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The reduction of CO2 is relevant for the production of compounds as part of the carbon capture and utilization research approaches. Thus, photocatalytic reduction of CO2 over a tailored BiOCl-based photocatalyst (BTEG) was tested under UV light (365 nm). BTEG was synthesized in the presence of triethylene glycol, which gave 4-nm crystallites, much smaller than the 30 nm crystallites of commercial BiOCl. Commercial BiOCl reduced CO2 mainly to methane with a minor fraction of ethanol, and was inactivated after 20 h. BTEG was a more active catalyst for CO2 photoreduction, producing approximately equal amounts of methane, methanol, and ethanol while consuming 0.38 &micro, mol g&minus, 1 h&minus, 1 of CO2 before the experiment was stopped after 43 h, with the catalyst still active. The different products formed by the BTEG photocatalyst samples were tentatively ascribed to its greater content of {110} facets. Thus, in addition to band-gap tuning, the relative fractions of BiOCl facets had a key role in the effective photocatalytic reduction of CO2, and the BiOCl-based BTEG catalyst promoted the formation of important compounds as methanol and ethanol.

12th International Conference on Chemical and Process Engineering (ICheaP), Milano, ITALY, MAY 19-22, 2015; International audience; Nowadays, the challenge of understanding relationships between catalysts properties and performance in the context of heterogeneous catalysis is a hot topic. Indeed, catalytic processes are generally affected by many different operational parameters that need to be modeled and optimized. The challenge can be addressed using artificial neural networks due to their flexibility to work without mathematical description of the process. The present work enters within the framework of the photodegradation of water contaminants using ZnO-based catalysts. ZnO is a non-toxic cheap material with an interesting photocatalytic potential. However, its application is reduced because of its poor efficiency, photocorrosion and difficulties for recovery. The objective of this work is to improve this efficiency, regarding particularly the photodegradation of an endocrinal disruptor: bisphenol-A (BPA), via the synthesis of a new catalytic system based on ZnO and the modeling of both the synthesis process and photocatalytic performance of this new catalytic system. Modeling and optimization will be carried out using artificial neural network tools coupled to an evolutionary algorithm. The connection between the two artificial neural network models will make it possible to identify the optimal synthesis parameters that lead to the maximum photocatalytic efficiency (within the studied domain), thus shedding light on the association of the system structure with its photocatalytic performance.

International audience

Accès restreint aux membres de l'Université de Lorraine jusqu'au 2015-08-29; The present work concerns photodegradation of water contaminants using ZnO-based catalysts. The first step consisted in designing a new catalytic system by functionalizing ZnO with silver nanoparticles. Two methods were used: photodeposition and impregnation of silver nanoparticles (AgNPs) on ZnO. The photocatalytic activity of the resulting catalyst towards the degradation of bisphenol-A, triclosan and rhodamine-B was studied. The effect of pH, photocatalyst and contaminant concentrations and wavelength, on bisphenol-A degradation was studied and the kinetic rate constant was determined. The optimization showed that a low silver content and an alkaline pH, during both functionalization of ZnO and photodegradation, maximized the kinetic rate constant of bisphenol-A degradation. A model also predicted that Ag/ZnO obtained by photodeposition showed higher photocatalytic activity that of Ag/ZnO obtained by impregnation.On the other hand, to overcome aggregation problems, Ag/ZnO were immobilized owing to their incorporation in a cross-linked poly(acrylic acid) matrix . The surface of Ag/ZnO was previously modified, using a silane coupling agentwhich allowed (i) dispersing and anchoring NPs on the polyacrylic matrix by formation ester bonds (ii) promoting crystallization of the polymer. The composites were successfully tested under UV light with an efficiency comparable to that of non-immobilized NPs. The immobilization provides additional advantages e.g. hindrance of catalyst photocorrosion and possible use of the composite in continuous mode; Le présent travail porte sur la photodégradation de polluants aqueux utilisant des catalyseurs à base de ZnO. La première étape a consisté à fonctionnaliser ZnO avec des nanoparticules d'argent. Deux méthodes ont été utilisées : la photodéposition et l'imprégnation des particules d'argent sur ZnO. L’activité des catalyseurs obtenus vis-à-vis de la dégradation du bisphenol-A, du triclosan et de la rhodamine-B a été ensuite étudiée. L'effet du pH, des concentrations du photocatalyseur et du polluant et de la longueur d'onde sur la dégradation du bisphenol-A a été analysée et la constante cinétique déterminée. L'optimisation a montré qu'une teneur faible en argent et un pH alcalin, tant pour la fonctionnalisation de ZnO que pour la photodégradation, maximisent la constante cinétique de dégradation du bisphenol-A. Un modèle a également prédit que le système obtenu par photodéposition présente une activité photocatalytique supérieure à celle de celui obtenu par imprégnation. D'autre part, pour surmonter des problèmes d'agrégation, les particules d’Ag/ZnO ont été immobilisées grâce à leur incorporation dans une matrice d'acide polyacrylique réticulé. La surface des particules de catalyseur a, au préalable, été modifiée grâce à un agent de couplage silané qui a permis (i) la dispersion et l'ancrage par estérification des nanoparticules sur la matrice polyacrylique (ii) de promouvoir la cristallisation du polymère. Les composites obtenus ont été testés avec succès sous rayonnement UV avec une efficacité comparable à celle des particules non-immobilisées. L'immobilisation permet par ailleurs d'empêcher la photocorrosion du catalyseur et d'utiliser ces composites en mode continu

