Dissertations / Theses on the topic 'Heterogeneous reactions'

Photochemical systems for the splitting of water into hydrogen and oxygen represent an attractive route for the conversion of solar energy into a chemical fuel. However, the success of such systems depends on the identification of suitable redox catalysts for the oxidation and reduction processes. While colloidal platinum has proved to be an efficient catalyst for the reduction of water, the development of stable and effective catalysts for water oxidation has been less successful. The work described in this thesis involves the study of ruthenium dioxide hydrate (RuO₂.xH₂)O as a heterogeneous catalyst for the oxidation of water to oxygen. Although this material has already been widely used as an oxygen catalyst, there have been many doubts as to its ability to act in this capacity. In Chapter Three an attempt is made to resolve this controversy via an investigation of the stability and catalytic activity of RuO₂.xH₂O when exposed to various oxidising agents. The results indicate that the catalytic activity and corrosion stability of an RuO₂.xH₂O sample is related to its degree of hydration. In Chapter Four an investigation is described into the effect of heat-treatment of RuO₂.xH₂O at different temperatures on its physical and chemical properties. From these results it appears that any sample of RuO₂xH₂O may be transformed into a stable, reproducible oxygen catalyst by simply heat-treating it at 140-150^oC in air for ca. 5 hours. The latter conditions represent an optimum for catalytic activity where anodic corrosion is absent. This 'thermally-activated' RuO₂.xH₂O is shown to compare favourably with alternative oxygen catalysts. Chapters Five and Six involve a kinetic study of the RuO₂.xH₂O-catalysed oxidation of water by Ce(IV) ions in an attempt to elucidate the mechanism of catalysis of the oxide powder. The study is based on an electrochemical model in which the RuO₂.xH₂O particles are considered as microelectrodes. The initial charging of the RuO₂.xH₂O prior to water oxidation is discussed in Chapter Five and in Chapter Six the effect of an increase in the redox potential of the Ce⁴⁺/Ce³⁺ couple by changing the acid medium is investigated.

This thesis summarizes studies which focus on addressing, using both theoretical and experimental methods, fundamental questions about surface phenomena, such as chemical reactions and bonding, related to processes in heterogeneous catalysis. The main focus is on the theoretical approach and this aspect of the results. The included articles are collected into three categories of which the first contains detailed studies of model systems in heterogeneous catalysis. For example, the trimerization of acetylene adsorbed on Cu(110) is measured using vibrational spectroscopy and modeled within the framework of Density Functional Theory (DFT) and quantitative agreement of the reaction barriers is obtained. In the second category, aspects of fuel cell catalysis are discussed. O2 dissociation is rate-limiting for the reduction of oxygen (ORR) under certain conditions and we find that adsorbate-adsorbate interactions are decisive when modeling this reaction step. Oxidation of Pt(111) (Pt is the electrocatalyst), which may alter the overall activity of the catalyst, is found to start via a PtO-like surface oxide while formation of α-PtO2 trilayers precedes bulk oxidation. When considering alternative catalyst materials for the ORR, their stability needs to be investigated in detail under realistic conditions. The Pt/Cu(111) skin alloy offers a promising candidate but segregation of Cu atoms to the surface is induced by O adsorption. This is confirmed by modeling oxygen x-ray emission (XES) and absorption spectra of the segregated system and near-perfect agreement with experiment is obtained when vibrational interference effects are included in the computed XES. The last category shows results from femtosecond laser measurements of processes involving CO on Ru(0001). Using free-electron x-ray laser experiments a precursor state to desorption is detected and also found in simulations if van der Waals effects are included. Resonant XES can be used to distinguish two different species of CO on the surface; vibrationally hot, chemisorbed CO and CO in the precursor state. Laser-induced CO oxidation on Ru(0001) is modeled and three competing mechanisms are found. Kinetic modeling reproduces the experiment qualitatively.

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 8: Manuscript.

The hydroxyl radical (OH), along with the closely coupled species the hydroperoxyl radical (HO2), have a profound effect on the concentration and distribution of most trace atmospheric species associated with climate change and poor air quality as they are essential to the daytime oxidizing capacity of the atmosphere. Tropospheric and mesospheric models that only consider gas-phase chemistry often over predict concentrations of HO2 indicating that heterogeneous reactions with aerosols could be a possible sink. In order to investigate the kinetics of such reactions, the HO2 uptake coefficient (γ(HO2), i.e. the probability that HO2 will collide and react within or on the surface of an aerosol) has been measured onto a variety of aerosols applicable to the troposphere, stratosphere and mesosphere using an aerosol flow tube experiment coupled to a highly sensitive HO2 detector, known as Fluorescence Assay by Gas Expansion (FAGE), and a Scanning Mobility Particle Sizer (SMPS). Deliquesced inorganic aerosols containing transition metal ions (TMI) have been shown to react rapidly with HO2. Measurements of γ(HO2) onto deliquesced inorganic aerosols doped with different concentrations of Cu(II), Fe(II), Mn(II), mixtures of Cu(II) and Fe(II) and I- are presented within this work. HO2 uptake onto deliquesced inorganic aerosols doped with transition metal ions may not be as significant as previously thought. The Thornton expression, used in global modelling studies of HO2 uptake, can predict γ(HO2) at a relative humidity (RH) of 65%, however at a RH of 43%, near the efflorescence point ((NH4)2SO4 = 37%), good agreement was only observed at higher concentrations of Cu(II) and Fe(II) (> 0.1 M) possibly indicating that HO2 solubility decreases as HO2 diffuses further into the bulk of the aerosol. It was expected that as deliquesced NaCl aerosols have a higher pH (7) that most HO2 accommodated within the aerosols will dissociated to the more reactive species O2-. This should result in high values of γ(HO2), however γ(HO2) onto Cu(II)-doped NaCl aerosols was measured to be lower than γ(HO2) onto Cu(II)-doped (NH4)2SO4 aerosols with a lower pH, possibly due to the formation of [Cu(Cl)4]2- complexes which are repelled into the bulk of the aerosol by enhanced concentrations of Cl- ions within the interfacial layer. Measurements of γ(HO2) onto Fe(II)-doped NaCl aerosols were relatively high and agreed with predictions made by the Thornton expression. When irradiated with UVA light, γ(HO2) onto Cu(II)-doped (NH4)2SO4 was lowered, however γ(HO2) onto Cu(II)-doped NaCl remained the same. When the effect of irradiating Fe(II)-doped (NH4)2SO4 aerosols on γ(HO2) was investigated, results indicated possible production of OH. Measurements of γ(HO2) onto mixed Cu(II) and Fe(II)-doped (NH4)2SO4 aerosols could not verify the Mao hypothesis that an electron transfer reaction occurs between Cu(I) and Fe(III) resulting in the conversion of HO2 to H2O, rather than H2O2. However, values of γ(HO2) did not simply equal the sum of γ(HO2) onto Cu or Fe-doped aerosols individually, indicating that the presence of both TMI in the aerosol does alter the chemistry of the aerosol in some way. Irradiation of Cu(II) and Fe(II)-doped aerosols resulted in an enhancement of γ(HO2), possibly indicating an alternative mechanism than that proposed by Mao, where HO2 is converted to H2O via a photochemical mechanism. The presence of I- within NaCl aerosols does not result in a change of γ(HO2), however when converted to I2 by reaction with Cu(II) an enhancement of γ(HO2) greater than when doped with Cu(II) alone was observed Measurements of γ(HO2) onto TiO2, a possible candidate aerosol for use within solar-radiation management (SRM) schemes, showed a positive dependence on Relative Humidity (RH) which correlated with the number of monolayers of water adsorbed onto the TiO2 nanoparticle. This dependence suggests a mechanism by which HO2 adsorbs to the surface of the TiO2 particle by forming complexes with water molecules bound to bridging OH groups. The TOMCAT chemical transport model was used by Professor Chipperfield to predict the possible effects of HO2 uptake (using an upper limit of γ(HO2) = 1) onto the surface of TiO2 nanoparticles on the stratospheric concentrations of HO2 and O3. The amount of TiO2 used was chosen to achieve a similar cooling to that following the Mt. Pinatubo eruption, but the model predicted a very small loss of both stratospheric HO2 and O3. Upon illumination of airborne TiO2 nanoparticles with UV light, significant quantities of HO2 was formed within the gas-phase, thought to be the first direct observations of radicals emitted from the surface of airborne particles. The reaction is dependent on the presence of gas-phase O2 and H2O within the system. The production of HO2 was shown to slow down as a function of time irradiated pointing towards a photochemical aging process occurring on the surface of the TiO2 particles. The dependence of HO2 production on O2 and H2O concentrations was determined, which shows a typical Langmuir adsorption saturation curve for O2 suggesting it is the gas-phase reactant in this process. The addition of H2O into the system inhibits the reaction and reduces the adsorption equilibrium coefficient for both species. Reduction of O2 by photogenerated electrons is likely to be the initial step in this process followed by reaction with a proton. Hydrogen extraction from hydroxyl bridging groups (OHbr) groups by O2- could explain the slow down observed in the rate of HO2 production. Production of gas-phase OH radicals was investigated and showed OH was produced only when large concentrations of TiO2 aerosols entered the aerosol flow tube, probably associated with the decomposition of H2O2 formed from reactive uptake. Although the production of HO2 by TiO2 aerosols initially would not be advantageous for its use within SRM schemes, the reaction ceases upon prolonged photocatalytic aging of the aerosol surface. Meteoric smoke particles (MSP) provide the only significant surfaces within the mesosphere for heterogeneous reactions to occur. To investigate whether such reactions could, in some part, be responsible for the ‘HOx Dilemma’ measurements of γ(HO2) onto analogues of MSP, forsterite, olivine and fayalite, were conducted at a RH of 10%. These experiments showed forsterite to have the lowest reactivity with HO2, similar to that of effloresced inorganic aerosols, and olivine and fayalite to have a similar reactivity that was more than an order of magnitude greater than that of forsterite, thus demonstrating that the presence of Fe within the MSP is required for significant reactivity with HO2. Electronic structure calculations, conducted by Professor Plane, predicts that the difference in reactivity is associated mechanistic and energetic differences between the binding of HO2 to Fe and Mg sites, however, the positive dependence of γ(HO2) with RH and similar values of γ(HO2) for olivine and fayalite suggests that OH bridging groups or complexing with water molecules adsorbed to such sites, as with TiO2 nanoparticles, are adsorption sites for HO2. Taking the measurements made in this work and the likely dependence of γ(HO2) on temperature and RH, a value of 0.2 for γ(HO2) was applied by Dr Sandy James in WACCM-CARMA. This modelling study predicted reductions in the HO2 volume mixing ratio of up to 40% in the polar vortex. Impact to HO2 budgets in the mesosphere was found to be dependent on latitude, giving agreement with the presence of MSPs in the polar night.

