Interfacial Electronic Interaction in Amorphous–Crystalline CeOx‐Sn Heterostructures for Optimizing CO2 to Formate Conversion

Abstract

AbstractFormate, a crucial chemical raw material, holds significant promise for industrial applications in the context of CO2 electroreduction reaction (CO2RR). Despite its potential, challenges, such as poor selectivity and low formation rate at high current densities persist, primarily due to the competing hydrogen evolution reaction (HER) and high energy barriers associated with *OCHO intermediate generation. Herein, one‐step chemical co‐reduction strategy is employed to construct an amorphous–crystalline CeOx‐Sn heterostructure, demonstrating remarkable catalytic performance in converting CO2 to formate. The optimized CeOx‐Sn heterostructures reach a current density of 265.1 mA cm−2 and a formate Faraday efficiency of 95% at −1.07 V versus RHE. Especially, CeOx‐Sn achieves a formate current density of 444.4 mA cm−2 and a formate production rate of 9211.8 µmol h−1 cm−2 at −1.67 V versus RHE, surpassing most previously reported materials. Experimental results, coupled with （density functional theory）DFT calculations confirm that robust interface interaction between CeOx and Sn active center induces electron transfer from crystalline Sn site to amorphous CeOx, some Ce4+of CeOx get electrons and convert to unsaturated Ce3+, optimizing the electronic structure of active Sn. This amorphous–crystalline heterostructure promotes electron transfer during CO2RR, reducing the energy barrier formed by *OCHO intermediates, and thus achieving efficient reduction of CO2 to formate.