Determination of Specific Electrocatalytic Sites in the Oxidation of Small Molecules on Crystalline Metal Surfaces

The identification of active sites in electrocatalytic reactions is part of the elucidation of mechanisms of catalyzed reactions on solid surfaces. However, this is not an easy task, even for apparently simple reactions, as we sometimes think the oxidation of adsorbed CO is. For surfaces consisting of non-equivalent sites, the recognition of specific active sites must consider the influence that facets, as is the steps/defect on the surface of the catalyst, cause in its neighbors; one has to consider the electrochemical environment under which the “active sites” lie on the surface, meaning that defects/steps on the surface do not partake in chemistry by themselves. In this paper, we outline the recent efforts in understanding the close relationships between site-specific and the overall rate and/or selectivity of electrocatalytic reactions. We analyze hydrogen adsorption/desorption, and electro-oxidation of CO, methanol, and ammonia. The classical topic of asymmetric electrocatalysis on kinked surfaces is also addressed for glucose electro-oxidation. The article takes into account selected existing data combined with our original works.M.J.S.F. is grateful to PNPD/CAPES (Brazil). J.M.F. thanks the MCINN (FEDER, Spain) project-CTQ-2016-76221-P

The Effects of a Low-Level Boron, Phosphorus, and Nitrogen Doping on the Oxygen Reduction Activity of Ordered Mesoporous Carbons

In order to elucidate the role of B, N, and P dopants in carbon materials on the kinetics of oxygen reduction reaction (ORR) and to provide a fair comparison of the effects of each dopant, a series of ordered mesoporous carbons (OMCs) with low concentration of heteroatoms ( lt 1 at%) has been prepared. Doped OMCs were characterized using X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), Raman spectroscopy, X-ray powder diffraction (XRD), and N-2 physisorption measurements. Comparative study of the ORR activity of these materials in alkaline solution was performed using rotating disk electrode voltammetry. The experiments evidenced that, compared to non-doped OMC, charge transfer kinetics was improved independently on the nature of the heteroatom. The decrease of the ORR overvoltage and the increase of the mass activity upon doping are similar for B and P and less prominent for N. On the other hand, OMCs doped with low levels of B and N were found to be selective for O-2 reduction to peroxide, while for P-doped OMCs, the apparent number of electrons consumed per O-2 molecule was up to 3.1. Experimental measurements were complemented by density functional theory (DFT) calculations