Ni-Decorated N-Doped Biomass-Derived Porous Carbon toward Efficient Electroreduction of CO₂ to CO

Electrochemical CO2 reduction reaction (CO2RR) holds great prospects for transforming CO2 into useful chemicals. However, there is still a long way to go to develop effective and affordable electrochemical CO2RR catalysts. In this work, a nickel-decorated nitrogen-doped biomass-derived porous carbon (Ni@N-BPC) catalyst was developed. The catalyst displayed a high specific surface area and superior CO2RR capability. The Faraday efficiency of CO exceeds ninety percent, ranging from a broad potential of 400 mV (−0.7 to −1.1 V vs RHE), reaching approximately 98.41% at −0.9 V vs RHE. The reaction pathway of CO2 conversion to CO on Ni@N-BPC was analyzed by the in situ Fourier transform infrared spectroscopy method. Based on theoretical calculations, the rate-determining step shifts from the *COOH creation to the *CO desorption step by Ni anchoring. Meanwhile, N doping modulates the electronic structure and facilitates charge transport, lowering the overpotential of the rate-determining step, thus facilitating the formation of CO. This work offers fresh perspectives on the development and utilization of biomass-derived carbon materials as CO2RR electrocatalysts.