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Promoting Effect of Electrostatic Interaction between a Cobalt Catalyst and a Xanthene Dye on Visible-Light-Driven Electron Transfer and Hydrogen Production
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2011 (engelsk)Inngår i: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 115, nr 30, s. 15089-15096Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The readily obtained noble-metal-free molecular catalyst systems, with xanthene dyes (Rose Bengal, RB(2-); Eosin Y, EY(2-); and Eosin B, EB(2-)) as photosensitizers, [Co(bpy)(3)]Cl(2) as catalyst, and triethylamine as sacrificial electron donor, are highly active for visible-light-driven (lambda > 450 nm) hydrogen production from water. The turnover frequency is up to 54 TON/min versus RB(2-) with a RB(2-)/[Co(bpy)(3)]Cl(2) molar ratio of 1:10 in CH(3)CN/H(2)O under optimal conditions in the first half hour of irradiation (lambda > 450 rim), and the turnover number is up to 2076 versus RB(2-). Comparative studies show the following: (1) The photocatalytic H(2)-evolving activity of the cationic cobalt complex [Co(bpy)(3)]Cl(2), is apparently higher than the neutral cobaloxime complexes with xanthene dyes as potosensitizers, and also much higher than the analogous system of [Ru(bpy)(3)]Cl(2)/[Co(bpy)(3)]Cl(2). (2) The UV-vis absorptions of xanthene dyes are red shifted to different extents upon addition of [Co(bpy)(3)]Cl(2) to the aqueous or CH(3)CN/H(2)O solutions of these dyes, while no change was observed in UV-vis absorptions of photosensitizer with addition of the cobaloximes to the aqueous solution of RB(2-) or addition of [Co(bpy)(3)]Cl(2) to the aqueous solution of [Ru(bpy)(3)]Cl(2). (3) The fluorescence of RB(2-) is significantly quenched by [Co(bpy)(3)]Cl(2), but not by the cobaloximes. These special performances of [Co(bpy)(3)]Cl(2) are attributed to the electrostatically attractive interaction between the anionic organic dyes and the cationic cobalt catalyst. The probable mechanism for photoinduced hydrogen production catalyzed by the system of RB(2-), [Co(bpy)(3)]Cl(2), and triethylamine is discussed in detail on the basis of fluorescence. fand transient absorption spectroscopic studies. "

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2011. Vol. 115, nr 30, s. 15089-15096
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Identifikatorer
URN: urn:nbn:se:kth:diva-37541DOI: 10.1021/jp2040778ISI: 000293192100081Scopus ID: 2-s2.0-79961036996OAI: oai:DiVA.org:kth-37541DiVA, id: diva2:434805
Forskningsfinansiär
Knut and Alice Wallenberg FoundationSwedish Research Council
Merknad
QC 20110816Tilgjengelig fra: 2011-08-16 Laget: 2011-08-15 Sist oppdatert: 2017-12-08bibliografisk kontrollert

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