Thesis advisor: Dunwei Wang / Atomically dispersed catalysts refer to substrate-supported heterogeneous catalysts featuring one or a few active metal atoms that are separated from one another. They represent an important class of materials ranging from single atom catalysts (SACs) and nanoparticles (NPs). The study of SACs has brought an attention of understanding the reaction mechanism at the molecular level. SACs is a promising field, however, there are still many challenges and opportunities in developing the next generation of catalysts. Catalysts featuring two atoms with well-defined structures as active sites are poorly studied. It is expected that this class of catalysts will show uniqueness in activity, selectivity, and stability. However, the difficulty in synthesizing such structures has been a critical challenge. I tackled this challenge by using a facile photochemical method to generate active metal centers consisting of two iridium metal atoms bridged by O ligands and bound to a support by stripping the ligands of the organometallic complex. My research also unveiled the structure of this dinuclear heterogeneous catalysts (DHCs) by integrating various characterization resources. Direct evidence unambiguously supporting the dinuclear nature of catalysts anchored on metal oxides is obtained by aberration-corrected scanning transmission electron microscopy. In addition, different binding modes have been achieved on two categories of metal oxides with distinguishable surface oxygen densities and interatomic distances of binding sites. Side-on bound DHCs was demonstrated on iron oxide and ceria where both Ir atoms are affixed to the surface with similar coordination environment. The binding sites on the OH-terminated surface of Fe2O3 and CeO2 anchor the catalysts to provide outstanding stability against detachment, diffusion and aggregation. The competing end-on binding mode, where only one Ir atom is attached to the substrate and the other one is dangling was observed on WO3. Evidence supporting the binding modes was obtained by in situ diffuse reflectance infrared Fourier transform spectroscopy. In addition, the synergistic effect between two adjacent Ir atoms and the uniqueness of different coordinative oxygen atoms around Ir atoms were investigated by a series of operando spectroscopy such as X-ray absorption spectroscopy and microscopy at atomic level under the reaction condition. The resulting catalysts exhibit high activities and stabilities toward H2O photo-oxidation and preferential CO oxidation. Density functional theory calculations provide additional support for atomic structure, binding sites modes on metal oxides, as well as insights into how DHCs may be beneficial for these catalytic reactions. This research has important implications for future studies of highly effective heterogeneous catalysts for complex chemical reactions. / Thesis (PhD) — Boston College, 2020. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Energy conversion processes such as the water splitting and CO2 hydrogenation reactions have emerged as attractive approaches to mitigate environmental concerns on CO2 emissions as well as to provide an alternative source of renewable fuels. These strategic processes can capitalize on the energy of renewable resources (e.g solar and wind) to drive chemical reactions to generate, in a green and sustainable way, fuels and value-added chemicals. Economically feaseable heterogeneous catalysts play a central role in advancing such processes for globally-relevant production scales. Hence, in this work, we focused on the synthetic development of several catalyst systems based on cost-effective earth-abudant 3d transition metals such as nickel (Ni), cobalt (Co), iron (Fe) and zinc (Zn). Specifically, we turned our attention to produce a series of catalysts comprised of: i) NiFe oxyhydroxide supported on carbon for application in oxygen evolution reaction (OER), a bottleneck reaction for the water splitting process, and ii) Ni and Co nanoparticles supported on Zinc oxide (ZnO) for the CO2 hydrogenation reaction. Regarding the NiFe oxyhydroxide systems, we evaluated the catalytic performance of these materials towards the OER and benchmarked those with that of state-of-the-art OER electrocatalyts such as Ir/C. In addition to that, we also focused on rationalizing the key reasons for the significant enhancements in OER activity of such catalysts in terms of their surface and bulk compositions. For Co/ZnO and Ni/ZnO catalysts, aside from assessing their catalytic activity and selectivity behavior, we performed a systematic investigation of the catalytically important properties of such catalyst interfaces under typical CO2 hydrogenation