Thèses : « Metal supported nanoparticle »

1

Hermans, S. « Mixed-metal clusters as precursors for bimetallic supported nanoparticle catalysts ». Thesis, University of Cambridge, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.603977.

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This thesis describes in a first part the synthesis of new mixed-metal clusters of ruthenium in association with palladium, platinum and tin. The use of monometallic dichloro complexes of Pd or Pt in reactions with negatively charged penta- or hexaruthenium clusters in the presence of a chlorine scavenger has been moderately successful in the case of Pd, but highly successful in the case of Pt. High yields were obtained in many instances. The mixed clusters [Ru₅C(CO)₁₄Pt(COD)], [Ru₆C(CO)₁₆Pt(COD)], [Ru₆C(CO)₁₅(Pt(COD))₂] and [{Ru₆C(CO)₁₆}₂Pt(MeCN)₂] were characterised by X-ray crystallography. On the other hand, the use of [Pt(PPh₃)₄] allowed the isolation and structure determination of [Ru₆C(CO)₁₆PPh₃] rather than mixed species. The reactivity of [Ru₅C(CO)₁₄Pt(COD)] and [Ru₆C(CO)₁₆Pt(COD)] with CO, PPh₃ and dppm was investigated, and led to the isolation of other mixed-metal and homometallic compounds. The crystal structures of the clusters [Ru₅C(CO)₁₁Pt(CO)(dppm)₂], [Ru₆C(CO)₁₃(dppm)₂] and [Ru₆C(CO)₁₆Pt₃(dppm)₂] were determined. Several Ru-Sn mixed clusters were also synthesised, and in particular reactions involving [PPN]₂[Ru₆C(CO)₁₆] and SnCl₄ led to the isolation of [PPN][Ru₆C(CO)₁₆SnCl₃] and [Ru₆C(CO)₁₆SnCl₂], which were characterised crystallographically. In a second part, some of the new mixed-metal clusters were used as precursors for nanoparticle heterogeneous catalysts, using the mesoporous silica MCM-41 or carbon nanotubes as supports. A Ru-Pd/MCM-41 catalyst derived from a Pd₆Ru₆ cluster was shown to be extremely active for the hydrogenation of alkenes to alkanes and of naphthalene to cis-decalin selectively. This material was characterised by STEM and in situ FTIR and EXAFS, which confirmed the bimetallic nature of the nanoparticles and their homogeneous small sizes and dispersion on the support. The shape of the nanoparticles was further assessed by theoretical calculations. A Ru-Sn/MCM-41 catalyst was prepared from [PPN][Ru₆C(CO)₁₆SnCl₃] and shown to hydrogenate selectively cyclic poly-enes to their mono-enes, under solvent-free and low temperature conditions. This catalyst was also characterised by STEM and in situ FTIR and EXAFS, which indicated that the tin atom is the anchoring point for the bimetallic nanoparticles on the siliceous walls of MCM-41. Finally, the clusters [Ru₅C(CO)₁₄Pt(COD)], [Ru₆C(CO)₁₆Pt(COD)], [PPN][Ru₆C(CO)₁₆SnCl₃] and [Ru₆C(CO)₁₆SnCl₂] were used as ideal precursors for small-sized and evenly dispersed bimetallic nanoparticles supported on carbon nanotubes.

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Kwon, Beatsam. « Catalytic reduction of organic pollutants using supported metal nanoparticles ». Master's thesis, Alma Mater Studiorum - Università di Bologna, 2021. http://amslaurea.unibo.it/23190/.

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Metal nanoparticle catalysts have in the last decades been extensively researched for their enhanced performance compared to their bulk counterpart. Properties of nanoparticles can be controlled by modifying their size and shape as well as adding a support and stabilizing agent. In this study, preformed colloidal gold nanoparticles supported on activated carbon were tested on the reduction of 4-nitrophenol by NaBH4, a model reaction for evaluating catalytic activity of metal nanoparticles and one with high significance in the remediation of industrial wastewaters. Methods of wastewater remediation are reviewed, with case studies from literature on two major reactions, ozonation and reduction, displaying the synergistic effects observed with bimetallic and trimetallic catalysts, as well as the effects of differences in metal and support. Several methods of preparation of nanoparticles are discussed, in particular, the sol immobilization technique, which was used to prepare the supported nanoparticles in this study. Different characterization techniques used in this study to evaluate the materials and spectroscopic techniques to analyze catalytic activities of the catalyst are reviewed: ultraviolet-visible (UV-Vis) spectroscopy, dynamic light scattering (DLS) analysis, X-ray diffraction (XRD) analysis and transmission electron microscopy (TEM) imaging. Optimization of catalytic parameters was carried out through modifications in the reaction setup. The effects of the molar ratio of reactants, stirring, type and amount of stabilizing agent are explored. Another important factor of an effective catalyst is its reusability and long-term stability, which was examined with suggestions for further studies. Lastly, a biochar support was newly tested for its potential as a replacement for activated carbon.

