<p>   Contamination of surface and ground water from industrial wastes and anthropogenic activities represents one of the greatest challenges to the sustainable development of human society. Heterogeneous photocatalysis, a kind of advanced oxidation process characterized by the production of highly oxidative hydroxyl radicals, is a relatively novel subject with tremendous potential in water treatment applications.</p><p>    The purpose of this research was first to develop feasible hydroxyl radical detection methods, which can be used to evaluate efficiency of photocatalytic process, and second to prepare immobilized TiO2 films with high photocatalytic activities by the sol gel method.</p><p>    The feasibility of Indigo carmine and phthalic hydrazide as OH-radical probes was investigated. The organic dye Indigo carmine absorbs visual light strongly at 610 nm and its destruction can be monitored conveniently in a spectrophotometer. Results showed that both ^·OH and HO₂^·can bleach Indigo carmine, and the bleaching yield of ^·OH was pH independent. The photocatalytic dye bleaching in black light UV illuminated Degussa P25 TiO2 aerated suspensions was then investigated. A strong pH dependency of the bleaching yield was found.  This implies that the quantum yield of OH radical at pH 3 is one fourth compared to that at pH 10. The reaction of the OH radical with phthalic hydrazide will form strongly chemiluminescent 3-hydroxyphthalic hydrazide. Using the more specific phthalic hydrazide as OH radical probe, an even stronger pH dependent quantum yield of OH radical was found. At pH 10 the quantum yield reached the same magnitude as that obtained by using Indigo carmine, whereas the quantum yields at acidic pH were close to zero. However it was found that the addition of phosphate and fluoride anions can substantially enhance the OH radical yield at acidic pH by blocking the adsorption of phthalic hydrazide onto the TiO2 surfaces. Hence the adsorption of phthalic hydrazide to TiO2 is an important factor to consider when this method is used. <em></em></p><p>    Photocatalytic TiO2 films coated on metal plates were prepared by a sol gel method using titanium isopropoxide as TiO2 precursor and isopropanol as solvent. The photocatalytic activity of the obtained films was evaluated by bleaching of indigo carmine at pH 9 under black light UV irradiation. The effect of the molar ratio of isopropanol, water and hydrochloric acid to titanium isopropoxide was studied. It was also shown that the activities of TiO2 films are considerably influenced by calcination temperature, coating cycles and the supporting materials.</p> / <p>    Förorening av yt- och grundvatten från industrier och humana aktiviteter utgör en av de största utmaningarna för en hållbar utveckling av det mänskliga samhället. Heterogen fotokatalys, en slags avancerad oxidations process som kännetecknas av att starkt oxidativa hydroxylradikaler produceras, är en relativt ny teknik med stor potential för vattenrening.</p><p>    Ett syfte med detta licentiatarbete var först att utveckla och genomföra olika metoder för att detektera bildningen av hydroxylradikaler såväl i laboratoriet som i tekniska miljöer. Det andra syftet med arbetet var att syntetisera immobiliserade TiO2 filmer med hög fotokatalytisk effektivitet med en sol-gel metod.</p><p>    Möjligheten att använda indigokarmin och ftalhydrazid som OH-radikalprob undersöktes. Det organiska färgämnet indigokarmin absorberar synligt ljus starkt vid 610 nm vilket gör att dess nedbrytning lätt kan följas i en spektrofotometer. Resultaten av gammaradiolys visade att båda ^•OH och HO₂^• kan bleka indigokarmin och att den blekning som härrör från ^•OH var oberoende av pH. Fotokatalytisk blekning av indigokarmin med blacklight UV bestrålning av  Degussa P25 TiO2 suspensioner undersöktes sedan. Ett starkt pH-beroende av blekningsutbytet erhölls vilket tolkas som att kvantutbytet av OH-radikaler vid pH 3 är en fjärdedel jämfört med det vid pH 10.</p><p>    När ftalhydrazid reagerar med OH-radikaler bildas starkt kemiluminiscent 3-hydroxy-ftalhydrazid. Med denna  specifika OH-radikalprob, erhölls ett ännu starkare pH beroende. Vid pH 10 var kvantutbytet i paritet med det som erhölls med indigokarmin, medan kvantutbytet vid lågt pH var nära noll. Tillsats av fosfat-  och fluoridjoner visade sig avsevärt öka OH-radikalutbytet vid lågt pH-värde genom att blockera adsorption av ftalhydrazid på TiO2 ytorna. Adsorptionen av ftalhydrazid på TiO2 är således en viktig faktor när denna metod används.</p><p>    Fotokatalytiskt verksamma TiO2-filmer på metallplattor framställdes med sol-gel metoden med titan-isopropoxide som TiO2-prekursor och isopropanol som lösningsmedel. Den fotokatalytiska aktiviteten av TiO2-belagda plattor utvärderades genom blekning av indigokarmin vid pH 9 under blacklight UV-bestrålning. Effekten av olika proportioner mellan isopropanol, vatten och saltsyra till titan isopropoxide undersöktes. Det visade sig att denfotokatalytiska aktiviteten av TiO2-plattorna i hög grad påverkades av kalcineringstemperatur, beläggningscykler och materialet i plattorna.</p>