>Magister Scientiae - MSc
This study describes the synthesis and characterisation of coordination polymers complexes of Cu(II) and VO(IV) with two polymeric ligands N,Nʹ -1,2-phenylene bis(5-methylenesalicylidenamine)(L1) and N,Nʹ -1,4-butylene bis(5 methylenesalicylidenamine) (L2). Ligands L1 and L2 formed by condensation of 5,5ʹ-methylene bis-(salicylaldehyde) with 1,2-phenylenediamine and 1,4-diaminobutane respectively. The ligands and the complexes were characterized by UV/Vis spectroscopy, proton and carbon nuclear magnetic resonance spectroscopy (1H and 13C-NMR), Fourier transform infrared spectroscopy (FTIR), high resolution scanning electron microscopy (SEM) and thermogravimetric Analysis (TGA)

The major part of this thesis concerns the development of catalytic methodologies based on palladium nanoparticles immobilized on aminopropyl-functionalized siliceous mesocellular foam (Pd0-AmP-MCF). The catalytic activity of the precursor to the nanocatalyst, PdII-AmP-MCF is also covered by this work. In the first part the application of Pd0-AmP-MCF in Suzuki-Miyaura cross-coupling reactions and transfer hydrogenation of alkenes under microwave irradiation is described. Excellent reactivity was observed and a broad range of substrates were tolerated for both transformations. The Pd0-AmP-MCF exhibited high recyclability as well as low metal leaching in both cases. The aim of the second part was to evaluate the catalytic efficiency of the closely related PdII-AmP-MCF for cycloisomerization of various acetylenic acids. The catalyst was able to promote formation of lactones under mild conditions using catalyst loadings of 0.3 - 0.5 mol% at temperatures of up to 50 oC in the presence of Et3N. By adding 1,4-benzoquinone to the reaction, the catalyst could be recycled four times without any observable decrease in the activity. The selective arylation of indoles at the C-2 position using Pd-AmP-MCF and symmetric diaryliodonium salts is presented in the third part. These studies revealed that Pd0-AmP-MCF was more effective than PdII-AmP-MCF for this transformation. Variously substituted indoles as well as diaryliodonium salts were tolerated, giving arylated indoles in high yields within 15 h at 20 - 50 oC in H2O. Only very small amounts of Pd leaching were observed and in this case the catalyst exhibited moderate recyclability. The final part of the thesis describes the selective hydrogenation of the C=C in different α,β-unsaturated systems. The double bond was efficiently hydrogenated in high yields both under batch and continuous-flow conditions. High recyclability and low metal leaching were observed in both cases.

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Submitted. Paper 5: Submitted.

 

Heterogeneous palladium catalysts for use in Suzuki-type reactions have been prepared using the molecular imprinting technique. Using this technique allows the preparation of a heterogeneous catalyst with uniform active sites which have a metal complex configuration that favours processes in the catalytic cycle, thus enhancing the rate of reaction. It was reasoned, from the general catalytic cycle for palladium cross-couplings, that a bisphosphine complex with a cis ligand geometry would be beneficial. Polymerisable phosphines were synthesised and the cis bisphosphine palladium complexes prepared. The geometry of the complexes was fixed by addition of a bidentate ligand (catechol). The resulting complexes were incorporated into a macroporous polymer framework using the molecular imprinting technique. This produced the heterogeneous palladium catalysts with uniform active sites and known palladium content. The catalysts were ~ested in model Suzuki reactions and were shown to give far superior yields to the homogeneous catalyst and control heterogeneous catalyst (derived from commercial ligand). The favoured square-planar cis-geometry was likely to increase the rate of reductive elimination, which takes place from that conformation. It is also reasonable to imply that the catalytically active palladium(O) species would be strained, being tetrahedral not square-planar, and so the rate of oxidative addition (the slow step in some cases) could also be accelerated. The improved yields shown by the imprinted catalysts for the Suzuki reactions suggest that this is the case.