reaction conditions using in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS). This allowed us to acquire important knowledge into the origin and the nature of the active sites associated with the catalytic activity and selectivity in these materials. / Processos de conversão de energia, como as reações de quebra de água e hidrogenação de CO2, têm surgirdo como abordagens atraentes para mitigar as preocupações ambientais das emissões de CO2, bem como para fornecer uma fonte alternativa de combustíveis renováveis. Esses processos estratégicos podem capitalizar a energia de recursos renováveis (por exemplo, solar e eólica) para realizar reações químicas que geram, de forma sustentável e ecológica, combustíveis e produtos químicos com valor agregado. Catalisadores heterogêneos economicamente viáveis desempenham um papel central no avanço de tais processos para escalas de produção globalmente relevantes. Assim, neste trabalho, nos concentramos no desenvolvimento sintético de vários sistemas catalisadores baseados em metais de transição 3d abudantes como o níquel (Ni), cobalto (Co), ferro (Fe) e zinco (Zn). Especificamente, voltamos nossa atenção para produzir uma série de catalisadores compostos de: i) oxi-hidróxido de NiFe suportado em carbono para aplicação na reação de evolução de oxigênio (OER), uma reação limitante para o processo de quebra de água, e ii) nanopartículas de Ni e Co suportadas em Óxido de zinco (ZnO) para a reação de hidrogenação do CO2. Com relação aos sistemas de oxi-hidróxido de NiFe, avaliamos o desempenho catalítico desses materiais frente a OER e comparamos estes com eletrocatalisadores para OER de última geração, como Ir/C. Além disso, também nos concentramos em racionalizar as principais razões para as melhorias significativas na atividade catalítica de tais catalisadores em termos de suas composições de superfície e volume. Para os catalisadores de Co/ZnO e Ni/ZnO, além de avaliar sua atividade catalítica e seletividade, realizamos uma investigação sistemática in situ das propriedades cataliticamente importantes de tais interfaces usando a Espectroscopia de Fotoelétrons de Raios X a Pressão Ambiente. (APXPS) sob condições típicas de reação de hidrogenação de CO2. Isso nos permitiu adquirir conhecimentos importantes sobre a origem e a natureza dos sítios ativos associados à atividade e seletividade catalítica nesses materiais.

Les catalyseurs hétérogènes sont des matériaux complexes dont les structures peuvent être modifiées en cours de fonctionnement. Une meilleure compréhension des relations entre propriétés catalytiques et propriétés structurales est nécessaire pour répondre à de nouveaux enjeux environnementaux et économiques. Seules les caractérisations in situ résolues dans le temps i.e. dans des conditions réelles, permettent d’apporter ces informations. Dans ce travail, nous nous sommes intéressés à la caractérisation operando par spectroscopie d’absorption des rayons X (XAS) résolue dans le temps de deux types de catalyseurs hétérogènes : les catalyseurs Fischer-Tropsch et les catalyseurs d’hydrodésulfuration. Si ces catalyseurs sont connus depuis de nombreuses années, peu de caractérisations sont réalisées in situ ou operando au cours de la réaction.Etant données leurs conditions réactionnelles (haute température et haute pression), la mise en œuvre de ces caractérisations a nécessité tout d’abord la construction des outils nécessaires à la caractérisation in situ de catalyseurs hétérogènes sous haute pression de gaz. Ensuite, nous avons réuni un ensemble cohérent de techniques de caractérisation autour du catalyseur Fischer-Tropsch afin de permettre son étude structurale à différentes échelles : l’ordre local avec le Quick-EXAFS et l’ordre à grande distance avec la diffraction des rayons X. Afin d’observer l’effet de la forme cristalline de la phase active sur les propriétés catalytiques, nous avons pour un même catalyseur, activé selon deux voies d’activation, quantifié son activité au moyen de la spectroscopie Raman et la spectrométrie de masse. D’autre part, la caractérisation simultanée de deux centres métalliques, accessible par le dispositif QEXAFS installé sur la ligne de lumière SAMBA, a permis d’obtenir une description fine des processus d’activation des catalyseurs bimétalliques d’hydrodésulfuration. Notre étude s’est portée, sur la comparaison de catalyseurs de même formulation avec des prétraitements différents (séché/calciné) et de deux catalyseurs promus par des métaux différents : le cobalt et le nickel. / Heterogeneous catalysts are complex material whose structures can change on working conditions. To tackle new environmental and economic issues a better knowledge of the relationship between