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Martelli, Francesca. « Supported metal nanoparticles for sustainable green catalytic processes ». Master's thesis, Alma Mater Studiorum - Università di Bologna, 2020. http://amslaurea.unibo.it/20699/.

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Preformed Au nanoparticles supported on activated carbon and TiO2 were synthesised by sol-immobilisation. Polyethylene glycol, polyvinyl pyrrolidone and polyvinyl alcohol were used as stabilisers for the gold nanoparticles at different polymer/Au wt/wt ratios for each polymer. The effect of polymer/Au wt/wt ratios was investigated on (i) the average nanoparticle size, (ii) catalytic activity for two reactions, 4-nitrophenol reduction and glucose oxidation to glucaric acid. 4-nitrophenol reduction is recognised as a model reaction for nanomaterial catalytic activity tests; glucose oxidation to glucaric acid is a reaction that is traditionally carried out with concentrated nitric acid, for which alternative reaction pathways are looked for in an effort to reduce its environmental impact. The catalysts were characterised from the nanoparticle synthesis by colloidal method by means of UV-vis spectroscopy and DLS analysis, to the immobilisation step by XRD and TEM. The effect of the polymer:Au wt/wt ratio on nanoparticle size depends on the polymer nature, and point out the need to optimise supported nanoparticle synthesis protocols in the future depending on the type of stabiliser. The catalytic tests revealed that the polymers interact with Au nanoparticles through different active sites. Activated carbon (AC) and TiO2 were compared as supports for Au nanoparticles stabilised by PVA at PVA/Au 0,65 wt/wt. AC-supported Au NPs were the most active for glucose oxidation while TiO2-stabilised Au NPs were five times more active in 4-nitrophenol reduction that AC-supported NPs. Hence support and stabiliser are important parameters that should be optimised in order to achieve high catalytic activity for a given reaction.

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Crites, Charles-Oneil. « Investigating the Interactions between Free Radicals and Supported Noble Metal Nanoparticles in Oxidation Reactions ». Thesis, Université d'Ottawa / University of Ottawa, 2015. http://hdl.handle.net/10393/33404.

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This thesis studies the interaction between free radical species and supported noble metal nanoparticles (silver and gold) in the context of oxidation reactions. The peroxidation of cumene is the first reaction to be discussed and the difference in peroxidation product distribution using silver nanoparticles (AgNP) versus gold nanoparticles (AuNP) is examined. Specifically, cumyl alcohol is obtained as the major product obtained when using supported AuNP, whereas cumene hydroperoxide is favoured for AgNP. Such variations in product distribution are partially explained by the differences in the nanoparticle Fenton activity, where the TiO2 support was proposed to enhance such activity due to possible electron shuttling capabilities with the nanoparticle surface. Use of hydrotalcite as a support was found to minimize this characteristic, due to its insulator properties. The stability of hydroperoxide was tested in the presence of various others supports (activated carbon, Al2O3, ZnO, SiO2 and clays) with little success, with hydroperoxide exhibiting stability in the presence of HT. Using an oxygen uptake apparatus, the interaction of the cumyl peroxyl radical with the AuNP surface was demonstrated. Furthermore, this interaction promotes decomposition leading to the corresponding alkoxyl radical and subsequent hydrogen abstraction to form the observed cumyl alcohol product. The radical interaction with supported nanoparticles, and its reversibility appear different for gold and silver and accounts for a large part of the product distribution differences observed between AuNP and AgNP, as illustrated below. The peroxidation of ethylbenzene and propylbenzene was studied and revealed the participation of a reactive surface oxygen species due to the decomposition of peroxyl radicals on the nanoparticle surface. The reactive oxygen species was found to be transient in nature in the case of AuNP . Furthermore, this surface species was found to be an important participant in hydrogen abstraction leading to peroxide product formation. Finally, supported nanoparticle catalyzed tetralin peroxidation was investigated to determine the influence of temperature on the peroxidation product distribution and how changes in the reaction temperature can effect the radical-nanoparticle surface interactions.

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Celik, Caglar. « Carbon Supported And Surfactant Stabilized Metal Nanoparticle Catalysts For Direct Methanol Fuel Cells ». Master's thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/12606368/index.pdf.