Des nouveaux catalyseurs bimétalliques à base de palladium et de cuivre ont été développés. Deux voies de préparation ont été testées : l'imprégnation successive (TSI) et la co-imprégnation (CI) en utilisant la zéolithe 4Å (4A) et l'oxyde mixte MgAlxOy comme support. Les catalyseurs ont été caractérisés à l'état frais et testés dans la réaction de couplage Suzuki–Miyaura afin de comparer leurs activités, sélectivités et stabilités. L'étude de stabilité nous a montré que le catalyseur Cu-Pd-4A-TSI restait actif pendant six cycles alors que l'activité du catalyseur Cu-Pd-4A-CI diminuait. Sur le support MgAlxOy, le catalyseur CI était stable pendant six cycles contrairement au catalyseur TSI. Nous avons montré que le point clé pour l'obtention d'une bonne activité et stabilité est la présence de la phase active correspondant à l'alliage Cu/Pd 1/1 identifiée grâce à la caractérisation des catalyseurs et ce quelle que soit la méthode de préparation des catalyseurs. Une différence cruciale existe entre les catalyseurs supportés sur MgAlxOy et 4A : le catalyseur Cu–Pd supporté sur MgAlxOy permet de réduire le temps de réaction de moitié pour une même conversion par rapport à Cu-Pd-4A-TSI. De plus, l'utilisation d'un support plus basique permet, dans une certaine mesure, la diminution de la quantité de la base ajoutée durant la réaction. La réaction Petasis-borono Mannich a été aussi effectuée avec succès sur ces catalyseurs
New bimetallic palladium/copper catalysts were developed by successive impregnation (TSI) and co-impregnation (CI) on 4Å molecular sieve (4A) and MgAlO mixed oxides supports. The fresh catalysts were characterised and tested in the Suzuki–Miyaura reaction to test their activity, selectivity and stability. It was observed that while the Cu-Pd-4A-TSI catalyst kept its activity during six cycles that of the Cu-Pd-4A-CI dropped. On MgAlO support the catalyst prepared with CI proved to be stable even for six runs contrary to TSI. The active phase of the reaction – namely the Cu–Pd alloy with atomic ratio 1:1 - was determined with the help of catalyst characterisation of the recovered catalysts. This observation confirms that whatever the way of preparation or the support is, the key-point is the presence of Pd-Cu 1:1 particles to enhance the catalytic performances. A crucial difference between the MgAlO and 4A supported catalyst was found in the reaction time necessary for the Suzuki–Miyaura reaction. With the Cu-Pd-MgAl-CI catalyst the reaction time could be reduced to thirty minutes contrary to one hour with Cu-Pd-4A-TSI. Moreover it was concluded that with a more basic support the reduction of the quantity of the base was possible however it brought slightly decreasing yield. The Petasis-borono Mannich reaction was also performed in the presence of each mono-and bimetallic catalysts

Copper is an inexpensive, earth-abundant, non-toxic metal that is found to have widespread applications in catalysis. Ullmann and Ullmann-type reactions and Glaser-Hay oxidative coupling of terminal alkynes are some of the well-established copper catalyzed coupling reactions used for the construction of important organic molecules, including pharmaceuticals, commodity chemicals and polymers. Those reactions have been mainly performed homogeneously, where the removal of residual copper from the reaction mixture is a challenge. Therefore, many researchers tried supporting copper precatalysts in order to help recover, and thus reduce final product contamination. Some studies showed that copper leached significantly from the support, with others showing that leached copper has a role in the catalysis. Nevertheless, many studies reported that the used supported catalysts were recyclable and claimed catalyst's heterogeneity. In most cases, the nature of the truly active copper species is still not clear. The objectives of this thesis were (1) to assess the heterogeneity/homogeneity of active copper species in popular catalytic C-N coupling reactions with already studied catalysts, mainly a copper exchanged zeolite and copper oxide nanoparticles, and (2) to use the collected information in designing a truly heterogeneous (stable and recyclable) catalyst. Initially, and because of its shape selectivity characteristics, copper-exchanged NaY zeolite, Cu(II)Y, was chosen to study the heterogeneity of copper catalyzed amination of aryl iodide with imidazole. The collected results from conducted shape selectivity tests indicated that Cu(II)Y might be heterogeneous catalyst, but because of the used base, that is crucial for this C-N coupling reaction, the crystallinity of the zeolite structure was diminished. Therefore, it was important to support copper on a framework that is stable under the basic conditions required for this type of reaction if a heterogeneous, recyclable catalyst were to be achieved. For this purpose, cerium oxide was chosen, and copper oxide supported on cerium oxide, CuO-CeO₂, was investigated as a potential heterogeneous catalyst for C-N coupling reaction. This investigation included the role of each reaction reagent in facilitating copper leaching into solution. It was found that copper leached from the support and it was demonstrated through hot filtration tests that the leached copper species was the main active catalyst. Leaching was caused by the solvent (DMSO) as well as the used reactants and the base. Similar conclusions were drawn when this CuO-CeO₂ catalyst was used for the direct synthesis of imines from amines under aerobic conditions. Although this CuO-CeO₂ catalyst has the advantages of being more recoverable and active than unsupported CuO nanoparticles at similar copper loadings, it is not fully recyclable, as the copper catalysis occurs in solution. These findings meant that designing a truly heterogeneous catalyst for this reaction is a challenging task. Understanding the effect of each individual factor of this complicated system might help in achieving the second goal - designing a truly heterogeneous catalyst. Therefore, further studies were carried out to understand the effect of reaction conditions, including temperature, base, support, and solvent, on copper leaching. Homocoupling of terminal alkynes was chosen as a model reaction for this study, and CuO was supported on TiO₂ (10CuO-TiO₂) and on γ-Al₂O₃ (10CuO-Al₂O₃). It was found that copper interaction with the support affects the extent of leaching as well as the nature and activity of leached species. High temperature also facilitates copper leaching especially when a ligating amine, like piperidine, is present in the system.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Nuclear Engineering, 2001.
Includes bibliographical references (p. 139-143).
The purpose of this work is to evaluate the potential for enhancing the performance of the once-through PWR fuel cycle by appropriate design of thorium containing fuel with concurrent consideration of neutronics, thermal-hydraulics, and proliferation resistance. CASMO-4 is employed to model a fuel assembly consisting of a homogeneously fueled ThO2-UO2 lattice of conventional design. It is found that homogeneously mixed ThO2-UO2 fuel in general has better physics behavior than all-UO2 fuel, e.g. more negative MTC and less reactivity swing. The H/HM ratio can be optimized to extend the burnup of both ThO2-UO2 and all-UO2 fuel about 10% and 5% respectively. However, it is found that the all-UO2 fuel provides higher potential energy generation (or achievable burnup) than the homogeneously mixed ThO2-UO2 fuel. MOCUP (MCNP+ORIGEN) is used to model unit cells of the micro-heterogeneous fuel. The key findings for the best micro-heterogeneous configurations are as follows: (1) For a given U-235 inventory, a 20% to 30% increase in fuel cycle achievable bumup above the homogeneous case is possible, therefore 10% to 15% above the all-UO2 fuel; (2) For certain axially heterogeneous configurations, a "burnable poison" reactivity suppression effect appears at the beginning of irradiation. Analysis of the possible mechanisms behind these effects shows that they are due to a combination of changes in self-shielding, local fissile worth, and conversion ratio.
(cont.) Economic evaluations show that the homogeneous ThO2-UO2 fuel is 20%-30% more expensive than the equivalent all-U fuel but micro-heterogeneous fuel can be comparable to or even cheaper than the all-UO2 fuel. In terms of the plutonium content, the micro-heterogeneous Th/U fuel is more proliferation-resistant than the homogeneous Th/U fuel, and the homogeneous Th/U fuel is more proliferation-resistant than the all-UO2 fuel. However, the uranium produced in the ThO2 zone of any undenatured micro-heterogeneous design should be considered of proliferative concern. Adding natural or depleted uranium to the ThO2 zone can make the material not weapon-usable at the expense of degrading the neutronic performance. Placing some enriched uranium within the thorium zone may be needed to reduce local thermal peaking to a manageable level.
by Xiaofeng Zhao.
Ph.D.

