Graphene has been shown to be very powerful as a transducer in many biosensor applications due to its high sensitivity. This enables smaller surfaces and therefore less material consumption when producing sensors and concequently cheaper and more portable sensors compared to the commercially available sensors today. The electrical properties of graphene are very sensitive to gas exposure why presence of molecules or small changes in concentration could easily be detected when using graphene as a sensing layer. Graphene is sensitive towards many molecules and in order to detect and possibly identify gas molecules the surface needs to be functionalized. The intention of this project was to use nanoparticles (NPs) to further increase sensitivity and specificity towards selected molecules and also enable biofunctionalization of the NPs, and by that tune the electrical properties of the graphene. This study proposes the use of Fe3O4 and TiO2 NPs to enable sensitive detection of volatile gases and possibly further functionalization of the NPs using biomolecules as a detecting agent in a liquid-phasebiosensor application. The interaction between graphene and NPs have been investigated using several surface charactarization methods and electrical measurements for detection of gaseous molecules and also molecules in a liquid solution. The characterizing methods used are XPS, AFM with surface-potential mapping and Raman spectroscopy with reflectance mapping in order to investigate the NPs interaction with the graphene surface. Sensors where manufactured for gas-phase detection of CO, formaldehyde, benzene and NH3 specifically and display differences in sensitivity and behavior of the Fe3O4 and TiO2 NPs respectively. For liquid measurements the difference in behavior in two buffers was investigated using an in-house flow-cell setup. The surface charecterizing measurements indicated that just a small difference could be found between the two NPs, however a significant change in sensor response could be detected as a function of coverage. The liquid and gas-phase measurements rendered information on differences in sensitivity between the NPs and between analytes where TiO2 showed a higher level of sensitivity towards most of the gases investigated. Both Fe3O4 and TiO2 NP coated graphene showed capability to detect formaldehyde and benzene down to 50 ppb and 5 ppb respectively. The sensitive gas detection could help protecting individuals being exposed to a hazardous level of volatile gases if concentrations increase rapidly or at a long term exposure with lower concentrations, improving saftey and health where these gases are present.

Ce travail est en relation avec la thématique "Chimie Verte" en particulier, le rôle de la catalyse,l’utilisation des matières premières renouvelables et l’élimination des produits nocifs.- Quatre échantillons commerciaux de zircone tungstatée de Mel-Chemicals.- deux séries de zircone tungstatée préparées par deux méthodes différentes avec une teneuren WO3 de 1 à 20 % en masse.- des oxydes binaires tels que WO3-ZrO2, B2O3-ZrO2, Al2O3-ZrO2, Ga2O3-ZrO2 et In2O3-ZrO2.- des oxydes binaires tels que WO3-Me2O3 (Me = B, Al, Ga et In) et finalement des oxydesternaires WO3/(Me2O3-ZrO2) (Me = B, Al, Ga et In) ont été étudiés et préparés lors de cettethèse.La performance catalytique de ces catalyseurs a été évaluée dans l’hydrolyse de la cellobiose, ladéshydratation du fructose et la réduction catalytique sélective des NOx. Les propriétés acides etredox de surface ont été corrélées aux performances catalytiques. En général, la conversion totale est liée à l’acidité des catalyseurs. Les catalyseurs les plus sélectifs pour la déshydratation du fructose et en deNOx sont ceux présentant une acidité modérée. / This work is related to the subject “Green Chemistry” in particular the role of the catalyst, the useof renewable raw materials and the decrease of hazardous materials.- Four commercial tungstated zirconia provided by Mel-Chemicals.- Two series of tungstated zirconia catalysts prepared by two different methods in a range of(1-20) WO3 wt.% loading- Binary zirconia-based oxides WO3-ZrO2, B2O3-ZrO2, Al2O3-ZrO2, Ga2O3-ZrO2 and In2O3-ZrO2.- Binary oxides WO3-Me2O3 (Me = B, Al, Ga and In) and ternary oxides WO3/(Me2O3-ZrO2)(Me = B, Al, Ga and In) were prepared and studied during my PhD thesis.The catalytic activity of these mixed oxide catalysts was evaluated in cellobiose hydrolysis, fructosedehydration and selective catalytic reduction of NOx. The catalysts were thoroughly characterizedin terms of their acidic and redox properties in order to find correlations between the identifiedactive sites and the catalytic properties. The total conversion is related in general to the acidity ofthe tested catalysts and the most selective catalysts for fructose dehydration and deNOx are thosewith moderate acidity.

