Enzyme‐Inspired Microenvironment Engineering of a Single‐Molecular Heterojunction for Promoting Concerted Electrochemical CO₂ Reduction

Abstract Challenges remain in the development of novel multifunctional electrocatalysts and their industrial operation on low‐electricity pair‐electrocatalysis platforms for the carbon cycle. Herein, an enzyme‐inspired single‐molecular heterojunction electrocatalyst ((NH_x)₁₆‐NiPc/CNTs) with specific atomic nickel centers and amino‐rich local microenvironments for industrial‐level electrochemical CO₂ reduction reaction (eCO₂RR) and further energy‐saving integrated CO₂ electrolysis is designed and developed. (NH_x)₁₆‐NiPc/CNTs exhibit unprecedented catalytic performance with industry‐compatible current densities, ≈100% Faradaic efficiency and remarkable stability for CO₂‐to‐CO conversion, outperforming most reported catalysts. In addition to the enhanced CO₂ capture by chemisorption, the sturdy deuterium kinetic isotope effect and proton inventory studies sufficiently reveal that such distinctive local microenvironments provide an effective proton ferry effect for improving local alkalinity and proton transfer and creating local interactions to stabilize the intermediate, ultimately enabling the high‐efficiency operation of eCO₂RR. Further, by using (NH_x)₁₆‐NiPc/CNTs as a bifunctional electrocatalyst in a flow cell, a low‐electricity overall CO₂ electrolysis system coupling cathodic eCO₂RR with anodic oxidation reaction is developed to achieve concurrent feed gas production and sulfur recovery, simultaneously decreasing the energy input. This work paves the new way in exploring molecular electrocatalysts and electrolysis systems with techno‐economic feasibility.