title: Highly efficient and robust molecular ruthenium catalysts for water oxidation.
abstract: 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.
authors: Department of Chemistry, School of Chemical Science and Engineering, Kungliga Tekniska Högskolan Royal Institute of Technology, 10044 Stockholm, Sweden.
authors: Lele
authors: L
authors: Duan
authors: Carlos Moyses
authors: CM
authors: Araujo
authors: Mårten S G
authors: MS
authors: Ahlquist
authors: Licheng
authors: L
authors: Sun
mesh_terms: D004583:Electrons; D006859:Hydrogen / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011522:Protons; D012428:Ruthenium / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D011522:Protons; D014867:Water; D012428:Ruthenium; D006859:Hydrogen; D010100:Oxygen