ENGLISH:<p>The natural nitrogen cycle has been and is significantly perturbed by anthropogenic emissions of reactive nitrogen (Nr) compounds into the atmosphere, resulting from our production of energy and food. In the last century global ammonia (NH3) emissions have doubled and represent nowadays more than half of total the Nr emissions. NH3 is also the principal atmospheric base in the atmosphere and rapidly forms aerosols by reaction with acids. It is therefore a species of high relevance for the Earth's environment, climate and human health (Chapter 1). As a short-lived species, NH3 is highly variable in time and space, and while ground based measurements are possible, they are sparse and their spatial coverage is largely heterogeneous. Consequently, global spatial and temporal patterns of NH3 emissions are poorly understood and account for the largest uncertainties in the nitrogen cycle. The aim of this work is to assess distributions and saptiotemporal variability of NH3 using satellite measurements to improve our understanding of its contribution to the global nitrogen cycle and its related effects.<p><p>Recently, satellite instruments have demonstrated their abilities to measure NH3 and to supplement the sparse surface measuring network by providing global total columns daily. The Infrared Atmospheric Sounding Interferometer (IASI), on board MetOp platforms, is measuring NH3 at a high spatiotemporal resolution. IASI circles the Earth in a polar Sun-synchronous orbit, covering the globe twice a day with a circular pixel size of 12km diameter at nadir and with overpass times at 9:30 and 21:30 (local solar time when crossing the equator). An improved retrieval scheme based on the calculation of Hyperspectral Range Index (HRI) is detailed in Chapter 2 and compared with previous retrieval methods. This approach fully exploits the hyperspectral nature of IASI by using a broader spectral range (800-1200 cm-1) where NH3 is optically active. It allows retrieving total columns from IASI spectra globally and twice a day without large computational resources and with an improved detection limit. More specifically the retrieval procedure involves two steps: the calculation of a dimensionless spectral index (HRI) and the conversion of this index into NH3 total columns using look-up tables (LUTs) built from forward radiative transfer simulations under various atmospheric conditions. The retrieval also includes an error characterization of the retrieved column, which is of utmost importance for further analysis and comparisons. Global distributions using five years of data (1 November 2007 to 31 October 2012) from IASI/MetOp-A are presented and analyzed separately for the morning and evening overpasses. The advantage of the HRI-based retrieval scheme over other methods, in particular to identify smaller emission sources and transport patterns over the oceans is shown. The benefit of the high spatial sampling and resolution of IASI is highlighted with the regional distribution over China and the first four-year time series are briefly discussed.<p><p>We evaluate four years (1 January 2008 to 31 December 2011) of IASI-NH3 columns from the morning observations and of LOTOS-EUROS model simulations over Europe and Western Russia. We describe the methodology applied to account for the variable retrieval sensitivity of IASI measurements in Chapter 3. The four year mean distributions highlight three main agricultural hotspots in Europe: The Po Valley, the continental part of Northwestern Europe, and the Ebro Valley. A general good agreement between IASI and LOTOS-EUROS is shown, not only over source regions but also over remote areas and over seas when transport is observed. The yearly analyses reveal that, on average, the measured NH3 columns are higher than the modeled ones. Large discrepancies are observed over industrial areas in Eastern Europe and Russia pointing to underestimated if not missing emissions in the underlying inventories. For the three hotspots areas, we show that the seasonality between IASI and LOTOS-EUROS matches when the sensitivity of the satellite measurements is taken into account. The best agreement is found in the Netherlands, both in magnitude and timing, most likely as the fixed emission timing pattern was determined from experimental data sets from this country. Moreover, comparisons of the daily time series indicate that although the dynamic of the model is in reasonable agreement with the measurements, the model may suffer from a possible misrepresentation of emission timing and magnitude. Overall, the distinct temporal patterns observed for the three sites underline the need for improved timing of emissions. Finally, the study of the Russian fires event of 2010 shows that NH3 modeled plumes are not enough dispersed, which is confirmed with a comparison using in situ measurements.<p><p>Chapter 4 describes the comparisons of IASI-NH3 measurements with several independent ground-based and airborne data sets. Even though the in situ data are sparse, we show that the yearly distributions are broadly consistent. For the monthly analyzes we use ground-based measurements in Europe, China and Africa. Overall, IASI-derived concentrations are in fair agreement but are also characterized by less variability. Statistically significant correlations are found for several sites, but low slopes and high intercepts are calculated in all cases. At least three reasons can explain this: (1) the lack of representativity of the point surface measurement for the large IASI pixel, (2) the use of a single profile shape in the retrieval scheme over land, which does therefore not account for a varying boundary layer height, (3) the impact of the averaging procedure applied to satellite measurements to obtain a consistent quantity to compare with the in situ monthly data. The use of hourly surface measurements and of airborne data sets allows assessing IASI individual observations. Much higher correlation coefficients are found in particular when comparing IASI-derived volume mixing ratio with vertically resolved measurements performed from the NOAA WP-3D airplane during CalNex campaign in 2010. The results demonstrate the need, for validation of the satellite columns, of measurements performed at various altitudes and covering a large part of the satellite footprint.