Structurally Characterized Iridium(III)-Containing Polytungstate and Catalytic Water Oxidation Activity
作者:Rui Cao、Huiyuan Ma、Yurii V. Geletii、Kenneth I. Hardcastle、Craig L. Hill
DOI:10.1021/ic900538g
日期:2009.7.6
The first structurally characterized iridium-substituted polyoxometalate, K-14[(IrCl4)KP2W20O72]center dot 23H(2)O [1; orthorhombic Pnnm, with a = 18.6546(7) angstrom, b = 19.5192(6) angstrom, c = 14.8670(5) angstrom, V = 5413.4(3) angstrom(3), and Z = 2, final R = 0.0730], is reported. Elemental analysis, X-ray crystallography, and NMR all indicate one Ir atom in each molecule, while IR and electronic absorption spectroscopy, thermal gravimetric analysis, and electrochemistry all indicate its purity in both solid and solution states. Complex 1 is a molecular model of iridium supported on redox-active metal oxides, and aqueous solutions of 1 catalyze oxidation of water to O-2.