Dissertations / Theses on the topic 'Calcium catalysts'

Abstract The aim of this thesis project was to gain new knowledge on the effect of phosphorus on the catalytic activity and characteristics of automotive exhaust gas catalyst components. The simultaneous roles of phosphorus and calcium were also studied. The first test series of powdery catalyst samples contained Rh and oxide (Test series 1) and the second, Pt and oxide or ZSM-5 (Test series 2). The catalysts were analyzed when fresh and after two ageing and phosphorus poisoning procedures developed in this work. The procedures consisted of adding poison via impregnation in an aqueous solution (for Test series 1) and in the gaseous phase under hydrothermal conditions (for Test series 2). The poison compounds formed and the changes in the washcoat were studied by using physisorption analyses, SEM, TEM, XRD, and FTIR-ATR. The poison content of the samples was determined by ICP-OES and XRF. Laboratory-scale activity measurements were done to investigate the catalytic activity. Thermodynamic calculations were used to obtain information about ageing conditions and phosphorus compounds formed during ageing. Phosphorus decreased the catalytic activity and the characteristic surface areas of the catalysts. Addition of calcium to a phosphorus-poisoned catalyst was found to have even a regenerating effect on the catalysts' activity. The poisoning methods developed in this study resulted in the same phosphorus compounds as can be found in vehicle-aged catalysts. Phosphorus was identified as cerium, zirconium, aluminium, and titanium phosphates. Phosphorus was detected in zeolites, but phosphorus-containing compounds were not observed. Phosphorus poisoning takes place in the gas phase at high operating temperatures and with high oxygen and water contents. It was also shown that the role of phosphorus poisoning was more pronounced than the role of hydrothermal ageing alone. Phosphorus poisoning mainly affects the oxide components used in this study, not the noble metals. The results can be utilized in the development of catalytic materials and catalyst compositions that can better tolerate phosphorus poisoning under hydrothermal conditions. The results can also be applied in evaluating the effects of phosphorus on different catalyst compositions and in estimating the age of commercial catalysts.

Parmi les produits issus de la biomasse ou de la transformation des déchets organiques, le CO2 et le CH4 sont des intermédiaires chimiques importants qui ont de forts impacts environnementaux. En effet, ils sont les principaux gaz responsables de l'effet de serre et leur atténuation est un enjeu majeur. Une voie intéressante pour la valorisation de ces gaz est le reformage à sec du méthane (DRM), qui convertit le CO2 et le CH4 en gaz de synthèse (mélange d'hydrogène et de monoxyde de carbone). Ce mélange peut être utilisé pour plusieurs applications telles que la production de méthanol, d'éther diméthylique, d'hydrogène et des hydrocarbures liquides. Malgré cet intérêt, l'exploitation du DRM à l'échelle industrielle n'a pas encore vu le jour. La raison principale est la désactivation rapide des catalyseurs en raison des conditions sévères de fonctionnement du procédé (température élevée, dépôt de carbone). Cette thèse porte sur le développement de nouveaux catalyseurs à base de phosphate de calcium (CaP) dopés avec des métaux de transition pour la valorisation du CO2 et du CH4 en gaz de synthèse par DRM. Les CaP sont utilisés car ils possèdent des propriétés avantageuses en catalyse hétérogène comme la présence simultanée de sites acides et basiques, bonne stabilité thermique, large gamme de surface spécifique ... Dans un premier temps, des études sur les méthodes de synthèse de catalyseurs et sur la performance de différents métaux de transition (Zn, Fe, Co, Cu, Ni) ont été effectuées dans le but de sélectionner le catalyseur et sa méthode de préparation. Un réacteur à lit fixe capable de fonctionner à hautes température et pression a ensuite été testé pour un long temps de réaction afin d'évaluer correctement la performance des catalyseurs préparés. Ensuite, une étude paramétrique détaillée a été menée. L'influence des paramètres tels que le prétraitement des catalyseurs, la température (T = 400-700°C) et la pression (P = 1-25bar) de la réaction et les différents supports (hydroxyapatite, alumine) ont été étudiés. Enfin, la stabilité thermique et catalytique a été étudiée durant 300h de réaction. Les catalyseurs à base de CaP ont montré des rendements plus élevés en gaz de synthèse en comparaison aux catalyseurs commerciaux. Ces catalyseurs sont donc compétitifs dans les mêmes conditions opératoires (T = 700°C, P = 1bar, WHSV = 12272mLh-1gcat-1, t = 300h). Ce travail a montré l'intérêt des catalyseurs à base de CaP pour des processus à haute température, tel que le reformage à sec du méthane
Among the products resulting from biomass or organic waste transformation, CO2 and CH4 are important chemical intermediates. They also have a strong environmental impact since they are primarily responsible for the greenhouse effect and their mitigation is a key issue. An attractive way of valorization of such gases is the dry reforming of methane (DRM), which converts CO2 and CH4 into syngas (mixture of hydrogen and carbon monoxide). This mixture can be used for several applications, such as the production of methanol, dimethyl ether, hydrogen and liquid hydrocarbons. Despite such interest, the exploitation of DRM on industrial scale has not emerged yet. The main reason is the rapid deactivation of the catalysts due to the severe operating conditions of the process (high temperature, carbon deposition). This thesis focuses on the development of new catalysts based on calcium phosphate (CaP) doped with transition metals for the valorization of CO2 and CH4 through DRM. Actually,CaP has advantageous properties in heterogeneous catalysis, as the simultaneous presence of acid and basic sites, good thermal stability, and wide range of surface area... Initially, a study on the catalyst synthesis methods and an investigation of the performance of different transition metals (Zn, Fe, Co, Cu, Ni) were carried out in order to select the catalyst system and the preparation method. Secondly, a fixed-bed reactor capable of operating at high temperature and pressure and for log time on stream was built and implemented during this work in order to properly evaluate the performance of the preparedcatalysts. Then, a detailed parametric study was conducted. The influence of parameters such as catalyst pre-treatment, temperature (T = 400-700°C) and pressure (P = 1-25bar) of the reaction and support (hydroxyapatite, alumina-based supports) were investigated. Finally, the catalytic stability was studied for 300h of time on stream (TOS). The CaP catalysts showing higher yields on syngas were compared to commercial catalysts. Our catalysts showed to be competitive in the same operating conditions (T = 700°C, P = 1bar, WHSV = 12272mLh-1gcat-1,TOS = 300h). This work shows the interest of CaP catalysts for high temperature process, such as dry reforming of methane

Grâce à leurs multiples sites de fonctionnalisation, les cyclopenténones sont des intermédiaires particulièrement utiles dans la synthèse de produits naturels d’intérêt thérapeutique. En particulier, les composés 4-aminocyclopenténones permettent l’accès au motif aminocyclopentitol présent dans des molécules bioactives telles que le peramivir, la pactamycine, ou encore la trehazoline. L’une des méthodes les plus efficaces pour accéder aux 4-aminocyclopenténones est la réaction de cyclisation d’aza-Piancatelli. Cette réaction est basée sur le réarrangement de 2-furylcarbinols en présence d’un nucléophile azoté suivant un mécanisme faisant intervenir une électrocyclisation 4π-conrotatoire. Au sein de notre laboratoire, un système catalytique simple, utilisant un complexe de calcium combiné à un sel d’ammonium, a été mis au point pour avoir accès à ces composés. Cette méthode présente de nombreux avantages : elle est efficace (rendements allant jusqu’à 98%), rapide (15 à 30 minutes), elle nécessite seulement 1 mol% de catalyseur dans des conditions commodes (solvants non distillés et réaction à l’air libre) sur une grande échelle (multi-grammes). Dans ce contexte, nous avons cherché à exploiter tout le potentiel de cette réaction en synthétisant des 2-furylcarbinols plus complexes dans le but de concevoir un accès direct à des squelettes de composés bioactifs. Nous nous sommes en particulier concentrés sur la synthèse totale de la jogyamycine. Par ailleurs, nous avons effectué la synthèse totale de la bruceolline D avec un rendement global de 16% sur 5 étapes. Nous avons également développé une nouvelle séquence réactionnelle impliquant une réaction d’aza-Piancatelli suivie d’une réaction d’hydroamination promue par des sels de cuivre qui fournit un large éventail de cyclopenta[b]pyrroles polyfonctionnels à partir de 2-furylcarbinols facilement accessibles incorporant un groupement alcyne. Par cette méthode, 42 cyclopenta[b]pyrroles ont été obtenus avec des rendements atteignant 98%. Une caractéristique originale de notre approche est liée à l'utilisation d'anilines ortho-substituées. En effet, dans ce cas, des atropisomères avec un excès diastéréomérique supérieur à 20:1 ont pu être obtenus, accompagnés par la création d'une chiralité axiale N-C lors de l'étape d'hydroamination. A ce jour, il n'existait aucun autre exemple de synthèse atropodiastéréosélective de cyclopenta[b]pyrroles. Au cours de nos recherches sur le champ d’application de la réaction, nous avons remarqué que les cyclopenta[b]pyrroles pouvaient se réarranger spontanément en cyclopenta[b]pyrrolines suivant une déaromatisation lorsque l’hexafluoroisopropanol était utilisé comme solvant, permettant d’obtenir 13 cyclopenta[b]pyrrolines avec des rendements variant de 44 à 73%. Nous nous sommes également intéressés à la fonctionnalisation du motif cyclopenta[b]pyrrole pour illustrer l'utilité de notre méthodologie, en combinant en particulier cette séquence réactionnelle avec des réactions de type Friedel-Crafts. L’un des objectifs du projet de thèse était le développement de la version énantiosélective de la réaction. Après la publication récente de trois articles utilisant des acides phosphoriques chiraux en tant que catalyseurs, nous avons envisagé une autre approche pour la synthèse asymétrique de 4-aminocyclopenténones, s’appuyant sur l’utilisation d’une copule chirale (sulfoxyde chiral) portée par l’aniline en collaboration, avec le Dr. Wencel-Delord et le Pr. Colobert (Université de Strasbourg). Ainsi nous avons pu générer les 4-aminocyclopenténones correspondantes avec d’excellents rendements et diastéréosélectivités
Due to their various functionalizable sites, cyclopentenones are very useful intermediates for the synthesis of natural products of therapeutic value. In particular, 4-aminocyclopentenones enable the access to the aminocyclopentitol frameworks, which are present in a variety of bioactive molecules such as peramivir, pactamycin, or trehazolin. One of the most efficient methods to access 4-aminocyclopentenones is the aza-Piancatelli reaction. It is based on the rearrangement of 2-furylcarbinols in the presence of a nitrogen nucleophile following a mechanism involving a 4π-conrotatory electrocyclization. In our laboratory, a simple catalytic system using a calcium complex combined with an ammonium salt was developed to gain access to these compounds. This method has many advantages : it is effective (yields up to 98%), fast (15 to 30 minutes), it requires only 1 mol% of catalyst under pratical conditions (undistilled solvents without an inert atmosphere) on a large scale (multi-gram). In this context, we sought to extend the scope of this reaction by designing more complex 2-furylcarbinols in order to directly access skeletons of bioactive compounds. In particular, we focused on the total synthesis of jogyamycin. In addition, we achieved the total synthesis of bruceollin D with an overall yield of 16% over five steps. We also developed a new reaction sequence involving an aza-Piancatelli reaction followed by a hydroamination reaction promoted by a copper salt. This sequence provides a wide range of highly functionalized cyclopenta[b]pyrroles from readily-available 2-furylcarbinols substituted by an alkyne moiety. Following this method, 42 cyclopenta[b]pyrroles were obtained with yields up to 98%. An original feature of this transformation is related to the use of ortho-substituted anilines. Indeed, in this case, atropisomers with a diastereomeric excess superior to 20:1 could be obtained accompanied by the creation of an chiral N-C axis during the hydroamination step. To date, no other example of atropodiastereoselective synthesis of cyclopenta[b]pyrroles has been reported. During our investigations on the scope of the reaction, we noticed that cyclopenta[b]pyrroles underwent a rearrangement into cyclopenta[b]pyrrolines, following a dearomatization when hexafluoroisopropanol was used as solvent. This transformation led to 13 cyclopenta[b]pyrrolines with yields ranging from 44% to 73%. We also investigated the functionalization of the cyclopenta[b]pyrrole motif to illustrate the synthetic utility of our methodology, notably by combining this reaction sequence with a Friedel-Crafts reaction. One of the objectives of this Ph.D. was the development of an enantioselective version of the reaction. After the recent publication of three papers using chiral phosphoric acids as catalysts, we devised another approach for the asymmetric synthesis of 4-aminocyclopentenones, relying on the use of a chiral auxiliary (chiral sulfoxide) in collaboration with Dr. Wencel-Delord and Pr. Colobert (University of Strasbourg). Thus, we were able to provide the corresponding 4-aminocyclopentenones with excellent yields and diastereoselectivity