<p><p>The six-year of IASI observations available at the end of this thesis are used to analyze regional time series for the first time (Chapter 5). More precisely, we use the IASI measurements over that period (1 January 2008 to 31 December 2013) to identify seasonal patterns and inter-annual variability at subcontinental scale. This is achieved by looking at global composite seasonal means and monthly time series over 12 regions around the world (Europe, Eastern Russia and Northern Asia, Australia, Mexico, South America, 2 sub-regions for Northern America and South Asia, 3 sub-regions for Africa), considering separately but simultaneously measurements from IASI morning and evening overpasses. The seasonal cycle is inferred for the majority of these regions. The relations between the NH3 atmospheric abundance and emission processes is emphasized at smaller regional scale by extracting at high spatial resolution the global climatology of the month of maxima columns. In some region, the predominance of a single source appears clearly (e.g. agriculture in Europe and North America, fires in central South Africa and South America), while in others a composite of source processes on small scale is demonstrated (e.g. Northern Central Africa and Southwestern Asia).<p><p>Chapter 6 presents the achievements of this thesis, as well as ongoing activities and future perspectives.<p>FRANCAIS:<p>Le cycle naturel de l'azote est fortement perturbé suite aux émissions atmosphériques de composés azotés réactifs (Nr) résultant de nos besoins accrus en énergie et en nourriture. Les émissions d'ammoniac (NH3) ont doublé au cours du siècle dernier, représentant aujourd'hui plus de la moitié des émissions totales de Nr. De plus, le NH3 étant le principal composé basique de notre atmosphère, il réagit rapidement avec les composés acides pour former des aérosols. C'est dès lors un constituant prépondérant pour l'environnement, le climat et la santé publique. Les problématiques environnementales y étant liées sont décrites au Chapitre 1. En tant que gaz en trace le NH3 se caractérise par une importante variabilité spatiale et temporelle. Bien que des mesures in situ soient possibles, elles sont souvent rares et couvrent le globe de façon hétérogène. Il en résulte un manque de connaissance sur l'évolution temporelle et la variabilité spatiale des émissions, ainsi que de leurs amplitudes, qui représentent les plus grandes incertitudes pour le cycle de l'azote (également décrites au Chapitre 1).<p><p>Récemment, les sondeurs spatiaux opérant dans l'infrarouge ont démontré leurs capacités à mesurer le NH3 et par là à compléter le réseau d'observations de surface. Particulièrement, l'Interféromètre Atmosphérique de Sondage Infrarouge (IASI), à bord de la plateforme MetOp, mesure le NH3 à une relativement haute résolution spatiotemporelle. Il couvre le globe deux fois par jour, grâce à son orbite polaire et son balayage autour du nadir, avec un temps de passage à 9h30 et à 21h30 (temps solaire local quand il croise l'équateur). Une nouvelle méthode de restitution des concentrations basée sur le calcul d'un index hyperspectral sans dimension (HRI) est détaillée et comparée aux méthodes précédentes au Chapitre 2. Cette méthode permet d'exploiter de manière plus approfondie le caractère hyperspectral de IASI en se basant sur une bande spectrale plus étendue (800-1200 cm-1) au sein de laquelle le NH3 est optiquement actif. Nous décrivons comment restituer ces concentrations deux fois par jour sans nécessiter de grandes ressources informatiques et avec un meilleur seuil de détection. Plus spécifiquement, la procédure de restitution des concentrations consiste en deux étapes: le HRI est calculé dans un premier temps pour chaque spectre puis est ensuite converti en une colonne totale de NH3 à l'aide de tables de conversions. Ces tables ont été construites sur base de simulations de transfert radiatif effectuées pour différentes conditions atmosphériques. Le processus de restitution des concentrations comprend également le calcul d'une erreur sur la colonne mesurée. Des distributions globales moyennées sur cinq ans (du 1 novembre 2007 au 31 Octobre 2012) sont présentées et analysées séparément pour le passage diurne et nocturne de IASI. L'avantage de ce nouvel algorithme par rapport aux autres méthodes, permettant l'identification de sources plus faibles de NH3 ainsi que du transport depuis les sources terrestres au-dessus des océans, est démontré. Le bénéfice de la haute couverture spatiale et temporelle de IASI est mis en exergue par une description régionale au-dessus de la Chine ainsi que par l'analyse de premières séries temporelles hémisphériques sur quatre ans.