Highly efficient and robust molecular ruthenium catalysts for water oxidation

Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H(2) driven by solar radiation (H(2)O + hν → 1/2O(2) + H(2)). The oxidation of water (H(2)O → 1/2O(2) + 2H(+) + 2e(-)) provides protons and electrons for the production of dihydrogen (2H(+) + 2e(-) → H(2)), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes Ru(bda)L(2) (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze Ce(IV)-driven Ce(IV) = Ce(NH(4))(2)(NO(3))(6) water oxidation with high oxygen production rates up to 286 s(-1) and high turnover numbers up to 55,400.