Custom synthesis of diamond nanoparticles for photocatalytic hydrogen production
Diamond nanoparticles (nanodiamonds) are used in nanomedicine, quantum technologies, lubricants and advanced composites [1-2]. Our recent results show that nanodiamond can also act as a photocatalyst, enabling the production of hydrogen under solar illumination [3]. Despite its wide band gap, its band structure is adaptable according to its nature and surface chemistry [4]. Moreover, the controlled incorporation of dopants or sp2 carbon leads to the generation of additional bandgap states that enhance the absorption of visible light, as shown in a recent study involving our group [5]. The photocatalytic performance of nanodiamonds is therefore highly dependent on their size, shape and concentration of chemical impurities. It is therefore essential to develop a "tailor-made" nanodiamond synthesis method, in which these different parameters can be finely controlled, in order to provide a supply of "controlled" nanodiamonds, which is currently lacking.
This PhD aims to develop a bottom-up approach to grow nanodiamond using a sacrificial template (silica beads) to which diamond seeds < 10 nm are attached by electrostatic interaction. The growth of diamond nanoparticles from these seeds will be achieved by microwave-enhanced chemical vapor deposition (MPCVD) using a homemade rotating reactor available at CEA NIMBE. After growth, the CVD-NDs will be collected after dissolution of the sacrificial pattern. Preliminary experiments have demonstrated the feasibility of this approach with the synthesis of faceted <100 nm nanodiamonds (so called CVD-ND), as shown in the scanning electron microscopy image.
During the PhD work, the nature of the diamond seeds (ultra-small NDs [size ˜ 5 nm] synthesized by detonation or HPHT, or molecular derivatives of adamantane) as well as CVD growth parameters will be studied to achieve better controlled CVD-NDs in terms of crystallinity and morphology. Nanodiamonds doped with boron or nitrogen will be also considered, playing on the gas phase composition. The crystalline structure, morphology and surface chemistry will be studied at CEA NIMBE using SEM, X-ray diffraction and Raman, infrared and photoelectron spectroscopies. A detailed analysis of the crystallographic structure and structural defects will be carried out by high-resolution transmission electron microscopy (collaboration). CVD FNDs will then be exposed to gas-phase treatments (air, hydrogen) to modulate their surface chemistry and stabilize them in water. The photocatalytic performance for hydrogen production under visible light of these different CVD-NDs will be evaluated and compared using the photocatalytic reactor recently installed at CEA NIMBE.
References
[1] Nunn et al., Current Opinion in Solid State and Materials Science, 21 (2017) 1.
[2] Wu et al., Angew. Chem. Int. Ed. 55 (2016) 6586.
[3] Marchal et al., Adv. Energy Sustainability Res., 2300260 (2023) 1-8.
[4] Miliaieva et al., Nanoscale Adv. 5 (2023) 4402.
[5] Buchner et al., Nanoscale 14 (2022) 17188.
Silver nanowires synthesized from end-of-life solar panels for CO2 reduction and transparent electrodes
Silver nanowires (AgNW) networks are remarkable materials with both the highest electrical and thermal conductivity at ambient temperature, and a good chemical stability. They are used in transparent electrodes, for instance in organic solar cells, heating films or electrochromic devices. Their synthesis has been upscaled at the industrial level with high yield and reproducibility. More recently, they also found promising applications in low-emissivity layers on windows, and in catalysis of CO2 reduction at ambient temperature as a selective electrocatalyst.
In this PhD project, we will turn to recycled sources of silver from dismantled end-of-life silicon solar panels for the synthesis of AgNWs, in a “green chemistry” approach. The quality of the nanomaterial will be checked directly in two relevant devices, namely IR-low-emissivity films for reduction of heat loss, and electroreduction of CO2 for the production of e-fuels. The project will focus on understanding the fundamental basis of the impact of impurities on the synthesis of AgNWs, the physical properties of the AgNW networks, their stability under electrical stress or chemical wear, and their performance as active material in the devices.