<p><p>Au Chapitre 3, nous évaluons quatre ans (du 1 janvier 2008 au 31 décembre 2011) de mesures matinales de IASI ainsi que de simulations du modèle LOTOS-EUROS, effectuées au-dessus de l'Europe et de l'ouest de la Russie. Nous décrivons une méthodologie pour prendre en compte, dans la comparaison avec le modèle, la sensibilité variable de l'instrument IASI pour le NH3. Les comparaisons montrent alors une bonne concordance générale entre les mesures et les simulations. Les distributions pointent trois régions sources: la vallée du Pô, le nord-ouest de l'Europe continentale et la vallée de l'Ebre. L'analyse des distributions annuelles montre qu'en moyenne, les colonnes de NH3 mesurées sont plus élevées que celles simulées, à part pour quelques cas spécifiques. Des différences importantes ont été identifiées au-dessus de zones industrielles en Europe de l'est et en Russie, ce qui tend à incriminer une sub-estimation voire une absence de ces sources dans les inventaires d'émissions utilisés en entrée du modèle. Nous avons également montré que la saisonnalité est bien reproduite une fois la sensibilité des mesures satellites prise en compte. La meilleure concordance entre le modèle et IASI est observée pour les Pays-Bas, ce qui est certainement dû au fait que le profil temporel des émissions utilisé pour les simulations LOTOS-EUROS est basé sur des études expérimentales réalisées dans ce pays. L'étude des séries temporelles journalières indique que la dynamique du modèle est raisonnablement en accord avec les mesures mais pointe néanmoins une possible mauvaise représentation du profil temporel ainsi que de l'ampleur des émissions. Finalement, l'étude des importants feux ayant eu cours en Russie à l'été 2010 a montré que les panaches modélisés sont moins étendus que ceux observés, ce qui a été confirmé grâce à une comparaison avec des mesures sols.<p><p>Le chapitre 4 est dédié à la confrontation des mesures IASI avec différents jeux de données indépendants acquis depuis le sol et par avion. Les distributions globales annuelles sont concordantes, bien que la couverture spatiale des mesures sols soit limitée. Des mesures effectuées à la surface en Europe, en Chine et en Afrique sont utilisées pour les comparaisons mensuelles. Ces dernières révèlent une bonne concordance générale, bien que les mesures satellites montrent une plus faible amplitude de variations de concentrations. Des corrélations statistiquement significatives ont été calculées pour de nombreux sites, mais les régressions linéaires sont caractérisées par des pentes faibles et des ordonnées à l'origine élevées dans tous les cas. Au minimum, trois raisons contribuent à expliquer cela: (1) le manque de représentativité des mesures ponctuelles pour l'étendue des pixels IASI, (2) l'utilisation d'une seule forme de profil vertical pour la restitution des concentrations, qui ne prend dès lors pas en compte la hauteur de la couche limite, (3) l'impact de la procédure utilisée pour moyenner les observations satellites afin d'obtenir des quantités comparables aux mesures sols mensuelles. La prise en compte de mesures en surface effectuées à plus haute résolution temporelle ainsi que de mesures faites depuis un avion permet d'évaluer les observations IASI individuelles. Les coefficients de corrélation calculés sont bien plus élevés, en particulier pour la comparaison avec les mesures effectuées depuis l'avion NOAA WP-3D pendant la campagne CalNex en 2010. Ces résultats démontrent la nécessité de ce type d'observations, effectuées à différentes altitudes et couvrant une plus grande surface du pixel, pour valider les colonnes IASI-NH3.<p><p>Les six ans de données IASI disponibles à la fin de cette thèse sont utilisées pour tracer les premières séries temporelles sub-continentales (Chapitre 5). Plus spécifiquement, nous explorons les mesures IASI durant cette période (du 1 janvier 2008 jusqu'au 31 décembre 2013) pour identifier des structures saisonnières ainsi que la variabilité inter-annuelle à l'échelle sous-continentale. Pour arriver à cela, des moyennes saisonnières composites ont été produites ainsi que des séries temporelles mensuelles au-dessus de 12 régions du globe (Europe, est de la Russie et nord de l'Asie, Australie, Mexique, Amérique du Sud, 2 sous-régions en Amérique du nord et en Asie du sud et 3 sous-régions en Afrique), considérant séparément mais simultanément les mesures matinales et nocturnes de IASI. Le cycle saisonnier est raisonnablement bien décrit pour la plupart des régions. La relation entre la quantité de NH3 atmosphérique et ses sources d'émission est mise en exergue à l'échelle plus régionale par l'extraction à haute résolution spatiale d'une climatologie des mois de colonnes maximales. Dans certaines régions, la prédominance d'un processus source apparait clairement (par exemple l'agriculture en Europe et en Amérique du nord, les feux en Afrique du Sud et en Amérique du Sud), alors que, pour d'autres, la diversité des sources d'émissions est démontrée (par exemple pour le nord de l'Afrique centrale et l'Asie du sud-ouest).<p><p>Le Chapitre 6 reprend brièvement les principaux aboutissements de cette thèse et présente les différentes recherches en cours et les perspectives associées.<p> / Doctorat en Sciences agronomiques et ingénierie biologique / info:eu-repo/semantics/nonPublished

[ES] En este trabajo estudiamos dos reacciones catalíticas relevantes para la industria y la localización del anión fluoruro en la zeolita RTH, sintetizada en medio fluoruro. El capítulo 3 es el primer capítulo de resultados, donde se estudia la reducción quimioselectiva del nitroestireno en las superficies Ni(111), Co(111), Cu(111) y Pd(111). El mecanismo generalmente aceptado de esta reacción está basado en el esquema propuesto por Haber en 1898, en el que la reacción puede transcurrir por dos rutas, la directa y la de condensación. En este capítulo exploramos ambas rutas, y observamos que la ruptura de los enlaces N-O y la consecuente formación de enlaces metal-O está más favorecida que la formación de enlaces N-H en las superficies Ni(111) y Co(111), debido al carácter oxofílico de ambos metales. Las etapas más lentas involucran la formación de enlaces N-H. En las superficies de metales nobles como Pt(111) y