Li Feng, Zhou Ce, Feygin Eliana, Roy Pierre-Nicholas, Chen Leanne D, Klinkova Anna
Department of Chemistry and Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, ON N2L 3G1, Canada.
Electrochemical Technology Centre, Department of Chemistry, University of Guelph, Guelph, Ontario, N1G 2W1, Canada.
Phys Chem Chem Phys. 2022 Aug 17;24(32):19432-19442. doi: 10.1039/d2cp02075k.
Improving the activity and selectivity of heterogeneous metal electrocatalysts has been the primary focus of CO electroreduction studies, however, the stability of these materials crucial for practical application remains less understood. In our work, the impact of the reaction intermediates (RIs) on the energetics and mechanism of metal-atom migration is studied with a combination of density functional theory (DFT) and molecular dynamics (AIMD) on pure transition metals Cu, Ag, Au, Pd, as well as three CuPd ( = 1,2, and 3) alloys. Reaction intermediates (RIs) for the CO reduction reaction, H evolution, and O reduction were considered. The effect of adsorbed RIs was observed to facilitate metal atom migration generally by decreasing the kinetic barriers for migration. The atomic mobility trends in the commonly used CORR metal electrocatalysts in the course of electrolysis conditions were established. This study provides theoretical insight into understanding how the electrocatalyst may undergo promoted restructuring in the presence of RIs under realistic electrochemical conditions.
提高非均相金属电催化剂的活性和选择性一直是CO电还原研究的主要重点，然而，这些材料对于实际应用至关重要的稳定性仍未得到充分理解。在我们的工作中，结合密度泛函理论（DFT）和分子动力学（AIMD），研究了反应中间体（RIs）对纯过渡金属Cu、Ag、Au、Pd以及三种CuPd（= 1、2和3）合金中金属原子迁移的能量学和机理的影响。考虑了CO还原反应、析氢反应和氧还原反应的反应中间体（RIs）。观察到吸附的RIs的作用通常是通过降低迁移的动力学势垒来促进金属原子迁移。确定了常用的CORR金属电催化剂在电解条件下的原子迁移趋势。这项研究为理解在实际电化学条件下，电催化剂在RIs存在下如何经历促进的结构重组提供了理论见解。