Bien que de très nombreuses applications soient recensées pour valoriser le glycérol coproduit par la filière biodiesel (à raison de 100 kg de glycérol par tonne de biocarburant), les solutions potentiellement les plus lucratives basées sur des transformations chimiques avancées n’atteignent aujourd’hui que rarement le stade commercial. Ceci est principalement dû à (i) une instabilité réglementaire sur les licences de production de biodiesel menaçant ainsi la disponibilité du glycérol et (ii) un prix du glycérol pouvant par conséquent fluctuer de manière imprévisible. Faire évoluer le concept d’unité de production de biodiesel, où le glycérol est le coproduit principal, en un concept de bioraffinerie oléagineuse, où notamment des produits à haute valeur ajoutée dérivés du glycérol sont produits avec le biodiesel, permettra de s’affranchir des incertitudes règlementaires liées à la production du biodiesel tout en favorisant un développement rapide des technologies de valorisation du glycérol par évolution d’unités de production existantes. Dans ce contexte, ce projet de thèse basé sur des résultats préliminaires très prometteurs de notre équipe vise à développer un procédé catalytique de valorisation efficace du glycérol en polyglycérols linéaires (PGs). Les PGs présentent une biocompatibilité exceptionnelle récemment démontrée. Ils possèdent en outre des applications directes (pharmacie, alimentation, etc.), et de grands industriels le voient aussi de plus en plus comme une base pour l’obtention d’autres molécules, notamment les esters de PGs, diversifiant considérablement les champs d’applications finaux (émulsifiants, stabilisateurs, etc.). Le programme de recherche proposé permettra de mieux comprendre et d’optimiser en retour un système catalytique performant et robuste, dans un contexte régional particulièrement propice (Hub2 de l’I-SITE, producteurs de biodiesel, plateformes REALCAT et UPCAT, CPER-FEDER Archi-CM, etc.)
Although many applications are listed to valorize glycerol as a co-produced of the biodiesel sector (at a rate of 100 kg of glycerol per ton of biofuel), the most potential solutions based on advanced chemical transformations today reach rarely the commercial stage. This is mainly due to (i) instability on biodiesel production licenses, thus threatening the availability of glycerol and (ii) a price of glycerol that can fluctuate unpredictably. In the concept of biodiesel production unit, where glycerol is the main co-product, into a concept of oilseed biorefinery, where in particular glycerol-derived products with high added value are produced with biodiesel, will make it possible to overcome uncertainties related to the production of biodiesel while promoting the rapid development of glycerol valorization technologies through the evolution of existing production units. In this context, this thesis project based on very promising preliminary results from our team aims to develop a catalytic process for the efficient valorisation of glycerol in linear polyglycerols (PGs). PGs have recently demonstrated exceptional biocompatibility. They also have direct applications (pharmacy, food, etc.), and large manufacturers also see it increasingly as a base for obtaining other molecules, including PGs esters. The proposed research program will provide a better understanding and optimization of a powerful and robust catalytic system in a particularly favorable regional context

This thesis discusses the synthesis, characterisation, and reactivity studies of a range of new chiral calcium complexes supported by various polydentate N-donor ligands and their suitability as catalysts for intramolecular hydroamination. Chapter One outlines the case for developing organocalcium complexes, including a general overview of their current application to a variety of heterofunctionalisation reactions. Chapter Two introduces the chiral ethylene diamines which are extensively used as calcium supporting ligands and later as precursors for the synthesis of bisimidazoline and potential imoxazoline ligands. Chapter Two provides details of the diamine synthesis and includes studies related to racemisation concerns of the chiral centre. Chapter Three discusses novel calcium complexes supported by the chiral ethylene diamine analogues presented in Chapter Two. Complex synthesis, characterisation, and catalytic performance in intramolecular hydroamination is probed and discussed. Chapter Four details a range of new bisimidazoline ligands and their employment as supporting ligands on calcium. The catalytic performance of the resulting complexes in intramolecular hydroamination is subsequently analysed and discussed. Chapter Five investigates the attempted development of a total synthetic pathway to a new class of imoxazoline ligand and related issues. Chapter Six contains all experimental procedures, characterising data pertaining to all new compounds and complexes presented in this Thesis. Appendices A-K contain additional catalytic figures and tables of crystallographic data for all new crystallographically characterised compounds. Summary sheets of every literature and new compound presented mentioned in this Thesis are also included, along with copies of both printed publications resulting from this Thesis at the time of submission.

A l’heure actuelle, il y a une forte demande de l’industrie de la chimie fine pour développer des procédures basées sur des réactions n’impliquant pas l’utilisation de métaux de transition et mettant en jeu des produits de départ facilement accessibles. Les principales raisons sont la disponibilité, le coût et la toxicité des métaux de transition ou des électrophiles. Dans ce contexte, utiliser d’alcools et alcènes pour la formation de liaisons carbone-carbone et carbone-hétéroatome est particulièrement attractif, cependant cela reste encore un challenge, surtout quand les substrats sont extrêmement désactivés ou susceptibles de piéger le catalyseur. Récemment, nous avons démontré que l’acidité de l’hexafluoroisopropanol (HFIP) pouvait être augmentée de façon significative par des sels de calcium(II) afin d’activer des liaisons C-O et C-C, surpassant les acides de Lewis et de Brønsted habituels que ce soit en termes d’activité ou de sélectivité grâce à la coordination de HFIP au calcium et la formation d’assemblages par liaison hydrogène. De plus, grâce à sa capacité à former des liaisons hydrogène fortes, HFIP peut faciliter la libération d’acides de Lewis piégés par une coordination non désirée avec le substrat (ou le produit), permettant, le turn-over du procédé catalytique. En particulier, l’association Ca²⁺/HFIP peut être un outil puissant pour promouvoir des électrocyclisations, hydroamidations, hydroarylations, hydroacyloxylations et des halofonctionnalisations. Ces réactions sont à la fois générales et compatibles avec un plus large éventail de substrats que les systèmes catalytiques classiques
Today, there is a strong demand from the fine chemicals industry to develop procedures based on transition metal-free reactions using readily available starting materials. The main reasons behind this are the availability, cost and toxicity of transition-metals or electrophiles. In that respect, employing simple alcohols and alkenes for C-C and C-heteroatom bond forming reactions is truly appealing, but it can remain challenging, notably when the substrates are highly deactivated or prone to sequester the catalyst. Recently, we have demonstrated that the acidity of hexafluoroisopropanol (HFIP) could be significantly harnessed by calcium(II) salts in order to activate C-O and C-C bonds, outperforming common Lewis and Brønsted acids in terms of activity or efficiency in several reactions through the coordination of HFIP to calcium and the formation of hydrogen-bond clusters. Moreover, due to its strong hydrogen-bond donor ability, HFIP has the capacity to facilitate the release of Lewis acids trapped by unwanted coordination to the substrate (or the product), allowing the catalytic process to turn over. In particular, the combination Ca²⁺/HFIP can be a powerful tool to promote electrocyclizations, hydroamidations, hydroarylations, hydroacyloxylations and halofunctionalizations. These reactions proved to be general and compatible with a wider range of substrates than the traditional catalytic systems

Nous avons mené des recherches approfondies sur plusieurs réactions innovantes dans le domaine de la synthèse organique. Dans un premier temps, nous avons développé une réaction de cyclisation déshydratante ainsi que deux réactions en tandem, initiées par une cyclisation intramoléculaire. Ces réactions se caractérisent par leur haute diastéréosélectivité et l'utilisation d'un catalyseur à base d'un métal du groupe principal, agissant en tant qu'acide de Lewis. Cette approche nous a permis de synthétiser 27 nouveaux composés cycliques, avec des rendements pouvant atteindre 97 %. Dans un deuxième temps, nous avons mis au point une réaction tandem combinant une réaction de métathèse carbonyl-ène et un couplage déshydratant, réalisée à l'aide d'un catalyseur cationique à base de gallium sur des dérivés du benzhydrol. Cette méthode a conduit à la synthèse de 15 nouveaux composés, avec des rendements pouvant aller jusqu'à 67 %. Enfin, nous nous sommes intéressés à la réactivité des dérivés du bicyclobutane dans des cycloadditions en présence d'espèces insaturées et d'un catalyseur à base d'or. Cette approche a permis la synthèse de 5 nouveaux bioisostères du benzène, avec des rendements pouvant atteindre 90 %
We conducted extensive research on several innovative reactions in the field of organic synthesis. Initially, we developed a dehydrating cyclization reaction, as well as two tandem reactions initiated by this cyclization. These reactions are characterized by high diastereoselectivity and the use of a main-group metal-based catalyst acting as a Lewis acid. This approach allowed us to synthesize 27 new cyclic compounds with yields reaching up to 97%. Furthermore, we also developed a tandem reaction combining carbonyl-ene metathesis and a dehydrating coupling, carried out using a gallium-based cationic catalyst on benzhydrol derivatives. This method led to the synthesis of 15 new compounds, with yields of up to 67%. Finally, we investigated the reactivity of bicyclobutane derivatives in cycloadditions with unsaturated species in the presence of a gold-based catalyst. This approach enabled the synthesis of 5 new benzene bioisosteres with yields reaching up to 90%

The calcium-catalysed intermolecular hydrophosphination reaction is an atom efficient synthetic route to organophosphines. Early experimental studies indicated a correspondence between the hydroamination and hydrophosphination reactions. However, we recognise a need for a theoretical investigation of the intermolecular hydrophosphination reaction particularly as many aspects of the mechanism remain poorly understood. The work within this thesis describes a theoretical investigation of the intermolecular hydrophosphination reaction catalysed by the [beta]-diketiminate stabilised Ca complex, [{HC(C(Me)N-2,6-iPr2C6H3)2}Ca{PPh2}(THF)]. Preliminary DFT calculations were performed on a simplified model of the experimental system. The intermolecular hydrophosphination of ethene is a stepwise mechanism involving alkene insertion and protonolysis, consistent with experimental results. Calculations demonstrate the importance of secondary stabilising interactions, particularly the Ca–[pi] interaction, which coordinates preferentially over a Ca–P interaction. Calculations involving the substitution of ethene for styrene and vinylpyridine were also performed (Chapter 4). Stabilisation of the alkylphosphine fragment through the arene ring allowed for considerably more interchange between important secondary bonding interactions. During the styrene hydrophosphination reaction the kinetically most favourable protonolysis pathway proceeded from an alkylphosphine fragment that exhibited no secondary stabilising interaction. Such a coordination mode has not been considered previously in previous hydroamination reaction studies. Calculations were also performed to investigate the hydrophosphination reaction mechanism for an experimentally representative catalyst (Chapter 5). A ligand-based proton-assisted mechanism was identified involving a multi-centre transition state. In the ligand-based mechanism the alkylphosphine product was generated alongside the active catalyst in a single step. The single step, ligand-based mechanism was a kinetically more favourable pathway and thermodynamically representative of experiment. To the best of the author’s knowledge, this is the first example of the Ae catalysed heterofunctionalisation reaction, which demonstrates preference for a ligand-based mechanism.

Lime is one of the largest manufactured chemicals in the United States. The conversion of calcium carbonate into calcium oxide is an endothermic reaction and requires approximately two to four times the theoretical quantity of energy predicted from thermodynamic analysis. With the skyrocketing costs of fossil fuels, how to decrease the energy consumption in the calcination process has become a very important problem in the lime industry. In the present study, many chemicals including lithium carbonate, sodium carbonate, potassium carbonate, lithium chloride, magnesium chloride, and calcium chloride have been proved to be the catalysts to enhance the calcination rate of calcium carbonate. By mixing these chemicals with pure calcium carbonate, these additives can increase the calcination rate of calcium carbonate at constant temperatures; also, they can complete the calcination of calcium carbonate at relatively low temperatures. As a result, the energy required for the calcination of calcium carbonate can be decreased. The present study has aimed at developing a physical model, which is called the extended shell model, to explain the results of the catalytic calcination. In this model, heat transfer and mass transfer are two main factors used to predict the calcination rate of calcium carbonate. By using the extended shell model, not only the catalytic calcination but also the inhibitive calcination of calcium carbonate have been explained.