Pd(111) se observa el comportamiento contrario. La superficie Cu(111) es un caso intermedio comparado con los metales nobles y no nobles. Además, el nitroestireno interactúa con los átomos de Cu de la superficie solo a través de grupo nitro, con lo cual es un candidato ideal para alcanzar selectividades cerca del 100%. Sin embargo, la superficie Cu(111) no es capaz de activar la molécula de H2. En este sentido, proponemos un catalizador bimetálico basado en Cu, dopado con otro metal capaz de activar al H2, tales como el Pd o el Ni. En los capítulos 4 y 5 se ha estudiado la reducción catalítica selectiva de los óxidos de nitrógeno (SCR, en inglés) con amoníaco. Usando métodos de DFT, hemos encontrado rutas para la oxidación de NO a NO2, nitritos y nitratos con energías de activación relativamente bajas. También, hemos encontrado que la reducción de Cu2+ a Cu+ requiere la participación simultánea de NO y NH3. Posteriormente, hemos estudiado la influencia del NH3 en este sistema con métodos de dinámica molecular. El NH3 interacciona fuertemente con el Cu+ de forma que dos moléculas de este gas son suficientes para romper la coordinación del catión Cu+ con los oxígenos del anillo 6r, y formar el complejo lineal [Cu(NH3)2]+. Además, los cationes Cu2+ pueden ser estabilizados fuera de la red mediante la formación del complejo tetraamincobre(II). Debido a la presencia de los cationes Cu+ y Cu2+ coordinados a la red de la zeolita, aparecen bandas en la región entre 800-1000 cm-1 del espectro infrarrojo. El análisis de las frecuencias IR de varios modelos con Cu+ y Cu2+ coordinados al anillo 6r, o formando complejos con amoniaco indica que cuando los cationes Cu+ y Cu2+ están coordinados a los oxígenos del anillo 6r aparecen vibraciones entre 830 y 960 cm-1. Frecuencias en esta zona también se obtienen en los casos en que NO, NO2, O2 y combinaciones de dos de ellos están adsorbidos en Cu+ y Cu2+. Sin embargo, cuando los cationes Cu+ y Cu2+ están fuera del anillo (no hay enlaces entre los cationes de cobre y los oxígenos del anillo 6r) no se obtienen vibraciones de IR en esta región del espectro. Estos resultados indican que con el seguimiento del espectro IR durante la reacción SCR es posible determinar si los cationes Cu+ y Cu2+ están coordinados o no al anillo de 6r en las etapas de oxidación y reducción. Por último, hemos simulado el desplazamiento químico de 19F, δiso,, en la zeolita sintetizada RTH. El análisis del δiso de los distintos modelos utilizados nos ha permitido reconocer la simetría del material sintetizado, el cual pertenece al grupo espacial P1 y la nueva celda unidad ha sido confirmada experimentalmente por difracción de rayos X. Finalmente, hemos asignado la señal experimental que aparece en el espectro de 19F a -67.2_ppm, al F- localizado en un sitio T2, el cual es a su vez la posición más estable. Además, la señal a -71.8 ppm se ha asignado al anión F- localizado en un sitio T4. / [CA] En aquest treball estudiem dues reaccions catalítiques rellevants per a la indústria i la localització de l'anió fluorur en la zeolita RTH, sintetitzada al mig fluorur. El capítol 3 és el primer capítol de resultats, on s'estudia la reducció quimioselectiva del nitroestireno en les superfícies Ni(111), Co(111), Cu(111) i Pd(111). El mecanisme generalment acceptat d'aquesta reacció està basat en l'esquema proposat per Haver-hi en 1898, en el qual la reacció pot transcórrer per dues rutes, la directa i la de condensació. En aquest capítol explorem totes dues rutes, i observem que la ruptura dels enllaços N-O i la conseqüent formació d'enllaços metall-O està més afavorida que la formació d'enllaços N-H en les superfícies Ni(111) i Co(111), a causa del caràcter oxofílico de tots dos metalls. Les etapes més lentes involucren la formació d'enllaços N-H. En les superfícies de metalls nobles com Pt(111) i Pd(111) s'observa el comportament contrari. La superfície Cu(111) és un cas intermedi comparat amb els metalls nobles i no nobles. A més, el nitroestireno interactua amb els àtoms de Cu de la superfície sol a través de grup nitre, amb la qual cosa és un candidat ideal per a aconseguir selectivitats prop del 100%. No obstant això, la superfície Cu(111) no és capaç d'activar la molècula d'H2. En aquest sentit, proposem un catalitzador bimetàl·lic basat en Cu, dopat amb un altre metall capaç d'activar a l'H2, com ara el Pd o el Ni. En els capítols 4 i 5 hem estudiat la reducció catalítica selectiva dels òxids de nitrogen (SCR, en anglés) amb amoníac. Usant mètodes de DFT, hem trobat rutes per a l'oxidació de NO a NO2, nitrits i nitrats amb energies d'activació relativament baixes. També, hem trobat que la reducció de Cu2+ a Cu+ requereix la participació simultània de NO i NH3. Posteriorment, hem estudiat la influència del NH3 en aquest sistema amb mètodes de dinàmica molecular. El NH3 interacciona fortament amb el Cu+ de manera que dues molècules d'aquest gas són suficients per a trencar la coordinació del catió Cu+ amb els oxígens de l'anell 6r, i formar el complex lineal [Cu(NH3)2]+. A més, els cations Cu2+ poden ser estabilitzats fora de la xarxa mitjançant la formació del complex tetraamincobre(II). A causa de la presència dels cations Cu+ i Cu2+ coordinats a la xarxa de la zeolita, apareixen bandes a la regió entre 800-1000 cm-1 de l'espectre infraroig. L'anàlisi de les freqüències IR de diversos models amb Cu+ i Cu2+ coordinats a l'anell 6r, o formant complexos amb amoníac indica que quan els cations Cu+ i Cu2+ estan coordinats als oxígens de l'anell 6r apareixen vibracions entre 830 i 960 cm-1. Freqüències en aquesta zona també s'obtenen en els casos en què NO, NO2, O2 i combinacions de dues d'ells estan adsorbidos en Cu+ i Cu2+. No obstant això, quan els cations Cu+ i Cu2+ estan fora de l'anell (no