Enriching Metal–Oxygen Species and Phosphate Modulating of Active Sites for Robust Electrocatalytical CO2 Reduction

Direct electrochemical reduction of CO2 (CO2 RR) into value-added chemicals is a promising solution to reduce carbon emissions. The activity of CO2 RR is influenced deeply by the reaction microenvironment and electronic properties of the catalysts. Herein, the surface PO4 3- anions are tuned to modulate the local microenvironment and the electronic properties of the indium-based catalyst with abundant metal-oxygen species enabling efficient electrochemical conversion of CO2 to HCOO- . Indium nanoparticles coupled with PO4 3- anions (PO4 3- -In NPs) achieve a high selectivity of HCOO- up to 91.4% at a low potential of -0.98 V versus reversible hydrogen electrode (versus RHE) and a high HCOO- partial current density of 279.3 mA cm-2 at -1.1 V versus RHE in the electrochemical flow cell. In situ and ex situ characterizations confirm the PO4 3- anions keep stable on the surface of indium during CO2 RR, accelerating the generation of OCHO* intermediate. From density functional theory calculations, PO4 3- anions enrich the metal-oxygen species on the substrate to optimize the electronic structure of the catalysts and induce a local microenvironment with massive K+ ions on the interface, thus reducing the activation energy barrier of CO2 RR.