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

Metal-organic framework catalysts bring new opportunities for CO2 electrocatalysis. Herein, we first conduct density-functional theory calculations and predict that Co-based porphyrin porous organic layers (Co-PPOLs) exhibit good activity for CO2 conversion because of the low *CO adsorption energy at Co-N4 sites, which facilitates *CO desorption and CO formation. Then, we prepare two-dimensional Co-PPOLs with exclusive Co-N4 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 CO2 adsorption capability, Co-PPOLs achieve a peak faradaic efficiency for CO production (FECO =94.2 %) at a moderate potential in CO2 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 (FECO >90 %) over 20 h in CO2 electrolysis.