Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis

Abstract Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist proton transfer in channels, few studies are dedicated to improving proton transfer at the local environments of active sites in porous materials. Herein, we report on new Co‐corrole‐based porous organic polymers (POPs) with improved proton transfer for electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). By tuning the pore sizes and installing proton relays at Co corrole sites, we designed and synthesized POP‐2‐OH with improved proton transfer both in channels and at local Co active sites. This POP shows remarkable activity for both electrocatalytic ORR with E 1/2 =0.91 V vs RHE and OER with η 10 =255 mV. Therefore, this work is significant to present a strategy to improve active site local proton transfer in porous materials and highlight the key role of such structural functionalization in boosting oxygen electrocatalysis.