Cheong Oskar, Bornhake Thomas, Zhu Xinwei, Eikerling Michael H
Institute of Energy and Climate Research (IEK-13), Forschungszentrum Jülich, Wilhelm-Johnen-Straße, 52425, Jülich, Germany.
Chair of Theory and Computation of Energy Materials, Faculty of Georesources and Materials Enginering, RWTH Aachen University, Intzestrasse 5, 52072, Aachen, Germany.
ChemSusChem. 2023 Nov 8;16(21):e202300885. doi: 10.1002/cssc.202300885. Epub 2023 Aug 24.
Herein, a comprehensive computational study of the impact of solvation on the reduction reaction of CO to formic acid (HCOOH) and carbon monoxide on Pb(100) and Ag(100) surfaces is presented. Results further the understanding of how solvation phenomena influence the adsorption energies of reaction intermediates. We applied an explicit solvation scheme harnessing a combined density functional theory (DFT)/microkinetic modeling approach for the CO reduction reaction. This approach reveals high selectivities for CO formation at Ag and HCOOH formation on Pb, resolving the prior disparity between ab initio calculations and experimental observations. Furthermore, the detailed analysis of adsorption energies of relevant reaction intermediates shows that the total number of hydrogen bonds formed by HCOO plays a primary role for the adsorption strength of intermediates and the electrocatalytic activity. Results emphasize the importance of explicit solvation for adsorption and electrochemical reaction phenomena on metal surfaces.
本文展示了一项关于溶剂化对一氧化碳在Pb(100)和Ag(100)表面还原生成甲酸(HCOOH)及一氧化碳的反应影响的全面计算研究。研究结果进一步加深了我们对溶剂化现象如何影响反应中间体吸附能的理解。我们应用了一种显式溶剂化方案，采用密度泛函理论(DFT)/微观动力学建模相结合的方法来研究一氧化碳还原反应。该方法揭示了在银表面生成一氧化碳以及在铅表面生成甲酸的高选择性，解决了之前从头算计算与实验观测之间的差异。此外，对相关反应中间体吸附能的详细分析表明，HCOO形成的氢键总数对中间体的吸附强度和电催化活性起着主要作用。研究结果强调了显式溶剂化对金属表面吸附和电化学反应现象的重要性。