<p>In this work we investigated fabrication of semiconductor nanomaterials and evaluated their potential for photo-chemical and photovoltaic applications. We investigated two different II-VI semiconductor nanomaterial systems; (i) ZnO oriented nanowire arrays non-epitaxially grown from a substrate; and (ii) colloidal CdTe nanotetrapods synthesized by solution-based thermal decomposition of organo-metallic precursors. In both the cases our main focus has been optimizing material synthesis for improving potential applications based on photon-electron interactions.</p><p>We have studied the synthesis of vertically aligned ZnO nanowire arrays (NWA), by a wet chemical process on various substrates. The synthesis is based on epitaxial growth of ZnO seed-layer on a substrate in a chemical bath consisting of an aqueous solution of zinc nitrate and hexamethylenetetramine (HMT). We have suggested an additional role played by HMT during the synthesis of ZnO nanowire arrays. We have also extended this synthesis method to fabricate hierarchical nanostructures of nanofibers of poly-L-lactide acting as a substrate for the radially oriented growth of ZnO nanowires. The combination of high surface area of the nanofibrous substrate with the flexibility of the PLLA-ZnO hierarchical nanostructure enabled the proof-of-principle demonstration of a ‘continuous-flow’ water treatment system that could effectively decompose single and combination of known organic pollutants in water, as well as render common waterborne bacteria nonviable.</p><p>We have studied another chemical synthesis that is commonly used for size controlled synthesis of colloidal quantum dots, which was modified to obtain anisotropic nanocrystals mainly for CdE (E=S, Se, Te) compositions. In this work we demonstrate by use of oleic acid (instead of alkylphosphonic acids) it is possible to synthesize CdTe and CdSe nanotetrapods at much lower temperatures (~180 ºC) than what is commonly reported in the literature, with significantly different  formation mechanism in the low-temperature reaction.</p><p>Finally, we have performed preliminary photoconduction measurements with CdTe nanotetrapods using gold ‘nanogap’ electrodes fabricated in-house, and obtain up to 100 times enhancement in current levels in the <em>I–V </em>measurements under illumination with a white light source.</p> / QC20100607

Device associated infections are a growing problem in the field of orthopaedics and dentistry. Bacteria adhering to implant surfaces and subsequent biofilm formation are challenging to treat with systemic administered antibiotics. Functionalization of implant surfaces with therapeutic coatings that are capable of inhibiting bacterial adhesion are therefore considered as a straight forward strategy to treat and prevent implant related infections. In this thesis, the use of crystalline, arc deposited TiO2 and biomimetic hydroxyapatite (HA) coatings were evaluated with respect to their potential as antibacterial surface modifications for bone-anchored implants. UV light induced photocatalysis of anatase dominated TiO2 coated surfaces was shown to provide a bactericidal effect against S. epidermidis under clinically relevant illumination times and doses. Major parts of the drug release work carried out was based on biomimetic HA (HA-B) coated fixation pins. The analysis of the coating characteristics revealed that the nanoporous structure of HA-B coatings in addition to the chemical composition and surface charge are essential parameters that influence the drug carrier performance. Loading by adsorption was demonstrated to be a feasible approach to quickly incorporate antibiotics. The controlled release of antibiotics was shown to facilitate bactericidal effects against S. aureus over application-relevant time periods, even when exposed to biomechanical forces during insertion into bone model materials. Antibiotic incorporation during coating growth was shown to promote somewhat longer drug release time periods than those obtained using adsorption loading. In summary, functionalization of implant surfaces with bioactive and biocompatible coatings is a promising concept to impact the clinical success for bone-anchored applications. The additional feature of optional, on-demand antibacterial properties of these coatings through either on-site drug release or photocatalytic antibacterial treatment is advantageous for the prevention and effective treatment of devices-associated infections. Both strategies provide an immediate response to the implant contamination by bacteria and are believed to contribute towards minimizing the origin of post-surgical infections, while at the same time improving the interfacial stability between implant and bone.

