Ru‐Pincer Complex‐Bridged Cu‐Porphyrin Polymer for Robust (Photo)Electrocatalytic H₂ Evolution via Single‐Atom Active Sites

Abstract Organic polymers have attracted much attention in the field of energy conversion owing to their excellent tailoring ability via heterometal incorporation and/or functionalization. Herein, a novel pincer complex‐bridged porphyrin polymer is synthesized using Cu‐porphyrin (CuPor) and Ru‐N′NN′‐pincer complex (RuN₃) as monomers. The resultant CuPor‐RuN₃ polymer delivers robust electrocatalytic hydrogen evolution reaction (HER) performance with outstanding durability and ultralow overpotentials of 73 and 114 mV at a current density of 10 mA cm^‐2 in acidic and alkaline media, respectively. Moreover, the CuPor‐RuN₃ polymer displays great potential to fabricate photoelectrochemical (PEC) cells with a BiVO₄ photoanode, where the additional photoinduced electrons from CuPor‐RuN₃ endow the BiVO₄||CuPor‐RuN₃ PEC cell with much better activity for overall water splitting than the BiVO₄||Pt/C one, demonstrating that CuPor‐RuN₃ would be a promising (photo)electrocatalyst to replace the benchmark Pt/C. The experimental and theoretical studies reveal that the Cu/Ru heterobimetallic centers in the polymer not only enhance the inherent electron transfer from Cu sites to Ru ones that serve as single‐atom catalytic sites (Ru‐N₃), but also efficiently regulate the electronic property of the Ru‐N₃ sites, and thus boosting (photo)electrocatalytic HER activity. The proposed strategy opens a new avenue to fabricate porphyrin‐based polymers with heteromultimetallic centers as effective HER (photo)electrocatalysts.