Abstract
Heterogeneous catalysts, especially metal oxides, play a curial role in improving energy conversion efficiency and production of valuable chemicals. However, the surface structure at the atomic level and the nature of active sites are still ambiguous due to the dynamism of surface structure and difficulty in structure characterization under electrochemical conditions. This paper describes a strategy of the multiscale simulation to investigate the SnO x reduction process and to build a structure-performance relation of SnO x for CO2 electroreduction. Employing high-dimensional neural network potential accelerated molecular dynamics and stochastic surface walking global optimization, coupled with density functional theory calculations, we propose that SnO2 reduction is accompanied by surface reconstruction and charge density redistribution of active sites. A regulatory factor, the net charge, is identified to predict the adsorption capability for key intermediates on active sites. Systematic electronic analyses reveal the origin of the interaction between the adsorbates and the active sites. These findings uncover the quantitative correlation between electronic structure properties and the catalytic performance of SnO x so that Sn sites with moderate charge could achieve the optimally catalytic performance of the CO2 electroreduction to formate.