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Bourassa, Louis. "Transition de Mott et supraconductivité dans les matériaux organiques". Mémoire, Université de Sherbrooke, 2017. http://hdl.handle.net/11143/10610.
Pełny tekst źródłaLantz, Gabriel. "Ultrafast electron dynamics in Mott materials". Thesis, Paris 11, 2015. http://www.theses.fr/2015PA112014/document.
Pełny tekst źródłaMott insulators are a perfect example of how local electronic correlations can change macroscopic properties of materials. Varying slightly the doping or the pressure can transform a metal to an insulator. These properties can be modified extremely rapidly by driving these materials far from equilibrium. We have investigated the model Mott-Hubbard material Cr-doped V2O3 using state of the art pump-probe techniques, namely angle resolved photoelectron spectroscopy, optical reflectivity, THz time-domain spectroscopy, and X-ray diffraction. We were able to unequivocally disentangle the electronic and the lattice response of the system to a femtosecond laser excitation, which was kept in all cases at a wavelength of 800 nm. We present a comparative study of these transient responses, which demonstrates the strong electron-phonon coupling of this strongly correlated model material. We show that before thermalization, spectral weight is transferred from the lower Hubbard band towards the Mott gap. On a longer time scale a metastable state is stabilized by the lattice structure. To further understand the transient response of Mott insulators, we have also studied another Mott compound, BaCo1-xNixS2. The general trends of photoexcitation in Mott insulators are analyzed using a two orbital model. We argue that the filling of the gap can be due to a change of the specific orbital fillings
Populoh, Sascha. "Investigation of the Mott transition in chromium doped V2 O3 by means of ultrasound and thermopower experiments". Paris 11, 2009. http://www.theses.fr/2009PA112044.
Pełny tekst źródłaThis work presents an experimental study of the high temperature Mott transition in chromium doped V2O3 by means of two different experimental techniques at pressures between ambient pressure and 6 kbar and temperatures from room T to 500 K. Ultrasound measurements as a direct probe of the compressibility were used to estimate the effects of the lattice on the Mott transition. We were able to present the first systematic study of the influence of the lattice degrees of freedom on the high temperature Mott transition in V2O3 and could verify the existence of a critical electronic temperature Telc that differs in the order of 3% or 4% from the temperature of the transition Tc of the bulk sample. Furthermore, observation of the behaviour of the transversal mode of the speed of sound allowed to conclude that this transition occurs without symmetry breaking and the order parameter is a scalar. In the second part the evolution of the Seebeck coefficient was investigated under the same experimental conditions. The studies around the critical point allowed us to establish an experimental phase diagram. Furthermore, we were able to show that the change of the Seebeck coefficient at the Mott transition is driven by the change in the resistivity rather than by the change of the particle-hole symmetry. As a consequence of this we could relate the scaling laws for the critical parameters related to conductivity to our data. In the vicinity of the transition our data were quite well reproduced by the mean field exponents found in the conductivity experiments
Koussir, Houda. "Multiscale study of the electric field induced transition in the Mott phase of GaMo4S8 crystals and TaSe2 monolayers". Electronic Thesis or Diss., Université de Lille (2022-....), 2024. http://www.theses.fr/2024ULILN004.
Pełny tekst źródłaIn the realm of condensed matter physics, Mott insulators are essential for exploring complex electronic phenomena, with significant implications for high-temperature superconductivity and quantum spin liquids. This thesis investigates two types of such materials, distinguished by their dimensionality : GaMo4S8 crystals and monolayer 1T-TaSe2.After presenting their properties in the first chapter, the second chapter addresses the local-scale characterization techniques used to characterize both materials, namely scanning tunneling microscopy and spectroscopy for structural and electronic studies, and multi-tip scanning tunneling microscopy for transport measurements. The latter technique was particularly employed to analyze transport in GaMo4S8. The study then delved into the material response to external electric fields, examining the threshold electric field in relation to the electrode geometry and exploring the temporal evolution of switching times in connection with inter-electrode distances. The achievement of volatile transitions opens prospects for applications such as the operation of a microneuron at room temperature.To enhance the control over phase transition properties of Mott insulators, it is beneficial to consider two-dimensional systems where the current flow is restricted within the crystal plane. The final chapter focuses on the 1T phase of TaSe2, epitaxially grown on gallium phosphide (GaP) semiconductor substrates. Low-temperature scanning tunneling microscopy studies reveal that 1T-TaSe2 monolayers exhibit not only the characteristic charge density modulation (Star of David) of the charge density wave phase but also a unique Moiré pattern due to the monolayer interaction with the GaP substrate. Scanning tunneling spectroscopy has identified a bandgap, hallmark of the Mott insulating state. This state is further substantiated by temperature-dependent transport measurements that show the persistence of the insulating phase up to 400 kelvins. Notably, spectroscopic measurements with varying tip-to-surface distances have unveiled insulator to metal transitions at low temperatures. The observation of such transitions suggests that this large-scale heterostructure could be a material of choice for neuromorphic applications
Brière, Benjamin. "Propriétés optiques de matériaux à fortes corrélations électroniques en conditions extrêmes". Thesis, Tours, 2018. http://www.theses.fr/2018TOUR4020/document.