>Magister Scientiae - MSc
This study describes the synthesis and characterisation of Cu(II) and V(IV) complexes of tri- and quadridentate ligands L1 and L2 formed by condensation of ethylenediamine with acetylacetonate in 1:1 and 1:2 molar ratio, respectively. Encapsulation of these metal complexes in the nanocage of zoilite-Y generates new heterogeneous catalysts. These catalysts were synthesized employing the flexible ligand method encapsulation technique.The structures of these encapsulated complexes were established on the basis of various physico-chemical and spectroscopic studies. The results indicated that the complexes did not hinder or modify the framework or structure of the zeolite, confirming successful immobilization of Schiff-bases through the voids of zeolite Y.These encapsulated complexes were screened as heterogeneous catalysts for various oxidation reactions such as such as phenol, benzene, styrene and cyclohexene using a green oxidant (H2O2). For comparison, the corresponding neat complexes were screened as potential homogeneous catalysts for these oxidation reactions. The results proved that the corresponding homogeneous systems described here represent an efficient and inexpensive method for oxidation of phenol, benzene, styrene and cyclohexene, having advantages over heterogeneous catalysis are its high activity and selectivity and short reaction times. Its major problem is its industrial application regarding principally the separation of the catalyst from the products.The size of the substrate has a significant effect on the conversion by encapsulated complexes such as in styrene oxidation. Therefore, it was established that steric effects of the substrates play a critical role in the poor reactive nature of the encapsulated complexes.In general, the percentage conversion decreased upon encapsulation of complexes in zeolite Y. All catalysts studied proved to be potential catalysts for the various oxidation reactions.It has been shown in this study that encapsulation can effectively improve product selectivity but requires a longer reaction time in most cases for maximum activity. Furthermore, oxovanadium complexes were more reactive than copper-based catalysts in all oxidation reactions tested in this study.A reaction mechanism study revealed that the activity of the encapsulated and neat complexes occurs through either formation of peroxovanadium (V) or hydroperoxidecopper(II) intermediate species.The studies in this thesis, therefore, conclude that the Cu(II) and V(IV) complexes encapsulated in Y-zeolite are active heterogeneous catalysts for the selective oxidation of various substrates. Encapsulation of the metal complexes in the super cages (-cages) of the zeolite matrix has the advantages of solid heterogeneous catalysts of easy separation and handling, ruggedness, thermostability, reusability (regeneration of the deactivated catalysts) as well as share many advantageous features of homogeneous catalysts.

Magnetic field effects (MFE) on electrochemical systems have been of interest to researchers for the past 60 years. MFEs on mass transport, such as magnetohydrodynamics and magnetic field gradients effects are reported, but MFEs on electron transfer kinetics have been rarely investigated. Magnetic modification of electrodes enhances electron transfer kinetics under conditions of high concentrations and low physical diffusion conditions, as shown by Leddy and coworkers. Magnetic microparticles embedded in an ion exchange polymer (e.g., Nafion) applied to electrode surfaces. Rates of electron transfer reactions to diffusing redox probes and to adsorbates are markedly enhanced. This work reports MFEs on hydrogen evolution on illuminated p-Si; MFEs on hydrogen evolution on noncatalytic electrodes; a model for MFEs on homogeneous self-exchange reactions; and a convolution based voltammetric method for film modified electrodes. First, a MFE on the photoelectrochemical hydrogen evolution reaction (HER) at p-Si semiconductors is demonstrated. The HER is an adsorbate reaction. Magnetic modification reduces the energetic cost of the HER by 400 - 500 mV as compared to Nafion modified electrodes and by 1200 mV as compared to unmodified p-Si. Magnetically modified p-Si achieves 6.2 % energy conversion efficiency. Second, from HER on noncatalytic electrodes, the MFE on photoelectrochemical cells arises from improved heterogeneous electron transfer kinetics. On glassy carbon electrodes, magnetic modification improves heterogeneous electron transfer rate constant, k₀,for HER 80,000 fold. Third, self exchange reaction rates are investigated under magnetic modification for various temperatures, outersphere redox probes, and magnetic particles. Arrhenius analyses of the rate constants collected from the experiments show a 30 - 40 % decrease in activation energy at magnetically modified electrodes. A kinetic model is established based on transition state theory. The model includes pre-polarization and electron nuclear spin polarization steps and characterizes a majority of the experimental results. Lastly, a convolution technique for modified with uniform films electrodes is developed and coded in Matlab (mathematical software) for simple and straightforward analysis of Nafion modified electrodes.

Our society has a problem with the use of fossil fuels, due to the vast and exceeding emissions derived from human activities. Two ways could be consider to mitigate these harmful effects. On the one hand, the capture, activation, and conversion of these hazardous gases towards valuable compounds, and on the other hand, the substitution of fossil fuels for renewable energies. This thesis encompasses the study of two different green chemistry reactions to convert the most abundant greenhouse gas in Earth's atmosphere and the production of a new environmental friendly fuel, the hydrogen. In the current search for new catalysts, Transition Metal Carbides (TMCs) have arisen as an appealing alternative, because their exhibit broad and amazing physical and chemical properties and their low cost. In particular, titanium carbide (001) was proposed from experimental and theoretical points of view as active catalyst and support of small metal particles for CO2 hydrogenation to methanol and water gas shift reaction. However, given that titanium carbide is a cumbersome support to be used in applications due to the difficulty of obtaining nanoparticles on working conditions, we have carried out these reactions on cubic δ-MoC (001) and orthorhombic β-Mo2C (001) surfaces. The adsorption and activation of a CO2 molecule on cubic δ-MoC (001) and orthorhombic β-Mo2C (001) surfaces have been investigated by means of periodic density functional theory based calculations using the Perdew-Burke-Ernzerhof exchange-correlation functional showing that both surface are promising catalyst for CO2 conversion because they are able to activate and bend the CO2 molecule. The β- Mo2C (001) surface is able to dissociate the CO2 molecule easily, with a low energy barrier, whereas δ-MoC (001) surface activates CO2 but it does not promote its direct dissociation. Experiments accomplished by the group of Dr. Jose Rodriguez revealed that CO and methane are the main products of the CO2 hydrogenation using β-Mo2C (001) as catalyst, and the amount of methanol is lower. On the other hand, only CO and methanol are produced using δ-MoC (001). Experiments revealed that the deposition of small copper particles on the carbide surfaces increase drastically the catalysts' activity and selectivity, which was demonstrated by theoretical calculations. On β-Mo2C, the amount of CO and methanol increase whilst the amount of methane decrease, since copper blocks reactive sites on surface. This is a positive fact since copper avoid the excessive oxygen deposition, which deactivated the catalysts. On the other hand, the deposition of copper on δ-MoC (001) increases a lot the amount of CO and methanol. In summary, our combining DFT- experimental study proposed the Cu/δ-MoC as promising catalyst for CO2 hydrogenation due to its activity (the amount of products is superior than other TMCS, metals, and the model of commercial catalysts), selectivity (only CO and methanol are produced), and stability ( this catalysts is not deactivated by the oxygen deposition). The results obtained in the first part of the thesis were used to study the water gas shift reaction. Given that the excellent features, experiments proposed Au supported on δ-MoC (001) as catalysts. Our theoretical calculations demonstrated that clean δ-MoC (001) is not a good catalysts for WGS, due to the fact that the reverse reactions are favorable respect the direct ones, which implies that the amount of products is lower. Nevertheless, the deposition of Au clusters change the reaction mechanism, favoring the direct barriers instead of reverse ones, and increasing the amount of produced H2. In summary, this thesis has displayed the prominent role of molybdenum carbides as support of small metal particles to catalyze green chemistry reactions.
En aquesta tesi es mostra un treball computacional sobre l'ús de catalitzadors econòmics per a la conversió de CO2, un perillós gas d'efecte hivernacle i també per a la producció d'hidrogen, el combustible del futur. En la recerca actual de nous catalitzadors, els carburs de metalls de transició (TMC) han sorgit com una alternativa atractiva pel el seu baix cost i per exhibir excel·lents propietats físiques i químiques. En aquest treball utilitzarem com a catalitzadors les superfícies cúbica δ-MoC (001) i ortoròmbica β-Mo2C (001). L'adsorció de la molècula de CO2 mostra que ambdues superfícies són capaces d'activar i doblegar la molècula. La superfície β-Mo2C (001) és capaç de dissociar fàcilment la molècula de CO2, mentre que la superfície δ-MoC (001) activa CO2 però no la dissocia. Els experiments realitzats pel grup del Dr. Jose Rodriguez van revelar que el CO i el metà són els principals productes de la hidrogenació de CO2 utilitzant β-Mo2C (001) com a catalitzador, i la quantitat de metanol és menor. D'altra banda, només es produeixen CO i metanol utilitzant δ-MoC (001). La deposició de partícules de coure a les superfícies del carbur augmenta dràsticament l'activitat dels catalitzadors, cosa que es va demostrar mitjançant càlculs teòrics. A la superfície β-Mo2C, la quantitat de CO i metanol augmenten mentre que la quantitat de metà disminueix. D'altra banda, la deposició de coure a δ-MoC (001) augmenta molt la quantitat de CO i metanol. En resum, el nostre estudi proposa el Cu/δ-MoC com a prometedor catalitzador de la hidrogenació de CO2 a causa de la seva activitat (la quantitat de productes és superior a la resta de TMCS, metalls i el model de catalitzadors comercials), selectivitat (només el CO i el metanol es produeixen) i l'estabilitat (aquests catalitzadors no es desactiven per la deposició d'oxigen). Tenint en compte els resultats previs, es va proposar la deposició d'or en la superfície δ-MoC per a la producció d'hidrogen. Els càlculs teòrics demostren que la superfície δ-MoC (001) no és un bon catalitzador per WGS, però la deposició dels clústers d'or canvia el mecanisme de reacció i augmenta la quantitat d'H2 produïda.

