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Nickel Complex with Internal Bases as Efficient Molecular Catalyst for Photochemical H-2 Production
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
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2014 (English)In: ChemSusChem, ISSN 1864-5631, E-ISSN 1864-564X, Vol. 7, no 10, p. 2889-2897Article in journal (Refereed) Published
Abstract [en]

A Ni complex with internal bases that contain bipyridine-derived ligands, [Ni(L)(2)(H2O)(2)](BF4)(2) ([1](BF4)(2), L=2-(2-pyridyl)-1,8-naphthyridine), and a reference complex that bears analogous bipyridine-derived ligands but without an internal base, [Ni(L)(3)](BF4)(2) ([2](BF4)(2), L=2-(2-pyridyl)quinoline), were synthesized and characterized. The electrochemical properties of these complexes were studied in CH3CN, H2O, and a mixture of EtOH/H2O. The fluorescence spectroscopic studies suggest that both dynamic and the sphere-of-action static quenching exist in the fluorescein Fl(2-)/[1](2+) and Fl(2-)/[2](2+) systems. These noble-metal-free molecular systems were studied for photocatalytic H-2 generation. Under optimal conditions, the turnover number of H-2 evolution reaches 3230 based on [1](2+), whereas [2](2+) displays only approximately one third of the turnover of [1](2+). A plausible mechanism for the catalytic H-2 generation by [1](2+) is presented based on DFT calculations.

Place, publisher, year, edition, pages
2014. Vol. 7, no 10, p. 2889-2897
Keywords [en]
density functional calculations, hydrogen, nickel, photochemistry, water splitting
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Identifiers
URN: urn:nbn:se:kth:diva-155466DOI: 10.1002/cssc.201402381ISI: 000342815400018Scopus ID: 2-s2.0-84925257946OAI: oai:DiVA.org:kth-155466DiVA, id: diva2:762843
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

QC 20141113

Available from: 2014-11-13 Created: 2014-11-06 Last updated: 2017-12-05Bibliographically approved

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Ahlquist, Mårten S. G.Sun, Licheng

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