Hydrogen energy has received significant attention in the renewable energy sector due to its high energy density and environmentally friendly nature. For the efficient hydrogen generation from water, the hydrogen evolution reaction (HER) has to be optimized, which requires a highly efficient electrocatalyst. In this work, a hybrid structure of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (Cmim TfO) and (TiO) nanoclusters with = 2-12 has been investigated in the pursuit of new catalyst materials for effective HER. We have employed state-of-the-art density functional theory (DFT) computations to depict the HER catalytic performance of IL/(TiO) hybrid systems through Gibbs free energy (Δ) and an exchange-current-based "volcano" plot. We have explored the effect of the TiO nanoclusters on the structural and electronic characteristics of the IL, calculating the adsorption energy, the energies of the highest occupied (HOMO) and lowest unoccupied molecular orbitals (LUMO), the HOMO-LUMO band gap , and the work function ϕ. The variation in size of the TiO nanocluster in the IL/(TiO) hybrid system was found to have a significant influence on the electronic properties. The obtained results suggest that the Δ of the hydrogen adsorption is remarkably close to the ideal value (0 eV) for the IL/(TiO) system, which also reflects from the volcano plot, suggesting that this complex is the best HER catalyst among the studied systems; it might be even better than the traditional Pt-based catalyst. Thus, the present work suggests ways for the experimental realization of low-cost and multifunctional IL-based hybrid catalysts for clean and renewable hydrogen energy production.
Grupo de Materiales y Sistemas Catalíticos, IFISUR, Universidad Nacional del Sur, CONICET, Departamento de Física - UNS, Av. L. N. Alem 1253, B8000CPB, Bahía Blanca, Argentina. Electronic address:
This article delves into the impact of nanoparticle shape on CO chemisorption and the reactivity of Pt nanocatalysts supported on reduced TiO(110). Distinct reactivity in carbon monoxide adsorption is observed among nanoparticles, all composed of 13 platinum atoms but varying in shape. The calculated formation and CO adsorption energies are correlated to the electronic properties of the system and the oxidation states of the Pt atoms involved.
UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA), Pretoria, South Africa.
The titanium dioxide (TiO) nanoparticles were prepared by hydrothermal methods at ambient temperature. Based on XRD analysis, the average crystallite size of pure TiO nanoparticles and those doped with ZnS was calculated to be 58 and 54 nm, respectively. At an angle of 25.
Strong interaction between the support surface and metal clusters activates the adsorbed molecules at the metal cluster-support interface. Using plane-wave DFT calculations, we precisely model the interface between anatase TiO and small Au nanoclusters. Our study focusses on the adsorption and activation of oxygen molecules on anatase TiO, considering the influence of oxygen vacancies and steps on the surface.
National Laboratory of Solid State Microstructures and Collaborative Innovation Center of Advanced Microstructures, Jiangsu Key Laboratory for Nano Technology, College of Engineering and Applied Science, Nanjing University, Nanjing 210093, People's Republic of China.
The conversion of woody biomass to H through photocatalysis provides a sustainable strategy to generate renewable hydrogen fuel but was limited by the slow decomposition rate of woody biomass. Here, we fabricate ultrasmall TiO nanoparticles with tunable concentration of oxygen vacancy defects (V-TiO) as highly efficient photocatalysts for photocatalytic conversion of woody biomass to H. Owing to the positive role of oxygen vacancy in reducing energy barrier for the generation of OH which was the critical species to oxidize woody biomass, the obtained V-TiO achieves rapid photocatalytic conversion of α-cellulose and poplar wood chip to H in the presence of Pt nanoclusters as the cocatalyst.
