Promoting Water Oxidation by Proton Acceptable Groups Surrounding Catalyst on Electrode Surface

Large‐scale hydrogen production through water splitting represents an optimal approach for storing sustainable but intermittent energy sources. However, water oxidation, a complex and sluggish reaction, poses a significant bottleneck for water splitting efficiency. The impact of outer chemical environments on the reaction kinetics of water oxidation catalytic centers remains unexplored. Herein, chemical environment impacts were integrated by featuring methylpyridinium cation group (Py+) around the classic Ru(bpy)(tpy) (bpy=2,2’‐bipyridine, tpy=2,2′ : 6′,2′′‐terpyridine) water oxidation catalyst on the electrode surface via electrochemical co‐polymerization. The presence of Py+ groups could significantly enhance the turnover frequencies of Ru(bpy)(tpy), surpassing the performance of typical proton acceptors such as pyridine and benzoic acid anchored around the catalyst. Mechanistic investigations reveal that the flexible internal proton acceptor anions induced by Py+ around Ru(bpy)(tpy) are more effective than conventionally anchored proton acceptors, which promoted the rate‐determining proton transfer process and enhanced the rate of water nucleophilic attack during O−O bond formation. This study may provide a novel perspective on achieving efficient water oxidation systems by integrating cations into the outer chemical environments of catalytic centers. The absorbed proton acceptor anions such as phosphate (Pi), acetate (Ac) and borate (Bi) by methylpyridinium in the outer chemical environment of Ru(bpy)(tpy) catalyst could act as flexible internal proton acceptors, which promoted the rate‐determining proton transfer process and enhanced the rate of water nucleophilic attack during O−O bond formation.