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

• Type: Article in International Scientific Journal
• Date: 2024

Authors

Batool, S (Author) Other; Schubert, JS (Author) Other; Ayala, P (Author) Other; Saito, H (Author) Other; Sampaio, M.J. (Author) FEUP; Da Silva, ES (Author) Other; Claudia G Silva (Author) FEUP; Joaquim Luís Faria (Author) FEUP; Eder, D (Author) Other; Cherevan, A (Author) Other

Journal

The Journal is awaiting validation by the Administrative Services.

Title: SUSTAINABLE ENERGY & FUELS

Vol. 8

Pages: 1225-1235

ISSN: 2398-4902

Publisher: ROYAL SOC CHEMISTRY

Indexing

ISI Web of Knowledge - 0 Citations

Scopus - 1 Citation

Associated Projects

LA LSRE-LCM - Financiamento Plurianual 2020-2023 para a Unidade LA LSRE-LCM Laboratório de Processos de Separação e Reacção - Laboratório de Catálise e Materiais

Other information

Authenticus ID: P-010-0CT

DOI: 10.1039/d3se01658g

Abstract (EN): 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 study investigates the hydrogen evolution reaction (HER) efficiency of two photosystems incorporating an all-inorganic molecular thiomolybdate [Mo3S13]2- cluster as a HER catalyst.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 12