Anode Based on a Molecular Ru Water Oxidation Catalyst Covalently Bonded to Polythiophene

The oxidative electropolymerization of a ruthenium complex containing thiophene groups with the formula [Ru­(tda)­(pyrS)2] (where tda is [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylate and pyrS is 4-(2-(thiophen-3-yl)­ethyl)­pyridine) affords a conductive polymeric material containing an embedded water oxidation catalyst precursor. The method is simple and versatile allowing us to work with different graphitic supports such as glassy carbon, carbon nanotubes, or carbon paper. After activation, the material is shown to perform as a powerful molecular anode for water oxidation with catalyst loadings in the range of 0.31–3.8 nmol·cm–2, current densities up to 90 mA·cm–2 at 1.40 V vs NHE, and over 5 × 104 turnover numbers in just 30 min with close to 100% faradic efficiency.将分子式为[Ru(tda)(pyrS)₂]、带有噻吩基团（thiophene groups）的钌配合物（ruthenium complex）进行氧化电化聚合（oxidative electropolymerization），可得到一种嵌入了水氧化催化剂前驱体（water oxidation catalyst precursor）的导电高分子材料；其中tda为[2,2′:6′,2″-三联吡啶]-6,6″-二羧酸酯，pyrS为4-(2-(噻吩-3-基)乙基)吡啶。该方法简便通用，可适配多种石墨载体（graphitic supports），例如玻碳（glassy carbon）、碳纳米管（carbon nanotubes）或碳纸（carbon paper）。经活化处理后，该材料可作为高性能分子阳极（molecular anode）用于水氧化反应，其催化剂负载量范围为0.31~3.8 nmol·cm⁻²，在相对于标准氢电极（normal hydrogen electrode, NHE）的1.40 V电位下，电流密度可达90 mA·cm⁻²；且仅需30分钟即可实现超过5×10⁴的转化数（turnover number），法拉第效率（faradic efficiency）接近100%。