Cette étude s’inscrit dans le cadre de l’amélioration des connaissances sur la dégradation photocatalytique des bioaérosols bactériens. La photocatalyse est une technique d’épuration basée sur l’excitation d’un semi-conducteur par un rayonnement le plus généralement ultraviolet. Cette technologie permet, en théorie, de minéraliser pas à pas les polluants. Or, si les conditions optimales ne sont pas réunies, la minéralisation incomplète peut conduire à des sous-produits de dégradation de toxicité potentiellement préoccupante.L’objectif de ces travaux a donc été d’apporter des éléments de compréhension quant aux mécanismes de dégradation photocatalytique d’un bioaérosol bactérien modèle d’E.coli, où de nombreux phénomènes sont couplés. Ainsi, pour distinguer les différents processus mis en jeu, deux approches expérimentales ont été menées. La première, nommée approche « batch », a permis d’isoler la réaction photocatalytique, à proprement parler, en étudiant les étapes d’inactivation, de libération de sous-produits et de minéralisation progressive. La seconde, appelée approche « dynamique » a permis quant à elle la mise en place d’un dispositif expérimental adapté à la dégradation photocatalytique d’un bioaérosol d’E.coli. Les capacités de la photocatalyse à inactiver et minéraliser des espèces bactériennes ont pu être démontrées. Les paramètres clés d’une dégradation efficace ont été mis en évidence et ont permis de décrire les verrous indispensables à une industrialisation sûre du procédé / This study comes within the scope of improving knowledge concerning the photocatalytic degradation of bacterial bioaerosol. Photocatalysis is a purification technology generally based on the excitation of a semiconductor by an ultraviolet radiation. This technology can, in theoretical ways, mineralize pollutants step by step. However, if optimal conditions are not gathered, this mineralization is incomplete and can lead to the formation of potentially toxic by-products. The aim of this work was therefore a better understanding of the mechanisms of photocatalytic degradation of a bacterial bioaerosol of E.coli, where numerous phenomenon are linked. Thus, to distinguish the different processes, two experimental approaches were used. The first one, called “batch approach”, allowed to consider the photocatalytic reaction itself, by studying the steps of inactivation, by-products formation and progressive mineralization. The second one, named “dynamic approach”, consisted to design an experimental setup suited to the photocatalytic degradation of a bioaerosol of E.coli. The abilities of photocatalysis to inactivate and mineralize bacteria could be demonstrated. The key parameters of an efficient degradation were highlighted and allowed to underline the problems to solve before having a safe industrialization of the photocatalysis

Tungsten oxide (WO3) is a semiconducting transition metal oxide with interesting electronic, structural, and chemical properties that have been exploited in applications including catalysis, gas sensing, electrochromic displays, and solar energy conversion. Nanocrystalline WO3 can absorb visible light to catalyze heterogeneous photooxidation reactions. Also, the acidity of the WO3 surface makes this oxide a good thermal catalyst in the dehydration of alcohols to various industrially relevant chemicals. This dissertation explores the photocatalytic and thermal catalytic reactivity of nanocrystalline porous WO3 microparticles. Furthermore, investigations into the changes in WO3 reactivity are carried out after modifying the porous WO3 particles with gold nanoparticles (Au NPs). On their own, Au NPs are an important class of materials that have had a large impact in many fields such as catalysis, biomedical imaging, and drug delivery. When combined with WO3, however, their influence as part of a composite Au/WO3 catalyst has not been widely studied. Porous WO3 microparticles were first prepared using mesoporous silica (SiO2) spheres as hard templates and the physical properties