Ion exchanged zeolites, ion exchanged clays, sulphated zirconia and silica supported phosphotungstic acid were prepared. Characterisation of the catalysts using pyridine adsorption revealed the catalysts contained both Brønsted and Lewis acid sites. When the catalytic activities for the acylation of toluene and anisole were studied there was found to be a correlation between the Brønsted acidity and the catalytic activity. The reactivity of the catalysts is dependant upon both the concentration and the chain length of the carboxylic acid. An optimum chain length being in the range Cm-C12. An aromatic:carboxylic molar ratio of 30: I was demonstrated to be preferable to either 300:1 or 3:1. The activation energies for the acylation of toluene were determined to be in the range 165-359 ki mol' and those for anisole 67-196 kJ mor 1 . Microwave experiments were performed in both batch and flow reactors. Under both reactor configurations microwave stimulation gave consistent increases in catalyst activity. Attempts were made to correlate this with the material dielectric properties, unfortunately, no correlation was found. Under the high E-field conditions Of the single mode (flow reactor) only the zeolites proved to be sufficiently robust as to provide any meaningful data. These catalysts displayed an increased selectivity to the ortho-isomer which was maximised when hexanoic acid was used as the acylating agent. The selectivity to the ortho-isomer increased with increasing microwave power.

The first examples of gold as the catalyst of choice were the hydrochlorination of acetylene using gold on carbon catalysts and the oxidation of carbon monoxide, both identified around 20 years ago. From that time most research interest has been focused on the use of gold as a catalyst for oxidation reactions, whereas although gold can be an excellent electrophilic agent is some of its oxidation states, few studies are available which display this. Chlorinated organic compounds are widely manufactured in industry for the production of chemicals that can be used as solvents, glues, anaesthetics, and precursor for plastics. However, the usual industrial conditions applied make use of high pressure and temperature. By focusing attention on the production of commodities like vinyl chloride monomer, and chloroethane we have seen that these kinds of products can be obtained under mild conditions when gold is used as a catalyst, and with high selectivity. Moreover, a tuneable effect can be obtained using different supports, or gold oxidation states. Although gold as a catalyst for the hydrochlorination of acetylene is known, no literature is available on the effect of adding another metal, either as a bimetallic or an alloy system, on final activity. For this reason, the effect of adding metals such as Pd, Pt, Ru, Rh, It has been investigated. Gold alone gives the most stable performance. However, when Au/Pd is used an initial promotional effect is observed. Although this effect is not a long term effect, it has been possible to detect an influence of the gold oxidation state and to identify clearly the gold oxidation state responsible for the hydrochlorination of acetylene and the mechanism of catalyst deactivation. Using carbon as a support, only carbon-carbon triple bonds are reacted and ethylene is unreactive. For this reason selectivity to vinyl chloride monomer in excess of 99% is achieved. This particular behaviour has been explained by postulating the formation of a C2H2/AU/HCI complex, and this hypothesis is supported by the use of deuterated reagents and molecular modelling investigations.

This thesis investigated new metal nanoparticle and semiconductor catalyst and photocatalyst systems for achieving fine chemical synthesis from both fossil-fuel sourced reactants and biomass carbohydrate-derived reactants. Photocatalysts for industrially important organic oxidation reactions were developed that efficiently worked with the aid of solar light irradiation, at low temperature and pressure, that avoided the use of hazardous chemicals. The effects on the organic reaction mechanisms of different noble metal nanoparticle and metal oxide nanostructures were explored for these chemical transformations. Success in developing the nanomaterial photocatalysts has contributed to the field of sustainable green chemical synthesis.

Heterogeneous catalysis is an important branch in catalysis, in which the catalyst and reactants are in different physical phases. In this thesis, we have carried out extensive first-principles calculations to explore the selected heterogeneous reactions catalyzed by the noble-metal nanoparticles. The major results of the thesis fall into two categories: (1) the discovery of the scaling relations for predicting the catalytic activity of nanoparticles; (2) the computational characterization of the catalytic activity and mechanism for specific catalytic reactions. For the first category, we have made efforts to develop the scaling relations for binary noble-metal nanoparticles. The obtained results show that the scaling relation not only holds at the nanoscale, but can also be unified with those obtained for the extended surfaces. Our findings shed new light for the efficient screening of nanoparticles with superior catalytic properties. The second part of the thesis summarizes our studies on different catalytic systems. One of the focuses is to study the catalytic properties of the single Pd-doped Cu55 nanoparticle toward H2 dissociation and propane dehydrogenation. The possible reaction mechanisms and effects of the single and multiple Pd doping on the catalytic activity have been extensively examined. Our calculations reveal that single-Pd-doped Cu55 cluster bears good balance between the maximum use of the noble metal and the high activity, and it may serve as a promising single-atom catalyst. We have also systematically studied the reduction process of graphene fluoride catalyzed by the Pt-coated metallic tip under different atmospheres, aiming to provide a feasible strategy for scanning probe lithography to fabricate electronic circuits at the nanoscale on graphene fluoride. It is found that the tip-induced reduction of graphene fluoride with assistance of pure hydrogen atmosphere is facile despite the release of hazard hydride fluoride. The ethylene molecule is predicted to be an excellent acceptor for fluoride abstraction from graphene fluoride, but the corresponding defluorination cycle can not be recycled. Our calculations have finally revealed that under the mixture hydrogen and ethylene atmosphere, the Pt-coated tip can effectively and sequentially reduce graphene fluoride with the release of relatively harmless reduction product, fluoroethane. The proposed cyclic reduction strategy is energetically highly favorable and is ready to be employed in experiments. Our theoretical studies provide yet another convincing example to demonstrate the power of the density functional theory for studying the nano-catalysis. It should also been mentioned that the present calculations are restricted to relatively small-sized clusters due to the limited computational resources. It is highly desirable to further study complicated interfacial systems and to provide a full picture of heterogeneous catalysis with the aid of ab initio molecular dynamics simulations in the future.

