Modulation of the electronic structure of nitrogen-carbon sites by sp3-hybridized carbon coupled to chloride ions improves electrochemical carbon dioxide reduction performance.

The challenges remain to develop cost-effective carbon-based catalysts with high activity and selectivity. Here, we synergistically modulate carbon-based electrocatalysts through Cl doping with intrinsic defects in sp3-hybridized carbon and apply them to the electrochemical CO2 reduction reaction (CO2RR). The designed electrocatalyst achieved high selectivity over a wide potential range (-0.7 to -1.0 V), with a faraday efficiency of 96.3 % at -0.8 V for CO. In situ Fourier transform infrared spectroscopy, and analytical studies show pyrrole N to be the active site of CO2RR, and doping Cl increases the content of sp3-hybridized carbon in the carbon substrate, which synergistically accelerates the supply of hydrolysis dissociated protons and facilitates the protonation process of the intermediate products from *CO2 to *COOH. Density functional theory calculations show that Cl coupled sp3-hybridized carbon inhibits the adsorption of H* in the pyrrole N site and facilitates the desorption of *CO, thus promoting the whole process of CO2RR.