Efficient Electron Transfer from Electron‐Sponge Polyoxometalate to Single‐Metal Site Metal–Organic Frameworks for Highly Selective Electroreduction of Carbon Dioxide

In this work, by combining the superiority of polyoxometalates (POMs) and catalytic single‐metal site Co of metalloporphyrin, a series of mixed‐valence POM‐based metal‐organic frameworks (MOFs) composites is synthesized by a post‐modification method. The electron‐transfer property of POM@PCN‐222(Co) composite is significantly enhanced owing to the directional electron‐transfer from POM to single‐metal site Co in PCN‐222(Co). In particular, H‐POM@PCN‐222(Co) gives a high Faradaic efficiency of 96.2% for electroreduction of CO2 into CO and good stability over 10 h. DFT calculations confirm that the directional electron transfer, which accelerates the multi‐electron transfer from the electrode to active single‐metal site Co, enriches the electron density of the Co center, and ultimately reduces the energy of the rate‐determining step, thus increasing the catalytic activity of CO2 reduction reaction (CO2RR). This work therefore suggests some new insight for the design of efficient electrocatalysts for CO2RR. By combining the superiority of polyoxometalates (POM) and single‐metal site Co in porphyrin, a series of POM‐based metal–organic frameworks composites have been synthesized. Directional electron transfer from POM to single‐metal site Co in PCN‐222(Co) accelerates the electron‐transfer efficiency, enriches the electron density of the active center, and ultimately gives rise to high electrocatalytic CO2 reduction reaction activity.