The present work concerns photodegradation of water contaminants using ZnO-based catalysts. The first step consisted in designing a new catalytic system by functionalizing ZnO with silver nanoparticles. Two methods were used: photodeposition and impregnation of silver nanoparticles (AgNPs) on ZnO. The photocatalytic activity of the resulting catalyst towards the degradation of bisphenol-A, triclosan and rhodamine-B was studied. The effect of pH, photocatalyst and contaminant concentrations and wavelength, on bisphenol-A degradation was studied and the kinetic rate constant was determined. The optimization showed that a low silver content and an alkaline pH, during both functionalization of ZnO and photodegradation, maximized the kinetic rate constant of bisphenol-A degradation. A model also predicted that Ag/ZnO obtained by photodeposition showed higher photocatalytic activity that of Ag/ZnO obtained by impregnation.On the other hand, to overcome aggregation problems, Ag/ZnO were immobilized owing to their incorporation in a cross-linked poly(acrylic acid) matrix . The surface of Ag/ZnO was previously modified, using a silane coupling agentwhich allowed (i) dispersing and anchoring NPs on the polyacrylic matrix by formation ester bonds (ii) promoting crystallization of the polymer. The composites were successfully tested under UV light with an efficiency comparable to that of non-immobilized NPs. The immobilization provides additional advantages e.g. hindrance of catalyst photocorrosion and possible use of the composite in continuous mode, Le présent travail porte sur la photodégradation de polluants aqueux utilisant des catalyseurs à base de ZnO. La première étape a consisté à fonctionnaliser ZnO avec des nanoparticules d'argent. Deux méthodes ont été utilisées : la photodéposition et l'imprégnation des particules d'argent sur ZnO. L’activité des catalyseurs obtenus vis-à-vis de la dégradation du bisphenol-A, du triclosan et de la rhodamine-B a été ensuite étudiée. L'effet du pH, des concentrations du photocatalyseur et du polluant et de la longueur d'onde sur la dégradation du bisphenol-A a été analysée et la constante cinétique déterminée. L'optimisation a montré qu'une teneur faible en argent et un pH alcalin, tant pour la fonctionnalisation de ZnO que pour la photodégradation, maximisent la constante cinétique de dégradation du bisphenol-A. Un modèle a également prédit que le système obtenu par photodéposition présente une activité photocatalytique supérieure à celle de celui obtenu par imprégnation. D'autre part, pour surmonter des problèmes d'agrégation, les particules d’Ag/ZnO ont été immobilisées grâce à leur incorporation dans une matrice d'acide polyacrylique réticulé. La surface des particules de catalyseur a, au préalable, été modifiée grâce à un agent de couplage silané qui a permis (i) la dispersion et l'ancrage par estérification des nanoparticules sur la matrice polyacrylique (ii) de promouvoir la cristallisation du polymère. Les composites obtenus ont été testés avec succès sous rayonnement UV avec une efficacité comparable à celle des particules non-immobilisées. L'immobilisation permet par ailleurs d'empêcher la photocorrosion du catalyseur et d'utiliser ces composites en mode continu

