For electrochemical CO2 reduction to HCOOH, an ongoing challenge is to design energy efficient electrocatalysts that can deliver a high HCOOH current density (JHCOOH) at a low overpotential. Indium oxide is good HCOOH production catalyst but with low conductivity. In this work, we report a unique corn design of In2O3-x@C nanocatalyst, wherein In2O3-x nanocube as the fine grains dispersed uniformly on the carbon nanorod cob, resulting in the enhanced conductivity. Excellent performance is achieved with 84% Faradaic efficiency (FE) and 11 mA cm-2 JHCOOH at a low potential of - 0.4 V versus RHE. At the current density of 100 mA cm-2, the applied potential remained stable for more than 120 h with the FE above 90%. Density functional theory calculations reveal that the abundant oxygen vacancy in In2O3-x has exposed more In3+ sites with activated electroactivity, which facilitates the formation of HCOO* intermediate. Operando X-ray absorption spectroscopy also confirms In3+ as the active site and the key intermediate of HCOO* during the process of CO2 reduction to HCOOH.
Keywords: Active sites; CO2 reduction; Corn design; Formate; Indium oxide.
© 2022. The Author(s).