Oxygen‐Substituted Porous C2N Frameworks as Efficient Electrocatalysts for Carbon Dioxide Electroreduction

The electrochemical carbon dioxide reduction reaction (CO2RR) provides a green avenue for decarbonizing the conventional chemical industries. Here, a structure-selectivity relationship of catalysts is pivotal for the control of a highly selective and active CO2RR pathway. We report the fabrication of an oxygen-substituted C2N as metal-free catalyst (O-C2N) for electrochemical CO2-to-CO conversion with tunable O microenvironment. Combined spectroscopic analysis reveals a fine tailored N-C-O moiety in O-C2N, where C-O-C species (e.g. ring in-plane ether) become the dominant oxygen configurations at higher pyrolysis temperatures. Based on experimental observations, a correlation between the exocyclic O-substituted N-C-O-C moieties and CO selectivity is established, giving clear chemical tools for active structure design. The optimized O-C2N electrocatalysts with the dominant appearance of C-O-C moieties exhibits an outstanding 2e- CO2RR performance with a CO selectivity up to 94.8%, which can be well maintained in a practical flow-cell reactor with an adjustable syngas feature.