Tesis (Doctorado en Ciencias Ambientales) "El ZnO es un material no tóxico de bajo costo con un interesante potencial fotocatalítico en la degradación de contaminantes en medio acuoso. Sin embargo, su aplicación se encuentra limitada por su baja eficiencia, fotocorrosión y el costo energético de su recuperación. Este trabajo tiene como objetivo incrementar la actividad fotocatalítica en la degradación de compuestos disruptores endócrinos a través de la funcionalización de ZnO con nanopartículas de plata. Además el desarrollo de un método para la inmovilización del fotocatalizador modificado, Ag/ZnO, en una matriz polimérica proyectando su uso en sistemas de tratamiento continuo de agua. Los resultados demuestran que el método de fotodeposición promueve la distribución homogénea de nanopartículas de plata. El incremento en los parámetros de red indican la inserción de iones Ag+ en la estructura cristalina del ZnO dando lugar a una fuerte interacción química entre las nanopartículas de plata y ZnO. Adicionalmente, la presencia de grupos hidroxilo, OH-, y el incremento en la absorción de luz visible promovió la degradación fotocatalítica bisfenol A, triclosan y rodamina B de manera más eficiente. Los resultados de degradación del bisfenol A a 302 nm por el fotocatalizador Ag/ZnO muestran una constante de velocidad aparente (kapp) 3.7 veces mayor al valor obtenido por ZnO: kapp =0.01929 min-1 m-2. Además, la degradación de bisfenol A (25%, 3h), triclosan (35%, 2h) y rodamina B (95%, 2h) en condiciones de luz visible se traduce en el potencial del catalizador de ser activado con luz solar. Por otra parte, las nanopartículas de fotocatalizador Ag/ZnO fueron inmovilizadas en una matriz de poli(ácido acrílico) entrecruzado. La superficie de las partículas fue previamente modificada por un agente acoplante (GLYMO®) que permitió (i) la dispersión y anclaje por esterificación de las nanopartículas en la matriz poliacrílica en formación y (ii) promover la cristalización y estabilidad térmica del polímero." "ZnO is a non-toxic catalyst of low cost with interesting photocatalytic potential, particularly for the degradation of water contaminants. However, its application has not been much developed because of its poor efficiency, its photocorrosion and energetic cost of recovery. Therefore, the main objectives of this research was to improve the efficiency of ZnO for the degradation of endocrine disrupting compounds and propose a method for the immobilization of the photocatalyst projecting a continuous water treatment process. The first step consisted in the design of a new photocatalytic system by functionalizing ZnO nanoagglomerates with silver nanoparticles (Ag/ZnO). The results showed that photodeposition method promotes a homogeneous distribution of AgNPs on ZnO surface. Moreover, the increment in lattice parameters suggests the insertion of Ag+ ions into the crystalline structure of ZnO and strong interactions between AgNPs and ZnO. In addition, hydroxyl surface content and the improved absorption under visible light allowed the enhancement in the photodegradation efficiency of bisphenol-A, triclosan and rhodamine-B. The obtained Ag/ZnO photocatalyst showed higher apparent rate constant (kapp) for the degradation of bisphenol-A at 302 nm: kapp=0.01929 min-1 m-2, which is 3.7 times the value for pure ZnO. Degradation of bisphenol-A (25%, 3h), triclosan (35%, 2h) and rhodamine-B (95%, 2h) was successfully carried out under visible light which is an important achievement in case of solar light use. On the other hand, to overcome aggregation problems, Ag/ZnO photocatalyst was immobilized owing to their incorporation in a cross-linked poly(acrylic acid) matrix. The surface of Ag/ZnO was previously modified, using a silane coupling agent: GLYMO® which allowed (i) dispersing and anchoring NPs on the polyacrylic matrix by formation of ester bonds, and (ii) promoting crystallization and thermal stability of the polymer."

