Parag A. Deshpande

New Insights into Selective Heterogeneous Nucleation of Metal Nanoparticles on Oxides by Microwave-Assisted Reduction: Rapid Synthesis of High-Activity Supported Catalysts

Microwave-based methods are widely employed to synthesize metal nanoparticles on various substrates. However, the detailed mechanism of formation of such hybrids has not been addressed. In this paper, we describe the thermodynamic and kinetic aspects of reduction of metal salts by ethylene glycol under microwave heating conditions. On the basis of this analysis, we identify the temperatures above which the reduction of the metal salt is thermodynamically favorable and temperatures above which the rates of homogeneous nucleation of the metal and the heterogeneous nucleation of the metal on supports are favored. We delineate different conditions which favor the heterogeneous nucleation of the metal on the supports over homogeneous nucleation in the solvent medium based on the dielectric loss parameters of the solvent and the support and the metal/solvent and metal/support interfacial energies. Contrary to current understanding, we show that metal particles can be selectively formed on the substrate even under situations where the temperature of the substrate is lower than that of the surrounding medium. The catalytic activity of the Pt/CeO(2) and Pt/TiO(2) hybrids synthesized by this method for H(2) combustion reaction shows that complete conversion is achieved at temperatures as low as 100 °C with Pt-CeO(2) catalyst and at 50 °C with Pt-TiO(2) catalyst. Our method thus opens up possibilities for rational synthesis of high-activity supported catalysts using a fast microwave-based reduction method.

Rapid synthesis of ultrahigh adsorption capacity zirconia by a solution combustion technique.

Tetragonal ZrO(2) was synthesized by the solution combustion technique using glycine as the fuel. The compound was characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and BET surface area analysis. The ability of this compound to adsorb dyes was investigated, and the compound had a higher adsorption capacity than commercially activated carbon. Infrared spectroscopic observations were used to determine the various interactions and the groups responsible for the adsorption activity of the compound. The effects of the initial concentration of the dye, temperature, adsorbent concentration, and pH of the solution were studied. The kinetics of adsorption was described as a first-order process, and the relative magnitudes of internal and external mass transfer processes were determined. The equilibrium adsorption was also determined and modeled by a composite Langmuir-Freundlich isotherm.

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts

Application of ZrO2, MnO2, palladium, palladium-substituted-zirconium oxide (Zr0.98Pd0.02O2) and palladium-substituted-manganese oxide (Mn0.98Pd0.02O2) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m3) was achieved in MFC with Mn0.98Pd0.02O2 catalyst, which was higher than that with MnO2 (0.58W/m3) alone; whereas, MFC having Zr0.98Pd0.02O2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m3, respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO2 with 20A/m3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO2 or ZrO2. Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications.

Highly Active Tungsten Oxide Nanoplate Electrocatalysts for the Hydrogen Evolution Reaction in Acidic and Near Neutral Electrolytes

An efficient, cost-effective, and earth-abundant catalyst that could drive the production of hydrogen from water without or with little external energy is the ultimate goal toward hydrogen economy. Herein, nanoplates of tungsten oxide and its hydrates (WO3·H2O) as promising electrocatalysts for the hydrogen evolution reaction (HER) are reported. The square-shaped and stacked WO3·H2O nanoplates are synthesized at room temperature under air in ethanol only, making it as a promising green synthesis strategy. The repeated electrochemical cyclic voltammetry cycles modified the surface of WO3·H2O nanoplates to WO3 as confirmed by X-ray photoelectron and Auger spectroscopy, which leads to an improved HER activity. Hydrogen evolution is further achieved from distilled water (pH 5.67) producing 1 mA cm–2 at an overpotential of 15 mV versus the reversible hydrogen electrode. Moreover, WO3·H2O and WO3 nanoplates demonstrate excellent durability in acidic and neutral media, which is highly desirable for practical application. Improved hydrogen evolution by WO3(200) when compared to that by Pt(111) is further substantiated by the density functional theory calculations.

On origin and evolution of carbonic anhydrase isozymes

Genetic evolution of carbonic anhydrase enzyme provides an interesting instance of functional similarity in spite of structural diversity of the members of a given family of enzymes. Phylogenetic analysis of α-, β- and γ-carbonic anhydrase was carried out to determine the evolutionary relationships among various members of the family with the enzyme marking its presence in a wide range of cellular and chromosomal locations. The presence of more than one class of enzymes in a particular organism was revealed by phylogenetic time tree. The evolutionary relationships among the members of animal, plant and microbial kingdom were developed. The study revises a long-established notion of kingdom-specificity of the different classes of carbonic anhydrases and provides a new version of the presence of multiple classes of carbonic anhydrases in a single organism and the presence of a given class of carbonic anhydrase across different kingdoms.

Computational Design of New Heterofullerene-Based Biomimetic α-Carbonic Anhydrase Analogues.

The biomimetic CO2 hydration activity of Ru/Rh-doped fullerenes was revealed by using density functional theory calculations. The mechanism of CO2 hydration on the proposed heterofullerenes followed the mechanistic action of α-carbonic anhydrases, and consisted of the adsorption and deprotonation of H2 O, CO2 interaction with hydroxyl groups, CO2 bending, and proton transfer to give the HCO-3 product. Free-energy landscapes for the reaction showed the catalysts to be active for the reaction. H2 O adsorption over the catalysts was exergonic whereas CO2 adsorption over the catalyst-OH complex was observed to be an endergonic process. Intramolecular proton transfer resulting in the final product, HCO-3 , was found to be the rate-limiting step for the reaction on C56 N3 M (M=Ru/Rh), whereas H2 O dissociation was found to be the rate-limiting step for the reaction on C59 M (M=Ru/Rh). C56 N3 M catalysts were found to be superior to C59 M catalysts for biomimetic CO2 hydration, as indicated by the free-energy landscapes and energy requirements.

QM/MM analysis of effect of divalent metal ions on OPRT action

The role of Mg2+ cofactor in orotate phosphoribosyltransferase (OPRT) catalyzed synthesis of orotidine monophosphate (OMP) from phosphoribosyl pyrophosphate (PRPP) and orotate (OA) in substrate binding and the influence of the identity of the divalent metal ion on the reaction mechanism were addressed in this study using quantum mechanics/molecular mechanics framework. Energetics of migration and binding of different substrate complexes in the active site cavity was established. A quantitative analysis of various processes indicated the reaction pathway to consist of complexation of Mg2+ with PRPP, migration of Mg2+-PRPP and OA towards the active site, binding of OA to OPRT, and binding of Mg2+-PRPP complex to OA-OPRT complex. The mechanism of the reaction was unaltered by the change in the identity of divalent metal ion. Experimentally reported inhibiting character of Co2+ was explained on the basis of large Co2+-PRPP binding and migration energies. Mg2+, Ca2+, Mn2+, Co2+ and Zn2+ ions were screened computationally to assess their inhibiting/activating characteristics. Trends obtained by our computational investigations were in correspondence with experimentally reported trends.