hi ha enllaços entre els cations de coure i els oxígens de l'anell 6r) no s'obtenen vibracions d'IR en aquesta regió de l'espectre. Aquests resultats indiquen que amb el seguiment de l'espectre IR durant la reacció SCR és possible determinar si els cations Cu+ i Cu2+ estan coordinats o no a l'anell de 6r en les etapes d'oxidació i reducció. Finalment, hem simulat el desplaçament químic de 19F, δiso, en la zeolita sintetitzada RTH. L'anàlisi del δiso dels diferents models utilitzats ens ha permés reconéixer la simetria del material sintetitzat, el qual pertany al grup espacial P1 i la nova cel·la unitat ha sigut confirmada experimentalment per difracció de raigs X. Finalment, hem assignat el senyal experimental que apareix en l'espectre de 19F a -67.2 ppm, al F- localitzat en un lloc T2, el qual és al seu torn la posició més estable. A més, el senyal a -71.8 ppm s'ha assignat a l'anió F- localitzat en un lloc T4. / [EN] In this work, we have studied two heterogeneous catalytic reactions and the localization of the fluoride anion in the as-made RTH framework, synthesized in fluoride medium. The first results, included in chapter 3, correspond to the chemoselective reduction of nitrostyrene on different metal surfaces, i.e, Ni(111), Co(111), Cu(111) and Pd(111). Until very recently, the reduction of the nitro group was explained on the basis of the general mechanism proposed by Haber in 1898 where the reaction can follow two routes, the direct and condensation route. We have explored the relevant elementary steps of both routes and found that because of the oxophilic nature of Ni and Co, the steps involving the dissociation of N-O bonds and formation of metal-O bonds are significantly favored compared with the other steps on both metal surfaces. In addition, the most demanding steps in terms of energy involve the formation of N-H bonds. These findings are in contrast to those of noble metals such as Pt and Pd, where the opposite behavior is observed. The behavior of Cu(111) lies in between the aforementioned cases, and also no chemical bonds between the carbon atoms of the aromatic ring of nitrostyrene and the Cu(111) surface is formed. For this reason, it might be an ideal candidate to achieve nearly 100 % selectivity. However, the Cu(111) surface does not seem to activate the H2 molecule. In this regard, we propose a bimetallic Cu-based catalyst whose surface is doped with atoms of a H2-activating metal, such as Ni or Pd. On another matter, we have also investigated the selective catalytic reduction of nitrogen oxides (SCR-NOx) and the main results are presented in the following two chapters, 4 and 5. By using static DFT methods, we found pathways for the oxidation of NO to NO2, nitrites and nitrates with relatively low activation energies. We also found, in agreement with experimental reports, that the reduction of Cu2+ to Cu+ requires the simultaneous participation of NO and NH3. Later, molecular dynamics simulations allowed us to assess the influence of NH3. The strong interaction of NH3 with the Cu+ cation is evidenced by its ability to detach Cu+ from the zeolite framework and form the mobile linear complex [Cu(NH3)2]+. Cu+ is no longer coordinated to the zeolite framework in the presence of two NH3 molecules. This observation and the fact that the T-O-T vibrations of the framework produce bands in the 800-1000 cm-1 region of the IR spectrum when perturbed by the coordination of Cu+ and Cu2+ cations, indicate that bands in the 800-1000 cm-1 regions should be observed when both copper cations are bonded to the framework oxygens. Finally, we have also studied NMR properties of the as-made pure silica RTH framework, aiming at locating the compensating fluoride anion. The calculation of the 19F chemical shift in different T sites and comparison with the experimental NMR spectra shows that the as-made RTH belongs to the P-1 space group with 16 Si, 32 O atoms, one fluoride anion and one OSDA cation. These results have been confirmed experimentally by XRD. In addition, we have assigned the experimental signal of 19F at -67.2 ppm to the fluoride anion in a T2 site, which in turn is the most stable location found, and the signal of -71.8 ppm to a fluoride anion sitting in a T4 site. / My acknowledgements to “La Caixa foundation” for the financial support through “La Caixa−Severo Ochoa” International PhD Fellowships (call 2015), to the Spanish Supercomputing Network (RES), to the Centre de Càlcul de la Universitat de València, to the Flemish Supercomputer Center (VSC) of Ghent University for the computational resources and technical support, and to the Spanish Government through the MAT2017-82288-C2-1-P programme / Millan Cabrera, R. (2021). Computational study of heterogeneous catalytic systems. Kinetic and structural insights from Density Functional Theory [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/161934 / TESIS

<p>Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (<i>i.e.</i> nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques.</p><p>The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures.</p><p>Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well.</p><p>Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger <i>vis-à-vis</i> Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups.</p><p>Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.</p>

Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (i.e. nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques. The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures. Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well. Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger vis-à-vis Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups. Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.

