Thiomolybdate cluster- A stable and efficient cocatalyst for photocatalytic H2 evolution reaction Samar Batool a , Sreejith P. Nandan a , Stephen Nagaraju Myakala a , AshweneRajagopal b , JasminS.Schubert a , Pablo Ayala a , Shaghayegh Naghdi a , Hikaru Saito c , Johannes Bernardi d , Carsten Streb b , AlexeyCherevan a AndDominik Eder a a TU Wien, Institute of Materials Chemistry, 1040, Vienna, Austria, b Ulm University, Institute of Inorganic Chemistry I, 89081 Ulm, Germany, c Institute for Materials Chemistry and Engineering, Kyushu University, Japan, d TU Wien, University Service Centre for Transmission Electron Microscopy (USTEM), 1040, Vienna, Austria Efficient conversion of solar energy to hydrogen fuel by visible-light-driven water splitting has been a challenging task for scientists. Photocatalysis is a promising strategy to generate hydrogen from renewable sources, however, the efficiencies of contemporary photocatalytic systems are not yet enough to contribute substantially to the world energy demand. One important issue is the design of earth-abundant, tunable, and selective co-catalyst. Among various candidates, transition-metal-based metal sulfides – such as those from the MoS x -family – have shown excellent co-catalytic properties due to the presence of suitable active sites for electrochemical H 2 production. In this work, [1] we bridge the homogenous and heterogeneous photocatalysis by immobilizing the noble-metal- and carbon-free thiomolybdate [Mo 3 S 13 ] 2- clusters – as molecular co-catalysts – onto photoactive metal oxide supports via covalent linkage for photocatalytic water splitting. We elaborate that [Mo 3 S 13 ] 2- clusters attach strongly to the oxide surfaces through Mo-O-Ti bonds, which is limited to the support surface. The [Mo 3 S 13 ] 2- clusters heterogenized onto TiO 2 are shown to be highly active and stable co-catalysts for HER. We further investigate the active sites taking part in the HER by applying heat treatments in air and N 2 . This work provides a prime example of 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. References 1. Batool, S.; Nandan, P.; Myakala, S.; Rajagopal, A.; Schubert, J.; Ayala, P.; Naghdi, S.; Saito, H.; Bernardi, J.; Streb, C.; Cherevan, A.; Eder, D. ACS Catalysis , 2022 , just accepted, DOI:10.1021/acscatal.2c00972.
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