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Metal atom clusters are well-defined nanoscale objects containing a precise number of metal atoms and ligands. Herein, we report new advances in the design of photoelectrodes using heterometallic Re4Mo2 cluster-based building blocks. The association of Mo and Re in {Re4Mo2Q8} cluster cores (Q = S and Se) leads to electronic properties and absorption properties significantly different from those of homometallic {Mo6I8} and {Re6Q8}. Indeed, beyond different molecular orbital diagrams, the {Re4Mo2Q8} cluster-based units exhibit 22 valence electrons per cluster (VEC) whereas the VEC value for {Mo6I8} and {Re6Q8} cluster units is 24. The mixing of rhenium and molybdenum within the same heterometallic cluster enables not only the optical and transport properties of the active layers to be optimized but it also enables the position of the energy levels to be tuned. This appears very appealing for band alignment engineering in order to design optimized photoelectrodes for solar energy conversion. We show herein that the energy levels of the photoelectrodes built on {Re4Mo2Q8} cluster-based layers immobilized on FTO surfaces are compatible with the photoelectrochemical water splitting.

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• https://creativecommons.org/licenses/by-nc/3.0/legalcode
  

Keyword: heterometallic cluster, nanoarchitectonics, photoelectrode, solar cell, water splitting

Date published: 2024-04-18

Publisher: Royal Society of Chemistry (RSC)

Journal:

• Journal of Materials Chemistry C (ISSN: 20507526) vol. 12 issue. 19 p. 6974-6984

Funding:

• Ambassade de France à Moscou
• Ministry of Science and Higher Education of the Russian Federation
• Agence Nationale de la Recherche ANR-22-CE09-0015

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1039/d3tc04635d

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Updated at: 2024-12-24 13:58:32 +0900

Published on MDR: 2024-12-24 13:58:32 +0900