El aumento de la cantidad de lodos y las dificultades inherentes a su aplicación agrícola y/o disposición en vertederos, hace necesario encontrar nuevas alternativas para su gestión. A nivel europeo, hoy en día se tiende hacia la aplicación de tratamientos térmicos (incineración, pirólisis y gasificación) que permiten una valoración energética de los lodos, si bien generan un residuo sólido que sigue siendo necesario gestionar. El problema medioambiental provocado por (malos) olores resulta difícil de abordar de una manera genérica, teniendo en consideración la propia naturaleza del olor y sus posibles causas. Los olores en las EDARs son provocados básicamente por la degradación de la materia orgánica en condiciones anaeróbicas y se detectan en todas las operaciones unitarias en diferentes niveles de concentración. Esta tesis incidiendo en ambos aspectos, tiene por objeto investigar la valorización de lodos como materiales precursores de adsorbentes/ catalizadores para la eliminación de olores en el entorno de las EDARs, maximizando la reutilización de los lodos.Para la realización de los experimentos se han seleccionado lodos procedentes de tres EDARs situadas en la región de Girona (SC, SB, SL) que difieren en cuanto al tratamiento de los lodos. Ambas muestras han sido caracterizadas con el fin de determinar las diferencias más importantes en los lodos de partida. Los parámetros de caracterización incluyen el análisis de composición química (análisis elemental e inmediato, determinación contenido en cenizas, medida pH, DRX, FT-IR, SEM / EDX) así como análisis de superficie (adsorción de N2 y CO2). En primer lugar los lodos caracterizados han sido sometidos a diferentes tratamientos térmicos de gasificación y pirólisis y los adsorbentes/ catalizadores obtenidos se han probado como adsorbentes para la eliminación de H2S. Como consecuencia de este estudio, se ha desechado el uso de uno de lodos (SC) puesto que se obtenían resultados muy similares a (SB), a continuación el estudio se centró en el lodo de SL. Con este objetivo se han preparado 12 muestras 6 de ellas pirolizadas y 6 gasificadas en el rango de temperaturas que comprende 600-1100 ºC. Posteriormente las muestras han sido caracterizadas y se ha determinado la capacidad de eliminación (x/M) del H2S. Los resultados muestran que hemos sido capaces de obtener unos materiales que si bien, presentan un bajo desarrollo de porosidad dan lugar a valores de capacidades de eliminación elevados y comparables a carbones y materiales adsorbentes comerciales (Centaur, Sorbalit). Las elevadas eficiencias de eliminación se atribuyen básicamente a la presencia de especies catalíticamente activas tales como los óxidos mixtos de calcio y hierro determinados por DRX en las muestras tratadas térmicamente. El segundo bloque de resultados se centra la mejora de las propiedades texturales de estos materiales adsorbentes. Con este objetivo se llevaron acabo procesos de activación física con CO2 y química con H3PO4 e hidróxidos alcalinos (NaOH y KOH), que hasta el momento no se había probado con este tipo de precursores. Los resultados indican que la activación física (CO2) y química (H3PO4) no son unos buenos métodos para la obtención de adsorbentes altamente porosos con este tipo de materia prima bajo las condiciones probadas, sin embargo la activación con hidróxidos alcalinos da lugar a materiales adsorbentes con superficies específicas de hasta 1600 m2g-1. En el caso de la activación con hidróxidos, tanto el incremento de la relación agente activante/ precursor como el incremento de la temperatura producen un descenso del rendimiento, al mismo tiempo que incrementan el valor de SBET.Los materiales resultantes de la activación con hidróxidos alcalinos se han probado como adsorbentes/ catalizadores para la eliminación de H2S. Los resultados indican que un incremento del área superficial no es indicativo de un aumento de la capacidad de eliminación dada la naturaleza ácida de estos materiales obtenidos. Con el fin de contrarrestar el efecto ácido de estos materiales se han realizado los mismos ensayos añadiendo NaOH al lecho de reacción llegando a valores de x/M de hasta 450 mgg-1. Posteriormente también se han realizado ensayos de eliminación de NH3 con algunas de estas muestras, y los resultados obtenidos de x/M son del orden de carbones activados comerciales. Los materiales adsorbentes obtenidos tras la activación con hidróxidos alcalinos se convierten en materiales muy atractivos para ser utilizados como adsorbentes/ catalizadores de múltiples contaminantes (COVs, Hg...). / During the last years there has been an increase in the number of wastewater treatment plants arising after the implementation of regulatory policies focused on sustainable development of contemporary societies. A large quantity of sewage sludge is produced and in addition, some traditional disposal routes are coming under pressure and others are being phased out. Therefore, it is necessary to seek cost-effective and innovate solutions to the problem incurred by sewage sludge disposal. Nowadays, the tendency in Europe is to use this residue to obtain energy by thermal treatments, such as incineration, pyrolysis and gasification, though during this treatment a residue that needs to be disposed is generated.Furthermore, the environmental problems prompted by odors are difficult to solve take considering the different origin and reasons for these bad smells. Bad smell in waste water treatment plants is produced basically by organic matter degradation. This thesis takes into account these two