Scania provides sustainable transport systems powered by bioethanol, biogas, biodiesel along with hybrid and conventional solutions. Today Scania offers the largest variety of engines operating on alternative fuels in the market. The number of the alternative fuel operated vehicles sold in 2016 increased by 40 % [1]. Nevertheless, one of the alternative fuels – biodiesel - is a source of inorganic contaminants. These impurities can detrimentally affect the diesel truck after-treatment system that is responsible for harmful emission abatement. As a consequence, better understanding of the alternative fuel impact on the after-treatment system is necessary for further development of a sustainable transportation system. This thesis is focused on the diesel oxidation catalyst (DOC) that is one of the major components in the diesel truck after-treatment system. Catalyst performance due to chemical deactivation of biodiesel derived inorganic contaminants (P, Na and Ca) is determined and analysed. The study covers PtPd/Al 2O3 DOC preparation and poisoning by the incipient wetness impregnation method, monolith dip-coating, fresh and poisoned catalyst characterization (BET, CO chemisorption, TPR, ICP-OES, TEM-EDS, SEM-EDS, XRD). Catalyst activity tests in a laboratory scale activity testing rig are performed to study carbon monoxide, nitric oxide and propylene oxidation reactions before and after the poisoning. Sulphur effect on the catalyst activity is determined after the gas-phase poisoning with SO2.

L'addition catalysée des amines ou phosphines sur des substrats insaturés (alcènes, alcynes ou allènes) constitue une méthode efficace pour la production d’amines et phosphines à hautes valeurs ajoutées. Pour ces réactions, les complexes hétéroleptiques des métaux alcalino-terreux ont émergé comme des précatalyseurs effi caces. Cette thèse décrit la synthèse de complexes des alcalino-terreux supportés par des ligands aminoalcoolates fluorés de type [{RO}AeN(SiMe2H)2] ({RO} = aminoalcoolate fluoré; Ae = Ca, Sr). Des études par diffraction de rayons X montrent que ces complexes utilisent des interactions Ae···F–C and β-Si–H···Ae pour être cinétiquement inertes. Étonnamment, la somme de ces interactions non-covalentes dites secondaires est prédominante par rapport à la coordination d'éthers sur le centre métallique. En outre, les ligands aminoalcoolates fluorés ont été utilisés pour préparer de rares exemples de complexes Ae hétéroleptiques impliquant la coordination intramoléculaire de donneurs d'électrons π (i.e. alcènes et alcynes). Ainsi, pour la première fois, des complexes Ae stabilisés par des combinaisons d’interactions Ae···Cπ, Ae···F−C et β-Si−H···Ae ont été synthétisés. La nature de ces interactions a été sondée par des moyens spectroscopiques, cristallographiques et calculatoires (DFT). En revanche, nos efforts pour obtenir des complexes Ca–aryles ont conduit à la formation de complexes trinucléaires originaux présentant des interactions secondaires β-Si-H···Ca extrêmement fortes. Certains de ces complexes de calcium ont ensuite été testés en catalyse d’hydrophosphination du styrène avec la diphénylphosphine. Ils ont démontré des activités remarquables (TOF ≈ 50 h−1) en conditions douces, ainsi qu’une régiosélectivité de 100% vers la formation du produit d'addition anti-Markovnikov. En collaboration avec le Pr. M. Etienne et le Dr C. Dinoi du Laboratoire de Chimie de Coordination (Toulouse), un précatalyseur hétéroleptique de calcium supporté par un ligand tris(indazolyl)borate fluoré a été utilisé pour l’hydroamination intramoléculaire du 2,2-diméthylpent-4-en-1-amine, et a fait preuve d’une activité catalytique parmi les plus élevées à ce jour
The catalysed additions of amines or phosphines across unsaturated substrates (alkenes, alkynes or allenes) constitute atom-efficient routes for the production of valuable fine chemicals such as amines and phosphines. For these reactions, heteroleptic alkaline-earth complexes have emerged as promising precatalysts. This PhD thesis describes the synthesis and characterisation of a series of alkaline-earth complexes of type [{RO}AeN(SiMe2H)2] supported by fluorinated aminoalkoxides ({RO} = fluorinated aminoalkoxide; Ae = Ca, Sr ). X-ray diffraction studies show that these complexes heavily involve Ae···F–C and β-Si–H···Ae secondary interactions to achieve kinetic stabilisation. Remarkably, these so-called secondary, non-covalent interactions can be more beneficial towards the stabilisation of the metallic species than the coordination of ethers onto the metal centre. Furthermore, fluorinated aminoalkoxo ligands were used to prepare rare examples of Ae heteroleptic complexes featuring intramolecular coordination from π donors (i.e. alkenes and alkynes). For the first time, Ae complexes stabilised by a combination of Ae···Cπ, Ae···F–C and β-Si–H···Ae interactions were described. The structural and electronic features of these unique complexes were probed by crystallographic, spectroscopic and computational (DFT) methods. The utilisation of aryl-containing ligands resulted in the formation of trinuclear complexes featuring a unique pattern of strong β-Si–H···Ca agostic interactions. Some of these calcium heteroleptic complexes were tested in the hydrophosphination of styrene and HPPh2. They displayed high activities (TOF ≈ 50 h–1) under mild conditions with 100% regioselectivity towards the anti-Markovnikov addition product. In a collaboration with Prof. M. Etienne and Dr. C. Dinoi from the Laboratoire de Chimie de Coordination (Toulouse), a heteroleptic calcium complex supported by a fluorinated tris(indazolyl)borate was used in the intramolecular hydroamination of 2,2-dimethylpent-4-en-1-amine, and it displayed excellent performances

Les charbons de bas rang contiennent des elements alcalins et surtout alcalino-terreurs qui agissent lors de leurs reactions de gazeification (h#2o, co#2) ou de combustion basse temperature en lit fluidise, a la fois comme catalyseurs et comme pieges chimiques a soufre. La nature des phases actives demeure relativement imprecise; dans le cas du calcium, la plus souvent citee est cao. Nos etudes ont porte sur un charbon bresilien de bas rang, demineralise. Nous avons egalement utilise, comme materiau modele, un coke obtenu par pyrolyse d'une resine phenolformaldehyde, sur lequel on a cree des sites d'echange cationique par oxydation avec l'acide nitrique. Du calcium a ete depose, en quantites variables, sur ces deux materiaux, par echange cationique. La reaction de gazeification par l'oxygene de l'air a ete suivie dans des conditions de non limitation par la diffusion thermique ou massique, en programmation lineaire de temperature (0,8 k. Min##1). Il a ete utilise la detection catharometrique de co#2 et co formes. L'energie apparente d'activation de la reaction est respectivement de 120 et 132 kj. Mol##1 pour les cokes issus du charbon et de la resine phenolformaldehyde. La presence du catalyseur calcium augmente simplement le nombre de sites actifs. L'ensemble de nos resultats, incluant des donnees de mesures physico-chimiques (texture, drx, esca, irtf, stem) et de spectrometrie de masse (suivi de la thermodecomposition des solides avant et apres differents traitements), suggere que des especes ca#+#+ echangees en surface du materiau carbone constituent la phase active, plutot que des particules individualisees de cao.

Plastic consumption has increased 8% annually since the 1950 reaching an estimated 300 million tonnes in 2014, where more than 50% was discarded after single-use. Many recycling methods have been proposed to manage this growing waste, but most have practical, environmental and economic limitations. Catalytic conversion, a chemical recycling method using a suitable catalyst, has been suggested as a viable option since it can return plastic to a chemical feedstock, which is the aim of this work. Four potential catalysts, namely sulphated zirconia SZ, calcium carbide CC, molybdenum carbide MC and zirconium oxide ZO were tested for HDPE conversion, which was selected from five different polymer samples due to its high thermal resistance. It was found that only calcined SZ and calcined CC showed some impact HDPE conversion. However, SZ was marked with high coke yield while calcined CC had low conversion with virtually no coke. Therefore a hybrid catalyst was considered, where the SZ and the CC were mixed together on equal weight bases forming the hybrid catalyst SZ1CC1. Fixed bed pyrolysis showed an excellent HDPE conversion of virtually 100wt% using the hybrid catalyst at 410oC with 66.0wt% liquid yield against a 98.0wt% conversion with only 39.0% liquid yield for the pure SZ and no conversion in the case of HDPE only. The hydrocarbon composition of the liquid fraction obtained changed significantly from 58% aromatic and 16% paraffinic for the SZ to 74% olefinic and 23% naphthenic for the SZ1CC1. The improvement in liquid yield and selectivity to non-aromatic liquid was strongly linked to a modification in the acidic strength of the hybrid catalyst SZ1CC1. The moderation in acidity and textural properties, such as surface area and porosity were found to suppress excessive cracking and limiting secondary cracking reactions, that promotes high gas yield and aromatisation in the SZ. Overall, it is concluded that the SZ on its own, which had high acidic strength and large surface area, promoted secondary reactions during HDPE cracking that yielded aromatics. However, the hybrid catalyst SZ1CC1, which had moderate acid strength and low surface area halted any secondary reaction and terminated the cracking reaction at stages that produced only olefinic and naphthenic hydrocarbons.

SESMR (Sorption Enhanced Steam Methane Reforming), SMR (Steam Methane Reforming) avec capture de CO2 in situ par un adsorbant solide, peut amener à une exploitation durable du gaz naturel pour la production de H2. La thèse, partie du projet de recherche ASCENT (Advanced Solid Cycles with Efficient Novel Technologies), concerne le développement de matériaux combinés adsorbants catalyseurs Ni-CaO-mayenite pour le SESMR, aux fins d’étudier les influences dues à la fraction de Ni, aux sels précurseurs du Ni (Ni acétate ou Ni nitrate), et à la fraction de CaO disponible. Les techniques ICP AES, XRD, BET/BJH, SEM/EDS, TEM/EDS, TPR et TGA ont été utilisés pour caractériser les matériaux synthétisés. La réactivité a été évaluée par des tests en lit fixe à l’échelle du microréacteur, qui ont aussi permis une sélection des matériaux les plus prometteurs pour une étude de l’applicabilité industrielle par tests multi cycliques SESMR/régénération de solides par un réacteur automatisé à lit fixe
Sorption enhanced steam methane reforming (SESMR), steam methane reforming (SMR) with in situ CO2 sorption by a solid sorbent, can lead to a sustainable exploitation of natural gas to produce H2. (CSCM). This thesis, as a part of ASCENT (Advanced Solid Cycles with Efficient Novel Technologies) project, deals with Ni-CaO-mayenite combined sorbent-catalyst material for SESMR, to study the effect of Ni fraction, its precursor salt (Ni nitrate or Ni acetate), and free CaO fraction. ICP AES, XRD, BET and BJH methods, SEM EDS, TEM EDS, TPR and TGA were used to characterize synthesized materials. Their reactivity was evaluated by tests in a packed bed microreactor, which served also as a screening tool to choose the most promising materials. Their industrial applicability was assessed by multicycle SESMR/regeneration tests in an automated packed bed bench scale rig

