Nanocrystallite Zeolite BEA for Regioselective and Continuous Acetyl Functionalization of Anisole Using Acetic Anhydride: Catalyst Deactivation Studies.

Ultrasonic pretreatment of gel composition followed by hydrothermal synthesis produces the nanocrystallite zeolite beta (ZB) with crystal sizes of 10.3, 22.6, and 9.1 nm for ZB-1, ZB-2, and ZB-3, respectively. The effect of ultrasonic pretreatment and the (SiO2/Al2O3) ratio of gel composition on physical, textural properties, and also on the catalytic activity of ZB catalysts with increasing time on stream (TOS) was investigated. The specific surface area and mesopore volume for ZB-1, ZB-2, and ZB-3 are 438, 380, and 429 m2/g and 0.17, 0.05, and 0.14 cm3/g, respectively. The activity studies of ZB-1 and ZB-3 catalysts were confirmed that the anisole conversion initially increased with TOS until it attained the maximum value and then started decreasing further with TOS due to the deactivation of the catalyst caused by the strong interaction of the product with the acidic sites in the mesopore region. However, in the case of ZB-2, the anisole conversion (>45%) was sustained for a longer TOS due to its smaller particle size, low mesopore volume, and more acidic sites in the micropore volume that are inclusively made for retardation in the catlytic deactivation rate. The CHNS and TGA analysis of the spent catalysts confirm that ZB-1 and ZB-3 catalysts are susceptible for a significant coke formation attributed due to strong product retention in their large mesopore volume, which lead to the catalytic deactivation.

Biomass derived efficient conversion of levulinic acid for sustainable production of γ-valerolactone over cobalt based catalyst.

Biomass feedstocks offer very promising sustainable production of fuels and chemicals as fossil fuels generate greenhouse gases and are going to become scarce. Nevertheless, establishing value addition to biomass waste to produce commodity chemicals by combining economic and environmental performances is complex. In this context, hydrogenation of biomass based levulinic acid at normal atmospheric reaction conditions using robust cobalt supported on porous heterogeneous catalyst has been studied at 200 °C in a continuous process. The systematic investigation of Lewis acidic sites and low reaction temperature contribute to achieve 99 % conversion of levulinic acid and 80 % selectivity of γ-valerolactone.

Ordered mesoporous ferrosilicate materials with highly dispersed iron oxide nanoparticles and investigation of their unique magnetic properties.

Ordered mesoporous ferrosilicate materials with highly dispersed iron oxide nanoparticles are directly synthesized through a hydrothermal approach under acidic conditions. The obtained samples possess a high surface area (up to 1236 m(2) g(-1)) and a large pore volume (up to 1.1 cm(3) g(-1)). By changing the amount of iron content, the magnetic properties can be tuned.

Polymeric micelle assembly for the direct synthesis of functionalized mesoporous silica with fully accessible Pt nanoparticles toward an improved CO oxidation reaction.

Pt-decorated mesoporous silica is directly prepared using a polymeric micelles assembly approach using an asymmetric triblock copolymer, poly(styrene-b-2-vinylpyridine-b-ethylene oxide) as the structure directing agent. Strongly immobilized, fully accessible, and uniformly dispersed Pt nanoparticles on mesoporous silica wall exhibit superior catalytic activity toward CO oxidation.

Direct carbonization of Al-based porous coordination polymer for synthesis of nanoporous carbon.

Nanoporous carbon (NPC) is prepared by direct carbonization of Al-based porous coordination polymers (Al-PCP). By applying the appropriate carbonization temperature, both high surface area and large pore volume are realized for the first time. Our NPC shows much higher porosity than other carbon materials (such as activated carbons and mesoporous carbons). This new type of carbon material exhibits superior sensing capabilities toward toxic aromatic substances.

Direct synthesis of nanoporous carbon nitride fibers using Al-based porous coordination polymers (Al-PCPs).

We report a new synthetic route for preparation of nanoporous carbon nitride fibers with graphitic carbon nitride polymers, by calcination of Al-based porous coordination polymers (Al-PCPs) with dicyandiamide (DCDA) under a nitrogen atmosphere.

Fabrication of mesoporous carbons with rod and winding road like morphology using NbSBA-15 templates.

