Supramolecular Anchoring of Octahedral Molybdenum Clusters onto Graphene and Their Synergies in Photocatalytic Water Reduction

"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.9b02529"[EN] Dihydrogen (H-2) production from sunlight should become one of the most important energy production means in the future. To reach this goal, low-cost and efficient photocatalysts still need to be discovered. Here we show that red near-IR luminescent metal cluster anions, once combined with pyrene-containing cations, are able to photocatalytically produce molecular hydrogen from water. The pyrene moieties act simultaneously as energy transmitters and as supramolecular linkers between the cluster anions and graphene. This association results in a hybrid material combining the emission abilities of pyrene and cluster moieties with the electronic conduction efficiency of graphene. Hydrogen evolution reaction (HER) studies show that this association induces a significant increase of H 2 production compared to that produced separately by clusters or graphene. Considering the versatility of the strategy described to design this photocatalytic hybrid material, transition-metal clusters are promising candidates to develop new, environmentally friendly, and low-cost photocatalysts for HER.The Severo Ochoa Program (SEV-2016-0683), Ministerio de Ciencia, Innovation y Universidades (PGC2018-099744), Consejo Superior de Investigaciones Cientificas (I-Link1063), and University of Rennes are thanked for financial support. We thank Dr. Marta Puche for her technical assistance with the preparation of dispersed graphene solutions at the ITQ.Feliz Rodriguez, M.; Atienzar Corvillo, PE.; Amela-Cortes, M.; Dumait, N.; Lemoine, P.; Molard, Y.; Cordier, S. (2019). Supramolecular Anchoring of Octahedral Molybdenum Clusters onto Graphene and Their Synergies in Photocatalytic Water Reduction. Inorganic Chemistry. 58(22):15443-15454. https://doi.org/10.1021/acs.inorgchem.9b025291544315454582