Rational Fabrication of Low‐Coordinate Single‐Atom Ni Electrocatalysts by MOFs for Highly Selective CO2 Reduction

Abstract Single‐atom catalysts (SACs) have attracted tremendous interests due to their ultrahigh activity and selectivity. However, the rational control over coordination microenvironment of SACs remains a grand challenge. Herein, a post‐synthetic metal substitution (PSMS) strategy has been developed to fabricate single‐atom Ni catalysts with different N coordination numbers (denoted Ni‐N x ‐C) on pre‐designed N‐doped carbon derived from metal‐organic frameworks. When served for CO 2 electroreduction, the obtained Ni‐N 3 ‐C catalyst achieves CO Faradaic efficiency (FE) up to 95.6 %, much superior to that of Ni‐N 4 ‐C. Theoretical calculations reveal that the lower Ni coordination number in Ni‐N 3 ‐C can significantly enhance COOH* formation, thereby accelerating CO 2 reduction. In addition, Ni‐N 3 ‐C shows excellent performance in Zn–CO 2 battery with ultrahigh CO FE and excellent stability. This work opens up a new and general avenue to coordination microenvironment modulation (MEM) of SACs for CO 2 utilization.