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ABSTRACT CARBON SUPPORTED AND SURFACTANT STABILIZED METAL NANOPARTICLE CATALYSTS FOR DIRECT METHANOL FUEL CELLS Ç
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aglar M.S., Department of Chemistry Supervisor: Assoc. Prof. Dr. Gü
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August 2005, 72 pages Carbon supported surfactant, such as 1-decanethiol and octadecanethiol, stabilized platinum and platinum/ruthenium species have been prepared recently. In this thesis, for the first time, 1-hexanethiol has been used as an organic stabilizer for the preparation of carbon supported platinum and platinum/ruthenium nanoparticle catalysts. These new catalysts were employed for methanol oxidation reaction, which were used for direct methanol fuel cells. Cyclic voltammetry, X-ray photoelectron spectroscopy and transmission electron microscopy have been used in order to determine the nature of the catalysts. The effect of temperature and time on catalytic activity of catalysts were examined and the maximum catalytic activity was observed for carbon supported 1-hexanethiol stabilized platinum nanoparticle catalyst (with 1:1 thiol/platinum molar ratio) which was heated up at 200oC for 5 hours. The particle size of platinum nanoparticles was determined to be ~ 10 nm in diameter. The size and distribution of metal nanoparticles on carbon support, the Pt/Ru surface composition, the relative amount of Pt(0), Pt(II) and Pt(IV) and the removal of organic surfactant molecules around the metal nanoparticles were found to be important in determining the catalytic activity of electrodes towards methanol oxidation reaction. A significant decrease in catalytic activity was observed for carbon supported 1-hexanethiol stabilized Pt75Ru25 and Pt97Ru3 (with 1:1 thiol/PtRu molar ratio) with respect to carbon supported 1-hexanethiol stabilized Pt (with 1:1 thiol/platinum molar ratio). This result might be due to unremoved stabilizer shell around platinum/ruthenium nanoparticles and increase in amount of Pt(II) and Pt(IV) compared to Pt(0) where the methanol oxidation occured.

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Bruzas, Ian R. « Biocompatible noble metal nanoparticle substrates for bioanalytical and biophysical analysis of protein and lipids ». University of Cincinnati / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1553250462519941.

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Ngandjong, Alain Cabrel. « Modélisation structurale des clusters d’alliages supportés : effet du support de silice et effet de taille ». Thesis, Orléans, 2015. http://www.theses.fr/2015ORLE2070/document.

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Les simulations numériques ont négligé jusqu’ici l’influence du support de silice amorphe sur la structure des nanoparticules métalliques déposées car l’interaction métal-silice amorphe est faible. Toutefois les études expérimentales montrent un effet de troncature sur la structure des nanoparticules. L’idée de ce travail a donc été d’étudier l’influence de ce support sur la structure et la morphologie des nanoparticules d’argent au moyen de la modélisation moléculaire (Monte Carlo et dynamique moléculaire). L’objectif de ce travail a été tout d'abord de déterminer le potentiel interatomique permettant de décrire l’interaction argent-silice. Ce potentiel a été obtenu sur la base des données expérimentales d'angles de mouillages en phase liquide et en phase solide. D’autre part, l'intensité d'interaction argent-silice a été déterminée par calculs DFT sur la cristobalite qui est un polymorphe de la silice cristalline présentant la même densité que la silice amorphe. Les énergies d'adhésions obtenues ont ainsi permis d'ajuster les paramètres du potentiel argent-silice de type Lennard-Jones. L’étude de la stabilité structurale des nanoparticules d'argent supportées à température nulle a été effectuée pour trois degrés d'approximation du support. (1) : un support parfaitement lisse décrit par un puits carré dont la profondeur est reliée à l’énergie d’adhésion, (2) : un support atomique de silice amorphe de surface plane et (3) : un support atomique de silice amorphe présentant une rugosité de surface. L’influence de la température sur la structure a été étudiée par fusion et recristallisation des nanoparticules d’argent sur les deux supports de silice amorphe. Afin d’étudier la stabilité structurale des nanoparticules en température, le calcul d’énergie libre des nanoparticules a été abordé
Numerical simulations have so far neglected the influence of amorphous silica substrate on the structure of metallic nanoparticles due to its relatively weak interaction with deposited nanoparticles. However, experimental studies have often shown a truncation effect on the structure of nanoparticles. The idea of this work was to study the influence of this substrate on the structure of silver nanoparticles using molecular modeling (Monte Carlo and molecular dynamics). The objective of this work was firstly to determine silver-silica interatomic potential. This was achieved using experimental data of wetting angles in solid and liquid phase. On the other hand, silver-silica interaction intensity was determined by DFT calculations on cristobalite which is a polymorph of crystalline silica having the same density as amorphous silica. The adhesions energies obtained were used to fit the Lennard-Jones parameters for the silver-silica interaction. The study of the structural stability of silver nanoparticles supported at zero temperature was performed for three levels of approximation of the support. (1): the smooth wall approximation where the support is described by a square-well whose depth is related to the adhesion energy of the nanoparticle, (2): an atomistic model of flat amorphous silica, (3): an atomistic model of rough amorphous silica. The influence of the temperature on the structure was investigated by melting and recrystallization of the silver nanoparticles deposited on the two silica supports. In order to study the temperature stability of the nanoparticles the free energy calculation of the nanoparticles was discussed

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Udumula, Venkata Reddy. « Synthesis, RNA Binding and Antibacterial Studies of 2-DOS Mimetics AND Development of Polymer Supported Nanoparticle Catalysts for Nitroarene and Azide Reduction ». BYU ScholarsArchive, 2015. https://scholarsarchive.byu.edu/etd/6031.