Pełny tekst źródłaMaterials with strongly correlated electrons belong to the most intriguing systems in condensed matter physics due to their great variety of properties discovered during the last decades such as high temperature superconductivity, molecular conductors and colossal magnetoresistance. During this thesis, two types of strongly correlated materials have been studied: the quadruple perovskite EuCu3fe4Oi2 and the molecular conductors [Au(Et-thiazdt)2J. EuCu3Fe4Oi2 undergoes a metal to insulator transition at low temperature (240K), and [Au(Et-thiazdt)2J goes from a Mott insulator to a correlated metal state under high pressure. Infrared microspectroscopy measurements allowed us to probe the low energy electrodynamic of these systems. Ab-initio calculations were also used to understand the mechanisms of the transitions and the role of electronic correlations in the material
Boissy, Clément. "Transport de matière au sein du film passif : Développement d’une méthodologie sélective corrélant les Point Defect Model et les modèles descriptifs". Thesis, Lyon, INSA, 2014. http://www.theses.fr/2014ISAL0136.
Pełny tekst źródłaDevelopments in metallic bipolar plate, to apply more widely fuel cells, require an improved of the constitutive material. The use of stainless steel calls for a good understanding of the passive film. The required specifications are for good electrical conductivity and a long life-time. Those two parameters correspond to a correlation between the semiconductive properties and the good corrosion behavior. Nevertheless, the main problems of the passivity lie on the multiplicity of the phenomena that alter the passive film behavior. Numerous models described in the literature can be used to characterize the passivation. The Point Defect Model (PDM) describes the passivation through electrochemical reactions at the metal / oxide and at the oxide / electrolyte interfaces. The reactivity is limited by mass transport through the oxide. From the literature, those phenomena seems to be a discriminating parameter in the choice of a model. The selective method proposed allows us to use each model taking into account their specifics. This methodology is based on the correlation between the mass transport characterization, thanks to the PDM, and the analysis of the Electrochemical Impedance Spectroscopy (EIS). The PDM determines the transport coefficient apart from EIS measurements, so to validate the consideration of the mass transport during the analysis of the electrochemical impedance spectra. The evolution of the main charge carrier density as a function of the oxide formation potential allows us to calculate the transport coefficient from PDM equations. Thanks to the thickness of the oxide (determined by X-ray Photoelectron Spectroscopy), the time constant of the mass transport is determined. Based on this value, a descriptive model is used to analyze the EIS data, avoiding overparametrization. This method is applied first on a model material, pure chromium exposed to acidic solution (pH 2) at several temperatures (30°C and 80°C). It shows that the mass transport has to be taken into account at 80°C and the EIS model considers an inner chromium oxide layer and an outer chromium hydroxide. Secondly, the method is used to characterize an industrial material, AISI 316L stainless steel, at several pH (1, 2 and 3) and at several temperatures (30°C and 80°C). In this case, the oxide is describe as a p-n semiconductor junction with an chromium rich inner layer and an outer iron rich layer. The present methodology permits to deeply characterize the AISI 316L stainless steel. Even if this study concerns the substrate, this step is decisive to improve the performances of the metallic bipolar plates
Devaux, Nicolas. "Étude par Monte Carlo quantique de la transition γ-α du cérium". Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066373/document.
Pełny tekst źródłaThe 4f electrons are strongly localized and their on-site Coulomb repulsion is large compared to bandwidth. Among all lanthanides, cerium is particularly fascinating, due to the strong hybridization with the 6s-6p-5d bands, all present at the Fermi level. The origin of the cerium volume collapse along the isostructural γ-α transition has been a puzzle since its discovery in 1927. Experimentally, pure cerium undergoes the γ-α transition always at finite temperature T. Recently, very accurate X-ray diffraction measurements undoubtedly confirmed the first-order Fm-3m isostructural character of the transition. The first-order line extrapolates to zero-T at negative pressures. The cerium γ-α phase transition is characterized by means of a many-body Jastrow-correlated wave function, which minimizes the variational energy of the first-principles scalar-relativistic Hamiltonian, and includes correlation effects in a non-perturbative way. Our variational ansatz reproduces the structural properties of the two phases, and proves that even at temperature T = 0 K the system undergoes a first order transition, with ab-initio parameters which are seamlessly connected to the ones measured by experiment at finite T. We show that the transition is related to a complex rearrangement of the electronic structure, with key role played by the localisation of t1u orbitals, which tunes the Coulomb repulsion, and the character of the chemical bond
Aeschlimann, Raphaël. "Magnetic and transport properties of rare-earth titanate thin films and heterostructures". Thesis, université Paris-Saclay, 2020. http://www.theses.fr/2020UPASS142.
