Light-harvesting photocatalysis for water oxidation using mesoporous organosilica.

Chemistry

Toyota Central R&D Labs., Inc., Nagakute, Aichi 480-1192 (Japan); JST/CREST, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Present address: Tokyo Institute of Technology, 2-12-1-NE-2, O-okayama, Meguro-ku, Tokyo 152-8551 (Japan).

Published: July 2014

An organic-based photocatalysis system for water oxidation, with visible-light harvesting antennae, was constructed using periodic mesoporous organosilica (PMO). PMO containing acridone groups in the framework (Acd-PMO), a visible-light harvesting antenna, was supported with [Ru(II)(bpy)3(2+)] complex (bpy = 2,2'-bipyridyl) coupled with iridium oxide (IrO(x)) particles in the mesochannels as photosensitizer and catalyst, respectively. Acd-PMO absorbed visible light and funneled the light energy into the Ru complex in the mesochannels through excitation energy transfer. The excited state of Ru complex is oxidatively quenched by a sacrificial oxidant (Na2S2O8) to form Ru(3+) species. The Ru(3+) species extracts an electron from IrO(x) to oxidize water for oxygen production. The reaction quantum yield was 0.34 %, which was improved to 0.68 or 1.2 % by the modifications of PMO. A unique sequence of reactions mimicking natural photosystem II, 1) light-harvesting, 2) charge separation, and 3) oxygen generation, were realized for the first time by using the light-harvesting PMO.

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http://dx.doi.org/10.1002/chem.201302815DOI Listing

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