Selective Electroreduction of CO2 to CO over Ultrawide Potential Window via Implanting Active Site with Long‐Range P Regulation on Periodic Pores

Electroreduction of CO2 to CO represents a highly promising way for artificial carbon cycling, but obtaining high selectivity over a wide potential window remains a challenge due to the sluggish CO generation and diffusion kinetics. Here we report an integration of long‐range P modified asymmetrical bismuth atomic site on an ordered macroporous carbon skeleton with mesoporous “wall” (MW‐BiN3‐POMC) for efficient electroreduction of CO2. In‐depth in‐situ investigations with theoretical computations reveal that the incorporation of long‐range P atom is able to strengthen the orbital interaction between the C 2p of CO2 and Bi 6p, thereby establishing an electronic transport bridge for the activation of CO2 molecule. Additionally, the ordered macropore with mesoporous wall effectively facilitates the diffusion of CO. As a result, MW‐BiN3‐POMC exhibits an ultrawide potential window of 1000 mV for high CO selectivity (>90%) and a maximal CO partial current density of 414 mA cm‐2. Moreover, MW‐BiN3‐POMC can also be employed as the cathode to integrate the solar‐driven electrolytic cell (anode of Co3O4‐OMC) toward CO2 reduction coupled with 5‐hydroxymethylfurfural oxidation to simultaneously yield CO and 2,5‐furandicarboxylic acid.