Pełny tekst źródłaTransition metal oxides possess a broad range of functionalities (superconductivity, magnetism, ferroelectricity, multiferroicity) stemming from the interplay between structural effects and electronic correlations. Recent work has revealed exciting physics at their interfaces, including conductivity and superconductivity in the two-dimensional electron system (2DES) that forms at the interface between two band insulators, LaAlO₃ and SrTiO₃. However, to embrace the immense potential of oxide interfaces and unveil unprecedented electronic phases, combining insulators with stronger electronic correlations is necessary. At the crossroad between strongly correlated electron physics, magnetism and spintronics, the present thesis project aims to harness electronic and magnetic instabilities in correlated oxides to craft new electronic phases controllable by external stimuli. We investigated rareearth titanates RTiO₃, a relatively unexplored family of Mott insulating perovskites with a crossover between antiferromagnetic and ferromagnetic orders upon changing the rare-earth size. Contrary to most previous works, we focused on ferromagnetic compounds, and their integration in 2DES. The thesis developed along two main axes. First, we explored several members of the rare-earth titanates family in epitaxial thin film form. We highlighted the presence of a magnetically active dead layer at the surface of thin films and established its origin as due to the overoxidation of titanium ions. We also studied the presence of an unexpected orbital moment carried by the titanium in some compounds, and discussed it in the light of the non-collinear spin arrangement promoted by the rare-earth orbital moment and of a structural gradient evidenced by transmission electron microscopy. In a second stage, we combined DyTiO₃ with SrTiO₃ to stabilize a conducting interface with puzzling magnetotransport properties that we interpreted with a model involving spin-orbit coupling as well as induced magnetism
Devaux, Nicolas. "Étude par Monte Carlo quantique de la transition γ-α du cérium". Electronic Thesis or Diss., Paris 6, 2015. http://www.theses.fr/2015PA066373.
Pełny tekst źródłaThe 4f electrons are strongly localized and their on-site Coulomb repulsion is large compared to bandwidth. Among all lanthanides, cerium is particularly fascinating, due to the strong hybridization with the 6s-6p-5d bands, all present at the Fermi level. The origin of the cerium volume collapse along the isostructural γ-α transition has been a puzzle since its discovery in 1927. Experimentally, pure cerium undergoes the γ-α transition always at finite temperature T. Recently, very accurate X-ray diffraction measurements undoubtedly confirmed the first-order Fm-3m isostructural character of the transition. The first-order line extrapolates to zero-T at negative pressures. The cerium γ-α phase transition is characterized by means of a many-body Jastrow-correlated wave function, which minimizes the variational energy of the first-principles scalar-relativistic Hamiltonian, and includes correlation effects in a non-perturbative way. Our variational ansatz reproduces the structural properties of the two phases, and proves that even at temperature T = 0 K the system undergoes a first order transition, with ab-initio parameters which are seamlessly connected to the ones measured by experiment at finite T. We show that the transition is related to a complex rearrangement of the electronic structure, with key role played by the localisation of t1u orbitals, which tunes the Coulomb repulsion, and the character of the chemical bond
Leriche, Raphaël. "Unconventional superconductivity in quasi-2D materials with strong spin-orbit coupling". Thesis, Sorbonne université, 2019. http://www.theses.fr/2019SORUS577.
Pełny tekst źródłaThe realization of topological superconductors is one of the main current goals of condensed matter physics. It was indeed predicted that such systems should host Majorana fermions. These Majorana fermions possess both a non-Abelian statistics and, because of their topological origin, a certain robustness against local disorder, which makes them attractive for quantum computing applications. One approach likely to lead to topological superconductivity consists in considering superconducting systems with strong spin-orbit coupling and with broken inversion symmetry. It is in this framework that, during this thesis, I performed scanning tunneling microscopy and spectroscopy measurements on quasi-2D materials : (LaSe)1,14(NbSe2)2 and Sr2IrO4. I first studied the electronic properties of misfit compound LaNb2Se5, which is a parent of transition metal dichalcogenide 2H-NbSe2. (LaSe)1,14(NbSe2)2 is a heterostructure made out of alternations of NbSe2 bilayers with trigonal prismatic geometry and LaSe bilayers with rocksalt structure. (LaSe)1,14(NbSe2)2 is a potential candidate for topological superconductivity because of the presence of both a strong spin-orbit coupling and of broken inversion symmetry in NbSe2 planes. Here, I present spectroscopic results showing that the electronic structure of(LaSe)1,14(NbSe2)2 is very similar to the one of electron-doped monolayer NbSe2 with a shift of the chemical potential of 0,3 eV, priorly never reached. I could also demonstrate the quasi- 2D nature of (LaSe)1,14(NbSe2)2 and more particularly the presence of a strong Ising spinorbit coupling. Moreover, the observed weakness of superconductivity against non-magnetic disorder combined with quasiparticle interferences measurements allowed me to exhibit the unconventional nature of (LaSe)1,14(NbSe2)2 superconducting order parameter. This study opens the possibility to use misfit heterostructures such as (LaSe)1,14(NbSe2)2 to study thephysics of transition metal dichalcogenides in the 2D limit, for which many theoretical studies predict topological superconductivity. In this thesis, I also present a study on the effects of doping on the electronic properties of iridate compound Sr2IrO4. Sr2IrO4 is a spin-orbit induced Mott insulator. Because inversion symmetry is locally broken in Sr2IrO4, some theoretical predictions suggest that Sr2IrO4 should turn into a topological superconductor once doped. Here, I exhibit a nanometer-scaleinhomogeneous doping-driven Mott insulator to pseudo-metallic phase transition. This work further justifies the importance of using a local probe such as scanning tunnelling microscopy in order to complete results on Mott physics obtained by integrative methods like angle-resolved photoemission spectroscopy
Souchier, Émeline. "Élaboration de couches minces de GaV4S8 par pulvérisation magnétron : du matériau au premier dispositif pour mémoire à transition résistive (RRAM)". Nantes, 2010. http://www.theses.fr/2010NANT2021.
