Exclusive Co‐N<sub>4</sub> Sites Confined in Two‐dimensional Metal‐Organic Layers Enabling Highly Selective CO<sub>2</sub> Electroreduction at Industrial‐Level Current
Wenjun Zhang, Shanshan Liu, Yue Yang, Haifeng Qi, Shibo Xi, Yanping Wei, Jie Ding, Zhu‐Jun Wang, Qunxiang Li, Bin Liu, Zupeng Chen
Abstract
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.