The work will take place in Grenoble, the second scientific hub in France. The PhD student will be hired by CEA, a major French research institution with a high focus on alternative energies. He/she will join the fundamental research lab SyMMES, expert in nanomaterial design and energy devices such as solar cells, batteries and electrolyzers. She/he will work in co-supervision in the partner lab LMGP expert in materials science, synthesis and implementation at Grenoble INP. SYMMES and LMGP belong to University Grenoble Alpes and host widely international teams. The project will be actively supported by a local industrial recycling company.
Applicants should hold a Master 2 degree in chemistry, physics or materials science with skills in nanomaterials, electrochemistry or physical chemistry and in basic science for energy. Good English proficiency and a strong interest for innovation and collaborative work are expected.
Optimising the durability of high-temperature metal alloys: exploring new oxidation conditions
The aim of the OPTIMIST exploratory project is to increase the service life of metal alloys (alumina and chromia forming alloys) by forming a protective oxide layer, as is almost always the case to protect alloys from corrosion. The great originality of OPTIMIST will consist in forming an oxide layer with a minimum of 0D (point defects) and 2D (grain boundaries) structural defects. This objective will be based on two distinct strategies: the first will consist of forming a so-called endogenous oxide layer, i.e. by pre-oxidising the substrate by carefully choosing the pre-oxidation conditions (temperature, oxidising medium, oxygen partial pressure) in two types of Rhines Pack specifically developed at CEA/DES and IJL; the second will consist of forming a so-called exogenous oxide layer, i.e. created by a deposition technique: the HiPIMS recently commissioned at the CEA/INSTN. Different pre-oxidation conditions (for the endogenous layer) and process conditions (for the exogenous layer) will be investigated, then their 0D and 2D defects will be characterised at SIMaP using a novel combination of cutting-edge structural (TEM-ASTAR), chemical (atom probe, SIMS, nano-SIMS) and electronic (PEC PhotoelEctroChemistry) techniques. Finally, these characterised samples will be corroded in two environments (in air and in molten salts) at high temperatures to assess the effectiveness of the protection compared with conventional pre-oxidation. The stages of oxide growth, its stoichiometry and its microstructure (grain size and shape, nature of the grain boundaries) will thus be identified as a function of the endo and exogenous growth conditions so as to control them in order to achieve an oxide layer containing as few defects as possible.
Development and study of laminated composite material with carbon nanotubes functionalisation dedicated to launcher linerless cryogenic tank
The use of composite materials in the space field has led to great weight improvements. To continue to achieve significant weight gain, composite cryogenic tank is the next technological application to reach by replacing the current metal alloy cryogenic propellant tanks. Lighter reinforced organic matrix composite materials (that are at least as efficient from a mechanical, thermal, chemical and ignition resistance point of view) are a realistic target to be reached that has been explored in recent years. Many research approaches tend to answer to this technological lock, but the potentialities of Carbon NanoTubes (CNTs) in terms of mechanical and physical properties, need to be explored deeper.
A first phase to assess the interest of CNTs for space applications (collaboration CNES/CEA/I2M/CMP Composite) was carried out to associate CNTs with a cyanate ester matrix in layered composite materials through three processes: (i) transfer of aligned CNTs mats by hot pressing (ii) dispersion of entangled CNTs mixed with resin, or (iii) growth of nanotubes aligned directly on the dry ply. Knowing mechanical and thermal loads, the aim is to demonstrate the efficiency of CNTs and influence of their characteristics with regard to damage tolerance of the material and consist in delaying the cracking process of the composite nearby the CNT layer and thus blocking the percolation of the cracking network which leads to the loss of tightness. For the preferred development process identified, the aim of this doctoral work is now to consolidate the material functionalisation with CNTs (shape, density, etc.) and the understanding of the mechanical behaviour (at room temperature and at low temperature) for the development of the layered material integrating CNTs.