Pełny tekst źródłaThe compounds of the lacunar spinel family AM4X8 (A = Ga, Ge ; M = V, Ta, Nb ; X = S, Se) are small gap Mott insulators which undergo a resistive switching under electric pulses. This non-volatile and reversible switching, discovered on single crystals, has potential applications in the field of RRAM non-volatile memories. To unlock this potential, a major challenge, the deposition of these chalcogenide materials in thin layers, remains. In this work, GaV4S8 thin layers were synthesized for the first time, using RF magnetron sputtering. This technique is compatible with the current technological fabrication steps used in microelectronics. We first prepared sputtering targets with a compacity higher than 90%. Through a thorough parametric study of the deposition and annealing conditions, crystallized and stoichiometric thin layers have been obtained with electronic properties identical to the bulk material. At room temperature, the thin layers exhibit both the resistive switching and cycling property induced by electric pulses. The study on the resistive switching reveals the existence of a threshold electric field, which suggests that it is related to an electric field effect. Our entire study demonstrates, on the one hand, that the mechanism behind the resistive switching differs from those identified in other systems reported so far and, on the other hand, that the cycling characteristics (amplitude, switching time and voltage) of GaV4S8 are competitive with respect to those encountered in other kind of emerging non-volatile memories
Demers, Isabelle. "Lourd comme un cheval mort : le récit matérialisé". Thesis, Université Laval, 2012. http://www.theses.ulaval.ca/2012/28858/28858.pdf.
Pełny tekst źródłaDuquesnes, Vincent. "De l'hydruration du titane et ses alliages : impact des paramètres de mise en forme du matériau et conséquences sur sa durabilité en milieu corrosif". Thesis, Dijon, 2016. http://www.theses.fr/2016DIJOS054/document.
Pełny tekst źródłaZhang, Huiming. "Iconographie de Mañjuśrī et du mont Wutai en Chine médiévale : une étude d’après les matériaux picturaux de Dunhuang du VIIe – au Xe siècle". Paris, EPHE, 2011. http://www.theses.fr/2011EPHE4023.
Pełny tekst źródłaOn plenty of Dunhuang paintings, painted between 7th and 10th centuries, Manjusri appears riding on a lion, and in relation with Mount Wutai. This is one of the most famous theme of Chinese Middle Age buddhist iconography. Most of wall-paintings dealing with that topic are located in Mogao caves. That pictural thematic originating in Indiana was perfectly adapted to the chinese cultural context. The purpose of the present work is the study of chinese buddhist and lay sources in China under Tang dynasty, particularly we provide an analysis of prototypes and models of representation within the frame of buddhist art development during that period. Thus, it was highlighted various phenomenons related to the evolution and transmission of buddhist iconographic items in a context of close exchanges between indian, bactrian, sogdian, chinese and tibetan cultures from 7th to 10th centuries. The analysis of iconographic and textual chinese materials also led us to define the development of a thematic related with religious or lay practices in Mount Wutai and Dunhuang regions, and its way getting into images. Each of these representations is given an interpretation in the chinese cultural context, and when possible, a link to textual sources or a model is suggested. Then, it turns out that these representations from Dunhuang constitute an exceptional documentation that gives us the possibility to restore an episode of the history of Buddhist iconography in China during the middle-age period
Almuneau, Guilhem. "Les lasers à cavité verticale infrarouge : d'une approche matériau à des géométries de composant innovantes". Habilitation à diriger des recherches, Université Paul Sabatier - Toulouse III, 2010. http://tel.archives-ouvertes.fr/tel-00473597.
Pełny tekst źródłaZerrad, Mehdi. "Caractérisation expérimentale et modélisation numérique du comportement vibratoire des matériaux polymères chargés en fibres courtes : Application à un carter d’huile de Groupe Moto-Propulseur thermique d’automobiles". Thesis, Lyon, 2018. http://www.theses.fr/2018LYSEI064.
Pełny tekst źródłaAs European standards for CO2 emissions are becoming more stringent, car manufacturers are seeking, among other strategies, to lighten their vehicles to reduce their consumption. Thus, the replacement of metal parts by others made from lighter materials such as polymeric composite materials filled with short fibers is increasingly used in the automotive industry. However, during the design process, engineers face difficulties when trying to numerically model the vibro-acoustic response of these parts and / or assemblies. Indeed, these materials are very sensitive to external parameters such as temperature, loading frequency and humidity. In addition, their behavior also depends on the injection process which has an influence on their local microstructure and more particularly on the orientation and dispersion of the reinforcing fillers. In turn, their numerical modeling is complex and the comparison with the experimental measurements unsatisfactory. In this research work, the influence of the ambient parameters on the dynamic behavior of an oil pan made of polyamide 6 reinforced with 35\% by mass of glass fibers was studied. Local mechanical and microstructural characterizations were performed to investigate the relationship between the microstructure and the properties of these composite materials. A numerical model was then developed on the basis of these experimental studies and allowed to evaluate the influence of the microstructure on the vibratory behavior of a model plate system. Finally, computation / test correlations were performed to compare the numerical modeling method to the measurements. These studies have made it possible to highlight the sensitivity of these materials to their environment, to establish a hierarchy of the influence of the various parameters on their vibration behavior and to propose a "low cost" numerical methodology based on the experimental characterization of constituent elements taken separately
Le, Losq Charles. "Rôle des éléments alcalins et de l'eau sur les propriétés et la structure des aluminosilicates fondus et vitreux : implications volcanologiques". Phd thesis, Université Paris-Diderot - Paris VII, 2012. http://tel.archives-ouvertes.fr/tel-00923471.
