Selective Electroreduction of CO ₂ to CO over Ultrawide Potential Window via Implanting Active Site with Long‐Range P Regulation on Periodic Pores

Abstract Electroreduction of CO 2 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 bismuth atomic site on an ordered macroporous carbon skeleton with mesoporous “wall” (MW‐BiN 3 ‐POMC) for efficient electroreduction of CO 2 . 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 CO 2 and Bi 6p, thereby establishing an electronic transport bridge for the activation of CO 2 molecule. Additionally, the ordered macropore with mesoporous wall effectively facilitates the diffusion of CO. As a result, MW‐BiN 3 ‐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‐BiN 3 ‐POMC can also be employed as the cathode to integrate the solar‐driven electrolytic cell (anode of Co 3 O 4 ‐OMC) toward CO 2 reduction coupled with 5‐hydroxymethylfurfural oxidation to simultaneously yield CO and 2,5‐furandicarboxylic acid.