Polyurethanes are thermosetting materials with significant environmental impacts. They are primarily synthesized from isocyanates, which are highly hazardous substances (toxic, sensitizing, and some even classified as CMR - Carcinogenic, Mutagenic, or Reprotoxic) and are subject to REACH restrictions. In this context, polyhydroxyurethanes (PHUs) offer several advantages: (i) they are more easily bio-based compared to conventional PUs, (ii) their synthesis does not involve isocyanates, but (iii) instead allows for CO2 sequestration. However, the precursors used in the synthesis of PHUs (cyclic carbonates and amines) exhibit much lower reactivity than isocyanates, resulting in curing times that are currently incompatible with the temperatures and production rates required for this type of material.
Several research directions have been proposed to optimize PHU curing kinetics, focusing on the identification of (i) new cyclic carbonate and amine precursors chemically substituted at the a or ß positions of the reactive group, and (ii) new high-performance catalysts capable of activating both types of precursors used in synthesis.
In this context, the PhD candidate will be tasked with synthesizing new cyclic carbonate and amine precursors and studying their reactivity to identify the most favorable conditions for the synthesis of highly reactive PHUs. The results obtained during this work will then be analyzed using symbolic Artificial Intelligence models developed at CEA.
This PhD project is part of the PHURIOUS project, funded by the PEPR DIADEM program, which aims to integrate high-throughput synthesis and characterization techniques in polymer chemistry with digital tools, including DFT calculations, molecular dynamics simulations AI approaches.
Using modelling to predict the migration of radioactive species through a well-known porous matrix, such as concrete, is a major challenge for society, particularly in the context of studies linked to the radioactive waste management. Demonstrating that the proposed model is robust through targeted laboratory experiments under extreme chemico-physical conditions is one of the scientific challenges proposed by the CEA as part of this PhD research project.
The young reseacher will be responsible for designing, carrying out and modelling experimental lab-tests on the retention and diffusion of radionuclides of interest in controlled cementitious conditions or under perturbation due to the nitrate plume leading to very high concentrations in the pore solution. The main expected result is to propose a predictive model coupling chemistry under extreme ionic strenght conditions and transport through complex cementitious matrices, validated by experimental data acquired on simple systems.
Surrounded by a team of experts in the field of measuring and modelling radionuclides migration in porous media, the PhD student will be able to develop or extend his/her skills in the following areas: chemistry, analytical chemistry, physico-chemistry, radiochemistry and modelling.
Rising energy demand and the need to reduce the use of fossil fuels to limit global warming have created an urgent need for clean energy collection technologies. One interesting solution is to use solar energy to produce fuels. Low-cost materials such as semiconductors have been the focus of numerous studies for photocatalytic reactions. Among them, 1D nanostructures are promising because of their interesting properties (high and accessible specific surface areas, confined environments, long-distance electron transport and facilitated charge separation). Imogolite, a natural hollow nanotubes clay, belongs to this category. Its particularity does not lies in its chemical composition (Al, O and Si) but in its intrinsic curvature, which induces a permanent polarization of the wall, effectively separating photo-induced charges. Several modifications of these materials are possible (coupling with metal nanoparticles, functionalization of the internal cavity), enabling their properties to be modulated.We have demonstrated that this clay is a nanoreactor for photocatalytic reactions (H2 production and CO2 reduction) under UV illumination. In order to obtain a useful photocatalyst, it is necessary to extend photon collection into the visible range. One strategy considered is to encapsulate and covalently graft dyes acting as antennae in the cavity. The aim of this thesis is to synthesize imogolites with different internal functionalizations, to study the encapsulation and grafting of dyes into the cavity of these functionalized imogolites, and finally to study the photocatalytic properties.
Advances in power electronics, electric motors and batteries, for example, are leading to a significant increase in heat production during operation. This increase in power density combined with reduced heat exchange surfaces amplifies the challenges associated with heat dissipation. The absence of adequate dissipation leads to overheating of electronic components, impacting on their performance, durability and reliability. It is therefore essential to develop a new generation of heat dissipating materials incorporating a structure dedicated to this structure.
The objective and innovation of the PhD student's work will lie in the use of highly thermally conductive (nano)fillers that can be oriented in an epoxy resin in a magnetic field. The first area of work will therefore be to electrically isolate the thermally conductive (nano)charges with a high form factor (1D and 2D). The electrical insulation of these charges of interest will be achieved by a sol-gel process. The synthesis will be controlled and optimised with a view to correlating the homogeneity and thickness of the coating with the dielectric and thermal performance of the (nano)composite. The second part will focus on the grafting of magnetic nanoparticles (NPM) onto thermally conductive (nano)fillers. Commercial NPMs will be evaluated as well as grades synthesised in the laboratory. The (nano)composites must have a rheology compatible with the resin infusion process.
