Jump to main content
Jump to site search

Issue 12, 2013
Previous Article Next Article

Photocatalytic water oxidation with cobalt-containing tungstobismutates: tuning the metal core

Author affiliations

Abstract

A new type of tungstobismutate water oxidation catalyst (WOC) with a disordered Co|W core, [{Co(H2O)3}2{CoBi2W19O66(OH)4}]10− (1) was tested for visible-light-driven performance and compared to a series of isostructural Co- and Mn-containing polyoxometalates with variable transition metal contents, ([Co2.5(H2O)6{Bi2W19.5O66(OH)4}]8− (2) and [Mn1.5(H2O)6{Bi2W20.5O68(OH)2}]6− (3)). All compounds were structurally characterized, and no indications for significant decomposition under catalytic conditions for visible-light-driven water oxidation ([Ru(bpy)3]2+ as photosensitizer (PS) and S2O82− as electron acceptor in different buffer systems) were found. For the first time, subtle differences in the core disorder patterns of isostructural POM-WOCs were revealed to be decisive for the catalytic activity of (1) (maximum TON of 21 with 97% oxygen yield for 115 μM (1)). Performance comparison of the POM series sheds new light on the structure–activity relationships for targeted POM-WOC construction. Indeed, the Co disorder differences between (1) and (2) exclusively affect the sterically more accessible external site of the two crystallographically independent Co core positions which has a 25% higher Co occupancy in (1). This points to a stereoselective reaction pattern for the tetranuclear POM core of WOC (1) which might open up novel construction strategies for the economic redesign of sandwich-type POM-WOCs. In parallel, we demonstrate for the POM series (1)–(3) that electrochemical measurements under catalytic conditions are a promising and convenient pre-screening strategy for WOC activity. Furthermore, POM/PS complex formation of (1) with [Ru(bpy)3]2+ is investigated in detail, and the different roles of Mn- and Co-centers in POM-WOC synthesis are compared.

Graphical abstract: Photocatalytic water oxidation with cobalt-containing tungstobismutates: tuning the metal core

Back to tab navigation

Supplementary files

Publication details

The article was received on 05 Jul 2013, accepted on 06 Sep 2013 and first published on 14 Oct 2013


Article type: Paper
DOI: 10.1039/C3CY00475A
Catal. Sci. Technol., 2013,3, 3117-3129
  • Open access: Creative Commons BY license
  •   Request permissions

    Photocatalytic water oxidation with cobalt-containing tungstobismutates: tuning the metal core

    F. Evangelisti, P. Car, O. Blacque and G. R. Patzke, Catal. Sci. Technol., 2013, 3, 3117
    DOI: 10.1039/C3CY00475A

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements