Issue 6, 2024

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

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
19 dek 2023
Accepted
31 yan 2024
First published
01 fev 2024
This article is Open Access
Creative Commons BY license

Sustainable Energy Fuels, 2024,8, 1225-1235

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

S. Batool, J. S. Schubert, P. Ayala, H. Saito, M. J. Sampaio, E. S. Da Silva, C. G. Silva, J. L. Faria, D. Eder and A. Cherevan, Sustainable Energy Fuels, 2024, 8, 1225 DOI: 10.1039/D3SE01658G

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