Towards a Molecular Level Understanding of the Multi-Electron Catalysis of Water Oxidation on Metal Oxide Surfaces

Earth abundant metal oxides play a central role as catalysts in the essential chemical transformations of sunlight to fuel conversion, which are the oxidation of water and the reduction of carbon dioxide. The rapidly growing interest in renewable fuel generation by using the energy of the sun has recently led to substantial breakthroughs in the use of first row transition metal oxides as catalysts for oxygen evolution from water. Substantive improvements of rates and lowering of overpotentials have been achieved by exploiting materials properties on the nanoscale, or taking advantage of the synergy of multiple metals. Moreover, knowledge derived from mechanistic investigations with structure specific spectroscopy is accelerating efficiency improvements. Monitoring by time-resolved FT-infrared spectroscopy reveals the molecular nature of active sites, while in situ X-ray and optical spectroscopy under reaction conditions provides insights into the electronic structure of the surface metal centers participating in the catalysis. By combining the bond specificity of vibrational spectroscopy with the metal electronic structure specificity of optical, X-ray absorption or photoelectron spectroscopy, a complete understanding of active surface sites on metal oxides begins to emerge. Charge flow driving the chemical transformations probed by optical spectroscopy across time scales from ultrafast to very slow reveals the processes that control the productive use of charges delivered to the catalyst. Coupling of the water oxidation catalysis at a metal oxide catalyst with carbon dioxide reduction at a heterobinuclear chromophore, which is the goal of the artificial photosystem approach, is demonstrated by a well-defined all-inorganic polynuclear unit. .