Immobilization of a [Co III Co II (H 2 O)W 11 O 39 ] 7- Polyoxoanion for the Photocatalytic Oxygen Evolution Reaction.

Autor: Nandan SP; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Gumerova NI; Universität Wien, Fakultät für Chemie, Institut für Biophysikalische Chemie, Althanstraße 14, 1090 Vienna, Austria., Schubert JS; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Saito H; Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen, Kasuga, Fukuoka 816-8580, Japan., Rompel A; Universität Wien, Fakultät für Chemie, Institut für Biophysikalische Chemie, Althanstraße 14, 1090 Vienna, Austria., Cherevan A; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Eder D; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria.
Jazyk: angličtina
Zdroj: ACS materials Au [ACS Mater Au] 2022 Jul 13; Vol. 2 (4), pp. 505-515. Date of Electronic Publication: 2022 May 25.
DOI: 10.1021/acsmaterialsau.2c00025
Abstrakt: The ongoing transition to renewable energy sources and the implementation of artificial photosynthetic setups call for an efficient and stable water oxidation catalyst (WOC). Here, we heterogenize a molecular all-inorganic [Co III Co II (H 2 O)W 11 O 39 ] 7- ({Co III Co II W 11 }) Keggin-type polyoxometalate (POM) onto a model TiO 2 surface, employing a 3-aminopropyltriethoxysilane (APTES) linker to form a novel heterogeneous photosystem for light-driven water oxidation. The {Co III Co II W 11 }-APTES-TiO 2 hybrid is characterized using a set of spectroscopic and microscopic techniques to reveal the POM integrity and dispersion to elucidate the POM/APTES and APTES/TiO 2 binding modes as well as to visualize the attachment of individual clusters. We conduct photocatalytic studies under heterogeneous and homogeneous conditions and show that {Co III Co II W 11 }-APTES-TiO 2 performs as an active light-driven WOC, wherein {Co III Co II W 11 } acts as a stable co-catalyst for water oxidation. In contrast to the homogeneous WOC performance of this POM, the heterogenized photosystem yields a constant WOC rate for at least 10 h without any apparent deactivation, demonstrating that TiO 2 not only stabilizes the POM but also acts as a photosensitizer. Complementary studies using photoluminescence (PL) emission spectroscopy elucidate the charge transfer mechanism and enhanced WOC activity. The {Co III Co II W 11 }-APTES-TiO 2 photocatalyst serves as a prime example of a hybrid homogeneous-heterogeneous photosystem that combines the advantages of solid-state absorbers and well-defined molecular co-catalysts, which will be of interest to both scientific communities and applications in photoelectrocatalysis and CO 2 reduction.
Competing Interests: The authors declare no competing financial interest.
(© 2022 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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