Exclusive Co‐N4 Sites Confined in Two‐dimensional Metal‐Organic Layers Enabling Highly Selective CO2 Electroreduction at Industrial‐Level Current

Abstract Metal‐organic framework catalysts bring new opportunities for CO 2 electrocatalysis. Herein, we first conduct density‐functional theory calculations and predict that Co‐based porphyrin porous organic layers (Co‐PPOLs) exhibit good activity for CO 2 conversion because of the low *CO adsorption energy at Co‐N 4 sites, which facilitates *CO desorption and CO formation. Then, we prepare two‐dimensional Co‐PPOLs with exclusive Co‐N 4 sites through a facile surfactant‐assisted bottom‐up method. The ultrathin feature ensures the exposure of catalytic centers. Together with large specific area, high electrical conductivity and CO 2 adsorption capability, Co‐PPOLs achieve a peak faradaic efficiency for CO production ( FE CO =94.2 %) at a moderate potential in CO 2 electroreduction, accompanied with good stability. Moreover, Co‐PPOLs reach an industrial‐level current above 200 mA in a membrane electrode assembly reactor, and maintain near‐unity CO selectivity ( FE CO >90 %) over 20 h in CO 2 electrolysis.