aspects. The aim of this work focuses on the revalorization of sewage sludge to obtain / prepare adsorbents / catalysts from various sewage-based precursors and their application in H2S and in NH3 abatement at ambient temperature. These two latter compounds are paradigmatic in odor related problems.The sewage sludge samples used in this study were obtained from three Spanish WWTPs located in Girona (SC, SB, SL). The influent of these selected facilities is mainly of domestic origin and differs in sludge treatment schemes. A detailed characterization of the solids under consideration is carried out, as a purpose to define the main differences. The techniques used to characterize precursors include chemical characterization (elemental analysis, ash content, pH determination, DRX, FT-IR, SEM / EDX), as well as their porosity characterization (physical adsorption of N2 and CO2).In the first part of the study we focused on dried samples that were subjected to different thermal treatments such as pyrolysis and gasification at different temperatures. The adsorbents/catalysts obtained were used for H2S removal. Afterwards, 12 samples were prepared from SL, 6 of them gasified between 600 - 1100 ºC and 6 pyrolysed at the same temperatures. The samples were characterized and used as an adsorbents for H2S removal. The results shown that we were able to obtain adsorbents with high removal efficiencies despite their low porosity development. These adsorption capacities values (x/M) are in the same range or even higher than x/M values from commercial active carbons (Centaur, Sorbalit). These high x/M values have been prompted to catalytic species such as dicalcium ferrite, identified by XRD.The second part of the study was focused on the preparation of adsorbents from these sewage sludge-based precursors (SB, SL) using different activation processes. Specifically, physical activation with CO2, H3PO4 activation and alkaline hydroxide activation were explored. It is worth noticing that, as far as we know, there are no previous studies in the literature dealing with the activation of sewage sludge by alkaline hydroxides (NaOH or KOH), whereas CO2 and H3PO4 have been scarcely used for the activation of this precursor. The results of the textural characterization of the materials prepared from physical activation by CO2 and chemical activation by H3PO4 show that, these precursors are not a suitable for the preparation of adsorbents by these two methods. Nevertheless, chemical activation by alkaline hydroxides can be a suitable method to develop porosity and surface areas higher than 1600 m2g-1 can be obtained from both sewage sludge precursors (SB, SL). An increase in the hydroxide: precursor ratio leads to an enhancement of the adsorption capacity of the adsorbents. The resultant materials were tested as adsorbents/catalyst for H2S abatement. The results shown that we are been able to obtain adsorbents from sludge-based materials with high surface areas but with relatively low adsorption capacities as a consequence of its acidic nature. NaOH was added to the adsorption bed to counteract the acidic nature of these materials. The x/M values obtained are higher than 450 mgg-1. In addition, some of these materials were used for NH3 removal being the results obtained comparable to those for commercial activated carbons x/M values, tested under similar experimental conditions. These "new" activated materials can be used as adsorbents for many environmental applications such as VOC, Hg removal, etc.

This thesis studies the interaction between the bare Cu{311} surface with NO and NH3,individually and co-adsorbed using reflection-absorption infrared spectroscopy (RAIRS). In addition to the bare Cu{311} surface, the interaction of NO and NH3 with the various oxygen phases of the Cu{311} surface phases was also studied. Several other techniques were used in tandem to support the study, such as low energy electron diffraction (LEED) and temperature programmed desorption (TPD) experiments using mass spectrometry. The study was carried out in pursuit an understanding of the underlying mechanism of the selective catalytic reduction (SCR) of NO using NH3 in current diesel engines. The dosing of NO onto the Cu{311} surface at 100 K leads to the initial adsorption of intact NO. After an exposure threshold is reached, individual NO molecules react with another NO molecule to form (NO)2 dimers. These dimer species subsequently form N2O, leaving O(a) on the surface. Oxygen was found to be an inhibitor for the reaction, either due to the reaction in a self-poisoning process or from oxygen pre-dosing onto the Cu{311} surface. Temperature plays a minor role with regards to NO/Cu{311}, as it only affects the amount of NO on the surface along with adsorbate surface mobility. Similarly, NH3 was found to adsorb intact onto the Cu{311} surface and not to react or dissociate at 100 K. Oxygen acts as a site blocker for the adsorption, but can also stabilise NH3 to remain on the surface at higher temperatures due to electronic effects. At 300 K, it was found that both the bare and oxygen pre-covered Cu{311} surface was able to dissociate NH3 into NH2. The co-adsorption of NO and that of NH3 onto the Cu{311} surface were found to be largely independent of each other and the interaction is dominated by the displacement of NO by NH3. However, as NO adsorption on the Cu{311} surface forms O(a), it indirectly affects the adsorption of NH3 by creating an oxygen covered Cu{311} surface, which changes how NH3 adsorbs onto the surface.

No description available.