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Photoinduced Oxygen Evolution Catalysis Promoted by Polyoxometalate Salts of Cationic Photosensitizers


Soriano-López, Joaquín; Song, Fangyuan; Patzke, Greta R; Galan-Mascaros, José Ramón (2018). Photoinduced Oxygen Evolution Catalysis Promoted by Polyoxometalate Salts of Cationic Photosensitizers. Frontiers in Chemistry:6:302.

Abstract

The insoluble salt Cs15K[Co9(H2O)6(OH)3(HPO4)2(PW9O34)3] (CsCo9) is tested as heterogeneous oxygen evolution catalyst in light-induced experiments, when combined with the homogeneous photosensitizer [Ru(bpy)3]2+ and the oxidant Na2S2O8 in neutral pH. Oxygen evolution occurs in parallel to a solid transformation. Post-catalytic essays indicate that the CsCo9 salt is transformed into the corresponding [Ru(bpy)3]2+ salt, upon cesium loss. Remarkably, analogous photoactivated oxygen evolution experiments starting with the [Ru(bpy)3](5+x)K(6−2x)[Co9(H2O)6(OH)3(HPO4)2(PW9O34)3]·(39+x)H2O (RuCo9) salt demonstrate much higher efficiency and kinetics. The origin of this improved performance is at the cation-anion, photosensitizer-catalyst pairing in the solid state. This is beneficial for the electron transfer event, and for the long-term stability of the photosensitizer. The latter was confirmed as the limiting process during these oxygen evolution reactions, with the polyoxometalate catalyst exhibiting robust performance in multiple cycles, upon addition of photosensitizer, and/or oxidant to the reaction mixture.

Abstract

The insoluble salt Cs15K[Co9(H2O)6(OH)3(HPO4)2(PW9O34)3] (CsCo9) is tested as heterogeneous oxygen evolution catalyst in light-induced experiments, when combined with the homogeneous photosensitizer [Ru(bpy)3]2+ and the oxidant Na2S2O8 in neutral pH. Oxygen evolution occurs in parallel to a solid transformation. Post-catalytic essays indicate that the CsCo9 salt is transformed into the corresponding [Ru(bpy)3]2+ salt, upon cesium loss. Remarkably, analogous photoactivated oxygen evolution experiments starting with the [Ru(bpy)3](5+x)K(6−2x)[Co9(H2O)6(OH)3(HPO4)2(PW9O34)3]·(39+x)H2O (RuCo9) salt demonstrate much higher efficiency and kinetics. The origin of this improved performance is at the cation-anion, photosensitizer-catalyst pairing in the solid state. This is beneficial for the electron transfer event, and for the long-term stability of the photosensitizer. The latter was confirmed as the limiting process during these oxygen evolution reactions, with the polyoxometalate catalyst exhibiting robust performance in multiple cycles, upon addition of photosensitizer, and/or oxidant to the reaction mixture.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > General Chemistry
Uncontrolled Keywords:General Chemistry
Language:English
Date:14 August 2018
Deposited On:07 Mar 2019 07:42
Last Modified:15 Apr 2020 23:18
Publisher:Frontiers Research Foundation
ISSN:2296-2646
OA Status:Gold
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.3389/fchem.2018.00302
Project Information:
  • : FunderSNSF
  • : Grant IDCRSII2_160801
  • : Project TitlePhotocatalytic Processes at Solvated Interfaces
  • : FunderMINECO
  • : Grant IDCTQ2015-71287-R
  • : Project Title
  • : FunderSevero Ochoa Excellence Accreditation
  • : Grant IDSEV-2013-0319
  • : Project Title
  • : FunderGeneralitat de Catalunya
  • : Grant ID2017-SGR-1406
  • : Project Title

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