International audience

Tesis (Maestría en Ciencias Ambientales) "El hidrógeno (H2) es un gas con potencial para cubrir las necesidades energéticas principalmente del rubro de transporte ya que por cada kilogramo se obtienen 34x103 kcal y 9 kg de agua como único producto durante el proceso de combustión. Las celdas de combustible son capaces de usar directamente H2 para generar electricidad sin el deterioro de la calidad de aire y de los recursos naturales que ocasiona el uso de combustibles fósiles. Actualmente, el H2 proviene del procesamiento del gas natural e hidrocarburos. Sin embargo, el uso de fuentes renovables como la biomasa para la generación de H2 permite la utilización de materiales de desecho lo que la convierte en una fuente de energía limpia y sustentable. Entre las tecnologías utilizadas está la fermentación que permite la conversión de los carbohidratos en bio-hidrógeno (Bio-H2) y otros productos (ácidos y alcoholes). Los principales obstáculos para la aplicación práctica de esta tecnología se encuentran en los bajos rendimientos molar de hidrógeno (RMH) y velocidades volumétricas de producción de hidrógeno (VVPH). Procesos de fermentación continuos empleando bacterias inmovilizadas (gránulos) ofrecen altas VVPH y permiten el uso de reactores de menores dimensiones como el de lecho de lodo anaerobio de flujo ascendente (UASB). El tiempo de formación de gránulos con capacidad de producir Bio-H2 gránulos hidrogenogénicos: GH) en reactores UASB puede reducirse a través del uso de gránulos metanogénicos, formados en un reactor alterno, con tratamiento para su enriquecimiento en bacterias productoras de hidrógeno. Este trabajo tiene como objetivo evaluar el uso de gránulos metanogénicos para el desarrollo de GH. Experimentos en lote permitieron determinar que el tratamiento térmico inactiva la actividad metanogénica y obtener altas VVPH. El uso de la solución tampón de fosfatos de sodio y pH inicial 6 genera RMH (2.4 mol H2/mol glucosa) y contenido de H2 en el biogás (60 a 75%) superiores a los reportados en la literatura, así como VVPH (250 mL/L/h) comparables. En experimentos en continuo, llevados a cabo en reactores UASB, se evaluó el efecto que tiene la velocidad de carga orgánica (VCO), sobre el desempeño de los reactores. Inicialmente la VCO se aumento por medio de incrementos en la concentración de sustrato desde 5.3 hasta 17 g/L de glucosa. La máxima VVPH, 1650 mL H2/L/d y RMH de 0.6 mol H2/mol glucosa se obtuvieron a una VCO de 23.4 g DQO/L/d y TRH de 17 h." "Hydrogen (H2) has the potential to supply energy needed for transportation, given the fact that 34x103 kcal of energy is obtained and 9 kg of water as only residue per kg of gas is produced during the combustion process. Fuel cells are capable of use H2 directly to generate electricity without the deleterious effects on the air quality and natural resources due to the use of fossil fuels. Currently, H2 is produced from natural gas and hydrocarbon processing. However, the use of biomass for H2 production allows the reuse of organic waste materials making H2 production a source of clean and sustainable energy. Among the current technologies in use, fermentation allows to convert carbohydrates to bio-hydrogen (Bio-H2) and other products (acids and alcohols). Main obstacles for practical application of this technology are low hydrogen yields (HY) and low volumetric hydrogen production rate (VHPR). Continuous fermentation processes using immobilized bacteria (granular sludge) yield high VHPR and permit the use of smaller reactors such as the upflow anaerobic sludge blanket (UASB) reactor. Time needed to form hydrogenogenic granules (hydrogen producing granules, H2PG) may be reduced through the use of methanogenic granular sludge treated for their enrichment in hydrogen producing bacteria. This work has the objective to evaluate the use of methanogenic granular sludge for the development of H2PG. Batch experiments showed that heat treating can suppress methanogenic activity of the methanogenic granular sludge obtaining high VHPR. The use of sodium phosphate buffer solution at initial pH of 6 generates higher values of HY, VHPR and H2 content in biogas than reported in literature. Continuous culture experiments, in UASB reactors, using the heat-treated methanogenic granular sludge were conducted. The effect of the organic loading rates (OLR) on the performance reactor was studied. OLR was changed by changing the substrate concentration and the HRT. Tested substrate concentrations were in the range of 5.3 to 17 g/L glucose. Maximum VHPR of 1650 mL H2/L/d and HY of 0.6 mol H2/mol glucose was obtained at an OLR of 23.4 g DQO/L/d and HRT of 17 h."