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Reference : UMR6502-ANNHEN-003
Workplace : NANTES
Date of publication : Tuesday, June 16, 2020
Scientific Responsible name : Thomas Devic
Type of Contract : PhD Student contract / Thesis offer
Contract Period : 36 months
Start date of the thesis : 1 October 2020
Proportion of work : Full time
Remuneration : 2 135,00 € gross monthly
Description of the thesis topic
The area of crystalline porous solids is largely dominated by oxygenated compounds, both in the field of inorganic (zeolites) and hybrid organic-inorganic (Porous Coordination Polymers, or Metal Organic Frameworks, MOFs) materials. Although these solids, thanks to their high sorption capacity and tunable porosity, are more than effective for many applications ranging from gas storage or capture to heterogeneous catalysis, they very often suffer from poor electronic properties, arising from the rather ionic character of the metal-oxygen bonds. The resulting lack of electronic conductivity is a clear drawback for various applications in which electron transfer is involved, such as (photo)electrocatalysis, sensing, photovoltaics or electrochemical energy storage. Elements less electronegative than oxygen, especially heavier chalcogens such as sulfur, giving rise to more covalent metal-ligand bonds, offer here great opportunities
The present project thus aims at developing new conductive porous coordination polymers based of sulfurated ligands and evaluate their redox properties.
More precisely, we will focus our attention of the use of a specific class of non-innocent ligands, the 1,2-dithiolene derivatives, whose coordination complexes present a strong organic-inorganic electronic coupling with mixed organic-inorganic frontiers orbitals. Although molecular dithiolene complexes are studied for decades, the extended dithiolene coordination networks has only recently emerged. By combining poly(dithiolene) ligands with suitable cations or polymetallic entities, we aim at building new 3-D coordination polymers which could offer interesting electronic properties.
Synthesis, structure determination solution and physico-chemical studies of new materials will be the core of the project. Hence, the applicant should hold a strong background in coordination chemistry (or materials chemistry) with a good knowledge in molecular chemistry. Knowledge in physical chemistry and structure determination by diffraction would be highly beneficial. The project will also involve the evaluation of the electrochemical properties in the solid state, for which the Ph.D candidate will be trained in the laboratory.
The Institut des Matériaux Jean Rouxel de Nantes (IMN, http://www.cnrs-imn.fr/ is a joint research unit between the Centre National de la Recherche Scientifique (CNRS) and the University of Nantes. It gathers about 80 permanent researchers and about 90 non permanents researchers (Ph.D students and post-doctorate associates), divided in five research groups, all in the field of materials science. The Ph.D student will belong to the research group 'Electrochemical storage and conversion of Energy (ST2E)'. He will join the doctoral school 3M from the University of Nantes, and be supervised by Thomas Devic (IMN)
This Ph.D fellowship is in the frame if the collaborative ANR project ThioMOFs, which aim at developing and thoroughly characterize multi-redox porous crystalline hybrid chalcogenides. Its gathers four research groups with complementary expertise in the field of dithiolene chemistry (ISC Rennes), MOFs synthesis and solid state electrochemistry (IM Nantes), structure determination and electrocatalysis (IL Versailles), in situ electrochemical studies and simulation (ICG Montpellier).
Constraints and risks
The Ph.D student will be located at the Institut des Matériaux in Nantes, but shorts stays in the partner's laboratories are also planned.
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