Lakshitha Pahalagedara

Understanding the Role of Gold Nanoparticles in Enhancing the Catalytic Activity of Manganese Oxides in Water Oxidation Reactions

The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5%) in α-MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2.

Heterogeneous acidic TiO2 nanoparticles for efficient conversion of biomass derived carbohydrates

Selective conversion of biomass derived carbohydrates into fine chemicals is of great significance for the replacement of petroleum feedstocks and the reduction of environmental impacts. Levulinic acid, 5-hydroxymethyl furfural (HMF) and their derivatives are recognized as important precursor candidates in a variety of different areas. In this study, the synthesis, characterization, and catalytic activity of acidic TiO2 nanoparticles in the conversion of biomass derived carbohydrates were explored. This catalyst was found to be highly effective for selective conversion to value-added products. The nanoparticles exhibited superior activity and selectivity towards methyl levulinate from fructose in comparison to current commercial catalysts. The conversion of fructose to methyl levulinate was achieved with 80% yield and high selectivity (up to 80%). Additionally, conversions of disaccharides and polysaccharides were studied. Further, the production of versatile valuable products such as levulinic esters, HMF, and HMF-derived ethers was demonstrated using the TiO2 nano-sized catalysts in different solvent systems.

Ordered mesoporous mixed metal oxides: remarkable effect of pore size on catalytic activity.

We report the synthesis of ordered mesoporous NiAl mixed metal oxides (MMOs) from NiAl-layered double hydroxides (LDHs) through a soft template method using pluronic-F127 as the structure-directing agent. Ordered mesopores were obtained by the thermal decomposition of as-synthesized LDHs at different temperatures. The effects of the pluronic-F127 amount and the calcination temperature on the pore size distribution of the MMO were investigated. NiAl MMOs exhibited excellent catalytic activity in the Knoevenagel condensation of benzaldehyde with acidic methylene group-containing malononitrile. Finally, the dependence of the catalytic activity on the surface properties of NiAl MMOs was investigated. The pore diameter and the pore volume of NiAl MMOs were well correlated with the performance of the catalysts. MMO obtained from the calcination of NiAl-F127(3%)LDH at 750 °C for 5 h gave the highest conversion (>99%) in the Knoevenagel condensation in 30 min. The optimum pore diameter for the model reaction described here was 7.7 nm, which gave rise to more than 99% conversion with 100% selectivity. Ethanol gave the best conversion at 60 °C. The regenerated catalyst showed 93.0 and 89.0% of the initial catalytic activity after the first and the second regeneration cycles, respectively.