of these materials were fully characterized. A facile sonochemical method was used to deposit Au NPs on the WO3 surface. Using methylene blue (MB) as a photocatalytic probe, the reaction products and the catalytic activity of WO3 and Au/WO3 catalysts were compared. Composite Au/WO3 photocatalysts exhibited significantly greater rates of MB degradation compared to pure WO3. Interestingly, the observed mechanism of MB degradation was not vastly different between the two types of catalysts. The gas-phase photocatalytic oxidation of methanol (MeOH) was studied to further understand the role of WO3 and Au NPs in these photocatalysts. Porous WO3 showed greater photooxidation rates compared to bulk WO3 because of its increased active surface area. Pure WO3 and Au NPs on porous SiO2 (SiO2-Au) were both active MeOH photooxidation catalysts and were highly selective to formaldehyde (HCHO) and methyl formate (MF), respectively. Two different mechanisms, namely band gap excitation of WO3 and surface plasmon resonance (SPR) on Au NPs, were responsible for this result. Again, the Au/WO3 composite catalysts showed greater photocatalytic activity than WO3, which increased with Au loading. This high activity led to the complete photooxidation of MeOH to carbon dioxide (CO2) over Au/WO3 catalysts. Finally, the thermal catalytic transformation of MeOH under aerobic conditions was carried out to further characterize the acid and redox active sites of WO3 and Au/WO3 catalysts. Pure WO3 was highly selective for MeOH dehydration to dimethyl ether (DME), whereas Au/WO3 showed increased oxidation selectivity to products such as HCHO, FM, and COx. The Au NPs increased the reducibility of the WO3 species, which made surface oxygen atoms more labile and reactive towards MeOH. Also, the WO3 facilitated the formation of cationic Au (Au δ+) species. This combination of effects created through a strong Au/WO3 interaction increased the activity of WO3 species, but it decreased the activity of the Au NPs.

Zinc Oxide (ZnO) is one of the most extensively studied semiconductors because of its unique properties, namely, its wide band gap (3.37 eV) and high excitation binding energy (60 meV). These properties make ZnO a promising material for uses in a broad range of applications including sensors, catalysis and optoelectronic devices. The presented research covers a broad spectrum of these interesting nanomaterials, from their synthesis and characterization to their use as photocatalyts. A new synthetic approach for producing morphology controlled ZnO nanostructures was developed using microwave irradiation (MWI). The rapid decomposition of zinc acetate in the presence of a mixture of oleic acid (OAC) and oleylamine (OAM) results in the formation of hexagonal ZnO nanopyramids and ZnO rods of varying aspect ratios. The factors that influence the morphology of these ZnO nanostructures were investigated. Using ligand exchange, the ZnO nanostructures can be dispersed in aqueous medium, thus allowing their use as photocatalysts for the degradation of malachite green dye in water. Photocatalytic activity is studied as a function of morphology; and, the ZnO nanorods show enhanced photocatalytic activity for the degradation of the dye compared to hexagonal ZnO nanopyramids. After demonstrating the catalytic activity of these ZnO nanostructures, various ways to enhance photocatalytic activity were studied by modification of this MWI method. Photocatalytic activity is enhanced through band gap modulation and the reduction of electron-hole recombination. Several approaches were studied, which included the incorporation of Au nanoparticles, N-doping of ZnO, supporting ZnO nanostructures on reduced graphene oxide (RGO), and supporting N-doped ZnO on N-doped RGO. ZnO-based nanostructures were studied systematically through the entire process from synthesis and characterization to their use as photocatalysis. This allows for a thorough understanding of the parameters that impact these processes and their unique photocatalytic properties.