Here we demonstrate for the first time the fabrication hexagonally ordered mesoporous carbon materials with different morphology and pore diameters using NbSBA-15 mesoporous silica template with different niobium content. The materials were characterized by several characterization techniques such as XRD, HRSEM, HRTEM, elemental mapping, ICP-AES, and EDS analysis. We also demonstrate that the morphology of the materials can be controlled by simply tuning the morphology of the parent NbSBA-15 template, whose morphology can be tuned by adjusting the loading of niobium in the framework wall structure of SBA-15. Nitrogen adsorption results reveal that the textural parameters of the mesoporous carbon materials prepared from NbSBA-15 are much better than those prepared with pristine SBA-15 template, and vary with the amount niobium present in the template. It was also found that the pore diameter of the NbMC-X increases with decreasing the amount of niobium in the framework wall structure of the template. The morphology and the topology of the materials were observed by HRSEM and HRTEM, respectively. The materials with rod and semi-spherical or winding road like morphology can be obtained using NbSBA-15 materials with different Nb content. It was found that the usage of NbSBA-15 as templates for the fabrication of mesoporous carbon materials can also allow us to decorate the pore channels of the materials with either niobium oxide or niobium silicate nanoparticles which are expected to show high performance when used in redox catalysis, and the biomolecule adsorption as the niobium has the strong tendency to adsorb the protein molecules.

A rapid method for the synthesis of nitrogen doped TiO2 nanoparticles for photocatalytic hydrogen generation.

A facile, fast, and economic method of doping TiO2, synthesized by conventional precipitation route with N has been developed. By this method, stable N doped TiO2 can be prepared within a short duration of time. The method adopted was to treat the TiO2 powder synthesized by simple precipitation with trioctyl amine (TOA) at 320 degrees C for 2 hours followed by calcination at 400 degrees C for 2 hours to obtain the N-doped TiO2. The sample along with NiO as co-catalyst showed significant photocatalytic activity for hydrogen generation from aqueous methanol solution under sunlight type irradiation. This synthesis method opens up a fast and easy route for doping the existing TiO2 or other wide band gap oxide semiconductors with nitrogen so that they can exhibit enhanced photocatalytic activity under solar irradiation.

Eu3+ and Dy3+ doped YPO4 nanoparticles: low temperature synthesis and luminescence studies.

Eu3+ and Dy3+ doped YPO4 nanoparticles dispersible in methanol/water were prepared by the reaction of Y3+ and Eu3+/Dy3+ ions with ammonium dihydrogen phosphate in ethylene glycol medium at 160 degrees C. Nature and extent of strain associated with lattice has been found to change with incorporation of Eu3+/Dy3+ ion in the nanoparticles as well as the heat treatment temperature. Based on the TEM studies, it has been established that particles are highly crystalline with an average particle size of around 5 nm. Co-doping YPO4:Eu nanoparticles with Dy3+ ions followed by annealing them at high temperature (900 degrees C) lead to reduction in both Eu3+ and Dy3+ luminescence intensities from the sample and this has been attributed to the clustering effect of the lanthanide ions.

Three-dimensional mesoporous gallosilicate with Pm3n symmetry and its unusual catalytic performances.

Three-dimensional, mesoporous-cage-type, GaSBA-1 materials with different n(Si)/n(Ga) ratios have been successfully prepared for the first time by using a low hydrochloric acid to silicon (n(HCl)/n(Si)) molar ratio in the synthesis gel by templating with cetyltriethylammonium bromide as the structure-directing agent in a highly acidic medium. The obtained materials have been unambiguously characterized in detail by several sophisticated techniques including X-ray diffraction (XRD), N(2) adsorption, high-resolution transmission electron microscopy, high-resolution scanning electron microscopy, energy dispersive spectroscopy, elemental mapping, and (29)Si magic-angle-spinning NMR spectroscopy. XRD and nitrogen adsorption results reveal that the structures of the GaSBA-1 materials resemble that of SBA-1, which possesses a cubic, three-dimensional, cage-type structure with open windows. In addition, the specific surface area and the specific pore volume of the GaSBA-1 materials are much higher than those of the SBA-1 silica, which are very important for the catalytic applications. The amount of Ga cation in the SBA-1 silica framework has been found to play a critical role in controlling the morphology and the pore diameter of the materials. Finally, the catalytic activity in the tert-butylation of phenol with tert-butanol as the alkylating agent has been investigated and the results are compared with those of other mesoporous catalysts such as AlMCM-41, FeMCM-41, FeAl-MCM-41, and FeSBA-1. Moreover, the effect of various reaction parameters such as the reaction temperature, reactant feed ratio, and time-on-stream on the phenol conversion in the tert-butylation of phenol over GaSBA-1 catalysts has been demonstrated. Among the catalysts examined, GaSBA-1(17), in which the number in the parenthesis denotes the n(Si)/n(Ga) ratio, showed remarkable activity with a high conversion of phenol and selectivity to 4-tert-butylphenol; it was found to be superior over other mesoporous catalysts used in the study.

Heteropoly acid encapsulated SBA-15/TiO2 nanocomposites and their unusual performance in acid-catalysed organic transformations.