Solid Oxide Fuel Cells (SOFC) are electrochemical energy conversion devices which allow fuel gases, e.g. hydrogen or natural gas, to be converted to electricity and heat at much high efficiencies than combustion-based energy conversion technologies. SOFC are particularly suited to employment in stationary energy conversion applications, e.g. micro-combined heat and power (μ-CHP) and base load, which are certain to play a large role in worldwide decentralisation of power distribution and supply over the coming decades. Use of high-temperature SOFC technology within these systems is also a vital requirement in order to utilise fuel gases which are readily available in different areas of the world. Unfortunately, the limiting factor to the long-term commercialisation of SOFC systems is the redox instability, coking intolerance and sulphur poisoning of the state-of-the-art Ni-based cermet composite anode material. This research explores the ‘powder to power' development of alternative SOFC anode catalyst systems by impregnation of an A-site deficient La0.20Sr0.25Ca0.45TiO3 (LSCT[sub](A-)) anode ‘backbone' microstructure with coatings of ceria-based oxide ion conductors and metallic electrocatalyst particles, in order to create a SOFC anode which exhibits high redox stability, tolerance to sulphur poisoning and low voltage degradation rates under operating conditions. A 75 weight percent (wt. %) solids loading LSCT[sub](A-) ink, exhibiting ideal properties for screen printing of thick-film SOFC anode layers, was screen printed with 325 and 230 mesh counts (per inch) screens onto electrolyte supports. Sintering of anode layers between 1250 °C and 1350 °C for 1 to 2 hours indicated that microstructures printed with the 230 mesh screen provided a higher porosity and improved grain connectivity than those printed with the 325 mesh screen. Sintering anode layers at 1350 °C for 2 hours provided an anode microstructure with an advantageous combination of lateral grain connectivity and porosity, giving rise to an ‘effective' electrical conductivity of 17.5 S cm−1 at 850 °C. Impregnation of this optimised LSCT[sub](A-) anode scaffold with 13-16 wt. % (of the anode mass) Ce0.80Gd0.20O1.90 (CGO) and either Ni (5 wt. %), Pd, Pt, Rh or Ru (2-3 wt. %) and integration into SOFC resulted in achievement of Area Specific Resistances (ASR) of as low as 0.39 Ω cm−2, using thick (160 μm) 6ScSZ electrolytes. Durability testing of SOFC with Ni/CGO, Ni/CeO2, Pt/CGO and Rh/CGO impregnated LSCT[sub](A-) anodes was subsequently carried out in industrial button cell test rigs at HEXIS AG, Winterthur, Switzerland. Both Ni/CGO and Pt/CGO cells showed unacceptable levels of degradation (14.9% and 13.4%, respectively) during a ~960 hour period of operation, including redox/thermo/thermoredox cycling treatments. Significantly, by exchanging the CGO component for the CeO2 component in the SOFC containing Ni, the degradation over the same time period was almost halved. Most importantly, galvanostatic operation of the SOFC with a Rh/CGO impregnated anode for >3000 hours (without cycling treatments) resulted in an average voltage degradation rate of < 1.9% kh−1 which, to the author's knowledge, has not previously been reported for an alternative, SrTiO3-based anode material. Finally, transfer of the Rh/CGO impregnated LSCT[sub](A-) anode to industrial short stack (5 cells) scale at HEXIS AG revealed that operation in relevant conditions, with low gas flow rates, resulted in accelerated degradation of the Rh/CGO anode. During a 1451 hour period of galvanostatic operation, with redox cycles and overload treatments, a voltage degradation of 19.2% was observed. Redox cycling was noted to briefly recover performance of the stack before rapidly degrading back to the pre-redox cycling performance, though redox cycling does not affect this anode detrimentally. Instead, a more severe, underlying degradation mechanism, most likely caused by instability and agglomeration of Rh nanoparticles under operating conditions, is responsible for this observed degradation. Furthermore, exposure of the SOFC to fuel utilisations of >100% (overloading) had little effect on the Rh/CGO co-impregnated LSCT[sub](A-) anodes, giving a direct advantage over the standard HEXIS SOFC. Finally, elevated ohmic resistances caused by imperfect contacting with the Ni-based current collector materials highlighted that a new method of current collection must be developed for use with these anode materials.

Influence catalytique des mineraux naturels sur l'evolution de composes naturels importants: le cholesterol et l'acide stearique. Les transformations de ces composes ont ete etudiees sur diverses roches: argiles, calcite, dolomite et anhydrite et sur des catalyseurs connus dans des conditions aussi representatives que possible du milieu naturel. Quel que soit le solide considere la transformation catalytique est beaucoup plus rapide que la reaction thermique

L’hydrogénation sélective d’hydrocarbures polyinsaturés présente un fort intérêt pour l’industrie pétrolière. Cette réaction est catalysée par des particules métalliques ou des alliages et a lieu sous pression d’hydrogène. Dans ce travail nous étudions la réaction d’hydrogénation sélective du butadiène en 1-butene en présence des catalyseurs Pt(111) et Sn/Pt-Pt(111). Cette étude a été menée à l’aide du programme VASP (Vienna Abinitio Simulation Package) qui permet de simuler des systèmes solides et surfaciques dans le cadre de la théorie de la fonctionnelle de la densité (DFT). Le choix des catalyseurs a été dicté par les communautés expérimentale et industrielle qui utilisent le plus souvent le platine car très actif, ou des alliages de platine-étain, moins actifs mais beaucoup plus sélectifs. L’hydrogénation du butadiène a déjà été étudiée par le passé mais uniquement à T=0 K et sans prendre en compte les conditions réelles de pression des réactifs. Notre but étant de comprendre les pas élémentaires de cette réaction, nous avons choisi de l’étudier à des conditions de T et de P proches de celles utilisées expérimentalement, c’est-à-dire 300-400 K et 1-10 bar. A cette fin, nous avons mis en place un modèle thermodynamique pour évaluer, dans un premier temps, la composition de la surface lors de la réaction. Il est alors apparu que la configuration de surface la plus stable correspond à une couverture de une monocouche d’hydrogène ce qui suggère un mécanisme de type Eley-Rideal. Puis nous avons étudié l’aspect cinétique ce cette réaction et calculé les chemins réactionnels pour différents recouvrements en hydrogène. Nous avons conclu qu’il existe une forte compétitivité entre le mécanisme pressenti, appelé Langmuir-Hinshelwood et impliquant des espèces fortement adsorbées, et le mécanisme Eley-Rideal proposant une adsorption faible de l’un des réactifs. Les calculs ont été effectués avec les fonctionnelles PBE et optPBE pour apporter un point de comparaison des méthodes
Petroleum industry has a strong interest in the selective hydrogenation of polyunsaturated hydrocarbons. This reaction is catalyzed by metallic particles or alloys and happens under pressure of hydrogen. In this work, we study the selective hydrogenation of butadiene into 1-butene, on two model catalysts which are Pt(111) and Sn/Pt-Pt(111). For this, we used the VASP code (Vienna Abinitio Simulation Package) that allows to perform periodic calculations in the framework of the Density Functional Theory (DFT). The choice of the catalysts was driven by the experimental and industrial communities who mostly use platinum because of its high activity, or alloys such as tin-platinum alloy, less active but more selective. Butadiene hydrogenation was already modeled in the past but only at T=0 K and without taking into account the real pressure conditions of the reactants. Our aim is to understand the impact of the reaction conditions which is why we ran this study at T and P conditions close to the one used experimentally, e.g. 300-400 K et 1-10 bar. For this, we setup a thermodynamic model to evaluate in a first step the surface composition when the reaction occurs. It came out that the most stable surface configuration corresponds to a coverage of 1 ML of hydrogen which suggests an Eley-Rideal type mechanism. Then we studied the kinetic aspect of this reaction and we calculated the hydrogenation pathways for different coverages of hydrogen. We concluded that there is a strong competition between the sensed mechanism, called Langmuir-Hinshelwood mechanism and implying strongly adsorbed species, and the Eley-Rideal mechanism, proposing a weak adsorption of one of the two reactants

Formation of hexagonal boron nitride (h-BN) by carbothermic reduction of B2O3 under nitrogen atmosphere at 1500oC was investigated. Reaction products were subjected to powder X-ray diffraction analysis, chemical analysis and were examined by SEM. B4C was found to exist in the reaction products of the experiments in which h-BN formation was not complete. One of the aims of this study was to investigate the role of B4C in the carbothermic production of h-BN. For this purpose, conversion reaction of B4C into h-BN was studied. B4C used in these experiments was produced in the same conditions that h-BN was formed, but under argon atmosphere. It was found that formation of h-BN from B4C&ndash
B2O3 mixtures was slower than activated C&ndash
B2O3 mixtures. It was concluded that B4C is not a necessary intermediate product in the carbothermic production of h-BN. Some additives are known to catalytically affect the h-BN formation. The second aim of this study was to examine the catalytic effect of some alkaline earth metal oxides and carbonates, some transition metal oxides and cupric nitrate. It was found that addition of 10wt% CaCO3 into the B2O3+C mixture was optimum for increasing the rate and yield of h-BN formation and decreasing the B4C amount in the products and that the reaction was complete in 2 hours. CaCO3 was observed to be effective in increasing the rate and grain size of the formed h-BN. Addition of cupric nitrate together with CaCO3 provided a further increase in the size of the h-BN grains.

Encore aujourd'hui, le développement de nouveaux catalyseurs est réalisé par expérimentation « essai-erreur ». Ces 10 dernières années, l'exploration et l'optimisation de formulations de catalyseurs a été accélérée par les technologies dites de Haut-Débit qui consistent à cribler une grande quantité de matériaux. Même si la puissance d'évaluation de catalyseurs a été multipliée, le nombre de combinaisons à tester est tel qu'il faut réaliser une sélection rationnelle a priori. Récemment, l'avènement de nouvelles techniques de calcul ab-initio telles que la DFT, a facilité voire permis la quantification de certaines propriétés physico-chimiques clés des catalyseurs, pouvant être utilisées comme indicateurs, aussi appelés descripteurs, des performances catalytiques. Cette thèse a pour objectif la prédiction de performances catalytiques de catalyseurs métalliques à partir d'un descripteur théorique. Une bibliothèque de catalyseurs monométalliques a été constituée et leurs performances catalytiques ont été évaluées dans les réactions d'hydrogénations sélectives du styrène et de l'isoprène. A l'aide d'un modèle cinétique de type Langmuir-Hinshelwood, il a été possible d'établir des modèles prédictifs de l'activité et de la sélectivité en fonction du descripteur Energie-métal-carbone (EMC). Grâce à ces modèles, des formulations bimétalliques ont été identifiées puis préparées et testées en expérimentation à haut débit (EHD). Il a ainsi été possible d'obtenir de nouveaux catalyseurs bimétalliques présentant les activités et sélectivités prédites par le modèle
Today, the development of new catalysts is still achieved by “trial-and-error” processes. In the last 10 years, the screening of a large amount of materials using High Throughput technologies has enhanced the optimization and discovery of new catalyst formulations. However, rational selection of key parameters is required to decrease the amount of possible combinations. Recently, advances in computational material science using methods such as density functional theory (DFT) have lead to the quantification of key physio-chemical properties of catalysts. These properties can be used as indicators (or descriptors) of catalytic performance. This thesis aims to predict performances of metallic catalysts from a theoretical descriptor. A range of monometallic catalysts were synthesized and their performances were assessed in the selective hydrogenation of styrene and isoprene. From a Langmuir-Hinshelwood kinetic model, it was possible to build predictive models of the activity and selectivity as a function of the metal-carbon bond energy descriptor (EMC). These models were used to identify bimetallic formulations which were prepared and tested in High Throughput Screening. Thus, it has been possible to obtain new bimetallic catalysts exhibiting activities and selectivities predicted by the model

De nouvelles hases obtenues lors de la synthèse des orthophosphates mixtes de calcium-cobalt sous haute pression et des orthophosphates mixtes de strontium-cobalt à pression ordinaire ont été décrites. La comparaison de l'activité catalytique des différents produits obtenus a permis de montrer que l'ion cobalt n'était actif qu'inclus dans une matrice de type phosphate tricalcique B.