catalytic and structural properties is needed. Only in situ time resolved characterisations i.e. in real working conditions can provide this information.In this study we worked with operando time-resolved X-ray Absorption Spectroscopy (XAS) on two types of heterogeneous catalysts: Fischer-Tropsch catalysts and hydrodesulfurisation catalysts. If these catalysts have been known for many years, only few characterisations are conducted in situ or operando during the reaction.Given their reaction conditions (high temperature and high pressure), these characterisations involved first the construction of tools for in situ characterisation of heterogeneous catalysts under high pressure of gas. Then we assembled a coherent set of characterisation techniques around the Fischer-Tropsch catalyst to enable the structural study at different scales: the local order with the Quick-EXAFS and long-range order with the X-ray diffraction. To observe the effect on the catalytic properties of the crystalline form of the active phase, we quantified for the same catalyst its activity by Raman spectroscopy and mass spectrometry after activation by two different treatments Besides, simultaneous characterisation of two metal species, accessible by the QEXAFS setup installed on the SAMBA beamline, allowed an accurate description of the activation process of bimetallic catalysts for hydrodesulfurisation. We focused our study on the comparison of catalysts with the same formulation with different pretreatments (dried / calcined) and two catalysts promoted by different metals: cobalt and nickel.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-03-23T18:15:53Z No. of bitstreams: 1 JANAINA MOREIRA DE MENESES - TESE 2015..pdf: 4807859 bytes, checksum: 499be3377ee460a1f5d615e32d1310c9 (MD5) / Made available in DSpace on 2018-03-23T18:15:53Z (GMT). No. of bitstreams: 1 JANAINA MOREIRA DE MENESES - TESE 2015..pdf: 4807859 bytes, checksum: 499be3377ee460a1f5d615e32d1310c9 (MD5) Previous issue date: 2015 / Diante de uma demanda crescente por energia no mundo e o aumento da poluição atmosférica causada pelo uso de combustíveis fósseis, a busca por fontes de energia renováveis vem crescendo consideravelmente. O processo utilizado pelas usinas de biodiesel emprega catalisadores homogêneos básicos, que apesar de conduzir a elevados rendimentos requer óleos altamente refinados e necessita de etapas de purificação do produto final o que vem a contribuir para um alto custo de produção. Partindo desta premissa, busca-se desenvolver um catalisador heterogêneo de baixo custo que simplifique o processo de produção, que seja estável e forneça altas conversões em temperaturas brandas de reação. Desta forma, o presente trabalho teve como objetivo preparar catalisadores metálicos suportados em carvão ativado comercial e aplicá-los na produção de biodiesel metílico e etílico a partir do óleo de algodão degomado e neutralizado, avaliando a conversão em ésteres. Os catalisadores foram preparados pelo método de impregnação úmida na concentração de 5% em massa. Foram caracterizados pelas técnicas de DRX, FRX, IFTR, MEV, titulação de Boehm e análise textural. Testes preliminares identificaram que o catalisador molibdênio ofereceu os melhores resultados na reação simultânea de esterificação/transesterificação metílica e etílica, com conversão de 43 % e 40 % respectivamente. Uma vez selecionado o catalisador este foi aplicado em um planejamento fatorial 23 para verificar o efeito das variáveis: temperatura de reação (80-160 °C), razão molar óleo:álcool (1:6 a 1:12) e concentração de catalisador (1 a 3 %); sob a resposta teor de ésteres. Verificou-se que a temperatura foi a variável de maior influência e atua de forma positiva nas reações de éster/transesterificação, conduzindo a conversão de 91 % em teor de ésteres. A partir de análise das superfícies de resposta, verificou-se que as condições ótimas de operação que conduzem a uma maior conversão em ésteres seriam: temperatura de 160 °C, razão molar óleo:álcool de 1:13 e concentração de catalisador de 3,2 %. Os resultados do ensaio de reuso mostrou que o catalisador pode ser reutilizado de forma consecutiva atingindo bons resultados, observou-se um decaimento de apenas 7 % no teor de éster ao ser reutilizado no 3° ciclo. O acompanhamento cinético demonstrou que com 5 horas de reação nas melhores condições reacionais é possível alcançar um teor de éster de 96,3 %. / Faced with a growing demand for energy in the world and the increase of air pollution caused by the use of fóssil fuels, the search for renewable energy sources has grown considerably. The processused in biodiesel plants use basic homogeneous catalysts, although they lead to high yields, this requires