组合化学
催化循环
激进的
水溶液
光催化
氧化还原
药物化学
光催化
绿色化学
作者
Ting Fan,Lele Duan,Ping Huang,Hong Chen,Quentin Daniel,Mårten S. G. Ahlquist,Licheng Sun
标识
DOI:10.1021/acscatal.6b03393
摘要
Many Ru water oxidation catalysts have been documented in the literature. However, only a few can catalyze the O–O bond formation via the radical coupling pathway, while most go through the water nucleophilic attack pathway. Understanding the electronic effect on the reaction pathway is of importance in design of active water oxidation catalysts. The Ru-bda (bda = 2,2′-bipyridine-6,6′-dicarboxylate) catalyst is one example that catalyzes the O–O bond formation via the radical coupling pathway. Herein, we manipulate the equatorial backbone ligand, change the doubly charged bda2– ligand to a singly charged tpc– (2,2′:6′,2″-terpyridine-6-carboxylate) ligand, and study the structure–activity relationship. Surprisingly, kinetics measurements revealed that the resulting Ru-tpc catalyst catalyzes water oxidation via the water nucleophilic attack pathway, which is different from the Ru-bda catalyst. The O–O bond formation Gibbs free energy of activation (ΔG⧧) at T = 298.15 K was 20.2 ± 1.7 kcal mol–1. The electro...
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