Metal Atom Clusters as Building Blocks for Multifunctional Proton-Conducting Materials Theoretical and Experimental Characterization

Gilles Daigre 1 Jérôme Cuny 2 Pierric Lemoine 1 Maria Amela-Cortes 1 Serge Paofai 1 Nathalie Audebrand 1 Annie Le Gal La Salle 3 Eric Quarez 3 Olivier Joubert 3 Nikolay G Naumov 4, 5 Stéphane Cordier 1
1 ISCR - Institut des Sciences Chimiques de Rennes
2 Modélisation, Agrégats, Dynamique (LCPQ)
LCPQ - Laboratoire de Chimie et Physique Quantiques
3 IMN - Institut des Matériaux Jean Rouxel
4 NSU - Novosibirsk State University
5 NIC - Nikolaev Institute of Inorganic Chemistry [Novosibirsk]
Abstract : The search for new multifunctional materials displaying proton-conducting properties is of paramount necessity for the development of electrochromic devices and supercapacitors as well as for energy conversion and storage. In the present study, proton conductivity is reported for the first time in three molybdenum cluster-based materials (H)[MoBrS(OH)]-12HO and (H)[MoX(OH)]-12HO (X = Cl, Br). We show that the self-assembling of the luminescent [MoL(OH)] cluster units leads to both luminescence and proton conductivity (σ = 1.4 × 10 S·cm in (H)[MoCl(OH)]-12HO under wet conditions) in the three materials. The latter property results from the strong hydrogen-bond network that develops between the clusters and the water molecules and is magnified by the presence of protons that are statistically shared by apical hydroxyl groups between adjacent clusters. Their role in the proton conduction is highlighted at the molecular scale by ab initio molecular dynamics simulations that demonstrate that concerted proton transfers through the hydrogen-bond network are possible. Furthermore, thermogravimetric analysis also shows the ability of the compounds to accommodate more or less water molecules, which highlights that vehicular (or diffusion) transport probably occurs within the materials. An infrared fingerprint of the mobile protons is finally proposed based on both theoretical and experimental proofs. The present study relies on a synergic computational/experimental approach that can be extended to other proton-conducting materials. It thus paves the way to the design and understanding of new multifunctional proton-conducting materials displaying original and exciting properties.
Document type :
Journal articles
Complete list of metadatas
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01862462
Contributor : Laurent Jonchère <>
Submitted on : Monday, August 27, 2018 - 1:23:27 PM
Last modification on : Thursday, May 23, 2019 - 10:28:11 AM

Identifiers

Collections

ISCR | UNIV-RENNES1 | IRSAMC | LCPQ | IMN | ST2E | UR1-UFR-SPM | ISCR-CSM | INC-CNRS | UNIV-NANTES | UNIV-RENNES | INSA-RENNES | LCPQ_MAD | INSA-GROUPE | UNIV-TLSE3

Citation

Gilles Daigre, Jérôme Cuny, Pierric Lemoine, Maria Amela-Cortes, Serge Paofai, et al.. Metal Atom Clusters as Building Blocks for Multifunctional Proton-Conducting Materials Theoretical and Experimental Characterization. Inorganic Chemistry, American Chemical Society, 2018, 57 (16), pp.9814-9825. ⟨10.1021/acs.inorgchem.8b00340⟩. ⟨hal-01862462⟩

Export

BibTeX TEI DC DCterms EndNote

Share

Metrics

Record views

67