Heterogeneous catalysts, especially metal oxides, play a curial role in promoting 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. In this respect, we describe a strategy by the multi-scale simulation to investigate SnO_x reduction process and build up a structure-performance relation of SnO_x for CO₂ electroreduction (CO₂ER). By employing high dimensional neural network (NN) potential accelerated molecular dynamics (MD) and global optimization (SSW), coupled with density functional theory (DFT) calculations, we propose a multi-unit equilibrium state simulation of the non-equilibrium SnO₂ reduction process. The results indicate that SnO₂ reduction is accompanied by surface reconstruction and charge density redistribution of active sites. A regulatory factor, the net charge of active site, is identified to predict the adsorption capability for key intermediates on active sites, resulting in successful tunable denaturation of the Sn-based catalyst for CO₂ reduction selectivity to formate. Finally, systematic electronic analyses reveal the origin of the interaction between the adsorbates and the active sites. The increased net charge would inject into the anti-bonding between active sites and adsorbates, thus regulating the interaction strength. These new insights could provide a practicable strategy for investigating structure-performance relationships on complex metal oxide surfaces and the intrinsic interaction between active sites and adsorbates by making a reasonable compromise between computational accuracy and efficiency, paving the way for the rational design of efficient metal oxide electrocatalysts.

The net charge of SnO<i><sub>x</sub></i> can be considered as an effective factor to regulate the adsorption strength of HCOO* and achieve superior CO<sub>2</sub>ER to formate performance.

The net charge of SnO_x can be considered as an effective factor to regulate the adsorption strength of HCOO* and achieve superior CO₂ER to formate performance.

Li Lulu

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