QC 20150211

[ES] Se han preparado varios materiales metal orgánicos de circonio MOF-808 para evaluar sus propiedades catalíticas en reacciones tipo Meerwein-Ponndorf-Verley (MPV) para la reducción de compuestos carbonílicos. En particular, se han sintetizado compuestos tipo MOF-808 modificados en los que una pequeña fracción de los ligandos trimesato presentes en el MOF original se ha reemplazado por ligandos dicarboxilato, como una estrategia para inducir la creación controlada de defectos estructurales. Los ligandos utilizados han sido: isoftalato (MOF-808-IPA), 3,5-piridindicarboxilato (MOF-808-Pydc), 5- aminoisoftalato (MOF-808-NH2) y 5-hidroxiisoftalato (MOF-808-OH). Todos los materiales obtenidos presentan una elevada cristalinidad y son isoreticulares respecto al MOF-808 original. Se ha evaluado la actividad catalítica del MOF-808 original y de los materiales modificados en reacciones tipo MPV, utilizando ciclohexanona como compuesto modelo. Todos los materiales presentan una elevada actividad catalítica, superior a la del tereftalato de circonio UiO-66 utilizado como referencia. Esta mayor actividad catalítica se corresponde a un mayor número de iones Zr4+ con insaturación coordinativa presentes en el MOF-808 con respecto al UiO-66. Además, los materiales MOF-808-IPA y MOF-808-Pydc presentan una mayor actividad que el MOF-808 original, lo que se debe a la presencia de centros activos menos congestionados estéricamente debido a la introducción de los ligandos dicarboxilato. Una ventaja adicional de compuestos MOF-808 con respecto al UiO-66 es su sistema de poros más grande, lo que permite la conversión de moléculas de mayor tamaño. Para evaluar esta característica, se ha utilizado un compuesto de gran tamaño, la estrona, capaz de penetrar en los poros del MOF-808 pero no en el UiO-66. En consecuencia, el MOF-808 es capaz de convertir por completo la estrona de forma selectiva a estradiol, mientras que el UiO-66 apenas presenta actividad. Además, cuando se usa el MOF-808 como catalizador, se produce una cantidad considerable del isómero 17alfa-estradiol, difícil de obtener por otros medios, por lo que las propiedades de diastereoselectividad del MOF-808 en reacciones MPV resultan de gran interés preparativo. Con el fin de estudiar en mayor detalle la diastereoselectividad de reacciones MPV catalizadas por MOF-808, se ha estudiado la reducción de ciclohexanonas substituidas: 3-metilciclohexanona (3MeCH), 2-metilciclohexanona (2MeCH) y 2-fenil-ciclohexanona (2PhCH). En función del alcohol utilizado como reductor y de la posición del grupo substituyente en la ciclohexanona, el MOF-808 favorece selectivamente la formación de uno u otro isómero, con una diastereoselectividad variable: 82%, 61% y 94%, respectivamente para 3MeCH, 2MeCH y 2PhCH. Es posible racionalizar estos resultados considerando la formación preferencial de uno u otro estado de transición en el espacio confinado disponible dentro de los poros del MOF. Las características energéticas del proceso se han analizado mediante el uso combinado de estudios cinéticos y cálculos teóricos. Finalmente, en vista las interesantes propiedades del MOF-808 como catalizador para reacciones MPV, se ha extendido con éxito el uso de este material a la preparación de compuestos hidroxiesteroides de difícil obtención y de interés farmacológico mediante la reducción quimio-, regioy diastereoselectiva del correspondiente oxoesteroide. De esta forma, se han conseguido obtener en un solo paso de reacción y con una elevada selectividad los siguientes compuestos: 17alfa-estradiol, 5alfa- androstan-3beta,17alfa-diol y epitestosterona, lo que demuestra el potencial del MOF-808 como catalizador para la síntesis de compuestos de alto valor añadido.
[CAT] S'han preparat varis materials metall orgànics de zirconi MOF-808 per avaluar les seves propietats catalítiques en reaccions tipus Meerwein-Ponndorf-Verley (MPV) per a la reducció de composts carbonílics. En particular, s'han sintetitzat composts tipus MOF-808 modificats en els que una petita fracció dels lligands trimesat presents en el MOF original s'han reemplaçat per lligands dicarboxilats, com una estratègia per induir la creació controlada de defectes estructurals. Els lligands utilitzats han sigut: isoftalat (MOF-808-IPA), 3,5-piridindicarboxilat (MOF-808-Pydc), 5-aminoisoftlatat (MOF-808- NH2) i 5-hidroxiisoftalat (MOF-808-OH). Tots els materials preparats presenten una elevada cristal·linitat i són isoreticular respecte al MOF-808 original. S'ha avaluat l'activitat catalític del MOF-808 original i dels materials modificats en reaccions tipus MPV, utilitzant ciclohexanona com a compost model. Tots els materials presenten una elevada activitat catalítica, superior a la del tereftalat de zirconi UiO-66 utilitzat com a referència. Aquesta major activitat catalítica es correspon a un major nombre d'ions Zr4+ amb insaturació coordinativa presents en el MOF-808 respecte a l'UiO-66. A més, els materials MOF-808-IPA i MOF-808-Pydc presenten una major activitat que el MOF-808 original, el que és debut a la presència de centres actius menys congestionats estèricament debut a la introducció dels lligands dicarboxilat. Un avantatge addicional dels MOF-808 respecte a l'UiO-66 és el seu sistema de porus més gran, que permet la conversió de molècules de major tamany. Per avaluar aquesta característica, s'ha utilitzat un compost de gran taman, l'estrona, capaç de penetrar en els porus del MOF-808 però no en els de l'UiO-66. En conseqüència, el MOF-808 és capaç de convertir completament l'estrona de forma sel·lectiva a l'estradiol, mentre que l'UiO-66 gairebé no presenta activitat catalítica. A més, quan s'usa el MOF- 808 com a catalitzador, es produeix una quantitat considerable de l'isòmer 17alfa-estradiol, difícil d'obtenir per altre medis, de manera que les propietats de diastereoselectivitat del MOF-808 en reaccions MPV resulten de gran interès preparatiu. Per tal d'estudiar en major detall la diastereoselectivitat de reaccions MPV catalitzades per MOF-808, s'ha estudiat la reducció de ciclohexanones substituïdes: 3-metilciclohexanona (3MeCH), 2- metilciclohexanona (2MeCH) i 2-fenil-ciclohexanona (2PhCH). En funció de l'alcohol usat com a reductor i de la posició del grup substituent en la ciclohexanona, el MOF-808 afavoreix selectivament la formació d'un o de l'altre isòmer, amb una diastereoselectivitat variable: 82%, 61% y 94%, respectivament per a 3MeCH, 2MeCH y 2PhCH. És possible racionalitzar aquest resultats considerant la formació preferent d'un o l'altre estat de transició en l'espai confinat disponible dins dels porus del MOF. Les característiques energètiques del procés s'han analitzat mitjançant l'ús combinat d'estudis cinètics i càlculs teòrics. Finalment, en vista de les interessants propietats del MOF-808 com a catalitzador per a reaccions MPV, s'ha estès amb èxit l'ús d'aquest material a la preparació de composts hidroxiesteroids de difícil obtenció i d'interès farmacològic mitjançant la reducció quimio-, regio- i diastereoselectiva del corresponent oxoesteroid. D'aquesta manera, s'ha aconseguit obtenir en un únic pas de reacció i amb una elevada selectivitat els següents composts: 17alfa-estradiol, 5alfa-androstan-3beta,17alfa-diol i epitestosterona, el que demostra el potencial del MOF-808 com a catalitzador per a la síntesi de composts d'alt valor afegit.
[EN] Various zirconium-containing MOF-808 compounds have been prepared as potential catalysts for the Meerwein-Ponndorf-Verley (MPV) reduction of carbonyl compounds. Modified MOF-808 have been synthethized in which a small fraction of the trimesate ligands present in pristine MOF-808 has been replaced by dicarboxylate ligands, as a strategy to induce a controlled creation of defects. The linkers used are: isophthalate (MOF-808-IPA), 3,5-pyridinedicarboxylate (MOF-808-Pydc), 5-aminoisophthalate (MOF-808-NH2) and 5-hydroxyisophthalate (MOF-808-OH). All these compounds are highly crystalline and isoreticular with pristine MOF-808. The catalytic activity of pristine and defect engineered MOF-808 has been evaluated for MPV reactions, using cyclohexanone as model substrate. All the materials show a higher catalytic activity than that of zirconium terephthalate UiO-66 used as reference. This higher activity is attributed to the higher amount of coordinatively unsaturated Zr4+ ions in MOF-808 than in UiO-66. Moreover, MOF- 808-IPA and MOF-808-Pydc are more active than pristine MOF-808, which is due to the creation of less sterically crowded sites due to the introduction of defective dicarboyxlate linkers. A further advantage of MOF-808 over UiO-66 is the presence of a wider pore system, which allows converting bulkier substrates. To evaluate this characteristic, a bulky ketone has been used; estrone, which can enter the pores of MOF-808 but not those of UiO-66. Accordingly, MOF-808 can fully convert estrone selectively to estradiol, while UiO-66 shows barely any catalytic activity. Interestingly, when MOF- 808 is used as catalysts, a noticeable amount of the isomer 17alpha-estradiol is produced, which is difficult to obtain by other means. Therefore, the diastereoselective properties of MOF-808 for MPV reactions are interesting from the preparative point of view. In order to investigate in more detail the diastereoselective properties of MOF-808 for MPV reactions, various substituted cyclohexanones have been considered: 3-methylcyclohexanone (3MeCH), 2- methylcyclohexanone (2MeCH) and 2-phenylcyclohexanone (2PhCH). Depending on the alcohol used as reducing agent and the position of the substituent in the cyclohexanone molecule, MOF-808 selectively favors the formation of one isomer or the other with a different diastereoselectivity: 82%, 61% and 94%, respectively for 3MeCH, 2MeCH y 2PhCH. These results can be rationalized by considering the preferential formation of a given transition state in the confined space available inside the MOF pores. The energetic characteristics of the process have been analyzed by a combined use of kinetic studies and theoretical calculations. Finally, in view of the interesting properties of MOF-808 as catalyst for MPV reactions, this material has been successfully applied to the preparation of a number of challenging hydroxysteroid compounds with pharmacologic interest through a chemo-, regio- and diastereoselective reduction of the corresponding oxosteroid. In this way, it has been possible to prepare in one single reaction step the following compounds: 17alpha-estradiol, 5alpha-androstan-3beta,17alpha-diol and epitestosterone. This demonstrates the high potential of MOF-808 as a catalysts for the synthesis of high added value compounds.
I want to thank the European Union’s Horizon 2020 research and innovation program for a contract under the Marie Sklodowska-Curie grant agreement No. 641887 (Project acronym: DEFNET).
Mautschke, H. (2019). Zirconium Metal Organic Frameworks as Heterogeneous Catalysts for Meerwein-Ponndorf-Verley Reactions [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/130203
TESIS