L'étude des nanoagrégats métalliques supportés sur des oxydes est d'une importance primordiale autant au niveau fondamental que technologique, notamment dans le domaine de l'énergie. Les nanoparticules à base de platine supportées sur alumine Gamma sont largement utilisées comme catalyseurs hétérogènes ultradispersés, en particulier sous atmosphère réductrice d'hydrogène. Leur réactivité et leur sélectivité sont intimement liés à la géométrie locale et à la densité électronique des sites actifs. Ces dernières sont particulièrement ardues à définir, étant donnée la très faible taille des agrégats étudiés (environ 0.8 nm de diamètre). La spectroscopie XANES (X-Ray Absorption Near Edge Structure), nécessitant un rayonnement synchrotron, est un des outils les plus appropriés pour étudier ces systèmes, en particulier in situ, à l'échelle atomique. En effet les spectres XANES sont influencés par la géométrie locale et la symétrie de l'environnement des atomes (en particulier les angles entre les liaisons), le degré d'oxydation, les types de liaisons mis en jeu, et la structure électronique du système. Tous ces facteurs sont néanmoins difficiles à différencier et même à interpréter. Il est donc impossible de déduire de manière précise la structure des particules métalliques par la seule expérience, sans aucune comparaison avec des spectres simulés. La mise en place de modèles théoriques devient alors nécessaire. Nous mettons donc en oeuvre une approche associant expériences XANES haute résolution in situ et simulations quantiques, ces dernières visant à la proposition de modèles structuraux pertinents, à la quantification de la réactivité des agrégats et au calcul des caractéristiques spectrales pour comparaison à l'expérience. L'identification de la morphologie des particules, de l'interaction métal-support et du taux de couverture en H est ainsi rendue possible par l'association de l'expérience et du calcul. La bibliothèque de modèles existants de particules monométalliques de Pt supportées sur de l'alumine Gamma avec ou sans hydrogène adsorbé, est complétée par des modèles hydrogénés sur la face (110) et par des modèles de différentes tailles hydrogénés sur la face (100). Cette bibliothèque devenue assez complète a permis une étude de l'influence de la taille des particules, de leur morphologie, de leur structure électronique, des différentes face de l'alumine Gamma, ainsi que du taux de couverture en hydrogène sur la signature des spectres XANES. Cette première étude des catalyseurs monométalliques de platine, se conclue par la discrimination de certaines morphologies, mais surtout la quantification du taux de couverture en hydrogène des particules. Ensuite, des modèles de particules bimétalliques platine – étain supportés sur la face (100) de l'alumine Gamma sont élaborés avec adsorption d'hydrogène. Ces modèles permettent de mieux comprendre l'influence de l'étain sur la morphologie, les propriétés électroniques et l'interaction avec le support et l'hydrogène de ces agrégats. Différentes compositions ont été explorées, ce qui a apporté des informations sur la dilution du platine par l'étain. L'adsorption d'hydrogène a alors été étudiée sur des agrégats de Pt10Sn3 supportées sur la face (100) de l'alumine Gamma. Bien que de nombreux paramètres ne sont pas encore pris en compte dans ces modèles, la comparaison à l'expérience permet déjà d'avoir une première approximation sur la description de systèmes bimétalliques
The study of metallic nanoclusters supported on oxides is of paramount fundamental and technological importance, particularly in the field of energy. The nanoparticles based on platinum supported on gamma alumina are widely used as highly dispersed heterogeneous catalysts especially under reducing hydrogen atmosphere. Their reactivity and selectivity are intimately related to the local geometry and the electronic density of active sites. These are particularly difficult to define, given the very small size of the studied particles (about 0.8 nm in diameter). XANES (X-Ray Absorption Near Edge Structure) spectroscopy requiring synchrotron radiation, is one of the most appropriate tools to study these systems, especially in situ, at the atomic scale. Indeed the XANES spectra are influenced by the geometry and symmetry of the atoms local environment (especially angles between bonds), the degree of oxidation, the bond types involved, and the electronic structure of the system . All these factors are nevertheless difficult to differentiate and even to interpret. It is therefore impossible to infer accurately the structure of the metal particles by experience alone, without any comparison with simulated spectra. The establishment of theoretical models becomes necessary. We are implementing an approach that combines high-resolution XANES experiments in situ and quantum simulations, the latter aimed at proposing relevant structural models to quantify the reactivity of the particles and calculating spectral characteristics for comparison to experiment. The identification of the clusters morphologies, the metal-support interaction and the hydrogen coverage is made possible combining experiments and quantum calculations. The library of existing monometallic Pt particles models supported on Gamma alumina with or without adsorbed hydrogen, is refined. New models considering the two main surface of Gamma alumina, the particle size and hydrogen adsorption are developed. This extended library of models enabled a study of the effect of particle size, morphology, electronic structure, different alumina faces, and the hydrogen coverage on the signature of XANES spectra. This first study of monometallic platinum catalysts, concludes with the discrimination of the morphologies, but especially with the quantification of the hydrogen coverage of the particles for each temperature and hydrogen pressure experimental condition. Then, models of bimetallic Platinum-tin particles supported on the (100) Gamma alumina face are performed with hydrogen adsorption. These models provide insights into the effect of tin on the morphology, the electronic properties and the interaction with the support and hydrogen of these clusters. Different compositions were explored, which provided information on the dilution of platinum by tin. The adsorption of hydrogen was then studied on Pt10Sn3 clusters supported on the (100) face of alumina. Although many parameters are not yet included in these models, the comparison to the experience already provides a first approximation to the description of bimetallic systems

Trois nouvelles sources chimiques d'oxygene excite a l'etat singulet, #1o#2(#1#g), ont ete etudiees. Il s'agit de systemes bases sur la decomposition du peroxyde d'hydrogene catalysee par les ions molybdates(vi), tungstates(vi) et calcium(ii). Dans un premier temps, nous avons tente d'elucider le mecanisme de ces reactions en identifiant les peroxometallates intermediaires formes. La spectroscopie rmn #9#5mo nous a permis de mettre en evidence les mono-, di-, tri- et tetraperoxomolybdates formes par reaction de moo#4#2#- avec differentes concentrations de h#2o#2 ainsi que leurs eventuelles formes protonees obtenues par acidification. Les constantes d'equilibres ont ete determinees et un diagramme de predominance a ete etabli. La comparaison de ces resultats avec une etude cinetique nous a conduits a proposer le triperoxomolybdate moo(o#2)#3#2#- comme principal precurseur d'oxygene singulet. Pour le systeme h#2o#2/wo#4#2#-, nous avons determine la stoechiometrie de la reaction par piegeage chimique de #1o#2 puis, nous avons mis en evidence la formation de certains peroxotungstates par spectroscopies uv/visible et rmn #1#8#3w. Quant au systeme h#2o#2/ca(oh)#2, nous avons prouve la formation de #1o#2 par piegeage chimique et detection de sa luminescence ir et les parametres influents ont ete reperes. Le peroxyde de calcium cao#2,2h#2o#2 a ete identifie comme le precurseur de #1o#2. Dans un deuxieme temps, nous nous sommes interesses aux proprietes oxydantes de chaque systeme. Tout d'abord, nous avons mis en evidence la double reactivite des systemes h#2o#2/moo#4#2#- et h#2o#2/wo#4#2#- en les confrontant a l'acide tiglique, derive olefinique susceptible de reagir soit par epoxydation soit par peroxydation suivant le ph du milieu. Nous avons ensuite applique la source chimique d'oxygene singulet, h#2o#2/moo#4#2#-, a la synthese organique, en oxydant, a une echelle preparative, differents substrats phenoliques. Enfin, nous avons evalue la reactivite du systeme h#2o#2/ca(oh)#2 vis-a-vis de l'oxydation en le confrontant a des derives phenoliques, anthraceniques, cyclohexadieniques et acryliques.

Ce travail de thèse a permis d’obtenir une caractérisation à l’échelle atomique des feuillets (Co)MoS2 et (Ni)WS2 de catalyseurs d’hydrotraitement supportés sur alumine et de déterminer l’impact d’un additif organique, l’acide citrique (CA). Dans cette étude des techniques avancées ont été mises en œuvre telles la caractérisation par adsorption de CO à basse température suivie par spectroscopie IR (IR/CO), des calculs DFT et des observations par microscopie électronique haute résolution en mode transmission et par STEM HAADF.Sur les catalyseurs non promu à base de W et de Mo, l’adsorption de CO permet de discriminer les sites des bords M- et des bords S- des feuillets de TMS. La détermination des coefficients d’extinction molaire des bandes liées au CO adsorbé permet de déduire la morphologie des feuillets. L’HR STEM HAADF confirme que l’addition de CA modifie la morphologie des feuillets TMS d’un triangle tronqué à une forme hexagonal.Sur les catalyseurs promus NiW et CoMo, la microscopie electronique montre que l’addition de CA diminue la taille des feuillets de TMS et conduit aussi à la création de petits clusters (<1 nm). L’analyse de particules isolées par HR STEM HAADF permet d’identifier la nature des atomes du bord du feuillet de TMS. Ainsi la microscopie et l’IR/CO mettent en évidence que au sein d’un même feuillet sulfure peuvent coexister des bords totalement promus, et partiellement promus
This work was focused on obtaining an atomic scale characterization of the (Co)MoS2 and (Ni)WS2 slabs of hydrotreating catalysts supported on alumina and to determine the impact of citric acid (CA) addition. In this study, advanced techniques were implemented such as low temperature CO adsorption followed by IR spectroscopy (IR/CO), DFT calculations and high resolution electron microscopy observations in transmission mode and by STEM HAADF.On the non-promoted W and Mo catalysts, CO adsorption makes it possible to discriminate between the sites of the M- and S- edges of the TMS slabs. The determination of the molar extinction coefficients of the adsorbed CO bands allows the morphology of the slabs to be deduced. HR STEM HAADF confirms that the addition of CA modifies the morphology of the TMS slabs from a truncated triangle to a hexagonal shape.On the promoted NiW and CoMo catalysts, electron microscopy shows that the addition of CA decreases the size of the TMS slabs and also leads to the creation of very small clusters (<1 nm). The analysis of isolated particles by HR STEM HAADF allows identifying the nature of the atoms on the edge of the TMS slabs. Thus microscopy and IR/CO show that within the same sulfide slabs, can coexist edges that are fully promoted and partially promoted

Notre travail a montre l'interet de l'utilisation des fluorures alcalins en synthese organique et en catalyse heterogene. Dans un premier temps, nous avons etudie des reactions dites en cascade catalysees par le fluorure de potassium sur alumine. Nous nous sommes interesses successivement a des reactions d'oxydations anioniques telles que la synthese de cyclopropanes fonctionnels a partir de composes a methylene acide. A des reactions concertees: condensation avec le disulfure de carbone alkylation, suivies ou non de rearrangement sigmatropique. Nous avons etudie egalement la conversion des phenols en thiophenols, ainsi que la synthese d'amines allyliques a partir d'alcools allyliques. Dans un deuxieme temps, nous nous sommes consacre a la recherche d'un catalyseur hyperbasique qui soit stable thermiquement et en milieu protique. Nous avons teste le reactif supporte csf-caf#2 dans des reactions de cyclisations anioniques telles que la synthese d'heterocycles. Nous avons effectue egalement une etude de determination de la basicite des solides en se basant sur la solvatochromie des complexes organometalliques

Différentes méthodes d'oxydation catalytique d'hydrolysats d'amidon ont été étudiées dans le but de synthétiser des polycarboxylates potentiellement biodégradables, possédant des propriétés séquestrantes vis-à-vis du calcium. Parmi les méthodes d'oxydation testées, deux systèmes ont retenu notre attention en raison de leur sélectivité vis-à-vis de la structure polysaccharidique. La première voie utilise les ions hypochlorites en présence de 2,2,6,6-tétraméthyl-1-pipéridinoxyle (TEMPO) comme catalyseur. Les fonctions alcools primaires et lactols des divers sucres étudiés ont été ainsi sélectivement oxydés en carboxylates, mais le pouvoir séquestrant des produits n'atteint pas le niveau de celui des polyphosphates ou des polyacrylates généralement utilisés comme séquestrants dans les détergents. La seconde voie utilise l'ozone comme cooxydant en présence de ruthénium comme catalyseur. L'oxydation transforme totalement les alcools primaires en carboxylates et permet la coupure d'une partie des diols en position 2,3 en dicarboxylates. La réaction est peu dégradante (très bons rendements) et les pouvoirs séquestrant obtenus sont très intéressants.

Dans ce travail nous étudions l'élaboration, la caractérisation et les applications de différents matériaux poreux. L'étude est organisée en trois parties majeures: la synthèse de zéolithes micro/mesoporeux et leur application potentielle dans l'industrie pétrochimique, l'étude théorique de mécanismes réactionnels sur des zeolites microporeux, et le design de métaux mesoporeux avec une chiralité intrinsèque de leur surface interne. Ces matériaux poreux montrent des propriétés excellentes, notamment pour des applications potentielles en catalyse et comme interfaces chirales.

碩士
義守大學
生物技術與化學工程研究所
101
Copper oxide impregnated on calcium-doped ceria prepared by reverse microemulsion was used as catalysts for the selective CO oxidation in a rich hydrogen environment. It was found that catalysts prepared by microemulsion have better activity performance than those made by co-precipitation method. Therefore, reverse microemulsion method was adopted in this study to prepare ceria of different percentages of calcium doping for the selective CO oxidation. Activity test results showed that the best activity performance was obtained by the catalyst of 5% calcium-doped ceria, which displays a CO conversion of almost 100% at 90 ℃ while still achieving high CO selectivity, which then decreased to 50 percent at 125℃. In addition, from the competitive oxidation tests of CO and H2 at 120℃, it has been demonstrated that CO is more easily oxidized than H2. The catalysts studied in this work can exhibit high CO selectivity and low hydrogen consumption at low temperatures. Activity results also match with those of BET surface area and TEM characterizations.

碩士
國立宜蘭大學
環境工程學系碩士班
103
Abstract Electroplating sludge from semiconductor factory contains high concentrations of mineral fluorspar (CaF2）. Generally, a lot of VOCs (Volatile Organic Compounds) were emitted from semiconductor factory. The aim of this study is to prepare the porous adsorbents (CF-MCM, CaF2 mesoporous material）and catalysts from the waste with sol-gel method for the treatment of HMDS (Hexamethyldislazane) and to investigate the cleaning time and the removal capability. The poisonous effect of HMDS on the catalysts, Fe-CF-MCM was also investigated. The characteristics of CF-MCM and Fe-CF-MCM were carried out using XRF, XRD, BET, and FTIR, TGA, SEM-EDS, TEM and ICP-AES. The results showed that the isothermal curves belong to the Type IV curves with the nitrogen absorption/desorption analyzer. The surface area of CF-MCM and Fe-CF-MCM was 918-211 and 763-365 m2 g-1, resprectively. The adsorption capcity of acetone ranged from 108 to 302 mg g-1 under retention time of 0.4 sec, concentrations of 500-2000 ppm with CF-MCM. The adsorption capcity was increased with decreasing operating temperature, increasing concentration, and decreasing space velocity. In this study, 10%Fe-CF-MCM is the best material with efficiency above 90% under 350oC. The adsorption capcity of HMDS was 40 and 86 mg g-1 for 100 and 500 ppm HMDS, respectively. From our results, the use of HMDS adsorption pretreatment equipment before controlling VOCs could avoid catalysts poisonous. The VOCs remval efficiency was only 60% without HMDS adsorption pretreatment equipment in field study. In contrast, the remval efficiency could be above 97% with pretreatment equipment for 3 days. In this study, the effects of opearation parameters, such as contact time and mixture concentration on adsorption performance were also assessed.