Knowing the potential final application as cryogenic tank or for the improvement of structural materials sustainability in dual application, relevant tests will be performed to demonstrate the impact in terms of damage development and tightness in comparison with the same material without CNTs.
Reactive neural network potentials: optimization of dataset construction and application to mechanochemical reactions
The spontaneous decomposition of organic molecules during synthesis, handling, or storage causes significant safety issues in the field of energetic materials. Besides thermal activation, recent studies suggest that intramolecular deformations, such as those induced by shock waves, significantly influence chemical reactivity and may alter decomposition mechanisms.
Molecular-level studies of these phenomena present significant challenges because they require both quantum-level accuracy for bond breaking and formation and the inclusion of condensed phase effect.
To bridge this gap, we propose the development and application of machine learning-based interatomic potentials (MLIPs),
In particular, we aim to significantly advance methodologies for building reactive structural datasets, specifically tailored to complex thermal and mechanochemical reactions with multiple decomposition pathways. Leveraging these improved datasets, we will develop MLIPs to study molecular decomposition under varying temperature and pressure conditions. Besides the safety concerns inherent to energetic molecules, the tools and knowledge developed during the project are expected to be of great value to the mechanochemistry community who currently lacks a molecular-level understanding of transformations in mechanochemical systems.
Study of the influence of the microstructure of a 316L steel produced by the L-PBF process on its mechanical properties: characterization and modeling of creep and fatigue behavior
Research into additive manufacturing for the nuclear industry shows that the production of 316L austenitic steel components using laser powder bed fusion (L-PBF) presents technical challenges, including process control, material properties, qualification and prediction of mechanical behaviour under service conditions. The final properties differ from traditional processes, often exhibiting anisotropy that challenges existing design standards.
These differences are linked to the unique microstructure resulting from the L-PBF process. Controlling the manufacturing chain, from consolidation to qualification, requires an understanding of the interactions between process parameters, microstructure and mechanical properties.
The aim of this thesis is to study the relationships between the microstructure, texture and mechanical properties of 316L steel manufactured by the L-PBF process, under static or cyclic loading. This includes the influence on creep and fatigue properties, and the development of a model to predict mechanical behaviour. Using samples of 316L steel with specific microstructures consolidated by L-PBF, the proposed study aims to establish links between microstructure and mechanical properties to better predict in-service behaviour.
Innovative syntheses of perovzalates and rationalization of the formation mechanism by synchrotron methods
“Perovzalates” are a new family of hybrid perovskites based on oxalate, with around ten examples listed since 2019 (AILi3MII(C2O4)3, with A = K+, Rb+, Cs+, NH4+; M = Fe2+, Co2+, Ni2+). Just like conventional perovskites, they are potentially interesting for countless applications (catalysis, optics, solar etc.), presenting additional advantages linked to the oxalate anion, which allows the incorporation of larger cations than in other hybrid pervovskites, while preserving a crystal structure similar to oxide perovskites.
However, this class of new materials is still barely explored, and the syntheses far from being mastered: the few reports to date systematically produce mixtures of phases, and relate to single crystals taken from heterogeneous solutions. In this context, the major problem is to synthesize an extended class of pure perovzalates.
This thesis addresses this challenge by exploiting a property discovered in the laboratory: the crystallization of metal oxalates by co-precipitation in water passes through transient “mineral emulsions”, that is to say nano-droplets rich in reagents which separate from water. The originality of this thesis is to exploit the nanostructuring provided by these mineral emulsions, and to test in particular using nanotomographic techniques accessible in synchrotron if they make it possible to confine the cations until crystallization.
Exploration of Diamond-Based Nanomaterials for (Sono)photocatalysis: Applications in Hydrogen Production and CO2 Reduction
Nanodiamonds (NDs) are increasingly being studied as semiconductors for photocatalysis, thanks in particular to the very specific positions of their valence and conduction bands, which can be modulated. For example, it has recently been shown that NDs can produce hydrogen under sunlight with an efficiency similar to that of TiO2 nanoparticles. Other studies also show the possibility of photogenerating solvated electrons from certain NDs for CO2 reduction or the degradation of stubborn pollutants.
