Surface Anchoring and Active Sites of [Mo 3 S 13 ] 2- Clusters as Co-Catalysts for Photocatalytic Hydrogen Evolution.

Autor: Batool S; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Nandan SP; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Myakala SN; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Rajagopal A; Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany., Schubert JS; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Ayala P; Institute of Materials Chemistry, TU Wien, Getreidemarkt 9/BC/02, 1060 Vienna, Austria., Naghdi S; 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., Bernardi J; University Service Centre for Transmission Electron Microscopy (USTEM), TU Wien, Wiedner Hauptstraße 8-10, 1040 Vienna, Austria., Streb C; Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany.; Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, 55128 Mainz, Germany., 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 catalysis [ACS Catal] 2022 Jun 03; Vol. 12 (11), pp. 6641-6650. Date of Electronic Publication: 2022 May 20.
DOI: 10.1021/acscatal.2c00972
Abstrakt: Achieving light-driven splitting of water with high efficiency remains a challenging task on the way to solar fuel exploration. In this work, to combine the advantages of heterogeneous and homogeneous photosystems, we covalently anchor noble-metal- and carbon-free thiomolybdate [Mo 3 S 13 ] 2- clusters onto photoactive metal oxide supports to act as molecular co-catalysts for photocatalytic water splitting. We demonstrate that strong and surface-limited binding of the [Mo 3 S 13 ] 2- to the oxide surfaces takes place. The attachment involves the loss of the majority of the terminal S 2 2- groups, upon which Mo-O-Ti bonds with the hydroxylated TiO 2 surface are established. The heterogenized [Mo 3 S 13 ] 2- clusters are active and stable co-catalysts for the light-driven hydrogen evolution reaction (HER) with performance close to the level of the benchmark Pt. Optimal HER rates are achieved for 2 wt % cluster loadings, which we relate to the accessibility of the TiO 2 surface required for efficient hole scavenging. We further elucidate the active HER sites by applying thermal post-treatments in air and N 2 . Our data demonstrate the importance of the trinuclear core of the [Mo 3 S 13 ] 2- cluster and suggest bridging S 2 2- and vacant coordination sites at the Mo centers as likely HER active sites. This work provides a prime example for the successful heterogenization of an inorganic molecular cluster as a co-catalyst for light-driven HER and gives the incentive to explore other thio(oxo)metalates.
Competing Interests: The authors declare no competing financial interest.
(© 2022 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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