Customizing pyridinic nitrogen coordination in Ni-N-C for electrocatalytic CO2 reduction towards CO

Abstract Nickel anchored N-doped carbon electrocatalysts (Ni–N–C) are rapidly developed for the electrochemical reduction reaction of carbon dioxide (CO 2 RR). However, the high-performanced Ni–N–C analogues design for CO 2 RR remains bewilderment, for the reason lacking of definite guidance for its structure-activity relationship. Herein, the correlation between the proportion of nitrogen species derived from various nitrogen sources and the CO 2 RR activity of Ni–N–C is investigated. The x-ray photoelectron spectroscopy (XPS) spectrum combined with the CO 2 RR performance results show that pyridinic-N content has a positive correlation with CO 2 RR activity. Moreover, density functional theory (DFT) demonstrates that pyridinic-N coordinated Ni–N 4 sites offers optimized free energy and favorable selectivity towards CO 2 RR compared with pyrrolic-N. Accordingly, Ni–N a –C with highest pyridinic-N content (ammonia as nitrogen source) performs superior CO 2 RR activity, with the maximum carbon monoxide faradaic efficiency (FE CO ) of 99.8% at −0.88 V vs. RHE and the FE CO surpassing 95% within potential ranging of −0.88 to −1.38 V vs. RHE. The building of this parameter for CO 2 RR activity of Ni–N–C give instructive forecast for low-cost and highly active CO 2 RR electrocatalysts.