highly refined oil sand purification steps of the final product which is contribute to a high production cost. Starting from this premise, we seek to develop a lowcost heterogeneous catalyst to simplify the production process, which could best able and provides high conversions under mild reaction temperatures. Thus, this study aimed to prepare metal catalysts supported on activated carbono and apply them in the production of methyl and ethyl biodiesel using degummed and neutralized cottonseed oil, in batch reactor with agitation, evaluating the conversion into esters. The catalysts were prepared by wet impregnation at a mass concentration of 5%. They were characterized by techniques of DRX, FRX, IFTR, MEV, Boehm tritation and textural analysis. Preliminary tests identified that the molybdenum catalyst offered the best results in the simultaneous reaction of methyl and ethyl ester/transesterification, with conversion of 43% and 40% respectively. Once selected the catalyst, this was applied to a 23 factorial design to determine the effect of variables: reaction temperature (80-160°C), molar ratio oil:alcohol (1:6 to 1:12) and catalyst concentration (1 to 3%); and the response variable was ester content. And it was found that the temperature variable was the greatest influence and acts positively on the ester/transesterification reactions, leading to 91% conversion in ester content. From analysis of response surfaces, it was found that the optimal operating conditions leading to a higher conversion to esters are: temperature 160°C oil molar ratio: 1:13 alcohol and catalyst concentration 3,2%. The results of the recycle showed that reuse of the catalyst can be reused consecutively achieving good results, there was a decay of only 7% in the ester content to be reused in the 3rd cycle. The kinetic monitoring demonstrated that 5 hours of reaction with the best reaction conditions it is possible to achieve a 97.3% ester content.

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-08-30T14:53:05Z No. of bitstreams: 1 ADRIANO SANT'ANA SILVA - PPGEP TESE 2011..pdf: 12696755 bytes, checksum: 3f702ca1b940a9bb7e2fc2feb1499709 (MD5) / Made available in DSpace on 2018-08-30T14:53:05Z (GMT). No. of bitstreams: 1 ADRIANO SANT'ANA SILVA - PPGEP TESE 2011..pdf: 12696755 bytes, checksum: 3f702ca1b940a9bb7e2fc2feb1499709 (MD5) Previous issue date: 2011-04 / Capes / 0 biodiesel é um biocombustível proveniente de fontes renováveis, tais como óleos vegetais e gordura animal, e que foi proposto como alternativa ao óleo diesel derivado do petróleo. Normalmente, este biocombustível é obtido a partir do óleo de soja, por meio da reação de transesterificação, a qual faz uso de catalisadores homogéneos alcalinos que ao término da reação não são reutilizados e ainda exigem matéria prima refinada e isenta de água. Diante disso, o uso de catalisadores heterogéneos tem-se consolidado cada vez mais no meio académico e industrial pela possibilidade do seu reuso e por permitir o uso de diferentes fontes lipídicas. Ademais, a busca por fontes lipídicas de menor custo, como óleo de algodão, e que não concorram com outros seguimentos industriais, como a indústria de alimentos, tornou-se foco atual de diversas pesquisas. Sendo assim, o objetivo desta tese foi sintetizar, caracterizar e avaliar os catalisadores suportados M0O3-MCM-41 e NiOMCM-41 nas reações de transesterificação e esterificação, etílica e metílica do óleo de algodão, usando sistema reacional estático. O suporte MCM-41 foi obtido pelo método de síntese a temperatura ambiente. Os catalisadores foram sintetizados pelo método de dispersão física em três concentrações distintas (1, 3 e 5% em massa) e foram caracterizados por DRX, FTIR, análise textural e EDX. Por meio de um planejamento fatorial 23 avaliou-se os efeitos das variáveis independentes: temperatura, razão molar de óleo: álcool e concentração de catalisador, sobre as variáveis dependentes éster e de triacilglicerídeo, na reação de transesterificação. Na reação de esterificação avaliou-se os efeitos destas variáveis sobre a conversão dos ácidos graxos livres em éster. Os resultados de caracterização indicaram que a fase hexagonal da MCM-41 foi obtida e que o procedimento de dispersão física dos óxidos foi viável para síntese dos catalisadores em estudo. Nos testes catalíticos o catalisador 5%Mo03-MCM-41 apresentou os melhores resultados para a transesterificação etílica e metílica; e esterificação metílica, com conversão de cerca de 53, 48,1 e 78,7%, respectivamente. Para a reação de esterificação etílica o catalisador 3%Mo03-MCM-41 apresentou o maior conversão, cerca de 67,9%. O catalisador NiO-MCM-41 não apresentou atividade catalítica nas reações estudadas. A