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Photoisomerization of active d-[Ru(tpy)(pynap)OH2]2+ water oxidation catalyst inhibited by immobilizing onto metal oxide electrodes

We have previously reported the mechanism of water oxidation catalyzed by d- and p-isomers of [Ru(tpy)(pynap)OH2]2+ (pynap = 2-(pyrid-2'-yl)-1,8-naphthyridine ) catalyst. While the d-isomer has shown high catalytic activity, the p-isomer was inactive toward water oxidation. In our new studies we have demonstrated the enhanced photoabsorption stability of the d-[Ru(tpy)(pynap)OH2]2+ catalyst when successfully attached onto oxide electrodes through a phosphonate linker. Electrochemical and photoelectrochemical results confirmed ruthenium oxidation chemistries and water oxidation proficiency remain largely unaffected by phosphonation and photo-isomerization of d-[Ru(H2PO3-tpy)(pynap)OH2]2+ is drastically inhibited when the catalyst is attached onto a rigid oxide electrode.

J. Catal. 2013, 307, 140–147, 10.1016/j.jcat.2013.07.018.