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Project I 2-Deoxystreptamine (2-DOS), the most conserved central scaffold of aminoglycosides, is known to specifically recognize the 5'-GU-'3 sequence step through highly conserved hydrogen bonds and electrostatic interactions within and without the context of aminoglycosides (Figure 1a). We proposed that a novel monomeric unnatural amino acid building block using 2-DOS as a template would allow us to develop RNA binding molecules with higher affinity and selectivity than those currently available. Conjugating two or more of the monomeric building blocks by an amide bond would introduce extra hydrogen bonding donors and acceptors that are absent in natural aminoglycosides and increase specificity of binding to a target RNA through a network of hydrogen bonds. In addition, the amide conjugation between the monomeric building blocks places two GU-base recognizing amines at 5 Å… distance, which is equal to the distance of neighboring base stacks in dsRNAs We hypothesized that targeting dsRNAs containing multiple consecutive 5'-GU-'3 sequence steps would become possible by connecting two or more of the monomeric building blocks by amide bonds. According to the proposed hypothesis, we designed three dimeric 2-DOS compounds connected by an amide bond. These three targets include the dimeric 2-DOS substrate connected by an amide bond, the dimeric 2-DOS containing the sugar moiety from Neamine, and a dimeric 2-DOS connected by a urea linker. These compounds were then tested for sequence specific binding against 8 different RNA strands, and for antibacterial activity against E. coli, actinobacter baumannii and klebsiella. Project II A dual optimization approach was used for to enhance the catalytic activity and chemoselectivity for nitro reduction. In this approach the composition of the nanoparticles and electronics effects of the polymer were studied towards nitro reduction. Bimetallic Ruthenium-Cobalt nanoparticles showed exceptional catalytic activity and chemoselectivity compared to monometallic Ruthenium nanoparticles. The electronic effects of the polymer also had a significant effect on the catalytic activity of the bimetallic nanoparticles. The electron-deficient poly(4-trifluoromethylstyrene) supported bimetallic nanoparticles undergo nitro reduction in 20 minutes at room temperature, whereas electron-rich poly(4-methylstyrene) and poly(4-methoxystyrene) supported bimetallic nanoparticles to longer reaction times to go to completion. Electronics of the polymers also effects the change in mechanism of nitroreduction. Polystyrene bimetallic Ruthenium-Cobalt nanoparticles showed excellent yields and chemoselectivity towards nitro functional group in the presence of easily reducible functional groups like alkenes, alkynes, allyl ethers, propargyl ethers. Monometallic ruthenium nanoparticles also showed excellent reactivity and chemoselectivity towards azide reduction in the presence of easily reducible functional groups. Interestingly monometallic ruthenium nanoparticles showed regioselective reduction of primary azides in the presence of secondary and benzylic azides, also aromatic azides can be selectively reduced in the presence of secondary azides. These polystyrene supported nanoparticles are heterogeneous and are easily separated from the reaction mixture and reused multiple times without significant of catalytic activity.

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杨纯臻 et Chunzhen Yang. « Metal/metal oxide nanoparticles supported on nanostructured carbons for electrochemical applications ». Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2013. http://hdl.handle.net/10722/193414.

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Among various electrochemical devices that have been developed for energy storage and conversion, electric double layer capacitors (EDLCs) and direct methanol fuel cells (DMFC) have received much research attention. Nanostructured carbon materials have been playing an important role in the development of these devices, due to such characteristics as good electrical conductivity, high chemical stability, high surface area and large pore volumes and etc. In an EDLC, nanostructured carbon electrodes, possessing pores of varied length scales, can deliver electric energy at high current loadings. This kind of pore structure also benefits the deposition of metal catalysts and the transport of reactants and products in the methanol oxidation reaction. In order to systematically study the structural effects on the electrochemical capacitance and ionic transport, a series of three-dimensional hierarchical carbons with hollow core-mesoporous shell (HCMS) structure were template-synthesized. Periodically ordered macroscopic hollow cores of 330 nm in diameter were surrounded by a mesoporous shell containing uniform pores of 3.9 nm. The shell thickness was stepwise increased from 0, 25, 50 to 100 nm. The HCMS structure was modeled by a 5-level transmission line model to study the capacitance contribution from the pores at different length scale. Results revealed that the HCMS carbon with thicker mesoporous shells can provide high capacitance, while thinner shells could deliver high power output. A series of HCMS carbon sphere supported Pt nanoparticles were synthesized via the “Carbonization over Protected and Dispersed Metal” (CPDM) method. Contrary to the conventional “polyol” synthetic method, whereas most of Pt nanoparticles were deposited on the external surface of carbon spheres; the Pt nanoparticles synthesized via the CPDM method were found encapsulated in the mesoporous carbon shells and highly dispersed throughout the carbon texture. „Accelerated stress tests‟ (ASTs) were conducted to investigate the nanopores confinement effect toward the electrochemical stability of these Pt catalysts. Results revealed that (1) the nanopores confined Pt nanoparticles on HCMS carbon spheres exhibited a stable electrochemical active surface area (ECSA) and catalytic activity; and (2) thick mesoporous carbon shells could provide better protection over the Pt nanoparticles. This “CPDM” method was further extended to synthesize highly alloyed PtRu nanoparticles supported electrocatalysts. It is expected that this CPDM method can also be applied to synthesize other metal/metal oxide supported catalysts with stable electrochemical performance. WO3 has been demonstrated as a promsing co-catalyst for Pt in the methanol oxidation reaction (MOR). The synthesis of Pt-WO3/C catalyst with well-controlled nanoparticle size (2.5 nm) and composition was achieved via a microwave-assisted water-oil microemulsion reaction. Hydrogen adsorption, CO-stripping and Cu- stripping methods were used to estimate the ECSA of Pt in the Pt-WO3/C catalysts. Among these, Cu-stripping method was relatively more reliable due to the overlapping involvement of the WO3 component in the other methods. The methanol oxidation measurement shows that a 1:1 Pt:W ratio catalyst exhibits the highest Pt-mass current density of 271 mA mg-1-Pt, 1.4 times higher than that of commercial E-TEK catalyst.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy

