Exclusive Co-N-4 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-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 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.

Automated summary

Metal-organic framework catalysts offer new opportunities for CO2 electrocatalysis. Through density-functional theory calculations, Co-based porphyrin porous organic layers (Co-PPOLs) are predicted to have good activity for CO2 conversion due to their low *CO adsorption energy at Co-N-4 sites. Experimental results show that the prepared 2D Co-PPOLs with exclusive Co-N-4 sites exhibit high faradaic efficiency for CO production and CO selectivity, along with good stability and industrial-level current output in CO2 electrolysis.