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Reference : UMR5069-DANPLA-001
Workplace : TOULOUSE
Date of publication : Tuesday, April 28, 2020
Scientific Responsible name : Supervisor: Montserrat Gómez. Co-supervisors: Daniel Pla, Jean-Christophe Remigy and Jean-François Lahitte.
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 development of efficient chemical processes to transform greenhouse gases (GHGs) remains a challenge for the scientific community and new strategies are required, in particular involving innovative catalytic processes for their transformation into value-added products. CO2 capture technologies are currently well identified despite their associated energy cost remains significant. This thesis project aims to train a high-level doctoral student in a multidisciplinary subject such as the transformation of CO2 into products of pharmacological interest based on the experience in the design of nano-catalysts and polymer membranes from the laboratories involved in the project, LHFA and LGC.
Thus, this project aims at the design of an innovative catalytic system made of polymeric membranes presenting dual properties: CO2 capture (thanks to polyamine functionalized membranes) and its reactivity with organic substrates (leveraged by immobilized metallic nanoparticles (MNP) on these membranes). By taking into account the constraints of the chemical reaction together with its related heat and matter transfer processes, we aim to develop a Hollow Fiber Catalytic Membrane Contactor (HFCMC), a new energy-efficient technology, reaching a high production capacity for the transformation of CO2 into heterocycles of interest for fine chemistry applications, especially in the pharmaceutical sector. For the design of an efficient catalytic membrane reactor, MNPs immobilized in a grafted polymer gel will be used, especially those from abundant metals.
We target the synthesis of oxazolid(in)ones whose interest for the synthesis of drugs (antibiotics: linezolid, posizolid; anticoagulants: rivaroxaban) is paramount. For this, we propose the study of the reactivity of aziridines and propargyl derivatives, using CO2, which will be activated by polymeric amines grafted on the membrane in the presence of Lewis acid type catalysts (such as Cu, Co, Ni), in order to improve the reactivity of the reagents while controlling the selectivity of the processes (chemo and regioselectivity). This approach shall avoid the use of expensive reagents based on halogens or epoxides, offering thus far a limited range of substrates and conditions. Similarly, stereo-selective hydrogenations catalyzed by MNPs (M = Ni, Pd, Pt) are envisaged for the synthesis of saturated heterocycles, key steps for the preparation of drugs. The catalytic systems based on catalytic membranes will be characterized by conventional techniques (IR, SEM, TEM, ICP, TGA), as well as by analytical techniques used for the evaluation of catalytic reactions (GC, HPLC, MS, NMR).
 a) I. Favier, D. Pla, M. Gómez, Chem. Rev. 2020, 120, 1146; b) G. Garg, S. Foltran, I. Favier, D. Pla, Y. Medina-González, M. Gómez, Catal. Today 2019, doi: 10.1016/j.cattod.2019.01.052; c) I. Favier, M.-L. Toro, P. Lecante, D. Pla, M. Gómez, Catal. Sci. Technol. 2018, 8, 4766; d) T. Dang-Bao, C. Pradel, I. Favier, M. Gómez, Adv. Synth. Catal. 2017, 359, 2832; e) A. Reina, I. Favier, E. Teuma, M. Gómez, AIChE J. 2019, 65:e16752, 11 pp; f) A. Reina, I. Favier, C. Pradel, M. Gómez, Adv. Synth. Catal. 2018, 360, 3544; g) A. Reina, A. Serrano-Maldonado, E. Teuma, E. Martin, M. Gómez, Catal. Commun. 2018, 104, 22.
 a) Y. Gu, I. Favier, C. Pradel, D. L. Gin, J.-F. Lahitte, R. D. Noble, M. Gómez, J.-C. Remigy, J. Membr. Sci. 2015, 492, 331; b) Y. Gu, P. Bacchin, J. F. Lahitte, J. C. Remigy, I. Favier, M. Gómez, D. L. Gin, R. D. Noble, AIChE J. 2017, 63, 698; c) M. López-Viveros, I. Favier, M. Gómez, J.-F. Lahitte, J.-C. Remigy, Catal. Today 2020, doi: 10.1016/j.cattod.2020.04.027.
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This project will be developed in Toulouse as part of the ongoing collaboration between LHFA and LGC since 2012; it will be funded by the CNRS (Mission for Cross-cutting and Interdisciplinary Initiatives, MITI). This thesis project provides a multidisciplinary training in Chemistry and Chemical Engineering. Thus, the candidate is expected to achieve a solid formation in green chemistry and intensification of sustainable processes for pursuing his/her research career, whether in an academic framework or in industry. For more information, visit: http://www.lhfa.cnrs.fr/ ; http://lgc.cnrs.fr/
Constraints and risks
There are no particular risks or constraints for this job, other than the standard ones corresponding to an experimental laboratory of synthesis, catalysis and chemical engineering. General and specific safety trainings (related to the work to be developed) are implemented.
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