Abstract A molecular [Ru(bda)]-type (bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand (Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene (3F) or styrene (St) blocking units on the surface of glassy carbon (GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via (1) the radical coupling interaction between the two metallo-oxyl radicals (I2M) in the homo-coupling polymer (poly-1), and (2) the water nucleophilic attack (WNA) pathway in poly-1+P3F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.

中文翻译：

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通过第二配位球工程调整电极表面分子水氧化催化剂的O-O键形成途径

摘要 以 4-乙烯基吡啶为轴向配体的分子 [Ru(bda)]-型 (bda = 2,2'-bipyridine-6,6'-dicarboxylate) 水氧化催化剂 (Complex 1) 与1-(三氟甲基)-4-乙烯基苯(3F)或苯乙烯(St)封闭单元在玻碳(GC)电极表面通过电化学聚合制备相应的poly-1@GC、poly-1+P3F @GC 和 poly-1+PSt@GC 功能电极。电极表面反应的动力学测量表明，[Ru(bda)] 通过 (1) 均偶联聚合物 (poly-1 )，以及 (2) poly-1+P3F 和 poly-1+PSt 共聚物中的水亲核攻击 (WNA) 途径。