Adavanced First-Principles Modeling of Electrocatalysis at Solid-Water Interface

Kinetic information, such as the activation energy and transition state, is critical to understanding the reaction. However, the kinetic information of electrochemistry at solid-water interface is challenging to obtain from conventional models of density functional theory (DFT), as they often neglect the presence and/or the dynamics of the surface charge [1] and the solvent configuration, which are further coupled. Here we present a new model that accounts for these effects, by combining hybrid solvation, constant-electron-potential, and slow-growth sampling techniques together. We then apply this model to elucidate the active site structure and the mechanism of electrochemical carbon dioxide reduction catalyzed by single-nickel-atom embedded in graphene, which shows high performance in experiments while is not well understood [2].
[1] D. Kim, J. Shi, Y. Liu, J. Am. Chem. Soc. 2018, DOI: 10.1021/jacs.8b03002
[2] X. Zhao, Y. Liu, J. Am. Chem. Soc. 2020, DOI: 10.1021/jacs.9b13872