Electron‐deficient ZnO induced by heterointerface engineering as the dominant active component to boost CO2‐to‐formate conversion.

Electrocatalytic CO2‐to‐formate conversion is considered an economically viable process. In general, Zn‐based nanomaterials are well‐known to be highly efficient electrocatalysts for the conversion of CO2 to CO, but seldom do they exhibit excellent selectivity toward formate. In this article, we demonstrate that a heterointerface catalyst ZnO/ZnSnO3 with nanosheet morphology shows enhanced selectivity with a maximum Faradaic efficiency (FE) of 86% at −0.9 V versus reversible hydrogen electrode and larger current density for the conversion of CO2 to formate than pristine ZnO and ZnSnO3. In particular, the FEs of the C1 products (CO + HCOO−) exceed 98% over the potential window. The experimental measurements combined with theoretical calculations revealed that the ZnO in ZnO/ZnSnO3 heterojunction delivers the valence electron depletion and accordingly optimizes Zn d‐band center, which results in moderate Zn–O hybridization of HCOO* and weakened Zn–C hybridization of competing COOH*, thus greatly boosting the HCOOH generation. Our study highlights the importance of charge redistribution in catalysts on the selectivity of electrochemical CO2 reduction. [ABSTRACT FROM AUTHOR]