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Bocelli, Ludovica. « Catalytic decomposition of formic acid using supported metal nanoparticles ». Master's thesis, Alma Mater Studiorum - Università di Bologna, 2016. http://amslaurea.unibo.it/11929/.

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Upgrade of hydrogen to valuable fuel is a central topic in modern research due to its high availability and low price. For the difficulties in hydrogen storage, different pathways are still under investigation. A promising way is in the liquid-phase chemical hydrogen storage materials, because they can lead to greener transformation processes with the on line development of hydrogen for fuel cells. The aim of my work was the optimization of catalysts for the decomposition of formic acid made by sol immobilisation method (a typical colloidal method). Formic acid was selected because of the following features: it is a versatile renewable reagent for green synthesis studies. The first aim of my research was the synthesis and optimisation of Pd nanoparticles by sol-immobilisation to achieve better catalytic performances and investigate the effect of particle size, oxidation state, role of stabiliser and nature of the support. Palladium was chosen because it is a well-known active metal for the catalytic decomposition of formic acid. Noble metal nanoparticles of palladium were immobilized on carbon charcoal and on titania. In the second part the catalytic performance of the “homemade” catalyst Pd/C to a commercial Pd/C and the effect of different monometallic and bimetallic systems (AuxPdy) in the catalytic formic acid decomposition was investigated. The training period for the production of this work was carried out at the University of Cardiff (Group of Dr. N. Dimitratos).

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ELAZAB, HANY. « Graphene-Supported Metal Nanoparticles For Applications in Heterogeneous Catalysis ». VCU Scholars Compass, 2013. http://scholarscompass.vcu.edu/etd/560.

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Due to its unique properties and high surface area, Graphene has become a good candidate as an effective solid support for metal catalysts. The Nobel Prize in Physics for 2010 was awarded to Andre Geim and Konstantin Novoselov "for groundbreaking experiments regarding the two-dimensional material graphene". Microwave-assisted synthesis of various metallic nanostructured materials was investigated for CO oxidation applications. These metallic nanostructured materials were used to convert CO to CO2 as an effective approach for carbon monoxide elimination due to its harmful effect on health and environment. In particular, this dissertation is focusing on palladium as a transition metal that has a unique ability to activate various organic compounds to form new bonds. The prepared graphene-supported metallic nanostructured materials were successfully used to investigate Suzuki cross-coupling reaction as an important reaction in the field of pharmaceutical applications. In this research, nanostructured materials were used as solid support catalysts which showed remarkable improvements in the aspects of size, surface structure, catalytic selectivity, shape and recyclability. The nano porous structure and superparamagnetic behavior of (Fe3O4) nano particles that were used as an effective ingredient in graphene-supported palladium catalyst improved the catalytic activity and the catalyst recyclability simply by using an external magnetic field. This research has been divided into two main categories; the first category is to investigate other metal oxides as a solid support for palladium to be used in CO oxidation catalysis. The second category will focus on improving of solid support systems of palladium – magnetite catalyst to increase recyclability. The final stage of this investigation will study the use of these solid supported metal catalysts in continuous heterogeneous processes under flow reaction conditions. The structural, morphological and physical properties of graphene-based nanocomposites described herein were studied using standard characterization tools such as TEM, SEM, X-ray diffraction, XPS and Raman spectroscopy.

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Lombardi, Erica. « Selective photo-oxidation of cellobiose with tio2-supported metal nanoparticles ». Master's thesis, Alma Mater Studiorum - Università di Bologna, 2013. http://amslaurea.unibo.it/6017/.

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Upgrade of biomass to valuable chemicals is a central topic in modern research due to the high availability and low price of this feedstock. For the difficulties in biomass treatment, different pathways are still under investigation. A promising way is in the photodegradation, because it can lead to greener transformation processes with the use of solar light as a renewable resource. The aim of my work was the research of a photocatalyst for the hydrolysis of cellobiose under visible irradiation. Cellobiose was selected because it is a model molecule for biomass depolymerisation studies. Different titania crystalline structures were studied to find the most active phase. Furthermore, to enhance the absorption of this semiconductor in the visible range, noble metal nanoparticles were immobilized on titania. Gold and silver were chosen because they present a Surface Plasmon Resonance band and they are active metals in several photocatalytic reactions. The immobilized catalysts were synthesized following different methods to optimize the synthetic steps and to achieve better performances. For the same purpose the alloying effect between gold and silver nanoparticles was examined.

