Analysis of oxide and vanadate supports for catalytic hydrogen combustion: Kinetic and mechanistic investigations

Combustion synthesized oxide and vanadate compounds (CeO2, Fe2O3, CeVO4, and FeVO4) were tested for catalytic hydrogen combustion. The compounds were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. All the four compounds showed good activity and stability for catalytic hydrogen combustion and more than 95% conversion was observed over all the compounds within 500 degrees C. The mechanisms for the reaction over the different classes of compounds (cerium-based and iron-based compounds) were proposed on the basis of spectroscopic observations. The main difference in the mechanisms was in the nature of adsorption of H2 over the sites. The elementary processes for the reaction were proposed, corresponding rate expressions were derived, and the rate parameters for the reaction were estimated using nonlinear regression. Langmuir-Hinshelwood and Eley-Rideal mechanisms were also tested for the reaction and the proposed mechanism was compared with these mechanisms. (c) 2011 American Institute of Chemical Engineers AIChE J, 2012

Exceptional activity of mesoporous beta-MnO2 in the catalytic thermal sensitization of ammonium perchlorate

Mesoporous beta-MnO2 has been prepared, characterized and demonstrated to possess excellent catalytic activity in the thermal decomposition of ammonium perchlorate. The observed unprecedentedly low decomposition temperatures, fast reaction rates and enhanced heat releases in the catalysed formulations make mesoporous beta-MnO2 promising as a high-performing ballistic modifier in AP-based composite solid rocket propellants.

Catalytic enantioselective construction of quaternary stereocenters by direct vinylogous Michael addition of deconjugated butenolides to nitroolefins

A direct vinylogous Michael reaction of gamma-substituted deconjugated butenolides with nitroolefins has been developed with the help of a newly identified quinine-derived bifunctional catalyst, allowing the synthesis of densely functionalized products with contiguous quaternary and tertiary stereocenters in excellent yield with perfect diastereoselectivity (>20 : 1 dr) and high enantioselectivity (up to 99 : 1 er).

Inter-domain interactions influence the stability and catalytic activity of the bi-domain protein tyrosine phosphatase PTP99A

The two protein tyrosine phosphatase (PTP) domains in bi-domain PTPs share high sequence and structural similarity. However, only one of the two PIP domains is catalytically active. Here we describe biochemical studies on the two tandem PTP domains of the bi-domain PTP, PTP99A. Phosphatase activity, monitored using small molecule as well as peptide substrates, revealed that the inactive (D2) domain activates the catalytic (D1) domain. Thermodynamic measurements suggest that the inactive D2 domain stabilizes the bi-domain (D1-D2) protein. The mechanism by which the D2 domain activates and stabilizes the bi-domain protein is governed by few interactions at the inter-domain interface. In particular, mutating Lys990 at the interface attenuates inter-domain communication. This residue is located at a structurally equivalent location to the so-called allosteric site of the canonical single domain PIP, PTP1B. These observations suggest functional optimization in bi-domain PTPs whereby the inactive PTP domain modulates the catalytic activity of the bi-domain enzyme. (C) 2012 Elsevier B.V. All rights reserved.

Catalytic Asymmetric Synthesis of alpha,beta-Disubstituted alpha,gamma-Diaminophosphonic Acid Precursors by Michael Addition of alpha-Substituted Nitrophosphonates to Nitroolefins

Michael additions of alpha-substituted nitrophosphonates to various nitroolefins are shown to proceed with high diastereo- and enantioselectivity when catalyzed by a quinine-derived thiourea-tertiary amine bifunctional catalyst and generate alpha,gamma-diaminophosphonic acid precursors with contiguous quaternary and tertiary stereocenters.

Self-Assembly and Catalytic Activity of Metal Nanoparticles Immobilized in Polymer Membrane Prepared via Layer-by-Layer Approach

Densely packed nanoparticles distributed in a stable and robust thin film is a highly preferred system for utilizing the various applications of nanoparticles. Here, we report covalent bond mediated layer-by-layer (LbL) self-assembled thin films of nanoparticles embedded in polymer membrane. Polymer with complementary functional group is utilized for fabrication of thin film via covalent bonding. UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to monitor the growth of LbL thin film. Subsequently, the composite thin film is used for catalysis of an organic electron transfer reaction of p-nitrophenol to p-aminophenol by sodium borohydride. The catalytic activity of these composite films is assayed multiple times, proving its applicability as a catalyst. The kinetic data obtained by monitoring reduction of p-nitrophenol suggest that the reaction rates are directly related to the sizes of the nanoparticle and porosity of the membrane.

Self-Assembled Pd6 Open Cage with Triimidazole Walls and the Use of Its Confined Nanospace for Catalytic Knoevenagel- and Diels-Alder Reactions in Aqueous Medium

The two-component self-assembly of a 90 degrees PdII acceptor and a triimidazole donor led to the formation of a water-soluble semi-cylindrical cage with a hydrophobic cavity, which was separately crystallized with hydrophilic- and hydrophobic guests. The parent cage was found to catalyze the Knoevenagel condensation reaction of a series of aromatic mono-aldehydes with active methylene compounds, such as Meldrum's acid or 1,3-dimethylbarbituric acid. The confined hydrophobic nanospace within this cage was also used in the catalytic DielsAlder reactions of 9-hydroxymethylanthracene with N-phenylmaleimide or N-cyclohexylmaleimide.