L'implantation dans l'industrie de la photocatalyse nécessite de nouvelles recherches afin de contrôler et dimensionner les réacteurs photocatalytiques. Une solution innovante concerne la microstructuration des réacteurs. En effet, elle permet d'augmenter l'efficacité catalytique en améliorant le contact du polluant avec le catalyseur. L'objectif de la thèse concernait la destruction d'un polluant modèle, l'acide salicylique, par un catalyseur (TiO2) déposé au fond d'un microcanal. La recherche repose sur des expérimentations mais aussi sur des simulations permettant de prévoir la dégradation photocatalytique pour une configuration de réacteur donnée. Dans nos conditions expérimentales de faible débit, nous avons mis en évidence une dispersion axiale et un gradient de concentration entre la surface catalytique et le milieu réactionnel. En tenant compte des conditions d'écoulement, nous avons montré que le gradient de vitesse est plus marqué dans les microréacteurs de faible section de passage. Ce gradient favorise la formation de zones de recirculation près de la surface catalytique créant ainsi des conditions favorables au contact entre le polluant et la surface catalytique. A l'aide d'un logiciel numérique, nous avons simulé la réaction de dégradation photocatalytique qui permet de rendre compte de nos résultats expérimentaux. D'une part, le rôle primordial de la diffusion vers la surface catalytique a été mis en évidence. D'autre part, la simulation numérique nous a permis d'établir la relation du nombre de Sherwood en fonction des nombres de Reynolds, de Schmidt et du diamètre hydraulique du microcanal. Cette relation permet d'estimer la constante de transfert de matière pour représenter correctement la dégradation quel que soit le type de microréacteur envisagé / Industrial photocatalysis applications requires further research to control and design photocatalytic reactors. The micro structuring of reactors is an innovative solution. It increases the catalytic efficiency by improving the contact of the pollutant with the catalyst. Thesis aim concerned the destruction of a model pollutant, salicylic acid, with deposited catalyst (TiO2) at the bottom of a microchannel. The research is based on experiments and simulations to predict the photocatalytic degradation for a given reactor configuration. In our experimental conditions of low flow, an axial dispersion and a concentration gradient between the catalyst surface and the reaction medium have been demonstrated. We have shown that the gradient of velocity is more pronounced in low cross section microreactors. This gradient allows the formation of recirculation zones near the catalytic surface thus creating favorable conditions for contact between the pollutant and the catalytic surface. Using numerical soft, we have simulated the reaction of photocatalytic degradation to represent our experimental results. On a one hand, the role of diffusion to the catalytic surface has been demonstrated. On the other hand, numerical simulation has allowed to establish a relationship between the Sherwood number as a function of Reynolds number, Schmidt and the hydraulic diameter of the microchannel. This relationship is used to estimate the mass transfer constant to represent correctly the photocatalytic degradation

La dégradation photocatalytique de deux amines, la méthylamine (MA) et la diméthylamine (DMA), a été étudiée en présence de TiO2 Degussa P25. Différents paramètres ont été étudiés: l'adsorption à l’obscurité et sous UV, la photolyse, les cinétiques de dégradation, l'effet du pH, l'effet de la nature et de l'intensité du flux photonique ainsi que les voies de dégradation de la MA et DMA.A l’obscurité, le taux de recouvrement des groupes OH est similaire pour la MA et DMA. Sous UV, ce taux devient deux fois plus élevé pour la MA. Les réactivités de MA et DMA sont directement corrélées à leur adsorption sous UV. Les atomes d'azote sont principalement décomposés en ammonium. Le nitrite a été également détecté, mais rapidement oxydé en nitrate. À pH basique, l'hydrolyse photo‐assisté et l'attaque de OH• sur l’atome N augmente. DMA est essentiellement transformé en MA. Les analyses du Carbone Organique Total (COT) montrent la présence de produits finaux contenant de l’azote difficilement minéralisables. Nous avons montré que, quelle que soit l'énergie des photons (UV‐A ou UV‐B), le rendement quantique reste constant et égal à 0,033.L'inactivation photocatalytique de E. coli en présence de la lumière solaire naturelle en absence (SODIS) et en présence de différents catalyseurs a été étudiée. L'effet de la température sur l'inactivation de E. coli a été aussi étudié. Les résultats ont montré que l’addition des différents types de catalyseurs accélère l'effet bactéricide du rayonnement solaire. Aucun phénomène de reviviscence bactérien n’a été observé après l'arrêt de l'exposition solaire durant au moins 72 heures. Seulement les ions ammonium et potassium ont été détectés au cours de l'inactivation de E. coli en accord avec la perforation de la membrane et l’oxydation des protéines. / The photocatalytic degradation of two amino‐compounds, methylamine (MA) and dimethylamine (DMA) was investigated in the presence of UV‐irradiated TiO2 aqueous suspensions. Different parameters were studied: adsorption under dark and UV conditions, photolysis, kinetics of degradation, effect of pH, effect of the nature and intensities of photonic flux and finally the chemical pathway MA and DMA degradation.While, the percentage of covered OH in the dark was equal for MA and DMA, it becomes twice higher for MA under UV. The reactivity of MA and DMA is directly correlated with the adsorption under UV. The nitrogen atoms were decomposed mainly to ammonium. Nitrite was also formed but was rapidly oxidized to nitrate. At basic pH, photo assisted hydrolysis and the attack of OH• on N‐atom increase. DMA is mainly transformed to MA. Total Organic Carbon (TOC) analysis show the presence of final slightly mineralised intermediate compounds containing nitrogen atom. We shown that, whatever the energy of photons (UV‐A or UV‐B), the same quantum yield equal to 0.033 was obtained.The photocatalytic inactivation of E. coli under natural solar irradiation in the absence (SODIS) as well in the presence of different concentrations of varied photocatalysts has also been investigated. The effect of temperature on E. coli inactivation was studied. Results show that the additions of any types of catalyst to the water accelerate the bactericidal action of solar irradiation and leads to a total disinfection. No bacterial regrowth was observed during the subsequent dark period. Ammonium and potassium ions were formed during E. coli inactivation in agreement with the membrane perforation and the oxidation of proteins.