Pełny tekst źródłaNgenda, Banka Richard. "Etude de valorisation des rejets des usines à zinc de Kolwezi, République démocratique du Congo". Doctoral thesis, Universite Libre de Bruxelles, 2010. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/210144.
Pełny tekst źródłaA l’aide des techniques modernes de caractérisation (physico–chimique, minéralogique et morphologique), nous sommes arrivés à cibler, à adapter et à justifier l’utilisation d’une technique de valorisation des matières minérales existantes. Les minéraux utiles contenus dans les rejets UZK ont été sulfatés par digestion et sélectivement mis en solution après un grillage. La sulfatation s’est avérée l’étape déterminante du procédé et un intérêt particulier a été focalisé sur cette étape en réalisant une étude cinétique approfondie.
Les données et informations récoltées tout le long de cette recherche nous ont permis de réaliser une simulation du procédé par le logiciel ASPEN PLUS. Ce qui a permis de faire une ébauche d’un schéma de traitement industriel. Ce dernier s’est avéré souple vis-à-vis de l’utilisation d’autres matières comme les calcines des concentrés sulfurés cuivre-zinc.
Residues from the Kolwezi Zinc Plant (Usines à Zinc de Kolwezi UZK) essentially contain zinc in a refractory (ferrite) form, which is difficult to recover by conventional hydrometallurgical methods. « Heavy» metals are also present that make them hazardous towards the environment in which they are currently stored. Most of these metals are valuable; thus, the UZK residues are a real secondary deposit. It is therefore imperative to develop an appropriate method of treatment, hence the theme of the present thesis: « Recovery study of values metals from Kolwezi Zinc Plant residues, DRC ».
Using modern techniques of characterization (physical and chemical, mineralogical and morphological), we focused, adapted and justified the use of a technique for efficient recovery of the existing valuable minerals. The minerals contained in UZK residues have been sulphated by digestion and thereafter selectively dissolved after roasting. Sulphatation proved to be the decisive step of the process and a particular attention has been given to this step by performing a detailed kinetic study.
The data and information collected throughout this research allowed a simulation of the developed method by using the « Aspen Plus » software. This allowed us to propose a draft scheme of industrial processing. The latter proved flexible towards the use of other materials such as calcines of copper-zinc sulphide concentrates.
Doctorat en Sciences de l'ingénieur
info:eu-repo/semantics/nonPublished
Boissy, Clémént. "Transport de matière au sein du film passif : Développement d’une méthodologie sélective corrélant les Point Defect Model et les modèles descriptifs". Thesis, 2014. http://www.theses.fr/2014ISAL0136/document.
Pełny tekst źródłaDevelopments in metallic bipolar plate, to apply more widely fuel cells, require an improved of the constitutive material. The use of stainless steel calls for a good understanding of the passive film. The required specifications are for good electrical conductivity and a long life-time. Those two parameters correspond to a correlation between the semiconductive properties and the good corrosion behavior. Nevertheless, the main problems of the passivity lie on the multiplicity of the phenomena that alter the passive film behavior. Numerous models described in the literature can be used to characterize the passivation. The Point Defect Model (PDM) describes the passivation through electrochemical reactions at the metal / oxide and at the oxide / electrolyte interfaces. The reactivity is limited by mass transport through the oxide. From the literature, those phenomena seems to be a discriminating parameter in the choice of a model. The selective method proposed allows us to use each model taking into account their specifics. This methodology is based on the correlation between the mass transport characterization, thanks to the PDM, and the analysis of the Electrochemical Impedance Spectroscopy (EIS). The PDM determines the transport coefficient apart from EIS measurements, so to validate the consideration of the mass transport during the analysis of the electrochemical impedance spectra. The evolution of the main charge carrier density as a function of the oxide formation potential allows us to calculate the transport coefficient from PDM equations. Thanks to the thickness of the oxide (determined by X-ray Photoelectron Spectroscopy), the time constant of the mass transport is determined. Based on this value, a descriptive model is used to analyze the EIS data, avoiding overparametrization. This method is applied first on a model material, pure chromium exposed to acidic solution (pH 2) at several temperatures (30°C and 80°C). It shows that the mass transport has to be taken into account at 80°C and the EIS model considers an inner chromium oxide layer and an outer chromium hydroxide. Secondly, the method is used to characterize an industrial material, AISI 316L stainless steel, at several pH (1, 2 and 3) and at several temperatures (30°C and 80°C). In this case, the oxide is describe as a p-n semiconductor junction with an chromium rich inner layer and an outer iron rich layer. The present methodology permits to deeply characterize the AISI 316L stainless steel. Even if this study concerns the substrate, this step is decisive to improve the performances of the metallic bipolar plates
WEI, Hua. "Development of Innovative Electrodes for the Electrocatalytic Conversion of Small Molecules". Doctoral thesis, 2021. http://hdl.handle.net/11570/3191397.
