Catalysis Theory Center, Department of Physics, Technical University of Denmark, 2800 Kogens Lyngby, Denmark.
Department of Chemical Engineering, University College London, Roberts Building, Torrington Place, London WC1E 7JE, UK.
Phys Chem Chem Phys. 2021 Dec 15;23(48):27150-27158. doi: 10.1039/d1cp04134g.
Hydrogen oxidation and evolution are important processes from both a fundamental and applied perspective. In interpreting experimental kinetic data, few studies have explicitly accounted for the impact of H* coverage and mass transport, which lead to discrepancies in the kinetic parameters and the resultant reaction mechanism. Here, we present how to determine the kinetic parameters accounting for both effects. We discuss the use of the kinetic parameters towards mechanistic interpretations for HOR/HER and show that, in general, knowledge of the coverage of H* or activation energies may be required to assign a reaction mechanism. We apply these ideas to activity data of several HOR and HER electrocatalysts, such as Au, Pt, MoS, and CoP.
氢的氧化和析氢反应从基础和应用角度来看都是重要的过程。在解释实验动力学数据时，很少有研究明确考虑到 H覆盖度和质量传输的影响，这导致动力学参数和反应机制存在差异。在这里，我们介绍如何确定同时考虑这两个因素的动力学参数。我们讨论了如何使用动力学参数来对 HOR/HER 的反应机制进行解释，并指出，通常情况下，需要知道 H的覆盖度或活化能才能确定反应机制。我们将这些想法应用于几个 HOR 和 HER 电催化剂（如 Au、Pt、MoS 和 CoP）的活性数据中。