The adsorption of methylene blue onto two types of commercial activated carbons, a mesoporous type (Norit CA1) and microporous type (207C) was analysed. Powdered TiO2 was mixed with the carbon and added to the dye solution to determine the influence of the photocatalyst during the adsorption process. Equilibrium and kinetics experiments were done with and without any addition of photocatalytic titanium dioxide (TiO2). Changes in capacity, heterogeneity, and heat of adsorption were detected and related to changes in the quantity of TiO2 added by evaluating the equilibrium parameter from 13 isotherm models. The influence of TiO2 on the adsorption kinetics of the dye was correlated using simplified kinetic-type model as well as mass transfer parameters. Using a formal design of experiments approach responses such as the removal of the dye, variation of pH, external mass transfer rate (KF) and intraparticle rate constant (Ki) were evaluated. Results indicated that TiO2 increased the uptake of methylene blue onto CA1, increased Ki and CA1-TiO2 interactions had electrostatic nature. In contrast, TiO2 was seen to inhibit the equilibrium adsorption for 207C by reducing its capacity. The 207C-TiO2 interaction was attributed to a specific adsorption of TiO2 on the coconut-based adsorbent, as zeta potential and pH measurements seemed to suggest. The regeneration of activated carbon using UV-C/TiO2 heterogeneous photocatalysis in a novel bell photocatalytic reactor, and in a standard-type coiled-tube photoreactor was also studied. Initially, response surface methodology was applied to finding the optimum conditions for the mineralization of methylene blue in both reactors using methylene blue as model compound and TiO2 as photocatalyst performing direct photocatalytic decolourization. Methylene blue concentration, TiO2 concentration and pH were the variables under study. Complete mineralization of the dye was achieved in the coiled-tube reactor using 3.07 mg/L of methylene blue at pH 6.5 with 0.4149 g/L TiO2. The regeneration experiments in the coiled-tube photoreactor were done using One Variable at Time (OVAT) method. The effect of the mass of TiO2 was the only studied variable. The study indicated an increase in regeneration of CA1 and a decrease in the pH during the oxidation step at higher concentration of the photocatalyst. In the case of the regeneration of 207C, the addition of TiO2 lowered the regeneration and made the suspension more basic during the photocatalytic step. However these results were not statistically significant. Experiments using the bell photoreactor were performed applying the same response surface method used in direct photocatalytic decolourization (control). The variables under study were pH, concentration of dye-saturated carbon and TiO2 concentration. The regeneration percentage was the chosen response. Low regeneration percentages were achieved (maximum 63%), and significant differences (95% confidence interval) were found between the regeneration of the activated carbons, being higher in the case of powdered CA1 as compared with granular 207C.