Pełny tekst źródłaNitrogen plays an indispensable role for all life on earth and for the development of human beings. Industrially, nitrogen gas is converted to ammonia (NH3) and nitrogen-rich fertilisers to supplement the amount of nitrogen fixed spontaneously by nature. At present, the only industrial-scale ammonia synthesis technology is the process developed by Haber and Bosch in the early 20th century using gas phase N2 and H2 as the feeding gases. However, the Haber-Bosch process requires harsh conditions, complex equipment and high energy consumption, and operates with low conversion rates, which are inconsistent with economic and social growing development requirements. Compared to the Haber-Bosch method, electrocatalysis is one of the promising routes that can integrate electricity produced from renewable energy technologies for the production of ammonia at room temperature and ambient pressure. A specific challenge is related to the development of novel electrocatalysts/electrodes with the aim to achieve a low-cost, large-scale and delocalized production of ammonia. In view of the above key scientific issues, this PhD work focuses on three main aspects of the electrocatalytic nitrogen reduction reaction (NRR): i) engineering and design of the electrocatalyst, ii) electrode and cell design of the electrochemical device and iii) improvement and optimization of the reaction conditions, to enhance the performances of ammonia synthesis. Most of the research activities of this PhD work about synthesis and characterization of the electrocatalytic materials and assembling/testing of the electrodes in unconventional electrochemical devices were carried out at the laboratory CASPE (Laboratory of Catalysis for Sustainable Production and Energy) of the University of Messina. Moreover, during the three years, a period of 12 months was spent in cotutelle with the École supérieure de chimie, physique, électronique de Lyon (CPE Lyon), where advanced synthesis routes were explored for the preparation of organometallic-based electrocatalysts to be used as more active electrodes in NRR. The PhD thesis is organized in five main chapters. Chapter 1 focuses on N2 fixation issues and on describing the industrial Haber-Bosch process, with an overview of the general implications related to its high energy requirements. The alternative methods based on the electrochemical nitrogen fixation are then presented, with a wide description of pros and cons related to the milder conditions (i.e., room temperature and atmospheric pressure) and by discussing the elements to be developed for a future implementation of this technology, including a description of the possible reaction mechanism, which is still unclear in literature. Chapter 2, instead, refers to the electrocatalytic materials developed in this PhD work for the preparation of the electrodes: 1) the Metal-organic Frameworks (MOFs), a class of porous materials very promising for their peculiar characteristics of high surface area, tunable properties, organic functionality and porosity, as well as for the possibility of creating specific catalytic active sites thanks to both the functional groups and the metal ion centres; 2) the MXenes, a class of metal carbide or nitride materials with a two-dimensional (2D) structure, which have recently attracted a large interest for a broad range of applications, including catalysis and N2 fixation, for their unique properties of metallic conductivity and hydrophilic nature of the hydroxyl or oxygen terminated surfaces. In Chapters 3-5, the experimental results are presented and discussed. Chapter 3 concerns the preparation of a series of Fe-MOF-based (Fe@Zn/SIM-1) electrodes and their testing in NRR by using an advanced engineered three-phase reactor, working in gas-phase. This novel device operates at room temperature and atmospheric pressure, with counter and reference electrodes immersed into an anode half-cell (where the oxidation of H2O to O2 occurs) containing a liquid electrolyte (the anolyte), while the cathode half-cell for NRR operates in gas phase without a liquid electrolyte (electrolyte-less conditions). This type of electrocatalytic reactor is thus quite different from the conventional electrocatalytic reactors operating in liquid phase, with the main advantages of avoiding issues related to the low N2 solubility and transport in the electrolyte, and allowing an easier recovery of ammonia. The results obtained from these electrocatalytic tests in gas-phase were very useful to improve the design of the MOFs-based electrodes, evidencing the limits of these kinds of materials in terms of N content, stability and possibility to prepare more advanced electrocatalysts by carbonization. A wide part of this chapter was dedicated to the development of new experimental strategies for avoiding false positive in the detection of ammonia, which is one of the topics most studied from scientists working in NRR in the last two years. As accurate protocols were recently suggested in literature, also using advanced analytical techniques (i.e. using 15N labelled nitrogen), an easier methodology based on UV-visible spectrophotometric analysis (coupled with blank tests with inert gases) was suggested in this work to avoid ammonia contaminations and false positives, although more sophisticated analytical techniques may definitely confirm the real source of ammonia. In Chapter 4, a series of improved Fe-MOF-based materials (Fe-based and Fe-alkali metal-based MOF UiO-66-(COOH)2), synthesized by cation exchange reaction technique to replace the proton of carboxylic acid with an iron cation, are presented. With respect to Fe@Zn/SIM-1, this new class of MOFs are more stable in water and do not contain nitrogen atoms in their structure. Results evidenced that 80% cation exchange Fe@UiO-66-(COOH)2 (with an effective Fe content of around 8 wt.%) was the best electrocatalyst among the tested Fe-based MOF synthesized materials. The performances in NRR highly depended on cell and electrode design. More in detail, an ammonia yield of 1.19 μg•h-1•mgcat-2 was obtained with an assembling configuration of layers ordered as i) Nafion (the membrane), ii) Fe-based MOF (the electrocatalyst), iii) GDL (the carbon gas diffusion layer) and iv) a further layer of Fe-MOF. The effect of applied voltage was also explored, indicating an optimal voltage of -0.5 V vs. RHE to maximize activity in NRR and limiting the side hydrogen evolution reaction. Moreover, as currently used in the industrial catalysts for Haber-Bosh process, the introduction of potassium in the electrocatalysts was also investigated, in order to facilitate charge transfer from K- ions to the iron-based catalyst surface, balancing the dissociative chemisorption between H2 and N2, and suppressing side reactions, thus improving both activity and stability. These results were very promising, although a further experimentation is needed to improve their performances in NRR, to overcome limitations related to MOF materials themselves, majorly due to their low conductivity and stability. Finally, Chapter 5 refers to the exploration of advanced MXene materials (Ti3C2 MXene) and to the attempt of synthesizing a 3D nanoarchitecture starting from 2D-dimensional MXene-based catalysts. To understand the role of the nanostructure of MXene materials in NRR, Ti3C2 nanosheets were treated with KOH to obtain a final shape of three-dimensional (3D) porous frameworks nanoribbons. Specifically, the objective of this research was to investigate how the conversion of Ti3C2 nanosheets to 3D-like nanoribbons influence the NRR reactivity in the gas-phase electrochemical device. A full characterization of MXenes nanoribbons (SEM, TEM, HRTEM, XRD, XPS and EDX) was also presented. Results showed that the 3D-type nanostructure (nanoribbons) leads to a significant enhancement of the N2 fixation activity due to the formation of exposed Ti-OH sites. A linear relationship was observed between ammonia formation rate and amount of oxygen on the surface of Ti3C2 MXene.