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Meduri, Kavita. « Carbon-Supported Transition Metal Nanoparticles for Catalytic and Electromagnetic Applications ». Thesis, Portland State University, 2018. http://pqdtopen.proquest.com/#viewpdf?dispub=10933285.

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Recently, there has been growing interest in using transition metals (TM) for catalytic and electromagnetic applications, due to the ability of TMs to form stable compounds in multiple oxidation states. In this research, the focus has been on the synthesis and characterization of carbon-supported TM nanoparticles (NPs), specifically palladium (Pd) and gold (Au) NPs, for catalytic applications, and transition metal oxides (TMO) NPs, specifically Fe₃O₄ NPs for electromagnetic applications. Carbon supports have several advantages, such as enabling even distribution of particles, offering large specific surface area with excellent electron conductivity, and relative chemical inertness.

In this dissertation, for catalytic applications, emphasis was on removal of trichloroethylene (TCE) from groundwater. For this application, carbon-supported Pd/Au NP catalysts were developed. Pd was chosen because it is more active, stable and selective for desired end-products, and Au has shown to be a good promotor of Pd’s catalytic activity. Often, commercially available Pd-based catalysts are made using harsh chemicals, which can be harmful to the environment. Here, an environmentally friendly process with aspects of green chemistry was developed to produce carbon-supported Pd/Au NP catalysts. This process uses a combination of sonochemistry and solvothermal syntheses. The carefully designed carbon-supported Pd/Au NP catalyst material was systematically characterized, tested against TCE, and optimized for increased rate of removal of TCE. Electron microscopy and spectroscopy techniques were used to study the material including structure, configuration and oxidative state. The Pd/Au NPs were found mainly to form clusters with an aggregate-Pd_ShellAu_Core structure. Using state-of-the-art direct detection with electron energy loss spectroscopy, the Pd NPs were found to have an oxidative state of zero (0). The formation of the catalyst material was studied in detail by varying several synthesis parameters including type of solvent, sonication time, synthesis temperature etc. The most optimized catalyst was found remove TCE at double the rate of corresponding commercial Pd-based catalysts in a hydrogen headspace. This material was found to catalyze the removal of TCE via traditional hydrodehalogenation and shows promise for the removal of other contaminants such as trichloropropane (TCP), carbon tetrachloride (CT).

This green approach to make and optimize TM materials for specific applications was extended to TMOs, specifically magnetite (Fe₃O₄) and further developed for the application of electromagnetism. As catalysts, Fe₃O₄ is used for removal of p-nitrophenol from water. However, since the carbon-supported Pd/Au material system was developed and optimized for catalysis, here, carbon-supported Fe₃O₄ NPs were developed for electromagnetic applications. There has been growing interest in tuning the magnetic properties of materials at room temperature with the use of external electric fields, for long-term applications in data storage and spintronic devices. While a complete reversible change of material properties has not yet been achieved, some success in partial switching has been achieved using multiferroic spinel structures such as Fe₃O₄. These materials experience a change in magnetic moment at room temperature when exposed to the electric fields generated by electrochemical cells such as lithium ion batteries (LIBs) and supercapacitors (SC). In the past, a 1% reversible change was observed in Fe₃O₄ using LIBs. Here, building on the developments from previous material system, Fe₃O₄ NPs were directly hybridized onto the graphene support in order to increase the observable change in magnetic moment. The material was systematically designed and tested for this application, including a study of the material formation. A simple, environmentally friendly synthesis using the solvothermal process was implemented to make the graphene-supported Fe₃O₄ NPs. This new material was found to produce a reversible change of up to 18% in a LIB. In order to overcome some of the difficulties of testing with a LIB, a corresponding hybrid SC was designed, built and calibrated. The graphene-supported Fe₃O₄ NPs were found to produce a net 2% reversibility in the SC, which has not been reported before. The results from both the LIB and SC were analyzed to better understand the mechanism of switching in a spinel ferrite such as Fe₃O₄, which can help optimize the material for future applications.

The focus of this dissertation was on the development of a methodology for carbon-supported TM and TMO NPs for specific applications. It is envisioned that this approach and strategy will contribute towards the future optimization of similar material systems for a multitude of applications.

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Wang, Fan. « Visible light photocatalysis with supported metal nanoparticles for organic synthesis ». Thesis, Queensland University of Technology, 2017. https://eprints.qut.edu.au/103567/1/Fan_Wang_Thesis.pdf.

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This project was a step forward in developing new effective photocatalysts for fine organic synthesis under visible light irradiation. These kind of new photocatalysts are able to facilitate reaction rates by using visible light under moderate reaction conditions through a green, economical and environmentally friendly pathway. This thesis investigated the catalyst synthesis, characterization and the application in organic reactions with high activity and selectivity. The discovery of these new metal nanoparticle photocatalysts may inspire further studies on other efficient photocatalysts and enhance the potential to utilize sunlight via a controlled and environmentally friendly process.