Among the various heterogeneous catalytic reactions three way catalysis (TWC), catalytic combustion of hydrogen, water gas shift reaction (WGS) and preferential oxidation of CO (PROX) in the hydrogen rich stream are some of the important reactions receiving the attention presently. Three-way catalysis (TWC) involves simultaneous removal of the three pollutants (i.e., CO, NOx, and HCs) from the automobile exhaust. Catalytic combustion of hydrogen by oxygen or hydrogen-oxygen recombination reaction is an industrially important reaction. It has variety of application such as in sealed lead acid batteries and nuclear reactors. Water gas shift (WGS) reaction is of specific importance to produce hydrogen from carbonaceous material. PROX is an important step to further purify hydrogen produced form WGS. Hydrogen purified using PROX can be directly fed to polymer electrolyte membrane fuel cells. By and large, noble metals Pt, Pd, Rh, Ru and some of their alloys are dispersed on oxide or high surface area carbon are the active catalysts. An alternative approach can be to make Pt2+, Pd2+, Rh3+, Ru4+ ions substituted in reducible support such as CeO2, Ce1-xTixO2-δ and TiO2 to increase the dispersion and bring down the cost. In this thesis we have followed this new approach and show that noble metal ionic catalysts are superior to noble metal nano particles. In the 1st chapter we present an overview of heterogeneous catalysis and important heterogeneous catalytic reactions. Monolithic catalyst and various ways to coat catalysts for application have been reviewed. Metal-support interaction till date is also reviewed. In the 2nd chapter, synthesis of noble metal ionic catalysts by solution combustion method is described. Coating of washcoat and active catalyst phase over ceramic honeycomb by a new combustion method is described. Solution combustion reaction and characterization of the catalyst by x-ray diffraction, x-ray photoelectron spectroscopy, temperature programmed reduction and reaction is given. We have fabricated experimental systems to carryout catalytic reaction and in this chapter they have been presented. In the 3rd chapter, we report a new process of coating of active exhaust catalyst over -Al2O3 coated cordierite honeycomb. The process consists of (a) growing  -Al2O3 on cordierite by solution combustion of Al(NO3)3 and oxylyldihydrazide (ODH) at 600 0C. Active catalyst phase, Ce0.98Pd0.02O2- is coated on - Al2O3 coated cordierite again by combustion of ceric ammonium nitrate and ODH with 1.2  10-3 M PdCl2 solution at 500 0C. In this way a coat layer over cordierite ceramic has been achieved and catalyst has the active sites in the form of Pd2+ ions rather than Pd metal. Weight of the active catalyst can be varied from 0.02 to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion [1]. Adhesion of catalyst to cordierite surface is via oxide growth on oxide ceramic which is very strong. 100 % conversion of CO is achieved below 80 oC at a space velocity of 880 h-1. At much higher space velocity of 21000h-1, 100 % conversion is obtained below 245 oC. Activation energy for CO oxidation is 8.4 kcal/mol. At a space velocity of 880 h-1 100% NO conversion is attained below 185 oC and 100 % conversion of ‘HC’(C2H2) below 220 oC. At the same space velocity 3-way catalytic performance over Ce0.98Pd0.02O2- coated monolith shows 100% conversion of all the pollutants below 220 o C with 15% excess oxygen. Catalytic activity of cordierite honeycomb coated by this new coating method for the oxidation of major hydrocarbons in exhaust gas is discussed further in this chapter. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. 3-way catalytic test is done by putting hydrocarbon mixture along with CO (10000ppm), NO (2000ppm) and O2 (15000ppm). Below 350 oC full conversion is achieved [2]. A comparison of the results shows that Ce1-xPdxO2-δ far superior to other catalysts. In this method, handling of nano material powder is avoided. In the 4th chapter we present a detailed study on the catalytic combustion of hydrogen by oxygen (hydrogen oxygen recombination reaction). Ever since Michel Faraday showed H2 + O2 recombination reaction over platinum metal plates, Pt metal has remained the only room temperature recombination catalyst. In search of an alternative catalyst, we discovered a new Pt free Ti0.99Pd0.01O2- compound which shows high rates of this reaction above 45 oC compared to Ce0.98Pt0.02O2-, Pt/Al2O3 and Pd/Al2O3. High rates of H2+O2 recombination over Pt and Pd ion respectively in CeO2 and TiO2 is due to the protonic type H2+ adsorption on Pt2+ or Pd2+ and dissociative chemisorption of O2 on the electron rich oxide ion vacancies [3]. In the case of Ce0.98Pt0.02O2-, H2/Pt ratio in a TPR experiment is ~2.3 at 0 oC. In the case of Ti0.99Pd0.01O2- also, H2 adsorption occurs below 0 oC and H2 / Pd ratio is ~2.2. Thus, more than 4-5 H atoms are adsorbed per metal ion. This is attributed to hydrogen spillover. H2 is known to be adsorbed as hydride ion (H-) over Pt, Pd, Rh, Ru, Os and Ir metals. Proton NMR studies of H2 adsorbed on Pd metal have shown upfield i.e. negative shift of 12 ppm with respect to TMS. We have studied proton NMR of Ti0.99Pd0.01O2- + H2 which show a downfield shift of 11.35 ppm confirming H+ or H2+ kind of species over Pd2+ ion in Ti0.99Pd0.01O2-. In Ce0.98Pt0.02O2- also H2 adsorption led to H2+ like species observed at 8 ppm and DFT calculations indeed showed H2+ kind species. H2+ is a precursor for dissociation and can readily induce O2 dissociation leading to high rates of recombination. In the 5th chapter we report water gas shift reaction (WGS) and preferential oxidation of CO (PROX) over Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ. The water gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nano crystalline catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2 and Ce1-xTixO2-δ. The catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS) and it has been shown that Pt2+ ions in these reducible oxides of the form Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ are highly active. These catalysts were tested for the water gas shift reaction both in presence and absence of hydrogen. It is shown that Ti0.99Pt0.01O2- exhibits higher catalytic activity than Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ [4]. Further, experiments were conducted to determine the deactivation of these catalysts by performing the daily startup and shutdown of the reactor for over 24 hours. There was no sintering of Pt and no carbonate formation and, therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ce4+, Ti4+ ions in the catalysts. Further, PROX activity of these catalysts has been studied. Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ showed high activity, large operating temperature window and low working temperature proving them to be highly effective PROX catalysts. In the 6th chapter we study the electrocatalysis of formic acid electro-oxidation and simultaneously mapping the electronic states of the electrodes by X-ray photoelectron spectroscopy (XPS). Ionically dispersed platinum in Ce1-xPtxO2-δ and Ce1-x-yTiyPtxO2-δ is very active towards oxygen evolution and formic acid oxidation. Higher electro-catalytic activity of Pt2+ ions in CeO2 and Ce1-xTixO2 compared to Pt0 in Pt/C is due to Pt2+ ion interaction with the supports, CeO2 and Ce1-xTixO2 respectively [5]. Further, ionic platinum does not suffer from CO poisoning effect unlike Pt0 in Pt/C. Utilization of lattice oxygen from the electrodes during the reaction has been demonstrated. This lattice oxygen exchange is responsible to convert CO to CO2 in the lower potential region to remove CO poisoning effect. In 7th chapter we repeat our study on the noble metal ion reducible oxide interaction in Ce1-xPtxO2- and Ce1-xPdxO2- (x= 0.02) system by a novel electrochemical method combined with XPS. Working electrodes made of CeO2 and Ce0.98Pt0.02O2- mixed with 30% carbon are cycled between 0.0-1.2 V in potentio-static (chronoamperometry) and potentio-dynamic (cyclic voltametry) mode with reference to saturated calomel electrode (SCE). Reversible oxidation of Pt0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y= 0.35) after applying +1.2 V which is not reversible. But Ce0.98Pt0.02O2- reaches a steady state with Pt2+: Pt4+ in the ratio of 0.60: 0.40 and Ce4+: Ce3+ in the ratio of 0.55: 0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V which is reversible [6]. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2- forms a stable electrode for oxidation of H2O to O2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction of Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple. Similar studies have been performed with Ce0.98Pd0.02O2- catalyst to show the redox coupling between Pd2+/Pd0 and Ce4+/Ce3+ redox couples. We expect similar redox coupling for Pd, Pt ions substituted TiO2, and Ce1-xTixO2. In the final chapter 8, a critical review and conclusion on the results presented in the thesis is presented. The combustion synthesized catalysts reported in this thesis stabilizes the Pt and Pd metals in their ionic state rather than zero valent metallic state. Thus, the catalysts are uniform solid catalysts. High activity and stability of these catalysts are shown to be due to the electronic interaction between noble metal ions and the reducible oxide. Redox couples Pt0/Pt2+, Pt2+/Pt4+ and Pd0/Pd2+ interact with Ce4+/Ce3+, Ti4+/Ti3+ couples such that metal is oxidized and the support is reduced. This has been established in the thesis by a combined use of electrochemistry and XPS thus solving a long standing problem of metal support interaction in catalysis. We hope that the results presented in the thesis is a worthwhile contribution to catalysis. (For mathematical equations pl refer pdf file.)

