Partially Nitrided Ni Nanoclusters Achieve Energy‐Efficient Electrocatalytic CO₂ Reduction to CO at Ultralow Overpotential

Abstract

Electrocatalytic CO₂ reduction reaction (CO₂ RR) offers a promising strategy to lower CO₂ emission while producing value-added chemicals. A great challenge facing CO₂ RR is how to improve energy efficiency by reducing overpotentials. Herein, partially nitrided Ni nanoclusters (NiN_x ) immobilized on N-doped carbon nanotubes (NCNT) for CO₂ RR are reported, which achieves the lowest onset overpotential of 16 mV for CO₂ -to-CO and the highest cathode energy efficiency of 86.9% with CO Faraday efficiency >99.0% to date. Interestingly, NiN_x /NCNT affords a CO generation rate of 43.0 mol g^-1 h^-1 at a low potential of -0.572 V (vs RHE). DFT calculations reveal that the NiN_x nanoclusters favor *COOH formation with lower Gibbs free energy than isolated Ni single-atom, hence lowering CO₂ RR overpotential. As NiN_x /NCNT is applied to a membrane electrode assembly system coupled with oxygen evolution reaction, a cell voltage of only 2.13 V is required to reach 100 mA cm^-2 , with total energy efficiency of 62.2%.