Walden Andrew G, Miller Alexander J M
Department of Chemistry , University of North Carolina at Chapel Hill , Chapel Hill , NC 27599-3290 , USA . Email:
Chem Sci. 2015 Apr 16;6(4):2405-2410. doi: 10.1039/c5sc00032g. Epub 2015 Feb 4.
The tris(2-pyridyl)phosphine oxide (PyPO) complex [Ru(PyPO)(bpy)(OH)] (bpy is 2,2'-bipyridine) is a pH-dependent water oxidation electrocatalyst that accelerates dramatically with increasing pH-up to 780 s at pH 10 (∼1 V overpotential). Despite retaining the pentakis(pyridine) ligand arrangement common to previously reported catalysts, the tripodal PyPO ligand framework supports much faster electrocatalysis. The early stages of the catalytic cycle are proposed to follow the typical pattern of single-site ruthenium catalysts, with two sequential 1H/1e proton-coupled electron transfer (PCET) oxidations, but the pH-dependent onset of catalysis and rapid rates are distinguishing features of the present system.
三（2-吡啶基）氧化膦（PyPO）配合物[Ru（PyPO）（bpy）（OH）]（bpy为2,2'-联吡啶）是一种pH依赖性水氧化电催化剂，随着pH值升高，其催化活性显著增强——在pH值为10时，加速至780秒（过电位约为1V）。尽管保留了先前报道的催化剂常见的五（吡啶）配体排列方式，但三脚架状的PyPO配体框架支持更快的电催化反应。催化循环的早期阶段被认为遵循单中心钌催化剂的典型模式，即连续进行两次1H/1e质子耦合电子转移（PCET）氧化反应，但本体系中催化反应的pH依赖性起始点和快速反应速率是其显著特征。