Among the various heterogeneous catalytic reactions three way catalysis (TWC), catalytic combustion of hydrogen, water gas shift reaction (WGS) and preferential oxidation of CO (PROX) in the hydrogen rich stream are some of the important reactions receiving the attention presently. Three-way catalysis (TWC) involves simultaneous removal of the three pollutants (i.e., CO, NOx, and HCs) from the automobile exhaust. Catalytic combustion of hydrogen by oxygen or hydrogen-oxygen recombination reaction is an industrially important reaction. It has variety of application such as in sealed lead acid batteries and nuclear reactors. Water gas shift (WGS) reaction is of specific importance to produce hydrogen from carbonaceous material. PROX is an important step to further purify hydrogen produced form WGS. Hydrogen purified using PROX can be directly fed to polymer electrolyte membrane fuel cells. By and large, noble metals Pt, Pd, Rh, Ru and some of their alloys are dispersed on oxide or high surface area carbon are the active catalysts. An alternative approach can be to make Pt2+, Pd2+, Rh3+, Ru4+ ions substituted in reducible support such as CeO2, Ce1-xTixO2-δ and TiO2 to increase the dispersion and bring down the cost. In this thesis we have followed this new approach and show that noble metal ionic catalysts are superior to noble metal nano particles. In the 1st chapter we present an overview of heterogeneous catalysis and important heterogeneous catalytic reactions. Monolithic catalyst and various ways to coat catalysts for application have been reviewed. Metal-support interaction till date is also reviewed. In the 2nd chapter, synthesis of noble metal ionic catalysts by solution combustion method is described. Coating of washcoat and active catalyst phase over ceramic honeycomb by a new combustion method is described. Solution combustion reaction and characterization of the catalyst by x-ray diffraction, x-ray photoelectron spectroscopy, temperature programmed reduction and reaction is given. We have fabricated experimental systems to carryout catalytic reaction and in this chapter they have been presented. In the 3rd chapter, we report a new process of coating of active exhaust catalyst over -Al2O3 coated cordierite honeycomb. The process consists of (a) growing  -Al2O3 on cordierite by solution combustion of Al(NO3)3 and oxylyldihydrazide (ODH) at 600 0C. Active catalyst phase, Ce0.98Pd0.02O2- is coated on - Al2O3 coated cordierite again by combustion of ceric ammonium nitrate and ODH with 1.2  10-3 M PdCl2 solution at 500 0C. In this way a coat layer over cordierite ceramic has been achieved and catalyst has the active sites in the form of Pd2+ ions rather than Pd metal. Weight of the active catalyst can be varied from 0.02 to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion [1]. Adhesion of catalyst to cordierite surface is via oxide growth on oxide ceramic which is very strong. 100 % conversion of CO is achieved below 80 oC at a space velocity of 880 h-1. At much higher space velocity of 21000h-1, 100 % conversion is obtained below 245 oC. Activation energy for CO oxidation is 8.4 kcal/mol. At a space velocity of 880 h-1 100% NO conversion is attained below 185 oC and 100 % conversion of ‘HC’(C2H2) below 220 oC. At the same space velocity 3-way catalytic performance over Ce0.98Pd0.02O2- coated monolith shows 100% conversion of all the pollutants below 220 o C with 15% excess oxygen. Catalytic activity of cordierite honeycomb coated by this new coating method for the oxidation of major hydrocarbons in exhaust gas is discussed further in this chapter. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. 3-way catalytic test is done by putting hydrocarbon mixture along with CO (10000ppm), NO (2000ppm) and O2 (15000ppm). Below 350 oC full conversion is achieved [2]. A comparison of the results shows that Ce1-xPdxO2-δ far superior to other catalysts. In this method, handling of nano material powder is avoided. In the 4th chapter we present a detailed study on the catalytic combustion of hydrogen by oxygen (hydrogen oxygen recombination reaction). Ever since Michel Faraday showed H2 + O2 recombination reaction over platinum metal plates, Pt metal has remained the only room temperature recombination catalyst. In search of an alternative catalyst, we discovered a new Pt free Ti0.99Pd0.01O2- compound which shows high rates of this reaction above 45 oC compared to Ce0.98Pt0.02O2-, Pt/Al2O3 and Pd/Al2O3. High rates of H2+O2 recombination over Pt and Pd ion respectively in CeO2 and TiO2 is due to the protonic type H2+ adsorption on Pt2+ or Pd2+ and dissociative chemisorption of O2 on the electron rich oxide ion vacancies [3]. In the case of Ce0.98Pt0.02O2-, H2/Pt ratio in a TPR experiment is ~2.3 at 0 oC. In the case of Ti0.99Pd0.01O2- also, H2 adsorption occurs below 0 oC and H2 / Pd ratio is ~2.2. Thus, more than 4-5 H atoms are adsorbed per metal ion. This is attributed to hydrogen spillover. H2 is known to be adsorbed as hydride ion (H-) over Pt, Pd, Rh, Ru, Os and Ir metals. Proton NMR studies of H2 adsorbed on Pd metal have shown upfield i.e. negative shift of 12 ppm with respect to TMS. We have studied proton NMR of Ti0.99Pd0.01O2- + H2 which show a downfield shift of 11.35 ppm confirming H+ or H2+ kind of species over Pd2+ ion in Ti0.99Pd0.01O2-. In Ce0.98Pt0.02O2- also H2 adsorption led to H2+ like species observed at 8 ppm and DFT calculations indeed showed H2+ kind species. H2+ is a precursor for dissociation and can readily induce O2 dissociation leading to high rates of recombination. In the 5th chapter we report water gas shift reaction (WGS) and preferential oxidation of CO (PROX) over Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ. The water gas shift reaction (WGS) is an important reaction to produce hydrogen. In this study, we have synthesized nano crystalline catalysts where Pt ion is substituted in the +2 state in TiO2, CeO2 and Ce1-xTixO2-δ. The catalysts have been characterized by X-ray diffraction and X-ray photoelectron spectroscopy (XPS) and it has been shown that Pt2+ ions in these reducible oxides of the form Ti0.99Pt0.01O2-, Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ are highly active. These catalysts were tested for the water gas shift reaction both in presence and absence of hydrogen. It is shown that Ti0.99Pt0.01O2- exhibits higher catalytic activity than Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ [4]. Further, experiments were conducted to determine the deactivation of these catalysts by performing the daily startup and shutdown of the reactor for over 24 hours. There was no sintering of Pt and no carbonate formation and, therefore, the catalyst did not deactivate even after prolonged reaction. There was no carbonate formation because of the highly acidic nature of Ce4+, Ti4+ ions in the catalysts. Further, PROX activity of these catalysts has been studied. Ce0.83Ti0.15Pt0.02O2- and Ce0.98Pt0.02O2-δ showed high activity, large operating temperature window and low working temperature proving them to be highly effective PROX catalysts. In the 6th chapter we study the electrocatalysis of formic acid electro-oxidation and simultaneously mapping the electronic states of the electrodes by X-ray photoelectron spectroscopy (XPS). Ionically dispersed platinum in Ce1-xPtxO2-δ and Ce1-x-yTiyPtxO2-δ is very active towards oxygen evolution and formic acid oxidation. Higher electro-catalytic activity of Pt2+ ions in CeO2 and Ce1-xTixO2 compared to Pt0 in Pt/C is due to Pt2+ ion interaction with the supports, CeO2 and Ce1-xTixO2 respectively [5]. Further, ionic platinum does not suffer from CO poisoning effect unlike Pt0 in Pt/C. Utilization of lattice oxygen from the electrodes during the reaction has been demonstrated. This lattice oxygen exchange is responsible to convert CO to CO2 in the lower potential region to remove CO poisoning effect. In 7th chapter we repeat our study on the noble metal ion reducible oxide interaction in Ce1-xPtxO2- and Ce1-xPdxO2- (x= 0.02) system by a novel electrochemical method combined with XPS. Working electrodes made of CeO2 and Ce0.98Pt0.02O2- mixed with 30% carbon are cycled between 0.0-1.2 V in potentio-static (chronoamperometry) and potentio-dynamic (cyclic voltametry) mode with reference to saturated calomel electrode (SCE). Reversible oxidation of Pt0 to Pt2+ and Pt4+ state due to the applied positive potential is coupled to simultaneous reversible reduction of Ce4+ to Ce3+ state. CeO2 reduces to CeO2-y (y= 0.35) after applying +1.2 V which is not reversible. But Ce0.98Pt0.02O2- reaches a steady state with Pt2+: Pt4+ in the ratio of 0.60: 0.40 and Ce4+: Ce3+ in the ratio of 0.55: 0.45 giving a composition Ce0.98Pt0.02O1.74 at 1.2 V which is reversible [6]. Composition of Pt ion substituted compound is reversible between Ce0.98Pt0.02O1.95 to Ce0.98Pt0.02O1.74 within the potential range of 0.0-1.2 V. Thus, Ce0.98Pt0.02O2- forms a stable electrode for oxidation of H2O to O2 unlike CeO2. A linear relation between oxidation of Pt2+ to Pt4+ with simultaneous reduction of Ce4+ to Ce3+ is observed demonstrating Pt-CeO2 metal support interaction is due to reversible Pt0/Pt2+/Pt4+ interaction with Ce4+/Ce3+ redox couple. Similar studies have been performed with Ce0.98Pd0.02O2- catalyst to show the redox coupling between Pd2+/Pd0 and Ce4+/Ce3+ redox couples. We expect similar redox coupling for Pd, Pt ions substituted TiO2, and Ce1-xTixO2. In the final chapter 8, a critical review and conclusion on the results presented in the thesis is presented. The combustion synthesized catalysts reported in this thesis stabilizes the Pt and Pd metals in their ionic state rather than zero valent metallic state. Thus, the catalysts are uniform solid catalysts. High activity and stability of these catalysts are shown to be due to the electronic interaction between noble metal ions and the reducible oxide. Redox couples Pt0/Pt2+, Pt2+/Pt4+ and Pd0/Pd2+ interact with Ce4+/Ce3+, Ti4+/Ti3+ couples such that metal is oxidized and the support is reduced. This has been established in the thesis by a combined use of electrochemistry and XPS thus solving a long standing problem of metal support interaction in catalysis. We hope that the results presented in the thesis is a worthwhile contribution to catalysis. (For mathematical equations pl refer pdf file.)

博士
國立中興大學
化學系所
94
Abstract Synthesis, characterization and catalytic activities of several b-diketiminato zinc complexes will be presented. Previous reports show that b-diketiminato zinc alkoxides exhibit two different structures, dinuclear or trinuclear. Factors affecting the aggregation of dinuclear and trinuclear zinc complexes and the proposed mechanism on the formation of the structures will also be described. A series of new dinuclear zinc complexes of the types [LZnEt]2 and [LZn(m-OBn)]2 (where L = NNO-tridentate Schiff base ligand) have been prepared. In addition, the activities of zinc alkoxides, [LZn(m -OBn)]2 toward the ring-opening polymerization of L-lactide have been investigated. Experimental results indicate that the reactivity of [LZn(m -OBn)]2 was dramatically affected by both the electronic and steric effects of the substituents on the Schiff base. The polymerization kinetics using [L2Zn(m -OBn)]2 as an initiator has been studied, and the experimental results reveal that the reaction rate is a first-order, dependent on both [LA] and [[L2Zn(m -OBn)]2]. Furthermore, the heterotactic PLA initiated by [L5Zn(m -OBn)]2 with Pr up to 91% can be achieved in CH2Cl2 at -55 °C. A novel calcium complex, [(DAIP)2Ca]2 (where DAIP-H = 2-[(2-dimethylamino-ethylimino)methyl]phenol) is prepared in one-pot reaction by the condensation of Ca(OMe)2 with DAIP-H in toluene/THF. In the presence of various alcohols, [(DAIP)2Ca]2 efficiently initiate the ring-opening polymerization of L-lactide in a controlled fashion, yielding functionalized polymers with expectative molecular weight and low polydispersity indexes. In addition, kinetic studies show a first-order dependency on both [LA] and [BnOH]

With the increasing demand for biodiesel, the accumulation of byproduct, crude glycerol has become a problem which needs to be solved. Lactic acid is one of the value-added chemical which can be produced from glycerol that has wide uses in food and chemical industry. Although glycerol can be converted to lactic acid with an alkali as the catalyst at high glycerol conversion (100 mol%) and lactic acid yield (around 90 mol%), the high alkalinity would cause severe corrosiveness to a stainless steel reactor. In this study two tasks were performed to convert glycerol to lactic acid with satisfactory conversion and selectivity, and to reduce the corrosiveness of reaction medium. First, CaO was used as solid base catalyst. The highest lactic acid yield achieved was 40.8 mol% with a 97.8 mol% glycerol conversion, when operating at 290°C after 150 min reaction with molar ratio of CaO: glycerol=0.3. Also CaO has advantages such as high lactic acid productivity (3.35 g/(min·L)) and reusability. Meanwhile, CaO can be used as the catalyst for both biodiesel production and the following crude glycerol conversion to lactic acid. Second, for glycerol conversion with NaOH as catalyst, a fed-batch reactor was applied to continuously supply NaOH during reaction process, compensating the OH- neutralized by newly formed lactic acid. The optimal lactic acid yield of 80.5 mol%, with 92.8% glycerol conversion was obtained at 300 °C for 220min, with 1.1 M glycerol initial concentration. A first-order kinetic model for glycerol concentration versus time was developed and verified experimentally under conditions with different initial glycerol concentration and reaction temperature. Although crude glycerol samples contained large amount of impurities, both methods, conversion with solid base catalyst and with fed-batch reactor, were applied successfully to three crude glycerol samples provided by biodiesel manufacturers, and the lactic acid yield reached 52.3 mol% and 72.7 mol% respectively. Finally, the corrosion issue of different methods was compared based on the Fe3+ concentration (analyzed with atomic-absorption spectroscopy) in the products. Both methods of glycerol conversions, with solid base catalyst and fed-batch reactor, can reduce the corrosiveness of glycerol conversion with an alkali as the catalyst.

碩士
國立臺灣科技大學
化學工程系
89
The kinetics of zinc recovery from the spent zinc oxide catalyst by carbon in the presence of calcium carbonate was studied using inductively coupled plasma mass spectrometer, elemental analyzer, X-ray diffractometer, atomic absorption spectrometer, surface area meter and scanning electron microscope. The spent zinc oxide catalyst was found to be composed of 87.5wt% zinc oxide and 3.1wt% zinc sulfide. Results of X-ray diffractometer indicated that calcium carbonate decomposed to calcium oxide and carbon dioxide while zinc oxide and zinc sulfide were reduced to zinc vapor and carbon monoxide evolving from solid sample and sulfur was scavenged as calcium sulfide remained in the solid. Results of surface area measurement indicated that the surface area of the solid sample increased with reaction time, reached a maximum and then decreased. The surface area of the reacted sample was found to decrease with reaction temperature. The variations of pore volume and average pore diameter were observed to be similar to that of surface area. A mechanism was proposed to explain the reaction. Experimental results of atomic absorption spectrometer indicated that the initial rate of zinc recovery and final zinc recovery can be increased by increasing sample height, reaction temperature or initial bulk density. Furthermore, they were found to increase with decrease in argon flow rate, molar ratio of Zntotal/C, molar ratio of Zntotal/CaCO3, grain size of the spent catalyst, agglomerate size of carbon or agglomerate size of calcium carbonate. Initial rate of zinc recovery and final zinc recovery were determined finally.