Catalytic Asymmetric Direct Vinylogous Michael Addition of Deconjugated Butenolides to Maleimides for the Construction of Quaternary Stereogenic Centers

Competition under control: A practical and efficient direct asymmetric vinylogous Michael reaction of deconjugated butenolides has been developed (see scheme). The products of this reaction, highly functionalized chiral succinimides, are obtained in excellent yield with high diastereoselectivity (up to d.r.=18:1) and outstanding enantioselectivity (up to e.r.=99.5:0.5).

Catalytic activity of Peptidase N is required for adaptation of Escherichia coli to nutritional downshift and high temperature stress

Peptidase N (PepN), the sole M1 family member in Escherichia coli, displays broad substrate specificity and modulates stress responses: it lowers resistance to sodium salicylate (NaSal)-induced stress but is required during nutritional downshift and high temperature (NDHT) stress. The expression of PepN does not significantly change during different growth phases in LB or NaSal-induced stress; however, PepN amounts are lower during NDHT stress. To gain mechanistic insights on the roles of catalytic activity of PepN in modulating these two stress responses, alanine mutants of PepN replacing E264 (GAMEN motif) and E298 (HEXXH motif) were generated. There are no major structural changes between purified wild type (WT) and mutant proteins, which are catalytically inactive. Importantly, growth profiles of Delta pepN upon expression of WT or mutant proteins demonstrated the importance of catalytic activity during NDHT but not NaSal-induced stress. Further fluorescamine reactivity studies demonstrated that the catalytic activity of PepN is required to generate higher intracellular amounts of free N-terminal amino acids; consequently, the lower growth of Delta pepN during NDHT stress increases with high amounts of casamino acids. Together, this study sheds insights on the expression and functional roles of the catalytic activity of PepN during adaptation to NDHT stress. (C) 2012 Elsevier GmbH. All rights reserved.

Influence of nature of support on the catalytic activity of supported molybdenum-oxo species in benzyl alcohol conversion

Supported catalysts containing 15 wt.% of molybdenum have been prepared by the incipient wetness impregnation method. CaO, MgO, Al2O3, Zr(OH)4 and Al(OH)3 have been used as supports for the preparation of supported Mo catalysts. Characterisation of all the materials prepared has been carried out through BET surface area measurement, X-ray diffractometry and FT-IR spectroscopy. Catalytic activity measurements have been carried out with reference to structure-sensitive benzyl alcohol conversion in the liquid phase. The percentage conversion of benzyl alcohol to benzaldehyde and toluene varied over a large range depending on the support used for the preparation of catalysts, indicating the importance of the support on catalytic activity of Mo catalysts. Al(OH)3 has been found to be the best support for molybdenum among all the supports used. Support–metal interaction (SMI) has been found to play an important role in determining the catalytic activity of supported catalysts.

Nanostructured Pd modified Ni/CeO2 catalyst for water gas shift and catalytic hydrogen combustion reaction

Nanostructured Pd-modified Ni/CeO2 catalyst was synthesized in a single step by solution combustion method and characterized by XRD, TEM, XPS, TPR and BET surface analyzer techniques. The catalytic performance of this compound was investigated by performing the water gas shift (WGS) and catalytic hydrogen combustion (CHC) reaction. The present compound is highly active and selective (100%) toward H-2 production for the WGS reaction. A lack of CO methanation activity is an important finding of present study and this is attributed to the ionic substitution of Pd and Ni species in CeO2. The creation of oxide vacancies due to ionic substitution of aliovalent ions induces dissociation of H2O that is responsible for the improved catalytic activity for WGS reaction. The combined H-2-TPR and XPS results show a synergism exists among Pd, Ni and ceria support. The redox reaction mechanism was used to correlate experimental data for the WGS reaction and a mechanism involving the interaction of adsorbed H-2 and O-2 through the hydroxyl species was proposed for CHC reaction. The parity plot shows a good correspondence between the experimental and predicted reaction rates. (c) 2012 Elsevier B.V. All rights reserved.

Self catalytic growth of SnO2 branched nanowires by thermal evaporation

For the first time, Tin oxide (SnO2) multiple branched nanowires (NWs) have been synthesized by thermal evaporation of tin (Sn) in presence of oxygen without use of metal catalysts at low substrate temperature of 500 degrees C. Synthesized product consists of multiple branched nanowires and were single crystalline in nature. Each of the nanowire capped with catalyst particle at their ends. Energy dispersive X-ray analysis on the nanowires and capped nanoparticle confirms that Sn act as catalyst for SnO2 nanowires growth. A self catalytic vapor-liquid-solid (VLS) growth mechanism was proposed to describe the SnO2 nanowires growth. (C) 2012 Elsevier B.V. All rights reserved.

Multicomponent self-sorting of a Pd-7 molecular boat and its use in catalytic Knoevenagel condensation

Unique three-component self-assembly of a cis-blocked 90 degrees Pd(II) acceptor with amixture of tri- and tetra-imidazole donors led to the self-sorting of a Pd-7 molecular boat with an internal nanocavity, which catalyses the Knoevenagel condensation of a series of aromatic aldehydes with 1,3-dimethylbarbituric acid and Meldrum's acid in aqueous media.