temperatura, de acordo com o planejamento experimental foi a variável de maior influência nas reações de transesterificação e esterificação. As reações conduzidas em sistema estático foram viáveis para a obtenção do biodiesel / Biodiesel is a biofuel produced from renewable sources such as vegetable oils and animal fat, which was proposed as an alternative to petroleum diesel. Typically, this biofuel is made from soybean oil, by transesterification with alkaline homogeneous catalysts that at the end of the reaction are not reused and still require refined oil. Thus, the use of heterogeneous catalysts has been increasingly in industry by the possibility of its reuse and for allowing the use of different lipid sources. Furthermore, the search for low cost lipid sources, such as cottonseed oil, has become the current focus of several studies. Therefore, the objective of this thesis was to synthesize, characterize and evaluate the catalysts M0O3-MCM-41 and NiO-MCM-41 in ethyl and methyl, transesterification and esterification reactions of cottonseed oil, using a static reaction system. The support MCM-41 was obtained by synthesis at room temperature. The catalysts were synthesized by the method of physical dispersion in three different concentrations (1, 3 and 5% in weight) and were characterized by XRD, FTIR, EDX and textural analysis. Through a 23 factorial design the effects of independent variables: temperature, molar ratio of oil: the percentage of alcohol and catalyst on the dependent variables éster and triglycerides in the transesterification reaction, were evaluated. In the esterification reaction the effects of these variables on the conversion of free fat acid was evaluated. The characterization results indicated that the hexagonal phase of MCM-41 was obtained and the procedure of physical dispersion of the oxides was viable for the synthesis of the catalysts under study. In the catalytic tests the catalyst 5%Mo03-MCM-41 showed the best results for the methyl and ethyl transesterification and for methyl esterification, with conversion of about 53, 48.1 and 78.7%, respectively. For the reaction of ethyl esterification, the catalyst 3%MoC«3-MCM-41 showed the highest conversion, about 67.9%. The catalyst NiO-MCM-41 showed no catalytic activity. The temperature, according to the experimental design, was the variable that most influenced the reactions.

La réaction de décarboxylation de l’acide palmitique en n-pentadécane a été étudiée en réacteur discontinu en présence de catalyseurs bimétalliques de type Ni-Me (où Me=Fe, Cu ou Ag) supportés sur charbon actif. Ces catalyseurs ont été préparés à l’aide d’un robot haut débit disponible sur la plateforme REALCAT de l’UCCS par déposition-précipitation en utilisant l’hydrazine comme agent réducteur afin de mieux maitriser la taille des nanoparticules métalliques, leur distribution et leur degré de réduction. Ces derniers ont été caractérisés par ICP, adsorption d’azote, XPS, XRD et TEM afin d’obtenir des informations relatives à leurs compositions, leurs propriétés texturales, surfaciques et morphologiques. Dans cette étude, l’optimisation du procédé catalytique a également été étudiée pour divers paramètres de réaction pour les catalyseurs les plus prometteurs. D’une part, l’impact de l’ajout d’un second métal sur les performances des catalyseurs à base de nickel a été étudié, et, d’autre part, l’effet de la température, de la durée de réaction, des concentrations initiales en réactifs, de l’atmosphère réactionnelle et de la masse de catalyseur utilisée ont été investiguées. Dans ce contexte, le catalyseur bimétallique 10%Ni10%Cu/C convertit complètement l’acide palmitique avec une sélectivité de 95 % en n-pentadecane à 320 °C sous une atmosphère contenant 10% de H2 dans N2 et pour une pression initiale de 20 bar. La réaction s’est déroulée pendant 6 h. Ce catalyseur a présenté une excellente stabilité après trois tests de recyclage consécutifs / The catalytic decarboxylation of palmitic acid to n-pentadecane was studied in a batch reactor in the presence of bimetallic Ni-Me catalysts (where Me = Fe, Cu or Ag) supported on activated carbon. These catalysts were prepared using a high-throughput robot of the REALCAT platform of UCCS by deposition-precipitation using hydrazine as reducing agent. These catalysts were characterized by ICP, N2 adsorption, XPS, XRD and TEM in order to obtain information relative to their compositions, textural properties, surfaces and morphologies. In this study, the optimization of the catalytic process was also investigated for various reaction parameters for the most promising samples. The main studied parameters were, on the one hand, the impact of the addition of a second metal on the performance of the nickel-based catalysts and, on the other hand, the effect of temperature, reaction time, initial reactant concentrations, atmosphere and mass of catalyst used. The conclusion of this study is that the 10%Ni10%Cu/C completely converts palmitic acid with a selectivity of 95 % to n-pentadecane in 6 h, at 320 °C under 10% H2 in N2 at an initial pressure of 20 bar. This catalyst exhibited excellent recyclability after three consecutive tests