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Martens, Sladana [Verfasser]. « Ultrasound supported electrodeposition of metals and preparation of metal/ceramic composites, colloidal nanoparticles and oxide materials / Sladana Martens ». Clausthal-Zellerfeld : Universitätsbibliothek Clausthal, 2012. http://d-nb.info/102166779X/34.

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Bamford, Rebecca. « Biopolymer supports for metal nanoparticles in catalytic applications ». Thesis, University of Bath, 2015. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.675702.

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Silver nanoparticles (sub 10 nm), supported on, or in, cellulose, have been demonstrated to be well stabilised and immobilised during application in a model continuous reaction: the reduction of 4-nitrophenol (4-NP) to 4-aminophenol with sodium borohydride. The production of these silver nanoparticles (NP), within the cellulose supports, was carried out by either in situ reduction of silver precursors absorbed into the preformed cellulose supports, or, by inclusion of ex situ synthesised NPs (prepared in DMSO solutions) in the dissolution of cellulose and trapping upon subsequent coagulation of cellulose. The effects of NP synthesis method (affecting particle size and agglomeration) and the cellulose morphology and porous structure were examined with respect to the catalytic activity of the materials. The in situ reduction of a silver salt with aqueous NaBH4 solutions (0.03 to 1.0 wt. %) led to tuneable Ag NP sizes with mean diameters of 5 to 11 nm (TEM) and metal loadings of 0.5-1.0 wt. %. The catalytic activity of these samples in the 4-NP reduction reaction (0.05 mM, 0.167 M NaBH4, 30 °C) was demonstrated to increase upon decreasing NP size: TOF values of 22–356 h-1, consistent with a Langmuir-Hinshelwood mechanism. The porous structure of these Ag-cellulose materials (0.2 to 294 m2 g-1) was demonstrated to be variable and dependent on drying treatments of the regenerated cellulose hydrogel. Thermal drying, freeze-drying and critical point drying resulted in materials with different bulk structure and porosity. In turn the different porosities resulted in extremely different catalyst activities, e.g. Ag-cellulose catalyst (0.3 mm disks) thin film, hydrogel and cryogel phases exhibited TOF values of 2, 12 and 178 h-1, respectively. In addition, the NP synthesis could be carried out in either the cellulose hydrogel or cryogel, which led to different extents of Ag NP catalyst stabilisation against agglomeration during the 4-NP reaction and catalyst recovery and recycling. The Ag NPs synthesised in the cryogel cellulose disks were observed to undergo agglomeration (TEM) after use in 4 repeat batch reductions, whilst those NPs synthesised in the hydrogel cellulose, prior to freeze-drying to the final cryogel catalyst material, did not exhibit any agglomeration upon 4 repeat reduction reactions. The ex situ reduction of Ag and Au NPs was carried out by the reduction of AgOAc and Au(OAc)3 by DMSO and variation of the NP synthesis parameters, such as time (10 min – 1h) and temperature (50 – 80 °C), allowed for control of the NP sizes (3 to 6 nm Ag NPs and 4 to 11 nm Au NPs, TEM). It was demonstrated that the addition of the polysaccharide starch (0.42 wt. % in DMSO) allowed for consistent Ag NP size (ca. 4 nm) to be achieved throughout the 8 h synthesis, the starch acting as both the reducing and capping agent, maintaining the small sizes and narrow particle size distributions of the NPs upon aging (72 h). A kinetic model with a bimolecular nucleation step was developed to describe this reduction of the silver acetate by the starch/DMSO system. However, contact of the NPs with solutions of imidazolium ILs, 1-Ethyl-3-methylimidazolium acetate (EmimOAc) and 1-Butyl-3-methylimidazolium chloride (BmimCl) in DMSO, used in the dissolution of cellulose, led to the oxidation of the Ag(0) and Au(0) NPs. Thus, when these NP solutions were mixed in cellulose solutions regeneration by phase inversion with the aim of preparing cellulose/NP composites led to materials with negligible metal loadings (AAS). This oxidation, of the metal NPS, was partially overcome by stabilisation of the starch capped Ag NPs by pre-treatment with cellulose (1:1 mixture of α and MC cellulose). However, the activity of the resulting Ag-cellulose catalyst (0.5 wt. % AAS, 6.7 nm TEM) was much lower than the Ag-cellulose catalysts prepared by in situ reduction of silver in the cellulose hydrogel, despite the comparable NP sizes. This was presumed to be a result of encapsulation of the Ag NPs by the cellulose, leading to a decrease in the accessible surface of the NPs. Finally, the use of Ag NP / cellulose composites, prepared by in situ reduction of silver in cellulose hydrogel beads (0.19 wt. %, 6.4 nm), were demonstrated in the continuous reduction of 4-NP in a packed bed reactor (τ’ 100 g s dm-3). The activation energies of the reactions of 4-NP catalysed by the Ag-cellulose catalyst materials were determined (3.2 to 9.4 kJ mol-1) from Arrhenius plots, which demonstrated that above 20 °C the reaction was likely subject to diffusion limitations in the cellulose beads. The high degree of stabilisation of the Ag NPs against agglomeration imparted by the cellulose support was demonstrated: the rate of reaction was observed to be constant over 120 h, treating 45 L of 4-NP solution, with the catalyst material after use demonstrating no significant leaching of silver, or agglomeration, of NPs (AAS, TEM).

