Selective Electroreduction of CO ₂ 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 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.