L'azote joue un rôle indispensable pour toute vie sur terre et pour le développement des êtres humains. Industriellement, l'azote gazeux est converti en ammoniac (NH3) et en engrais riches en azote pour compléter la quantité d'azote fixée spontanément par la nature. À l'heure actuelle, la seule technologie de synthèse de l'ammoniac à l'échelle industrielle est le procédé mis au point par Haber et Bosch au début du XXe siècle, qui utilise les phases gazeuses N2 et H2. Cependant, le procédé Haber-Bosch nécessite des conditions difficiles, des équipements complexes et une consommation d'énergie élevée, et fonctionne avec de faibles taux de conversion, ce qui est incompatible avec les exigences d’un développement durable. Par rapport à la méthode Haber-Bosch, l'électrocatalyse est l'une des voies prometteuses qui permet d'intégrer l'électricité produite à partir de technologies d'énergies renouvelables pour la production d'ammoniac à température ambiante et à pression ambiante. Un défi spécifique est lié au développement de nouveaux électrocatalyseurs/électrodes dans le but de parvenir à une production d'ammoniac à faible coût, à grande échelle et délocalisée. Compte tenu ces défis scientifiques, ce travail de doctorat se concentre sur trois aspects principaux de la réaction électrocatalytique de réduction de l'azote (NRR) : i) ingénierie et conception de l'électrocatalyseur, ii) conception de l'électrode et de la cellule du dispositif électrochimique et iii) amélioration et optimisation des conditions de réaction, afin d'améliorer les performances de la synthèse de l'ammoniac. La plupart des activités de recherche de ce travail de doctorat sur la synthèse et la caractérisation des matériaux électrocatalytiques et l'assemblage/le test des électrodes dans des dispositifs électrochimiques non conventionnels ont été menées au laboratoire CASPE (Laboratory of Catalysis for Sustainable Production and Energy) de l'université de Messine. En outre, une période de 12 mois a été passée en cotutelle avec l'École supérieure de chimie, physique, électronique de Lyon (CPE Lyon), où des voies de synthèse avancées ont été explorées pour la préparation d'électrocatalyseurs à base de composés organométalliques qui ont été utilisés comme électrodes plus actives dans la RRN. Cette thèse de doctorat est organisée en cinq grands chapitres. Le chapitre 1 se concentre sur les questions de fixation de l'azote et sur la description du processus industriel de Haber-Bosch, avec un aperçu des implications générales liées à ses besoins élevés en énergie. Les méthodes alternatives basées sur la fixation électrochimique de l'azote sont ensuite présentées, avec une large description des avantages et des inconvénients liés aux conditions plus douces (c'est-à-dire la température ambiante et la pression atmosphérique) et en discutant des éléments à développer pour une future mise en œuvre de cette technologie, y compris une description du mécanisme de réaction possible, encore débattu dans la littérature. Le chapitre 2 fait référence aux matériaux électrocatalytiques développés pour la préparation des électrodes : 1) les matériaux hybrides organiques-inorganiques de type MOF, une classe de matériaux poreux très prometteurs pour leurs caractéristiques particulières de surface spécifique élevée et leurs propriétés ajustables ainsi que pour la possibilité de créer des sites catalytiques actifs spécifiques grâce aux groupes fonctionnels et aux centres d'ions métalliques ; 2) les MXènes, une classe de matériaux en carbure ou nitrure de métal à structure bidimensionnelle (2D), qui ont récemment suscité un grand intérêt pour un large éventail d'applications, notamment la catalyse et la fixation de N2, pour leurs propriétés uniques de conductivité métallique et de nature hydrophile des surfaces terminées par un hydroxyle ou un oxygène. Les chapitres 3 à 5 présentent et analysent les résultats expérimentaux. Le chapitre 3 concerne la préparation d'une série d'électrodes à base de Fe-MOF (Fe@Zn/SIM-1) et leur test dans la réaction NRR en utilisant un réacteur triphasé de pointe, fonctionnant en phase gazeuse. Ce nouveau dispositif fonctionne à température ambiante et à la pression atmosphérique, avec des électrodes de comptage et de référence immergées dans une demi-cellule anodique (où se produit l'oxydation de H2O en O2) contenant un électrolyte liquide (l'anolyte), tandis que la demi-cellule cathodique pour le NRR fonctionne en phase gazeuse sans électrolyte liquide. Ce type de réacteur électrocatalytique