During the past 20 years, « Biomass-to-liquid » processes have considerably grown. They aim at producing a large range of fuels (gasoline, kerozene, diesel, marine diesel oil) by coupling a biomass gazéification into syngaz unit (CO+CO2+H2 mixture) and a Fischer-Tropsch (FT) synthesis unit. Many demonstration pilots have been operated within Europe. Nevertheless, the low H/C ratio of bio-based syngaz from gasification requires the recycling of a huge quantity of CO2 at the inlet of gaseification process, which implies complex separation and has a negative impact on the overall valorization of biobased carbon. Moreover, the possibility to realize, in the same reactor, the Reverse Water Gas Shift (RWGS) and Fischer-Tropsch (FT) reaction in the same reactor with promoted iron supported catalysts has been proved (Riedel et al. 1999) and validated in the frame of a CEA project (Panzone, 2019).
Therefore, this concept coupled with the production of hydrogen from renewable electricity opens new opportunities to better valorize the carbon content of biomass.
The PhD is based on the coupled RWGS+FT synthesis in the same catalytic reactor. On the one hand a kinetic model will be developed and implemented in a multi-scale reactor model together with hydrodynamic and thermal phenomena. The model will be validated against experimental data and innovative design will be proposed and simulated. On the other hand, the overall PBtL process will be optimized in order to assess the potential of such a process.
Critical metals are essential for a range of technologies that are vital to reduce our carbon dioxide emissions. However, the global recycling rate for metals contained in electronic waste is below 20%, indicating that electronic waste is a relatively untapped source of metals. Additionally, it is increasingly urgent to develop effective processes for recycling waste from products like solar panels, as the volume of waste solar pannels generated is set to rise significantly in the coming years. Currently, conventional hydrometallurgical methods often rely on toxic aqueous solutions to dissolve metals, which presents substantial environmental challenges.
This project proposes an innovative alternative by using concentrated brines (aqueous salt solutions) to oxidize and dissolve metals. This thesis will investigate the fundamental properties of brines and their ability to dissolve metals through various techniques, particularly electrochemical methods. Artificial intelligence methods developed within the lab will be employed to screen a wide range of brines that would allow metal dissolution. Subsequently, brine-based recycling processes will be developed to recover metals from printed circuit boards and solar panels. Finally, metal separation and the treatment of used brines will be explored using membrane and electrochemical processes.
In the context of climate change, we need to reduce our CO2 emissions by using less energy. Another approach is to capture, store and use CO2, with the aim of moving towards a circular carbon economy and, ultimately, defossilization. With this in mind, the direct hydrogenation of CO2 enables it to be transformed into molecules of interest such as hydrocarbons, via the coupling of the reverse water gas shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS).
Computational operando catalysis has recently emerged as a reasoned alternative to the development of new catalysts, thanks to a multi-scale approach from the atom down to the active particle, to model catalyst selectivity and activity. New tools combining ab initio simulations (DFT) and molecular dynamics (MD) via machine learning algorithms bridge the gap between the precision of DFT calculations and the power of atomistic simulations. Current bifunctional catalysts (active for RWGS, and FTS) for direct CO2 hydrogenation are based on doped iron oxides (metal promoters).
The aim of this project is the theoretical study of Na-FeOx and K-FeOx catalysts doped with Cu, Mn, Zn and Co, in 4 stages: DFT simulations (adsorption energies, density of states, energy barriers, transition states), microkinetic modeling (reaction constants, TOF), construction of interatomic potentials by DFT/machine learning coupling, simulation of whole particles (selectivity, activity, microscopic quantities).
This theoretical study will go hand in hand with the synthesis and experimental measurements of the studied catalysts, and optimized catalysts emerging from the computational results. All the accumulated data (DFT, MD, catalytic properties) will be fed into a database, which can eventually be exploited to identify descriptors of interest for CO2 hydrogenation.
Technetium (Tc), an artificial radioactive element, makes up about 6% of the fission products in spent nuclear fuel. The PUREX process is used to separate uranium and plutonium from other fission products. However, Tc is co-extracted with these actinides, requiring an additional stripping step. In this stage, a stabilizing agent, hydrazinium nitrate (NH), is used, but due to its toxicity and CMR classification (Carcinogenic, Mutagenic, Reprotoxic), it is being replaced by less toxic alternatives such as oximes. Although promising, oximes exhibit slower stripping kinetics compared to NH. In the context of the PUMAS process, this thesis aims to understand the complex redox mechanisms of Tc and the kinetic differences between oximes and NH. The PhD student will study the reduced forms of Tc and analyze the reduction kinetics in the presence of U(IV) and anti-nitrous agents. A methodology will be developed to characterize the oxidation states of Tc, and reaction rate constants will be determined as a function of temperature and reactant concentrations.
The candidate will work closely with the supervising team to develop autonomy, adaptability, and the ability to propose innovative ideas. By the end of this journey, the candidate will have gained not only advanced technical skills but also abilities in project management, collaborative work, and scientific writing and communication. These competencies will provide strong prospects for a career in academic research or industry.