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Tuning Iridium Photocatalysts and Light Irradiation for Enhanced CO2 Reduction

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journal contribution
posted on 18.11.2016, 00:00 by Andrea Genoni, Danielle N. Chirdon, Manuel Boniolo, Andrea Sartorel, Stefan Bernhard, Marcella Bonchio
Efficient photocatalytic conversion of carbon dioxide into valuable reduction products is a priority goal for artificial photosynthesis. Iridium­(III) photocatalysts with a combined 2-phenylpyridine (ppy) and 2,2′:6′,2″-terpyridine (tpy) ligand set have been shown to selectively reduce CO2 to CO. Here, terpyridine modifications have been investigated that yield a turnover number (TON) of up to 265, a quantum yield of 0.10, and a photocatalyst lifespan of over 10 days. The key to success is the combined effect of adding aromatic substituents to the tpy ligand 4′-position and optimizing lighting conditions. Insights into the photocatalyst fate are provided by kinetics analysis and spectroelectrochemistry, which point out the critical role of the reductively quenched catalyst and its evolution to a spent “green” state via a dark deactivation pathway. The stereoelectronic effect of adding a 9-anthryl substituent together with the use of low-energy blue light proves instrumental in the management of excited and reduced species, dictating the overall performance of the molecular photocatalyst.