Three-way catalysis (TWC) involves simultaneous removal of the three pollutants (i.e., CO, NOx, and HCs) which led to the branch of auto-exhaust catalysis. CeO2 has become the main component of TWC catalyst because of its oxygen storage storage (OSC) property to supply oxygen under excess fuel condition and store oxygen under lean condition. Substitution of smaller isovalent cations like Ti4+, Zr4+ and Hf4+ ions in CeO2 forming Ce1-xMxO2 (M = Ti, Zr &Hf) solid solution enhance the OSC property. XRD along with EXAFS study showed that cations arrange in FCC lattice but oxygen coordination around metal ions is split into 4 + 4 coordination in Ce1-xMxO2 instead of ideal 8 coordination in CeO2. The longer Ce/Ti/Zr – O bonds are weakly bound and can be easily removed by H2 giving high OSC value than pure CeO2. Among the three OSC systems studied here, Ce0.5Zr0.5O2 showed exceptionally high OSC which lead to formation of a new a pyrochlore, Ce2Zr2O6.3. This compound is nearly metallic. Ce0.85-xTi0.15PtxO2- (x = 0.01 & 0.02) crystallizes in fluorite structure and Pt is ionically substituted with 2+ and 4+ oxidation states. H/Pt atomic ratio at 30 oC over Ce0.84Ti0.15Pt0.01O2- is 5 and over Ce0.99Pt0.01O2-δ is 4 against just 0.078 for 8 nm Pt metal particles. Carbon monoxide and hydrocarbon oxidation activity are much higher over Ce1-x-yTixPtyO2 (x= 0.15, y= 0.01, 0.02) compared to Ce1-xPtxO2 (x= 0.01, 0.02). Synergistic involvement of Pt2+/Pt0 and Ti4+/Ti3+ redox couples in addition to Ce4+/Ce3+ due to the overlap of Pt(5d), Ti(3d), and Ce(4f) bands near EF is shown to be responsible for enhanced redox property and higher catalytic activity. On substitution of Pd ion in Ce1-xTixO2, more lattice oxygen is found to be more labile than Pd in CeO2. The easy removal of oxygen from the more reducible Ti4+ containing support plays a major role in showing higher catalytic activity of this material for CO oxidation, N2O and NO reduction by CO. The catalyst shows 100% N2 selectivity  240 oC in NO+CO reaction. It has been shown that oxide ion vacancy creation created by removal of lattice oxygen by CO is responsible for dissociation of NO or N2O at a lower temperature. Ionicity of Pd2+ ion in different support could be varied by varying the ionicity of the oxide support itself. Rates of CO oxidation increases or activation energy decreases over Ce1-xPdxO2-δ, Ti1-xPdxO2-δ and Ce1-x-yMxPdyO2-δ (M = Ti, Zr, Hf ; x = 0.25, 0.4 ; y = 0.02) is increased with ionicity of Pd2+ ion. The substitution of Sn in CeO2 forming Ce1-xSnxO2 (x = 0.1-0.5) solid solution was prepared using tin oxalate precursor by solution combustion method. These oxides can be promising support for noble metals because of the Sn4+  Sn2+ redox couple in addition to Ce3+/Ce4+. The two electron process involved in the redox reaction of Sn as well as easy reducibility of Sn4+ to Sn2+ offers a far better redox catalytic system hitherto not reported. Ce1-xSnxO2 solid solutions as well as Pd ion substituted Ce1-xSnxO2 was prepared for the first time.

Three-way catalysis (TWC) involves simultaneous removal of the three pollutants (i.e., CO, NOx, and HCs) which led to the branch of auto-exhaust catalysis. CeO2 has become the main component of TWC catalyst because of its oxygen storage storage (OSC) property to supply oxygen under excess fuel condition and store oxygen under lean condition. Substitution of smaller isovalent cations like Ti4+, Zr4+ and Hf4+ ions in CeO2 forming Ce1-xMxO2 (M = Ti, Zr &Hf) solid solution enhance the OSC property. XRD along with EXAFS study showed that cations arrange in FCC lattice but oxygen coordination around metal ions is split into 4 + 4 coordination in Ce1-xMxO2 instead of ideal 8 coordination in CeO2. The longer Ce/Ti/Zr – O bonds are weakly bound and can be easily removed by H2 giving high OSC value than pure CeO2. Among the three OSC systems studied here, Ce0.5Zr0.5O2 showed exceptionally high OSC which lead to formation of a new a pyrochlore, Ce2Zr2O6.3. This compound is nearly metallic. Ce0.85-xTi0.15PtxO2- (x = 0.01 & 0.02) crystallizes in fluorite structure and Pt is ionically substituted with 2+ and 4+ oxidation states. H/Pt atomic ratio at 30 oC over Ce0.84Ti0.15Pt0.01O2- is 5 and over Ce0.99Pt0.01O2-δ is 4 against just 0.078 for 8 nm Pt metal particles. Carbon monoxide and hydrocarbon oxidation activity are much higher over Ce1-x-yTixPtyO2 (x= 0.15, y= 0.01, 0.02) compared to Ce1-xPtxO2 (x= 0.01, 0.02). Synergistic involvement of Pt2+/Pt0 and Ti4+/Ti3+ redox couples in addition to Ce4+/Ce3+ due to the overlap of Pt(5d), Ti(3d), and Ce(4f) bands near EF is shown to be responsible for enhanced redox property and higher catalytic activity. On substitution of Pd ion in Ce1-xTixO2, more lattice oxygen is found to be more labile than Pd in CeO2. The easy removal of oxygen from the more reducible Ti4+ containing support plays a major role in showing higher catalytic activity of this material for CO oxidation, N2O and NO reduction by CO. The catalyst shows 100% N2 selectivity  240 oC in NO+CO reaction. It has been shown that oxide ion vacancy creation created by removal of lattice oxygen by CO is responsible for dissociation of NO or N2O at a lower temperature. Ionicity of Pd2+ ion in different support could be varied by varying the ionicity of the oxide support itself. Rates of CO oxidation increases or activation energy decreases over Ce1-xPdxO2-δ, Ti1-xPdxO2-δ and Ce1-x-yMxPdyO2-δ (M = Ti, Zr, Hf ; x = 0.25, 0.4 ; y = 0.02) is increased with ionicity of Pd2+ ion. The substitution of Sn in CeO2 forming Ce1-xSnxO2 (x = 0.1-0.5) solid solution was prepared using tin oxalate precursor by solution combustion method. These oxides can be promising support for noble metals because of the Sn4+  Sn2+ redox couple in addition to Ce3+/Ce4+. The two electron process involved in the redox reaction of Sn as well as easy reducibility of Sn4+ to Sn2+ offers a far better redox catalytic system hitherto not reported. Ce1-xSnxO2 solid solutions as well as Pd ion substituted Ce1-xSnxO2 was prepared for the first time.

The extensive growth of nanotechnology has necessitated the development of economical and robust methods for large scale production of nanomaterials. It requires detailed quantitative understanding of lab-scale processes to enable effective scale-up and development of new contacting strategies for their controlled synthesis. In this thesis, attempts are made in both the directions using experimental and modelling approaches for synthesis of different nanoparticles. The two-phase Brust--Schiffrin protocol for the synthesis of gold nanoparticles was investigated first. The mechanism of transfer of reactants from aqueous to organic phase using phase transfer catalyst (PTC) was investigated using the measurement of interfacial tension, viscosity, SLS, SAXS, 1H NMR, DOSY-NMR, and Karl-Fischer titration. The study shows that the reactants are transferred to organic phase through the formation of hydrated complexes between reactants and PTC rather than through the solubilization of reactants in water core of inverse micelles of PTC, proposed recently in the literature. The particle synthesis reactions thus occur in the bulk organic phase. The extensive body of seemingly disparate experimental findings on Brust--Schiffrin protocol were put together next. The emerging picture ruled out both thermodynamic considerations and kinetics based arguments as exemplified by the classical LaMer's mechanism with sequential nucleation growth capping for size control in Brust--Schiffrin protocol. A new model for particle synthesis was developed. The model brought out continued nucleation--growth--capping based size control, an hitherto unknown mechanistic route for the synthesis of monodisperse particles, as the main mechanism. The model not only captured the reported features of the synthesis but also helped to improve the uniformity of the synthesized particles, validated experimentally. The two-step mechanism of Finke--Watzky---first order nucleation from precursor and autocatalytic growth of particles---proposed as an alternative to LaMer model to explain an induction period followed by a sigmoidal decrease in precursor concentration for the synthesis of iridium nanoparticles was investigated next. The mechanism is tested using an equivalent population balance model for its ability to explain the experimentally observed near constant breadth of the evolving size distribution as well. The predictions show that while it captures precursor conversion well, it fails to explain particle synthesis on account of its inability to suppress nucleation. A minimal four-step mechanism with additional steps for nucleation from reduced iridium atoms and their scavenging using particle surface is proposed. The new mechanism when combined with the first or second order nucleation, or classical nucleation with no scavenging of reduced atoms also fails to suppress nucleation. A burst like onset of nuclei formation with homogeneous nucleation and the scavenging of reduced atoms by particles are simultaneously required to explain all the reported features of the synthesis of iridium nanoparticles. A new reactor is proposed for continuous production of CaCO3 nanoparticles in gas-liquid reaction route. The key feature of the new reactor is the control of flow pattern to ensure efficient mixing of reactants. A liquidliquid reaction route for production of CaCO3 nanoparticles is also optimized to produce nanoparticles at high loading. Optimum supersaturation combined with efficient breakup of initial gel-like structure by mechanical agitation and charge control played a crucial role in producing nano sized CaCO3 particles.

The extensive growth of nanotechnology has necessitated the development of economical and robust methods for large scale production of nanomaterials. It requires detailed quantitative understanding of lab-scale processes to enable effective scale-up and development of new contacting strategies for their controlled synthesis. In this thesis, attempts are made in both the directions using experimental and modelling approaches for synthesis of different nanoparticles. The two-phase Brust--Schiffrin protocol for the synthesis of gold nanoparticles was investigated first. The mechanism of transfer of reactants from aqueous to organic phase using phase transfer catalyst (PTC) was investigated using the measurement of interfacial tension, viscosity, SLS, SAXS, 1H NMR, DOSY-NMR, and Karl-Fischer titration. The study shows that the reactants are transferred to organic phase through the formation of hydrated complexes between reactants and PTC rather than through the solubilization of reactants in water core of inverse micelles of PTC, proposed recently in the literature. The particle synthesis reactions thus occur in the bulk organic phase. The extensive body of seemingly disparate experimental findings on Brust--Schiffrin protocol were put together next. The emerging picture ruled out both thermodynamic considerations and kinetics based arguments as exemplified by the classical LaMer's mechanism with sequential nucleation growth capping for size control in Brust--Schiffrin protocol. A new model for particle synthesis was developed. The model brought out continued nucleation--growth--capping based size control, an hitherto unknown mechanistic route for the synthesis of monodisperse particles, as the main mechanism. The model not only captured the reported features of the synthesis but also helped to improve the uniformity of the synthesized particles, validated experimentally. The two-step mechanism of Finke--Watzky---first order nucleation from precursor and autocatalytic growth of particles---proposed as an alternative to LaMer model to explain an induction period followed by a sigmoidal decrease in precursor concentration for the synthesis of iridium nanoparticles was investigated next. The mechanism is tested using an equivalent population balance model for its ability to explain the experimentally observed near constant breadth of the evolving size distribution as well. The predictions show that while it captures precursor conversion well, it fails to explain particle synthesis on account of its inability to suppress nucleation. A minimal four-step mechanism with additional steps for nucleation from reduced iridium atoms and their scavenging using particle surface is proposed. The new mechanism when combined with the first or second order nucleation, or classical nucleation with no scavenging of reduced atoms also fails to suppress nucleation. A burst like onset of nuclei formation with homogeneous nucleation and the scavenging of reduced atoms by particles are simultaneously required to explain all the reported features of the synthesis of iridium nanoparticles. A new reactor is proposed for continuous production of CaCO3 nanoparticles in gas-liquid reaction route. The key feature of the new reactor is the control of flow pattern to ensure efficient mixing of reactants. A liquidliquid reaction route for production of CaCO3 nanoparticles is also optimized to produce nanoparticles at high loading. Optimum supersaturation combined with efficient breakup of initial gel-like structure by mechanical agitation and charge control played a crucial role in producing nano sized CaCO3 particles.