The preparation of SBA-15/TiO(2) nanocomposites with different loadings of Keggin-type 12-tungstophosphoric acid (TPA) nanocrystals in their mesochannels through a simple and effective vacuum impregnation method is reported for the first time. The catalysts have been characterised by various sophisticated techniques, including XRD, HRSEM, and TEM. It has been found that the acidity and the textural parameters of the nanocomposites can be controlled by simply changing the loadings of TPA and TiO(2) or the calcination temperature. TPA and TiO(2) loadings of 15 and 22.4 wt %, respectively, and a calcination temperature of 1123 K have proved to be optimal for obtaining mesoporous nanocomposite materials with the highest acidity. Moreover, the activities of these catalysts in promoting hydroamination as well as Mannich and Claisen rearrangement reactions have been extensively investigated. The results show that the amount of TPA has a great influence on the activity of the nanocomposites in all of the reactions studied. The effects of other reaction parameters, such as temperature and reaction time, on the conversion and product selectivity have also been studied in detail. A kinetic analysis of the formation of the products under various reaction conditions is presented. It has been found that the activity of the nanocomposite composed of 15 wt % TPA deposited on 22.4 wt of TiO(2) on SBA-15 in promoting the studied reaction is remarkably higher than the catalytic activities shown by pure TPA, TiO(2)-loaded SBA-15, or TPA-loaded SBA-15. The results obtained have indicated that the acidity and the structural control of the nanocomposite materials are highly critical for obtaining excellent catalytic activity, and the presented highly acidic nanocomposites are considered to show great potential for use as catalysts in promoting many acid-catalysed organic transformations.

Carboxyl group functionalization of mesoporous carbon nanocage through reaction with ammonium persulfate.

Carbon nanocage, a three dimensional cage type mesoporous carbon with very high surface area and pore volume, has been functionalized with carboxyl groups for the first time via a simple oxidation using ammonium persulfate solution (APS). The carboxyl groups functionalized carbon nanocage materials have been unambiguously characterized by various sophisticated instruments such as FT-IR, HRSEM-EDX, XRD, nitrogen adsorption, and HRTEM. The degree of carboxyl group functionalization has been controlled by the simple adjustment of the oxidation parameters such as oxidation time, APS concentration and oxidation temperature. FT-IR spectroscopy combined with the HRSEM-EDX has been used to provide a quantitative analysis of the carboxyl groups on the surface of the carbon nanocage materials before and after the APS treatment. In addition, the effect of the oxidation parameters on the structural order and the textural parameters of the carbon nanocage materials has been studied. It has been found that the role of oxidation parameters is highly critical to obtain carbon nanocage materials with a high density of carboxyl groups without affecting the structural order and the pore parameters. Thus, the reaction parameters have been carefully optimized and the best condition for the preparation of carboxyl group functionalized carbon nanocage with well-ordered structure has been proposed.

Novel microporous carbon material with flower like structure templated by MCM-22.

Novel flower like microporous carbons with very high surface area have been synthesized for the first time using MCM-22 zeolite as a template and sucrose as a carbon source. The textural parameters of the materials can easily be tuned by the simple adjustment of the sucrose to MCM-22 weight ratio. It has been also found that the specific surface area of the microporous carbon materials is much higher as compared with that of its parent zeolite template.

Characterization and catalytic performances of three-dimensional mesoporous FeSBA-1 catalysts.

Iron substituted cubic cage type mesoporous molecular sieves (FeSBA-1) were synthesized for the first time in a highly acidic media using cetyltriethylammonium bromide as a template. The amount of Fe incorporation in SBA-1 can easily be controlled by the simple adjustment of the molar hydrochloric acid-to-silicon ratio. All the materials were unambiguously characterized by AAS, XRD, N2 adsorption, UV-Vis DRS, XPS, and ESR spectroscopy. The results from AAS, XRD, and N2 adsorption reveal that the iron atom can be incorporated in the framework of SBA-1 matrix without altering the structural order and the textural parameters. The nature and the coordination of iron atoms were extensively studied by XPS spectroscopy, and the results revealed that most of the iron atoms in FeSBA-1 are in +3 coordination state. UV-Vis DRS and ESR studies confirmed that the majority of the Fe atoms in FeSBA-1 exist in a tetrahedral coordination environment (most probably occupying framework positions). tert-Butylation of phenol employing tert-butanol as the alkylation agent was carried out over FeSBA-1 catalysts with different iron content and the results are compared with one-dimensional mesoporous catalysts. The influence of various reaction parameters such as reaction temperature, reactant feed ratio, weight hourly space velocity, and time-on-stream affecting the activity and selectivity of FeSBA-1 were also studied. Under the optimized reaction conditions, the FeSBA-1(36) catalyst showed superior catalytic performance for the tert-butylation of phenol as compared to the uni-dimensional mesoporous catalysts.