PhD offer (E-POM group) – (Photo)reduction of polyoxotungstatesfor selective organic transformations

The E-POM group is looking for a candidate for a PhD scholarship on the topic:

(Photo)reduction of polyoxotungstates
for selective organic transformations

Project overview :  

The concerted transfer of protons and electrons, or proton-coupled electron transfer (PCET), makes it possible to activate inert substrates without the need for energy-intensive intermediates.

The aim of the proposed research is to understand and attempt to control PCET processes in nanometric clusters of polyoxometallate (POM) type for the activation of small molecules. The approach is to take advantage of the remarkable properties of POMs, which are robust, modular, redox-active and also photo-active species, to direct electron transfers.1 POMs can be charged with electrons by chemical,2 electrochemical or photochemical activation (using a sacrificial reductant). The factors triggering the release of electrons (coupled with a proton) from reduced POMs to the substrate of interest will then be studied in detail. A first thematic area will, for example, aim to control the selectivity of the reduction of O2 to 2e-/2H+ to form hydrogen peroxide in situ. The ‘on-demand’ formation of hydrogen peroxide may make it possible to envisage its continued use in sustainable (ep)oxidation reactions, a subject of research by the team.3,4 The sequence of this complex reaction, reduction of O2 to H2O2 / oxidation of a substrate, may be envisaged as a tandem reaction in batch and/or flow (compartmentalisation of the two reactions). The methodology could be extended to the reduction of other small molecules of interest (NOx, N2, etc.).

Profiles : 

– The candidate must be highly motivated to work in the fields of inorganic chemistry and (photo)catalysis.
– With a Master’s degree in chemistry specialising in molecular chemistry or materials chemistry, the candidate must be able to organise his/her work programme independently.
– Good adaptability, teamwork and communication skills are also required to report effectively on the progress of work (in French and English).

Duration:

36 months from October 2024

Application:

– Send a cover letter
– a detailed CV
– and letter of recommendation

Contact :  G. Guillemot (e-mail)

References:

(1)     K/Bidi, L.; Desjonquères, A.; Izzet, G.; Guillemot, G. H2 Evolution at a Reduced Hybrid Polyoxometalate and Its Vanadium-Oxo Derivative Used as Molecular Models for Reducible Metal Oxides. Inorg. Chem. 202362 (5), 1935–1941. https://doi.org/10.1021/acs.inorgchem.2c01741.

(2)     Zhang, T.; Solé-Daura, A.; Hostachy, S.; Blanchard, S.; Paris, C.; Li, Y.; Carbó, J. J.; Poblet, J. M.; Proust, A.; Guillemot, G. Modeling the Oxygen Vacancy at a Molecular Vanadium(III) Silica-Supported Catalyst. J. Am. Chem. Soc. 2018140 (44), 14903–14914. https://doi.org/10.1021/jacs.8b09048.

(3)     Solé-Daura, A.; Zhang, T.; Fouilloux, H.; Robert, C.; Thomas, C. M.; Chamoreau, L.-M.; Carbó, J. J.; Proust, A.; Guillemot, G.; Poblet, J. M. Catalyst Design for Alkene Epoxidation by Molecular Analogues of Heterogeneous Titanium-Silicalite Catalysts. ACS Catal. 202010 (8), 4737–4750. https://doi.org/10.1021/acscatal.9b05147.

(4)     Makrygenni, O.; Vanmairis, L.; Taourit, S.; Launay, F.; Shum Cheong Sing, A.; Proust, A.; Gérard, H.; Villanneau, R. Selective Formation of Epoxylimonene Catalyzed by Phosphonyl/Arsonyl Derivatives of Trivacant Polyoxotungstates at Low Temperature. European Journal of Inorganic Chemistry 20202020 (7), 605–612. https://doi.org/10.1002/ejic.201901152.