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Manganese‐Substituted Polyoxometalate as an Effective Shuttle Redox Mediator in Z‐Scheme Water Splitting under Visible Light
Author(s) -
Tsuji Kohei,
Tomita Osamu,
Higashi Masanobu,
Abe Ryu
Publication year - 2016
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201600563
Subject(s) - polyoxometalate , photocatalysis , redox , water splitting , selectivity , manganese , photochemistry , chemistry , visible spectrum , stoichiometry , inorganic chemistry , electron acceptor , electron transfer , catalysis , materials science , organic chemistry , optoelectronics
In the present study, a polyoxometalate is for the first time applied as a shuttle redox in two‐step (Z‐Scheme) photocatalytic water splitting. Photocatalytic H 2 evolution using a Mn‐substituted polyoxometalate [SiW 11 O 39 Mn II (H 2 O)] 6− as an electron donor proceeded over a Ru‐loaded SrTiO 3 :Rh photocatalyst under visible light with relatively high selectivity, accompanied by the stoichiometric production of its oxidized form [SiW 11 O 39 Mn III (H 2 O)] 5− . Photocatalytic O 2 evolution using the oxidized [SiW 11 O 39 Mn III (H 2 O)] 5− as an electron acceptor proceeded over PtO x ‐loaded WO 3 photocatalyst under visible light with relatively high quantum efficiency and selectivity, whereas the loading of effective PtO x cocatalyst was necessary to facilitate the reduction of polyoxometalate. Finally, a two‐step water splitting into H 2 and O 2 was demonstrated under visible light using the couple of Mn‐substituted polyoxometalate as shuttle redox between Ru/SrTiO 3 :Rh and PtO x /WO 3 photocatalysts, under mildly acidic conditions with pH≈4.5.