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Reference : UMR5069-MONGOM-001
Workplace : TOULOUSE
Date of publication : Monday, April 06, 2020
Scientific Responsible name : Prof. Montserrat GOMEZ
Type of Contract : PhD Student contract / Thesis offer
Contract Period : 36 months
Start date of the thesis : 1 September 2020
Proportion of work : Full time
Remuneration : 2 135,00 € gross monthly
Description of the thesis topic
To illustrate how innovative methodologies can be applied in synthesis, this doctoral thesis project aims at the recovery of industrial wastes derived from the food industry and pesticides thanks to the design of new catalytic materials based on metals with high active surfaces, including abundant metals (e.g. Cu, Fe, Ni, Co) (Figure 1).
This project aims at the design and development of nanomaterials for applications in catalysis through the optimization of different parameters (nature of metal precursors, concentration, temperature, additives) with a particular interest in both the nature of the stabilizer (polymer, ligand) and support, towards enabling sustainable processes. In particular, the liquid phase-immobilized nanocatalysts will be prepared in solvents with negligible vapor pressures and low environmental impact (such as glycerol and derivatives, and choline-based ionic liquids) in order to immobilize the metallic species and thus avoid leaching, allowing their stabilization without deactivation. Furthermore, we envisage strategies for catalyst heterogenization on solid supports in order to increase the efficiency of the catalytic materials by means of studying the synergies between catalyst and support, as well as their recyclability properties. The new composite materials will be characterized both in solution and solid state by standard characterization techniques (TEM, HR-TEM, XPS, XRD, IR, ICP, elementary analysis, etc.).
These nanocatalysts will be applied for the transformation of raw materials arising from industrial wastes, in particular fats from the food industry, as well as lindane, a highly toxic organochlorine insecticide stored in large quantities in the Pyrenees area, towards products of interest. Thus, this PhD thesis will focus on the design of sustainable catalytic processes in terms of high atom economy and energy efficiency by means of boosting reaction kinetics and thus permitting to work at moderate temperatures. Moreover, the as-prepared catalytic systems will be used in multi-step cascade processes, comprising the activation of C-Cl bonds (coupling reactions) and hydrogenations, for the production of products with high-added value, such as fatty amines and alcohols. Standard analytical techniques will be used for the evaluation of the catalytic reactions (GC, HPLC, MS, NMR).
This PhD project is part of the TRIPyr network funded by the Interreg-POCTEFA program, a European network gathering other students (doctoral students and post-docs) from different laboratories (ICIQ, Tarragona), as well as companies (SAPOVAL, Toulouse) and technology centers in France (MEPI, Toulouse) and Spain (AIN, Navarre). This framework will offer the candidate a multidisciplinary environment, both academic and industrial, with the possibility of making short stays in other laboratories of the network and actively participating in the meetings and activities planned during the three year PhD thesis, including science divulgation in collaboration with ECOCENE (Pau), the partner of the project in charge of communication and public engagement aspects of TRIPyr.
 a) I. Favier, D. Pla, M. Gómez, Chem. Rev. 2020, 120, 1146; b) T. Dang-Bao, D. Pla, I. Favier, M. Gómez, Catalysts 2017, 7, 207.
 T. A. G. Duarte, I. Favier, C. Pradel, L. M. D. R. S. Martins, A. P. Carvalho, D. Pla, M. Gómez, ChemCatChem, doi: 10.1002/cctc.201902305.
 A. Reina, I. Favier, C. Pradel, M. Gómez, Adv. Synth. Catal. 2018, 360, 3544.
 a) T. Dang-Bao, C. Pradel, I. Favier, M. Gómez, ACS Appl. Nano Mater. 2019, 2, 1033; b) T. Dang-Bao, C. Pradel, I. Favier, M. Gómez, Adv. Synth. Catal. 2017, 359, 2832.
The LHFA (http://lhfa.cnrs.fr/index.php/en/), belonging to the Doctoral School of Sciences of Matter (http://www.edsdm.ups-tlse.fr/), is a joint laboratory of the National Center for Scientific Research and the University Toulouse 3 - Paul Sabatier (UMR 5069) in Toulouse (France), constituted by 5 research teams (16 researchers and professors, 9 technical engineers and administrative staff; ca.40 doctoral students, post-docts and master students per year). Research activities are centered on molecular chemistry of the elements of p-block, with transversal actions in the fields of organometallic chemistry, metallic nanoparticles, catalysis and polymers, including mechanistic studies. The SYMAC research team, led by M. Gómez and working on the design of metal-based (nano) catalysts for innovative processes, is interested in the application of catalytic materials in synthesis, involving a wide range of transformations, in particular one-pot multi-step processes (sequential/tandem processes). In teh last years, we have been interested in alternative solvents, with the concern of working under "homogeneous" conditions in an environment which can allow the stabilization of metallic species and their immobilization (ionic liquids, glycerol) and consequently promoting an easy recycling of the catalytic phase. We also develop original functionalized supports capable of immobilizing metallic nanoparticles. Understanding the observed reactivity is at the heart of our researches, leading us to in-depth mechanistic studies through reaction monitoring using different techniques (ReactIR, NMR, EPR, SAXS).
The LHFA offers a very dynamic and international framework (ca. 40% of foreign students), with cutting-edge research. The different teams have (inter)national collaborations, both academic and with industrial partners. The LHFA takes part in the organization of (inter)national conferences as well as Summer Schools, and it is involved in various dissemination activities.
Constraints and risks
For the realization of this thesis work, there are no particular risks or constraints, other than the standard ones corresponding to an experimental laboratory of synthesis and catalysis. General and specific safety trainings (related to the work to be developed) are implemented.
This doctoral program is aimed at highly qualified students with an enthusiastic interest in the design and development of sustainable processes, including fundamental studies and going as far as applications. Students must have solid knowledge in organic and inorganic chemistry, with a knowledge of spectroscopic techniques; acquaintance of materials chemistry will be appreciated.
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