Journal of Electroanalytical Chemistry, Vol.791, 185-195, 2017
Use of chemical descriptors approach and DFT to analyze the C-C bond cleavage on Pt3Re1 alloy in the ethanol oxidation reaction for fuel cells
Design of selective catalysts able to cleave C-C bond in ethanol oxidation reaction at low temperatures is primor-dial for improving the direct ethanol proton exchange membrane fuel cells (DEFCs). Pt-Re mixture could be an appropriate alloy for the C-C bond cleavage in ethanol decomposition, but yet, it has not been studied in detail the reactivity of this alloy for this step. In this work, the reactivity of Pt3Re1 surface for the C-C bond cleavage is studied and compared with pure metal surfaces Pt and Re, using chemical descriptors through density functional theory (DFT) calculations. The adsorption energies of CHCO, CO and CH molecules are the chemical descriptors investigated and the results are analyzed with respect to the electronic structure of the surface in order to understand the nature of the active sites. It is found that the addition of Re to Pt leads to form an active site with a Re atom, which is more reactive for the C-C bond cleavage in CHCO, but the sites without Re become less reactive for this step. Then the addition of Re to Pt has not a significant effect on the promotion of full oxidation of ethanol, since not all sites at the Pt3Re1 surface are more active towards C-C bond cleavage. (C) 2017 Elsevier B.V. All rights reserved.
Keywords:PtRe alloy;C-C bond cleavage;Ethanol oxidation reaction;Fuel cell;Density functional theory