Dans le contexte de la valorisation de la biomasse par catalyse hétérogène, la chimie théorique est essentielle pour guider la détermination de la nature des sites actifs en combinaison avec des caractérisations expérimentales. Ensuite, le mécanisme de réaction peut être étudié pour déterminer l’état de transition et intermédiaire déterminant la vitesse et ensuite concevoir de meilleurs catalyseurs in silico. Nous avons mis en œuvre cette approche dans plusieurs réactions impliquant des alcools qui jouent un rôle clé dans le passage du pétrole à la biomasse comme source de matière première pour les produits chimiques de commodités ou spécialités. Tout d'abord, nous nous sommes concentrés sur l'oxydation des alcools en phase liquide par l'oxygène, une réaction qui nécessite généralement un environnement alcalin, ce qui nuit à l'économie d’atomes du processus car il génère le sel carboxylate au lieu de l'acide carboxylique. Nous avons proposé un modèle d'interface métal / eau basique incluant l'adsorption d'anion hydroxyde. Cet anion charge la surface métallique et modifie son activité catalytique. Ce modèle a tout d’abord été validé en comparant l’activité prédite de Au et de Pt en présence et en l’absence de base, puis a été utilisé pour étudier l’oxydation d’éthoxylates d’alcool par des bimétalliques. Ensuite, nous sommes passés à la déshydratation en phase gazeuse d’alcools en C3 et C4 en utilisant des catalyseurs à base de phosphate. La modélisation des surfaces s’est basée sur des caractérisations expérimentales. La couverture moléculaire de l'eau à la surface en fonction de la pression et de la température a été établie à l'aide de la thermodynamique ab initio. Les simulations de spectres infrarouges d'adsorption de CO, NH3 et C2H2 nous ont permis d'identifier les sites acido-basiques qui jouent un rôle important dans l'investigation du mécanisme de réaction qui a suivi
In the context of biomass valorization by heterogeneous catalysis, computational chemistry is key to provide guidance to establish the nature of the active sites in combination with experimental characterizations. Then, the reaction mechanism can be studied to determine the rate determining transition state and intermediate and further design in silico better catalysts. We implemented this approach in several reactions involving alcohols that are key in the shift from a petroleum chemical feedstock to a biomass-based feedstock. Firstly, we focused on liquid phase alcohol oxidation by oxygen, a reaction that generally requires an alkaline environment, which is detrimental to the atom economy of the process since it generates the carboxylate salt instead of the carboxylic acid. We proposed a model of metal/basic water interface that includes the adsorption of hydroxide anion. It charges the metallic surface and modifies its catalytic activity. This model was first validated comparing the predicted activity of Au and Pt in presence and in absence of a base, and then used oxidation of alcohol ethoxylates by bimetals. Then, we switched to gas phase dehydration of C3 and C4 alcohols using phosphate-based catalysts. The modeling of the surfaces was based on experimental characterizations. The molecular coverage of water on the surface in function of the pressure and temperature was established using ab initio thermodynamic. The simulations of infrared spectra of CO, NH3 and C2H2 adsorption allowed us to identify the acido-basic sites which play an important role in the reaction mechanism investigation that followed

In this thesis, a new aerosol module is developed for the STEM model (the Sulfur Transport and dEposition Model) to better understand the chemical aging of dust during long range transport and assess the impact of heterogeneous reactions on tropospheric chemistry. The new aerosol module is verified and first applied in a box model, and then coupled into the 3-Dimentional STEM model. In the new aerosol model, a non-equilibrium (dynamic or kinetic) approach to treat gas-to-particular conversion is employed to replace the equilibrium method in STEM model. Meanwhile, a new numerical method solving the aerosol dynamics equation is introduced into the dynamic aerosol model for its improved computational efficiency and high accuracy. Compared with the equilibrium method, the new dynamic approach is found to provide better results on predicating the different hygroscopicity and chemical aging patterns as a function of size. The current modeling study also takes advantage of new findings from laboratory experiments about heterogeneous reactions on mineral oxides and dust particles, in order to consider the complexity of surface chemistry (such as surface saturation, coating and relative humidity). Modeling results show that the impacts of mineralogy and relative humidity on heterogeneous reactions are significant and should be considered in atmospheric chemistry modeling with first priority. Finally, the upgraded 3-D STEM model is utilized to explore the observations from the Intercontinental Chemical Transport Experiment - Phase B (INTEX-B). The new dynamic approach for gas-to-particular conversion and RH-dependent heterogeneous uptake of HNO3 improve the model performance in term of aerosol predictions under different conditions. It is shown that these improvements change the modeled nitrate and sulfate concentrations, but also modify their size distributions significantly.