L'objectif de ce projet de thèse a été d’étudier l’activité catalytique de catalyseurs commerciaux contenant de nanoparticules métalliques pour l'hydrogénation du limonène. La réaction a été réalisée en l'absence de solvants et dans des conditions douces c’est à dire à basse température (30°C) et sous faible pression d'hydrogène (3 bar), conduisant à une production stable du (+)-p-1-menthene. Dans notre étude, les nanoparticules métalliques actives (Pt, Pd et Ru) et les supports (carbone, silice et alumine) ont été systématiquement modifiés et testés dans des conditions de réaction modérées (température ambiante, 3 bar H2). Notre étude a révélé une activité et sélectivité importante du catalyseur hétérogène Pt/C pour la réduction du R-(+)-limonène en (+)-p-1-menthène qui est le produit partiellement hydrogéné. Le Pt/C ainsi que Pt/Al2O3 est l’un des systèmes les plus actifs parmi les catalyseurs actuellement disponibles dans le commerce. De plus, l'activité catalytique et la stabilité de Pt/C ont été maintenues au cours des essais de recyclage en réacteur fermé. Ce catalyseur a également été utilisé en réacteur à flux continu, donnant des résultats prometteurs. L'hydrogénation sélective de la liaison C=C terminale du limonène par rapport de la liaison interne a été rationalisée par des études cinétiques détaillées qui révèlent une vitesse 8 fois plus importante par la double liaison terminale. Cette première étude nous a permis de développer la synthèse de nouveaux catalyseurs hétérogènes contenant diverses nanoparticules métalliques (Pt, Ru, Pt3Sn et Ni). Ils ont été préparés à partir d'une approche colloïdale et ont été testés dans l'hydrogénation de limonène. Ces catalyseurs contiennent la même charge métallique et des tailles de particules similaires (environ 2 nm) dispersées de façon homogène sur des oxydes non structurés (silice et d'alumine), du carbone, ou incorporés à l'intérieur des murs ou à la surface des pores de matériaux mésostructurés siliciques (SBA-15). L’ensemble des catalyseurs de la série du Pt ont révélés une activité accrue lors de l'hydrogénation sélective du limonène en p-menthène puis en p-menthane avec une vitesse de réaction très élevé. Parmi tous ces catalyseurs, celui contenant des nanoparticules de Pt dans les murs de la silice a montré au bout de deux heures de réaction un TOF d'environ 2200 h-1 et un rendement maximal pour le p-menthène d'environ 85% après 10 heures de réaction. Ce même catalyseur a été testé dans un réacteur en flux continu et affiche après 6 heures un rendement en p-menthene stable de 80%. Aucun produit d'isomérisation n’a été détecté dans le mélange brut au cours de la réaction. En conclusion, nous pouvons dire que l'utilisation d'un catalyseur hétérogène commercial comme le Pt/C ou l’utilisation d’un catalyseur hétérogène métallique développé à partir d'une approche colloïdale, Pt@SBA-15{murs}, permet d'obtenir une conversion sélective du limonène en p-menthène en réacteur fermé ainsi également en réacteur à flux continu. Des informations sur la cinétique de cette réaction ont également pu être obtenues / The goal of this PhD project was in an early stage to study the activities of several commercial metal nanoparticles based catalysts for the mild hydrogenation of limonene. The hydrogenation of limonene has been performed in neat limonene and under mild conditions, e.g. low temperature (30°C) and low molecular hydrogen pressure (3 bar), aiming at a sustainable production route for (+)-p-1-menthene. In our study, the active metal nanoparticles (Pt, Pd and Ru) and supports (carbon, silica and alumina) were systematically varied and tested. It was found that the heterogeneous catalyst Pt/C alongside Pt/Al2O3 under mild reaction conditions (room temperature and 3 bar H2) was highly active and selective in the reduction of R-(+)-limonene to the partial hydrogenation product (+)-p-1-menthene. Moreover, the catalytic activity and stability of Pt/C were maintained during recycling tests under batch conditions and thus allowed the implementation of this catalytic system into continuous flow operation. The selective hydrogenation of terminal C=C bond over the internal one in limonene was rationalized by detailed kinetic studies which revealed an 8-fold