With a view to accelerating the development of nanodiamond-based ‘solar-to-X’ technologies, we propose in this thesis to integrate nanodiamonds as photocatalysts in a sonophotocatalytic approach. Acoustic cavitation, generated by ultrasound, can improve mass transfer by dispersing catalytic particles and can produce additional reactive species (hydroxyl radicals, superoxides). It also emits sonoluminescence, which can promote the photogeneration of charges and should limit the recombination of charge carriers.
The first phase of the work will focus on the synthesis of nanodiamond-based photocatalysts, exploring various surface chemistries and their association with co-catalysts. Both classical and sonochemical synthesis methods will be used, as preliminary studies have shown that sonochemistry can effectively modify the surface chemistry of NDs. The photocatalytic properties of these materials will first be evaluated, leading to the design of a sonophotocatalytic cell. Further studies will explore the synergies between sonochemistry and photocatalysis for hydrogen production or CO2 reduction. This thesis will be carried out as part of a collaboration between the NIMBE at the Saclay CEA centre and the ICSM at the Marcoule CEA centre.
Design of plasmonic nanocomposite membranes for biomolecule detection
Detection of specific small biomolecules amounts is usually challenging. Recently, nanomaterials have provided new materials with interesting optical properties for such an application, especially plasmonic nanomaterials.
In this project, we propose the design of a specific type of nanocomposite made from the incorporation of plasmonic nanoparticles (NPs) within track-etched functionalized polymer membranes. The tuning of the material plasmonic response will be achieved by a controlled in situ NP synthesis directly within the membrane nanopores, through chemical and physico-chemical processes. Especially, the use of radiation (electron beam, ?-rays) to induce the in situ reduction of the metallic precursor will be studied. Ionizing beams (Swift Heavy ions) will also serve to structure the polymer matrix in nanoporous membrane with controlled nanoporosity. The relation between the composite nanostructure and its optical properties will be thoroughly investigated in order to determine the ideal material for biomolecule detection, which will be tested on model molecules such as proteins or virus-like particles (VLPs) in the final part of the project.
Influence of chromium doping of UO2 fuel on fission product speciation under accidental conditions
The development of nuclear reactors is part of a drive to improve safety, with, for example, the deployment of nuclear fuels with improved properties in terms of their behavior under accident conditions, the so-called E-ATF (Enhanced Accident Tolerant Fuel). Industrial operator FRAMATOME is developing the Cr2O3-doped UO2 fuel as E-ATF. However, very little data is available on the behavior of fission products from Cr-doped fuel under accident conditions.
This thesis proposes to develop a synthesis process for Cr-doped UO2 fuel that simulates irradiated fuel, in order to study the behavior of the elements (Cr and fission products) at different temperatures and under different oxygen partial pressures. The methodology is based on an experimental approach combining synthesis of model materials and in-depth chemical characterization, complemented by a theoretical approach (thermodynamic calculations) enabling thermal sequences to be dimensioned and the proposed reaction mechanisms to be confirmed.
The thesis will be carried out at CEA Cadarache (France), within IRESNE (Research Institute on Nuclear Systems for Low-Carbon Energy Production). The PhD student will be hosted in a laboratory dedicated to the study of uranium-based compounds in the Department of Fuel Studies (DEC). Depending on the densification processes chosen, experiments of various duration may be carried out in other laboratories in France or Europe.
The PhD student will have the opportunity to learn advanced characterization techniques for ceramic materials, gain access to experiments on large-scale instruments (synchrotron) and take part in exchanges with the academic community(CNRS, Universities, JRC). He or she will be able to promote his work through publications and participation in conferences.
At the end of this thesis, the PhD student will have acquired skills in materials science and solid state characterization that he/she will be able to use in various materials fields, as well as experience in the nuclear environment of interest to the nuclear industry.