First-principles based microkinetic modeling of borohydride oxidation on a Au(1 1 1) electrode |
| |
Authors: | Gholamreza RostamikiaAlfonso J. Mendoza Michael A. HicknerMichael J. Janik |
| |
Affiliation: | a Department of Chemical Engineering, Pennsylvania State University, University Park, PA 16802, United States b Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802, United States |
| |
Abstract: | Borohydride oxidation electrokinetics over the Au(1 1 1) surface are simulated using first-principles determined elementary rate constants and a microkinetic model. A method to approximate the potential dependent elementary step activation barriers based on density functional theory calculations is developed and applied to the minimum energy path for borohydride oxidation. Activation barriers of the equivalent non-electrochemical reactions are calculated and made potential dependent using the Butler-Volmer equation. The kinetic controlled region of the borohydride oxidation reaction linear sweep voltammogram over the Au(1 1 1) surface is simulated. The simulation results suggest that B-H bond containing species are stable surface intermediates at potentials where an oxidation current is observed. The predicted rate is most sensitive to the symmetry factor and the BH2OH dissociation barrier. Surface-enhanced Raman spectroscopy confirms the presence of BH3 as a stable intermediate. |
| |
Keywords: | Borohydride oxidation DBFC DFT Electrocatalysis Raman |
本文献已被 ScienceDirect 等数据库收录! |