difference in reaction rate between the two reactions. This previous study with commercial catalysts gave the possibility to tune the synthesis of heterogeneous metal-based catalysts for the next step of the study, where different heterogeneous metal based catalysts (Pt, Ru, Pt3Sn, and Ni), developed from a colloidal-based approach were tested in the hydrogenation of limonene. Those catalysts contain the same metal loading and similar particle sizes (ca. 2 nm) homogeneously dispersed onto non structured oxides (silica and alumina), carbon, or embedded into the walls or at the pore surface of a mesostructured silica materials (SBA-15). All the catalysts from the Pt series were particularly active in the selective hydrogenation of limonene towards p-menthene with further conversion into p-menthane, showing a very high reaction rate. Among of all those catalysts, the one containing Pt nanoparticles embedded in the walls of the silica showed the highest TOF, of ca. 2200 h-1 after two hours of reaction and a maximum yield in p-menthene of ca. 85 % was obtained after 10 hours of reaction. The same catalyst was tested in a continuous flow system and a stable yield of ca. 80% during 6 hours of reaction was reached. No products of isomerization were detected in the crude mixture during the reaction. We could therefore conclude that, using either a heterogeneous commercial catalyst like Pt/C or using a heterogeneous metal based catalyst developed from a colloidal-based approach like SBA-15{walls}, it was possible to achieve a selective conversion of limonene into p-menthene in batch and in continuous flow conditions

L'objectif de cette thèse fut de développer un process pour la production d'acide peroxycarbolique à partir du peroxyde d'hydrogène et d'un acide carboxylique dans un réacteur continu. Dans un premier temps, la stabilité des espèces peroxydées fut étudiée en utilisant une méthode d'analyse en direct (spectromètre de masse). Un effort particulier a été apporté pour trouver un catalyseur hétérogène ne provoquant pas la décomposition des espèces peroxydées et ayant une activité catalytique similaire à l'acide sulfurique. Un réacteur en continu en lit fixe a été construit en utilisant des résines échangeuses de cation. / The purpose of this thesis was to find a way to produce peroxycarboxylic acid from hydrogen peroxide and carboylic acid in a continuous reactor by using heterogeneous catalysts. In the first step the stability of peroxyde species xas studied by using an online analytic method (Mass spectrometer). One of the main challenge was to find a suitable solid acid catalyst, wich does no decompose the peroxyde species and can catalyze the reaction as sulfuric acid. A continuous fixed bed reactor was built by using caion exchange resins as a catalyst.

The first-principles methods such as density functional theory (DFT) often produce quantitative predictions for physics and chemistry of materials with explicit descriptions of electron’s behavior. We were able to provide information of electronic structures with chemical doping and metal-insulator transition of rare-earth nickelates that cannot be easily accessible with experimental characterizations. Moreover, combining with mean-field microkinetic modeling, we utilized the DFT energetics to model water gas shift reactions catalyzed by Fe3O4at steady-state and determined favorable reaction mechanism. However, the high computational costs of DFT calculations make it impossible to investigate complex chemical processes with hundreds of elementary steps with more than thousands of atoms for realistic systems. The study of molecular high energy (HE) materials using the reactive force field (ReaxFF) has contributed to understand chemically induced detonation process with nanoscale defects as well as defect-free systems. However, the reduced accuracy of the force fields canalso lead to a different conclusion compared to DFT calculations and experimental results. Machine learning force field is a promising alternative to work with comparable simulation size and speed of ReaxFF while maintaining accuracy of DFT. In this respect, we developed a neural network reactive force field (NNRF) that was iteratively parameterized with DFT calculations to solve problems of ReaxFF. We built an efficient and accurate NNRF for complex decomposition reaction of HE materials such as high energy nitramine 1,3,5-Trinitroperhydro-1,3,5-triazine (RDX)and predicted consistent results for experimental findings. This work aims to demonstrate the approaches to clarify the reaction details of materials using the first-principles methods and machine learning force fields to guide quantitative predictions of complex chemical process.