est donc très différent des réacteurs électrocatalytiques classiques fonctionnant en phase liquide, avec les principaux avantages d'éviter les problèmes liés à la faible solubilité et au transport de N2 dans l'électrolyte, et de permettre une récupération plus facile de l'ammoniac. Les résultats obtenus lors de ces essais électrocatalytiques en phase gazeuse ont été très utiles pour améliorer la conception des électrodes à base de MOFs, mettant en évidence les limites de ce type de matériaux en termes de teneur en N, de stabilité et de possibilité de préparer des électrocatalyseurs plus avancés par carbonisation. Une grande partie du chapitre 3 a été consacrée au développement de nouvelles stratégies expérimentales pour éviter les faux positifs dans la détection de l'ammoniac, qui est l'un des sujets les plus étudiés par les scientifiques travaillant dans la NRR ces deux dernières années. Comme des protocoles précis ont été récemment suggérés dans la littérature, utilisant également des techniques analytiques avancées (c'est-à-dire utilisant de l'azote marqué à 15N), une méthodologie plus facile basée sur l'analyse spectrophotométrique UV-visible (couplée à des essais à blanc avec des gaz inertes) a été suggérée dans ce travail pour éviter les contaminations par l'ammoniac et les faux positifs, bien que des techniques analytiques plus sophistiquées puissent définitivement confirmer la source réelle d'ammoniac. Dans le chapitre 4, une série de matériaux améliorés à base de Fe-MOF (incluant un dopage additionel par un métal alcalin du MOF UiO-66-(COOH)2), synthétisés par une technique de réaction d'échange de cations pour remplacer le proton de l'acide carboxylique par un cation de fer, sont présentés. En ce qui concerne le Fe@Zn/SIM-1, cette nouvelle classe de MOF est plus stable dans l'eau et ne contient pas d'atomes d'azote dans sa structure. Les résultats ont montré que l'échange cationique à 80 % Fe@UiO-66-(COOH)2 (avec une teneur effective en Fe d'environ 8 % en poids) était le meilleur électrocatalyseur parmi les matériaux synthétisés de MOF à base de Fe testés. Les performances du NRR dépendaient fortement de la conception de la cellule et de l'électrode. Plus en détail, un rendement en ammoniac de 1.19 μg•h-1•mgcat-2 a été obtenu avec une configuration d'assemblage de couches ordonnées comme i) Nafion (la membrane), ii) MOF à base de Fe (l'électrocatalyseur), iii) GDL (la couche de diffusion de gaz carbonique) et iv) une autre couche de Fe-MOF. L'effet de la tension appliquée a également été exploré, indiquant une tension optimale de -0,5 V par rapport à la RHE pour maximiser l'activité dans le NRR et limiter la réaction latérale d'évolution de l'hydrogène. En outre, comme c'est le cas actuellement dans les catalyseurs industriels pour le procédé Haber-Bosh, l'introduction de potassium dans les électrocatalyseurs a également été étudiée, afin de faciliter le transfert de charge des ions K- à la surface du catalyseur à base de fer, en équilibrant la chimisorption dissociative entre H2 et N2, et en supprimant les réactions secondaires, ce qui améliore à la fois l'activité et la stabilité. Ces résultats étaient très prometteurs, bien qu'une nouvelle expérimentation soit nécessaire pour améliorer leurs performances dans les NRR, afin de surmonter les limitations liées aux matériaux MOF eux-mêmes, principalement en raison de leur faible conductivité et de leur stabilité. Enfin, le chapitre 5 fait référence à l'exploration des matériaux avancés à base de MXène (Ti3C2 MXène) et à la tentative de synthèse d'une nanoarchitecture 3D à partir de catalyseurs à base de MXène en 2D. Pour comprendre le rôle de la nanostructure des matériaux à base de MXène dans la NRR, des nanofeuilles de Ti3C2 ont été traitées au KOH pour obtenir une forme finale de nanorubans à armature poreuse tridimensionnelle (3D). Plus précisément, l'objectif de cette recherche était d'étudier comment la conversion des nanofeuilles de Ti3C2 en nanorubans tridimensionnels influençait la réactivité du NRR dans le dispositif électrochimique en phase gazeuse. Une caractérisation complète des nanorubans MXenes (SEM, TEM, HRTEM, XRD, XPS et EDX) a également été présentée. Les résultats ont montré que la nanostructure de type 3D (nanorubans) conduit à une amélioration significative de l'activité de fixation du N2 en raison de la formation de sites Ti-OH exposés. Une relation linéaire a été observée entre le taux de formation d'ammoniac et la quantité d'oxygène à la surface du Ti3C2 MXene.