Porphyrin Conjugated Polymer with Periodic Type II‐Like Heterojunctions and Single‐Atom Catalytic Sites for Broadband‐Responsive Hydrogen Evolution

Abstract A novel heterometallic Zn‐/Co‐porphyrin conjugated polymer (ZnCoP‐F CP) with its Co‐porphyrin bridging unit bearing two perfluorophenyls is synthesized via a Sonogashira coupling reaction. The resulting ZnCoP‐F CP without the Pt cocatalyst exhibits broadband (UV–vis–NIR) light‐driven hydrogen evolution activity of 83 µmol h −1 , which is more than twice that (39 µmol h −1 ) of its counterpart (ZnCoP CP) with the Co‐porphyrin unit bearing two phenyls. Furthermore, an apparent quantum yield of 6.92%, 5.50%, 5.78%, 3.17%, and 0.73% is achieved from the ZnCoP‐F CP illuminated at 400, 500, 550, 700, and 850 nm monochromatic light, respectively. The enhanced performance of ZnCoP‐F CP can be attributed to the high electron‐withdrawing capacity of its perfluorophenyls and the highly dispersed Co centers in Co‐porphyrin bridging units serving as single‐atom catalytic sites (CoN 4 ), which facilitate the formation of periodic type II‐like heterojunctions and the fast charge transfer from Zn‐porphyrin to Co‐porphyrin units for hydrogen evolution reaction. The broadband‐responsive feature is due to the large π‐conjugated system through the whole 2D internal framework of the porphyrin polymer. This work opens a new path to fabricate porphyrin‐based polymer with an efficient and broadband‐responsive hydrogen evolution system.