Promoting CO2Dynamic Activation via Micro‐Engineering Technology for Enhancing Electrochemical CO2Reduction

Abstract

AbstractOptimizing the coordination structure and microscopic reaction environment of isolated metal sites is promising for boosting catalytic activity for electrocatalytic CO2reduction reaction (CO2RR) but is still challenging to achieve. Herein, a newly electrostatic induced self‐assembly strategy for encapsulating isolated Ni‐C3N1moiety into hollow nano‐reactor as I‐Ni SA/NHCRs is developed, which achieves FECO of 94.91% at −0.80 V, the CO partial current density of ≈−15.35 mA cm−2, superior to that with outer Ni‐C2N2moiety (94.47%, ≈−12.06 mA cm−2), or without hollow structure (92.30%, ≈−5.39 mA cm−2), and high FECOof ≈98.41% at 100 mA cm−2in flow cell. COMSOL multiphysics finite‐element method and density functional theory (DFT) calculation illustrate that the excellent activity for I‐Ni SA/NHCRs should be attributed to the structure‐enhanced kinetics process caused by its hollow nano‐reactor structure and unique Ni‐C3N1moiety, which can enrich electron on Ni sites and positively shift d‐band center to the Fermi level to accelerate the adsorption and activation of CO2molecule and *COOH formation. Meanwhile, this strategy also successfully steers the design of encapsulating isolated iron and cobalt sites into nano‐reactor, while I‐Ni SA/NHCRs‐based zinc‐CO2battery assembled with a peak power density of 2.54 mW cm−−2is achieved.