Une nouvelle famille de vitrocéramiques, avec une microstructure inédite, a été fabriquée par une cristallisation contrôlée des verres dans le système GeSe2-Sb2Se3-CuI. L'influence de la composition et du processus de cristallisation des verres de base, sur la microstructure et sur l’intensité du photo-courant des vitrocéramiques a été étudiée. Une composition optimisée, le 40GeSe2-40Sb2Se3-20CuI, a été particulièrement étudiée avec des résultats suivants: (1) Après une étude systématique , il a été constaté que cette composition donne la plus forte intensité de photo-courant parmi tous les verres étudiés dans ce système pseudo-ternaire GeSe2-Sb2Se3-Cul. Il a été également démontré que le photo-courant généré par différentes vitrocéramiques est non seulement déterminé par la composition, mais aussi par la microstructure composite de la vitrocéramique, qui est déterminée par le processus de céramisation. Ce processus de céramisation a ensuite été optimisé. Par rapport au procédé de traitement thermique en deux étapes, le procédé en une seule étape à basse température est une stratégie plus appropriée pour obtenir une microstructure efficace, favorisant la séparation des charges, construisant des canaux conducteurs et donnant une intensité de photo-courant élevée dans la vitrocéramique. (2) La microstructure composite inédite, discutée ci-dessus est composée de micro-domaines conducteurs interconnectés, formées par des cristaux Sb2Se3 faiblement conducteur en forme de tiges, couverts par des nano-cristaux de Cu2GeSe3 beaucoup plus conducteurs. Le procédé le plus probable de la photo-génération efficace des charges est le suivant: les photons sont efficacement et essentiellement absorbés par Sb2Se3 ainsi que par Cu2GeSe3. Les hétérojonctions formées par les Sb2Se3 du type n et les Cu2GeSe3 du type p, favorisent la séparation de charges, tandis que les Cu2GeSe3 interconnectées et conductrices fournissent des canaux conducteurs et jouent ainsi le rôle de collecteur efficace de charges. Il en résulte ainsi une très longue durée de vie des porteurs de charge et un fort photo-courant. (3) La formation de nano-hétérojonctions entre les cristaux Sb2Se3 et Cu2GeSe3 dans un seul micro-domaine peut conduire à une séparation efficace des électrons et des trous photo-générés. Par conséquent, pour application photo-catalytique, il n’est pas nécessaire de former des canaux conducteurs (conducteurs interconnectés des micro-domaines) dans l'ensemble de la vitrocéramique. De plus, la formation de ces canaux conducteurs, nécessiterait une augmentation de la durée ou/et la température de recuit, pouvant conduire à une diminution de l'activité photo-catalytique à cause de la taille relativement grande des grains cristallins. Les vitrocéramiques optimisées montrent une bonne capacité de désamination oxydative et une forte activité photo-catalytique en général, démontrant ainsi son potentiel en tant que photo-catalyseur efficace. / A totally new family of glass ceramics with a unique microstructure was fabricated by controlling the crystallization of the GeSe2-Sb2Se3-CuI glass system. The influences of the material composition and the crystallizing process of the precursor glasses on the microstructure and photocurrent of the prepared glass ceramics were investigated. An optimized composition, 40GeSe2-40Sb2Se3-20CuI, was particularly studied with the following significant results: (1) After a systematic study, it was found that this particular composition shows the highest photocurrent density among all studied glasses in the pseudo-ternary GeSe2-Sb2Se3-CuI system. It is also demonstrated that the photocurrent generated by different glass ceramics is not only determined by the composition, but also by the composite microstructure of the glass ceramic, which is determined by the ceramisation process. This process was then carefully studied. Compared with the two-step heat treatment process, the single-step process at a low temperature is a more efficient strategy to build up an efficient composite microstructure, which promotes charge carrier separation and provides a conductive channel, leading to a high photocurrent intensity in the glass ceramic. (2) The above-mentioned unique composite microstructure is composed of interconnected conductive microdomains, formed by low conductive rod-like Sb2Se3 crystals, covered by relatively high conductive Cu2GeSe3 nanocrystals. The most likely process for efficient photogeneration of charges is proposed as follows: photons are efficiently and essentially absorbed by Sb2Se3 as well as by Cu2GeSe3, and then the heterojunction formed by n-type Sb2Se3 and p-type Cu2GeSe3 promotes the charge separation, whereas the oriented and relatively conductive Cu2GeSe3 aggregate provides a conductive channel and plays the role of efficient charge collector. This structure results in exceptionally long lifetime of charge carriers (around 16 µs) and high photocurrent (at least 100 times higher than any of Sb2Se3 and Cu2GeSe3 individually). (3) The formation of nano-heterojunctions between Sb2Se3 and Cu2GeSe3 crystals within a single conductive microdomain can fully lead to an efficient separation of photo-generated electrons and holes. Therefore, for the photocatalytic application, it is unnecessary to form conductive channels (interconnected conductive microdomains) in the whole glass ceramic. Moreover, in order to form conductive channels, the necessary increase of annealing time or/and temperature may decrease the photocatalytic activity due to its relatively large crystal grain size. The optimized glass ceramic exhibits a good oxidative deamination ability and high photocatalytic activity, demonstrating its potential as an efficient photocatalyst.