High performance of PtCu@TiO2 nanocatalysts toward methanol oxidation reaction: from synthesis to molecular picture insight.

The electrocatalytic production of hydrogen from methanol dehydrogenation successfully uses platinum catalysts. However, they are expensive and Pt has the tendency to be poisoned from the intermediate compounds, formed during the methanol oxidation reaction (MOR). For these two reasons, there has been active research for alternative bi- and tri-component Pt-based catalysts. Herein, PtCu nanoparticles deposited on titania were studied and proposed to be efficient MOR catalysts. The catalyst was prepared by photo-deposition of Cu on a high-surface-area TiO2 powder support, followed by a partial galvanic displacement of the Cu deposit by platinum. The morphology and structure of the catalyst were characterized by physicochemical methods. The PtCu@TiO2 electro-catalyst has higher intrinsic catalytic activity and comparable mass specific activity for MOR in comparison with a commercial Pt/C catalyst. The experimental analyses were complemented by density functional theory-based computations. The theoretical results revealed that the most energetically favorable Pt and Cu arrangement in the supported PtCu nanoparticles was core (Cu)-shell (Pt) and/or phase-separated. The inter-atomic interactions responsible for the bimetallic cluster stabilization on titania were highlighted from the computed electronic charge distribution.

First-principles study of Au-Cu alloy surface changes induced by gas adsorption of CO, NO, or O2.

The surface composition of bimetallics can be strongly altered by adsorbing molecules where the metal with the strongest interaction with the adsorbate segregates into the surface. To investigate the effect of reactive gas on the surface composition of Au-Cu alloy, we examined by means of density functional theory to study the segregation behavior of copper in gold matrices. The adsorption mechanisms of CO, NO, and O2 gas molecules on gold, copper, and gold-copper low index (111), (100), and (110) surfaces were analyzed from energetic and electronic points of view. Our results show a strong segregation of Cu toward the (110) surface in the presence of all adsorbed molecules. Interestingly, the Cu segregation toward the (111) and (100) surface could occur only in the presence of CO and at a lower extent in the presence of NO. The analysis of the electronic structure highlights the different binding characters of adsorbates inducing the Cu segregation.