<p>The strong metal support interaction (SMSI) is among the best-known classes of metal-oxide interfacial interactions in heterogeneous catalysis, which is defined by the coverage of surface oxide on metal nanoparticles, forming a metal-oxide interface. However, there is limited insight in the atomic scale understanding of the structure of the SMSI oxide. In this work, surface science techniques including scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS) and low energy electron diffraction (LEED) were employed to investigate interfacial interactions in multiple catalytic systems, including ZnO-Pd, ZnO-Pt, and MoOx-Pt. To utilize the capabilities of the surface science techniques and to mimic a catalytic metal nanoparticle in SMSI state, ultrathin oxide films were prepared on metal single crystals as inverse model catalysts.</p> <p>The structural and chemical transformations of ultrathin zinc (hydroxy)oxide films on Pd(111) were studied under varying gas phase conditions (UHV, 5×10−7 mbar of O2 and D2/O2 mixture). Under oxidative conditions, zinc oxide forms partially hydroxylated bilayer islands on Pd(111). Sequential treatments of the submonolayer ZnOxHy films in D2/O2 mixture (1:4) at 550 K evoked structural transformations from bilayer to monolayer and to a PdZn near-surface alloy, in accompany with the reduction of Zn, demonstrating that zinc oxide as a non-reducible oxide, can spread on metal surface and show an SMSI-like behavior in the presence of hydrogen. A mixed canonical – grand canonical phase diagram revealed that the monolayer intermediate structure is a metastable structure formed during the kinetic transformation, and the near-surface alloys are stable under the D2/O2 conditions. Grand canonical phase diagram predicted that under real SMSI conditions zinc oxide films on Pd nanoparticles would be stabilized by hydroxylation with stoichiometries such as ZnOH and Zn2O3H3. Based on the experimental and theoretical observations, we propose that the mechanism of metal nanoparticle encapsulation involves both surface (hydroxy)oxide formation as well as alloy formation, depending on the environmental conditions.</p> <p>Hydroxylation plays a more important role in the ZnO/Pt(111) system. Different from Pd(111), zinc oxide tends to form monolayer graphite-like ZnO films on Pt(111) under oxidative conditions at submonolayer coverages. This structure is extremely susceptible to hydroxylation at room temperature, leading to spontaneous formation of honeycomb-like Zn6O5H5 films in hydrogen. The interaction of the two distinct structures with Pt were investigated by XPS, STM, and HREELS with CO, C2H4, and NO as probe molecules. Zn exhibits a partially reduced oxidation state in Zn6O5H5 and donates negative charge to surface Pt in the confined rings, leading to a switch from linear CO adsorption to bridged CO adsorption in accompany with a 50 cm-1 shift of ν(CO) towards lower frequencies. C2H4 readily forms ethylidyne (*CCH3) species at room temperature once adsorbed on Pt(111), while the formation of ethylidyne is weakened on the Zn6O5H5/Pt(111) surface. In summary, this study demonstrated a unique metal-hydroxide interaction, which serves as a novel approach for the modification of metal catalysts.</p> <p>The partial coverage of metal surfaces by oxides could be utilized to passivate specific sites of catalysts, improving the activity and stability. Herein, we studied the structure of surface Mo oxides on Pt(111) and Pt(544) using STM, XPS, and HREELS. At 0.08 ML coverage, Mo oxide tends to form 1~2 nm clusters and the majority of Mo is in +5 oxidation state. The Mo oxide clusters tend to aggregate near the monoatomic Pt steps, showing a higher local density compared to the wide terraces. Therefore, our results provide experimental evidence for the site-selective growth of Mo oxides at step sites, which could prevent the leaching of active component in catalysts under real reaction conditions.</p> <p>Overall, through atomic-level characterization of inverse model catalysts, we provided insights into the nature of metal-oxide interactions in multiple systems. The surface oxide films influence the property of metal surfaces in various ways, including migration, alloy formation, electronic perturbation, geometric confinement, and site-selective blocking. These findings emphasize the necessity of understanding the real structure of catalytic surfaces under different reaction conditions and shed light on rational design of oxide supported metal nanoparticle catalysts.</p>