Surface Anchoring and Active Sites of [Mo3S13]2– Clusters as Co-Catalysts for Photocatalytic Hydrogen Evolution

• DOI: 10.1021/acscatal.2c00972
• Publication Date: 2022-05-20T14:00:15Z
• Authors: Samar Batool; Sreejith P. Nandan; Stephen Nagaraju ...; Ashwene Rajagopal; Jasmin S. Schubert; Pablo Ayala; Shaghayegh Naghdi; Hikaru Saito; Johannes Bernardi; Carsten Streb; Alexey Cherevan; Dominik Eder
• Keywords: 01 natural sciences; 0104 chemical sciences

Achieving light-driven splitting of water with high efficiency remains a challenging task on the way to solar fuel exploration. In this work, combine advantages heterogeneous and homogeneous photosystems, we covalently anchor noble-metal- carbon-free thiomolybdate [Mo3S13]2- clusters onto photoactive metal oxide supports act as molecular co-catalysts for photocatalytic splitting. We demonstrate that strong surface-limited binding surfaces takes place. The attachment involves loss majority terminal S22- groups, upon which Mo-O-Ti bonds hydroxylated TiO2 surface are established. heterogenized active stable hydrogen evolution reaction (HER) performance close level benchmark Pt. Optimal HER rates achieved 2 wt % cluster loadings, relate accessibility required efficient hole scavenging. further elucidate sites by applying thermal post-treatments in air N2. Our data importance trinuclear core suggest bridging vacant coordination at Mo centers likely sites. This work provides prime example successful heterogenization an inorganic co-catalyst gives incentive explore other thio(oxo)metalates.