The non-hydrolytic sol-gel process was invented in the laboratory in the early 1990s. It is based on the formation of oxo bridges by condensation reactions in an anhydrous medium, e.g. the condensation between M-Cl and M-OR groups with elimination of alkyl chloride. Changing the reactions and medium overcome several problems met in conventional sol-gel. This non-hydrolytic process allows us to obtain oxides and mixed oxides displaying original structure, texture, or morphology (amorphous non-hydrated aluminas; mesoporous xerogels, organosoluble nanoaparticles...).
Over the last 10 years we have been developing the one-step and template-free synthesis of mesoporous mixed oxide catalysts (Si-Ti, Si-Zr, Ti-V5, Si-Al-Mo, Si-Al-Re, Ag-Al-Nb...) with high activity and selectivity in various reactions (mild and total oxidation, DeNOx, metathesis, etc.). This demonstrates that the interest of non-hydrolytic sol-gel is far from being purely academic. We also used non-hydrolytic sol-gel for the surfactant-free synthesis of organosoluble oxide nanoparticles (SiO2-TiO2, SnO2, TiO2).
Recently, we started investigating the use of cellulose-based materials (cotton, paper, aerogels...) as templates, oxygen donors, and carbon source to prepare metal oxides and carbon/oxide nanocomposites with hierarchical architectures. The growth of metal oxide nanocrystals nucleating from the surface of the cellulosic material leads to a large variety of morphologies depending on the conditions. These materials appear promising for applications in (photo)catalysis and in energy storage (electrode material for batteries).
Main research activities
- Mesoporous mixed oxides and nanoparticles by non-hydrolytic sol-gel processing
- Metal oxides and carbon/oxide nanocomposites by minéralization of biopolymers in non-aqueous medium or by non-hydrolytic sol-gel
Selected publications
- (1) Recent advances in the synthesis of inorganic materials via non-hydrolytic condensation and related low-temperature routes, Mutin, P. H.; Vioux, A. J. Mater. Chem. A 2013, 1, 11504-11512.
- (2) Mesoporous mixed oxide catalysts via non-hydrolytic sol-gel, A review, Debecker, D. P.; Hulea, V.; Mutin, P. H. Applied Catalysis A: General 2013, 451, 192-206.
- (3) Hybrid metal oxide@biopolymer materials precursors of metal oxides and metal oxide-carbon composites, Plumejeau, S.; Alauzun, J. G.; Boury, B. J. Ceram. Soc. Jpn. 2015, 123, 695-708.
- (4) Mild oxidation of bulky organic compounds with hydrogen peroxide over mesoporous TiO2-SiO2 xerogels prepared by non-hydrolytic sol-gel, A. M. Cojocariu, P.H. Mutin, E. Dumitriu, F. Fajula, A. Vioux, V.Hulea, Applied Catalysis B: Environmental 2010, 97, 407-413.
- (5) Conversion of Nanocellulose Aerogel into TiO2 and TiO2@C Nano-thorns by Direct Anhydrous Mineralization with TiCl4. Evaluation of Electrochemical Properties in Li Batteries , Henry, A.; Plumejeau, S.; Heux, L.; Louvain, N.; Monconduit, L.; Stievano, L.; Boury, B. ACS Appl. Mater. Interfaces 2015, 7, 14584-14592.
- (6) Olefin metathesis with mesoporous rhenium-silicium-aluminum mixed oxides obtained via a one-step non-hydrolytic sol-gel route. , Bouchmella, K.; Mutin, P. H.; Stoyanova, M.; Poleunis, C.; Eloy, P.; Rodemerck, U.; Gaigneaux, E. M.; Debecker, D. P. Journal of Catalysis 2013, 301, 233-241.
- (7) Reactive and Organosoluble Anatase Nanoparticles by a Surfactant-Free Nonhydrolytic Synthesis, Aboulaich, A.; Boury, B.; Mutin, P. H. Chem. Mater. 2010, 22, 4519-4521.
Collaborations (outside ICGM)
- Dr. Michèle Besson (IRCELyon)
- Dr. Véronique Bounor-Légaré (IMP Lyon)
- Prof. Damien Debecker, Prof. Eric Gaigneaux (Université Catholique de Louvain)
- Prof. Emil Dumitriu (Université de Iasi)
- Dr. Alexandra Chaumonnot (IFPEN)
- Dr. Laurent Heux (CERMAV, Grenoble)
- Dr. Helena Kaper (CREE Saint-Gobain)
Financing
CNRS, University of Montpellier, FUI REDNOX, French Embassy in India (Sandwich PhD Fellowship), Sumitomo Chemical, IFPEN, European commission (FAME NOE, H2020 IA project POROUS4APP), ANR (NHYSCAB, SYNCOPE).