partially homogeneously dispersed in microspheres and showed more stable peroxidase-like activity than free Hb. Moreover, it had substantially increased storage stability as well as pH stability. It was used as biocatalyst to remove aniline in aqueous solution and gave a reduction of 65% aniline removal, while 76% in the presence of additive PEG. No significant activity loss was observed after ten runs. These experimental results suggest that the resultant product was a promising biocatalyst for aromatic wastewater treatment.

Optimizing the matching between the acid and the base of cooperative catalysis to inhibit dehydration in the aldol condensation.

A series of acid-base bifunctional catalysts were prepared, and high yields and excellent selectivity in the aldol condensation were achieved through adjustment of the matching between the acid and the base. The results indicated that proper matching between the acid and the base can both efficiently activate the substrate through cooperative activation and inhibit dehydration without diminishing the yield.

Periodic mesoporous organosilicas with bis(8-quinolinolato) dioxomolybdenum(VI) inside the channel walls.

Novel periodic mesostructured organometallic silicas of MCM-41 type bearing homogeneously distributed bis(8-quinolinolato)dioxomolybdenum(VI) inside the channel walls (denoted as MoO(2)Q(2)@PMO-x) are synthesized via a convenient one-pot method and examined as catalysts in the epoxidation of cyclooctene. The ordered mesoporous structures as well as the organometallic groups incorporated into the framework are fully determined by comprehensive characterization techniques such as XRD, TEM, N(2) adsorption/desorption, SEM, FT-IR, UV-vis spectroscopy, solid-state NMR, ICP-AES, XPS and TG/DSC. MoO(2)Q(2)@PMO-6% catalyst exhibits higher activity for the epoxidation of cyclooctene with tert-butyl hydroperoxide than other MoO(2)Q(2)@PMO materials and its homogeneous or randomly grafted analogue.

Direct synthesis of acid-base bifunctionalized hexagonal mesoporous silica and its catalytic activity in cascade reactions.

A series of efficient acid-base bifunctionalized hexagonal mesoporous silica (HMS) catalysts contained aminopropyl and propanesulfonic acid have been synthesized through a simple co-condensation by protection of amino group. The results of small-angle XRD, TEM, and N(2) adsorption-desorption measurements show that the resultant materials have mesoscopic structures. X-ray photoelectron spectroscopies, elemental analysis (EA), back titration, (29)Si NMR and (13)C NMR confirm that the organosiloxanes were condensed as a part of the silica framework. The resultant catalysts exhibit excellent acid-basic properties, which make them possess high activity for one-pot deacetalization-Knoevenagel and deacetalization-nitroaldol (Henry) reactions.

Synthesis of Beta/MCM-41 composite molecular sieve with high hydrothermal stability in static and stirred condition.

Beta/MCM-41 micro/mesoporous composite materials have been prepared through assembly of zeolite Beta nanoclusters and their hydrolysis products in the presence of CTAB under static or stirred conditions. The resulting materials were characterized by powder XRD, TEM and nitrogen adsorption-desorption. Hydrothermal stability of the obtained Beta/MCM-41 composites was evaluated by boiling in distilled water for different periods of time under refluxing. All materials exhibit very high hydrothermal stability.