Thesis (Master)--İzmir Institute of Technology, İzmir, 2006.
Keywords:Suzuki reactions, palladium, NaYzeolite, heterogeneous catalyst, C-C coupling. Includes bibliographical references (leaves. 71-81).

Atmospheric heterogeneous reaction could modify the physical properties and chemical composition of aerosol particles, thereby affecting their roles in climate, air pollution, and human health. The current knowledge of heterogeneous reactions between nighttime gas-phase oxidants and organic aerosols is very limited. The goal of this thesis was to contribute to the understanding of such reactions, particularly to the kinetics of NO₃ and N₂O₅ reactions with a variety of organic substrates and mixtures that can serve as proxies for aerosol particles. In the first series of studies, we investigated the reactive uptake of NO₃ with binary organic mixtures of an unsaturated organic (methyl oleate) and saturated molecules as “matrix molecules”. For liquid mixtures, the uptake coefficients (γ) of the matrices were significantly increased with the addition of small amounts of methyl oleate. The increase can vary by a factor of 5 depending on the type of matrix used. For solid-liquid mixtures, the uptake coefficient decreased by a factor of 10 after exposure to NO₃ for 90 minutes. For all liquid mixtures, the atmospheric lifetime was estimated on the order of a few minutes (with an upper limit of 35 mins), whereas, for liquid-solid mixtures, a lower limit to the lifetime was estimated to be 1-2 hours. In the second series of studies, we investigated NO₃ uptake on solid tridecanal and the uptake on liquid binary mixtures containing tridecanal and saturated organics as matrices. Uptake on the solid tridecanal was shown to be efficient, with γ = (1.6 ± 0.8) ×10–². For liquid binary mixtures, the uptake coefficient also depended on the matrix molecule. The atmospheric lifetime of aldehydes was estimated to range from 1.9–7.5 h due to NO₃ oxidation. In the third series of studies, we investigated the N₂O₅ uptake kinetics on alcohols. The uptake coefficients of N₂O₅ for five different alcohols at 293 K varied by 2 orders of magnitude, ranging from 3×10–⁴ to 1.8×10–². The atmospheric lifetime of alcohols was calculated to range from 0.6–130 h, depending on the physical and chemical properties of the organic liquid.

We systematically studied the preparation method of magnesium oxide as cheap heterogeneous basic catalysts, and found a very simple method to obtain MgO with high surface area and high catalytic activity. Furthermore, the structure of MgO was characterized using many techniques, such as BET, TGA, XRD and SEM. The relationship of catalytic activity and structure of MgO has been investigated in detail. At last, the obtained MgO was used in the liquid phase reactions, including Meerwein-Pondorf-Verley reaction, Michael addition, Knoevenagel condensation, transesterification of vegetable oil to biodiesel and synthesis of P-Keto 1,3-dithianes. The prepared magnesium oxide catalyst was used in the liquid phase Meerwein-Pondorf-Verley reaction of benzaldehyde with alcohol. Effect of preparation method on the catalytic activity and structure of MgO has been investigated in detail. The experimental result showed that the optimal calcination temperature was 450 °C. Lithium supported magnesium oxide was also studied. Magnesium oxide obtained using a novel but simple procedure was systematically investigated as a heterogeneous base catalyst for the Michael addition and Knoevenagel condensation. The activity of MgO was studied in detail, together with the effects of solvent and of substrate on the catalytic activity for each type of reaction. A key finding is that the formation of enols affected the activity of MgO. The preparation method and activity of MgO was determined and compared with CaO. MgO was used for the first time as a heterogeneous basic catalyst to synthesis P-keto-1,3-dithianes from conjugated ynones and ynoates. It was found that MgO is an active catalyst with activity better than or comparable with previously identified homogeneous or heterogeneous catalysts for this reaction. The effect of preparation methods on the activity of MgO is described. Transesterification of vegetable oil to biodiesel with MgO as catalyst was studied at 60 °C and 200 °C, respectively. Effect of methanol-to-oil molar ratio, catalyst loading, reaction temperature and calcination temperature was investigated. 90% yield can be obtained at 60 °C for 3h, and 80% at 200 °C for 15min. The results showed that the prepared MgO was active for the synthesis of biodiesel.

Heterogeneous catalysis is a key industrial process involved in the synthesis of nearly all chemicals currently produced. The environmental impact of these processes is huge so improvements must be made to current catalysts. Should a new material provide better yields at lower energy cost the benefits to both the industry and the planet are significant. There are many ways to change the behaviour of a catalyst, the addition of dopants, the selective blocking of active sites, and changing the strength of the support interaction to name a few. One technique that has become increasingly investigated is interstitial modification, the insertion of a light element into a metal lattice to change the metal's catalytic properties. The work presented in this thesis devises greener synthetic routes to the known Pd-^interstitialB/C catalyst and investigates potential routes to a novel interstitial material, Pd-^interstitialLi/C. Initially, successful verification of interstitial modification comes from the characteristic increase in palladium lattice parameter from 3.89 to 4.00 Å and the blocking of the β-hydride formation. Initial catalytic screening determines the synthetic route which yields the most active catalyst which subsequently undergoes thorough characterisation. The wealth of evidence generated confirms the interstitial location of lithium within the palladium lattice, as well as adding to the current understanding of the Pd-^interstitialB/C material. EELS analysis on Pd-^interstitialB is the closest to direct observation of boron within the palladium lattice to date. PDF on Pd-^interstitialLi shows 13.7 % of the palladium octahedral interstitial sites are occupied by lithium. This is the first report of interstitial lithium within palladium to date. The effect of the interstitial modification on catalytic hydrogenation by two elements that have opposite effects on the surface electronics of the host palladium gives intriguing results. The effect on catalysis varies depending on the conditions investigated. This bank of hydrogenation data allows an informed choice as to which interstitial material would be best suited to the gas or liquid phase catalytic hydrogenation under investigation.

The aim of this thesis work was the synthesis, characterization and application of new catalysts to be used in reactions as hydrogenation, Heck reaction, Friedel-Crafts acylations, etc., in homogeneous or heterogeneous and/or in biphase systems. These reactions were applied first on model substrates and then for the synthesis of target pharmaceuticals and for fine chemicals intermediate. In particular it was studied the hydrogenation of carbon-carbon double bonds catalyzed by: 1) new heterogeneous catalysts with a low content of precious metal (Pd 0.28%, Rh 0.18%) on alumina: these catalysts were very easily prepared in a new greener solvent and showed a very high activity and selectivity; 2) Rhodium and Palladium catalysts, with suitable ligands (in particular polysaccharides and lactic acid derivatives), able to operate in both aqueous biphasic or homogeneous system. Heck reactions were carried out in homogeneous system by using palladium based catalysts in the presence or absence of suitable phosphino ligands; Friedel-Crafts acylations of heterocyclic compounds were studied by using different metal catalysts, in particular new iron and gallium polymeric fluorosulphonate, easily prepared by a convenient protocol. Most of these reactions were applied for the synthesis of the two target pharmaceuticals, the calcimimetic Cinacalcet and the antimigrane Eletriptan. Finally, some reactions for the synthesis of Cinacalcet were carried out under microwaves conditions in order to reduce the catalyst amount, the reaction time and to increase the chemical yield. Moreover, these reactions were carried out in more environmentally friendly solvents as Me-THF, CPME and -valerolactone. When possible the activity of these new catalysts was compared to that of commercially available catalyst and in some cases they showed better performances with respect to largely applied industrial catalysts, appearing so suitable for a possible commercial development.