A thiomolybdate cluster for visible-light-driven hydrogen evolution: comparison of homogeneous and heterogeneous approaches

Samar Batool; Jasmin S. Schubert; Pablo Ayala; Hikaru Saito; Maria J. Sampaio; Eliana S. Da Silva; Cláudia G. Silva; Joaquim L. Faria; Dominik Eder; Alexey Cherevan

doi:10.1039/D3SE01658G

A thiomolybdate cluster for visible-light-driven hydrogen evolution: comparison of homogeneous and heterogeneous approaches†

Samar Batool,

^a Jasmin S. Schubert,^a Pablo Ayala,

^a Hikaru Saito,^b Maria J. Sampaio,

^cd Eliana S. Da Silva,

‡^cd Cláudia G. Silva,

^cd Joaquim L. Faria,

^cd Dominik Eder

^a and Alexey Cherevan

*^a

Author affiliations

* Corresponding authors

^a TU Wien, Institute of Materials Chemistry, Getreidemarkt 9/BC/02, Vienna, Austria
E-mail: alexey.cherevan@tuwien.ac.at

^b Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasugakoen, Kasuga, Fukuoka 816-8580, Japan

^c LSRE-LCM – Laboratory of Separation and Reaction Engineering – Laboratory of Catalysis and Materials, Faculty of Engineering, University of Porto, Rua Dr Roberto Frias, 4200-465 Porto, Portugal

^d ALiCE – Associate Laboratory in Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr Roberto Frias, 4200-465 Porto, Portugal

Abstract

This study investigates the hydrogen evolution reaction (HER) efficiency of two photosystems incorporating an all-inorganic molecular thiomolybdate [Mo₃S₁₃]²⁻ cluster as a HER catalyst. First, we delve into the performance of a homogeneous [Mo₃S₁₃]²⁻/[Ru(bpy)₃]²⁺ (Mo₃/Ru) dyad which demonstrates high turnover frequencies (TOFs) and apparent quantum yields (AQYs) at 445 nm approaching the level of 0.5%, yet its performance is marked by pronounced deactivation. In contrast, a heterogeneous approach involves anchoring [Mo₃S₁₃]²⁻ onto graphitic carbon nitride (GCN) nanosheets through weak electrostatic association with its triazine/heptazine scaffold. [Mo₃S₁₃]²⁻/GCN (Mo₃/GCN) displays effective H₂ generation under visible light, with TOF metrics on par with those of its homogeneous analog. Although substantial leaching of [Mo₃S₁₃]²⁻ species from the Mo₃/GCN surface occurs, the remaining {Mo₃}-based centers demonstrate impressive stability, leading to enduring HER performance, starkly distinguishing it from the homogeneous Mo₃/Ru photosystem. Photoluminescence (PL) quenching experiments confirm that the performance of Mo₃/GCN is not limited by the quality of the inorganic interface, but could be optimized by using higher surface area supports or a higher concentration of [Mo₃S₁₃]²⁻ sites. Our findings showcase complexities underlying the evaluation and comparison of photosystems comprising well-defined catalytic centers and pave the way for developing analogous surface-supported (photo)catalysts with broad use in energy applications.

This article is part of the themed collections: Recent Open Access Articles and Solar Fuels and Chemicals: Photocatalytic Water Splitting and CO2 Reduction

Sustainable Energy & Fuels

A thiomolybdate cluster for visible-light-driven hydrogen evolution: comparison of homogeneous and heterogeneous approaches†

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A thiomolybdate cluster for visible-light-driven hydrogen evolution: comparison of homogeneous and heterogeneous approaches

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