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Jones, Daniel R. « Using supported metal nanoparticles for the conversion of biomass derived molecules ». Thesis, Cardiff University, 2016. http://orca.cf.ac.uk/99652/.

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The energy demand of the world is increasing and the depletion of its reserves of fossil fuels are making energy production more expensive. The challenge therefore falls on researchers to develop novel ways of meeting this increased energy demand which are both cost-effective and environmentally friendly. Utilisation of biomass will be vital in achieving this goal because of its abundance and availability. In particular, levulinic acid has been identified as a valuable chemical feedstock. It can be easily converted into γ-valerolactone, which has vast potential applications in both the fuel and chemicals industries. The work presented in this thesis primarily focusses on the hydrogenation of levulinic acid into γ- valerolactone. Hydrogenation of levulinic acid is well known, but catalysts that facilitate it usually incorporate expensive precious metals. In order for a process to become truly sustainable, the catalysts should also be sustainable. This requirement makes research into the use of cheap and abundant materials as catalysts desirable. The work presented in this thesis investigated the use of critical, precious metal catalysts compared with the cheaper, abundant, and non-critical base metals as potential replacements. An investigation into lactic acid hydrogenation to 1,2-propanediol as a model reaction for levulinic acid hydrogenation was also carried out. Chapter 3 provides comparative data of a 5 wt.% Ru/C catalyst prepared by the sol immobilisation method and a commercial 5 wt.% Ru/C catalyst. In Chapter 4, a variety of preparation parameters for the synthesis of 1 wt.% Ru/C catalysts were investigated, including the choice of Ru precursor, carbon support, and preparation method. 1 wt.% Ru/C from this chapter was set as the benchmark for base metals. The second half of this thesis describes an investigation into the use of base metals as potential catalysts for levulinic acid hydrogenation. Chapter 5 shows that Cu-ZrO2 catalysts were active for levulinic acid hydrogenation under much harsher reaction conditions compared with the benchmark (1 wt.% Ru/C). The synthesis of Cu-ZrO2 was optimised through variation of the various preparation parameters and a detailed investigation was performed. Chapter 6 shows that the incorporation of Ni into Cu-ZrO2 improved the activity of Cu-ZrO2, with a product yield of 100 % obtained after 90 minutes. This was attributed to an increased surface area and the formation of a Ni-Cu alloy. Modifying the preparation method further by adding a ball-milling step further increased the surface area of the catalyst and resulted in a product yield of 100 % after 30 minutes of reaction. It was found that there was more metal that required present in these catalysts, indicating a requirement of further work in order to produce catalysts with comparable catalytic activity.

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McPherson, Ian James. « An infrared spectroelectrochemical approach for understanding electrocatalysis at supported metal nanoparticles ». Thesis, University of Oxford, 2015. https://ora.ox.ac.uk/objects/uuid:eed82bd8-1863-4645-b853-7540dac6d1bc.

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This thesis describes the development and application of a new in situ infrared (IR) approach to studying electrocatalysis at supported nanoparticle catalysts that are used in proton exchange membrane (PEM) fuel cells. Such fuel cells running on small organic molecules are an attractive technology for use in transport applications and portable electronic devices, however one major challenge facing this technology is the slow oxidation of the organic molecules at the electrode surface. Furthermore, the mechanisms by which these organic molecules are oxidised are still not clear, hampering the design of new electrode materials. In situ IR spectroscopy has been used extensively to investigate the mechanism of reactions on model catalysts, however extension of these techniques to real fuel cell catalysts is challenging and much less advanced. A new approach to in situ IR spectroscopy of supported electrocatalysts is therefore developed, inspired by the geometry of PEM fuel cell electrodes. The approach overcomes many of the limitations of previous approaches, allowing solution flow over the catalyst layer, cyclic voltammetry up to scan rates of 1 V s-1 and spectroscopic detection of surface adsorbed species with time resolution of 0.5 s. The utility of this approach is demonstrated through a study of the mechanism of two model reactions, carbon monoxide (CO) and formic acid (FA) oxidation, on a commercial fuel cell catalyst. In situ IR measurements made during CO stripping experiments on a commercial carbon-supported Pt catalyst reveal two strongly bipolar IR peaks in the CO stretching region. An empirical model for the bipolar peak shape is developed and used to extract peak parameters. Electrochemical measurement of the CO coverage then enables calibration of the IR peak intensity with coverage. This quantitative relationship enables features such as dipole-dipole coupling in the CO adlayer to be discussed. In situ IR spectra recorded during the stripping voltammogram reveal the presence of two linear CO peaks, assigned to different sites on the catalyst. The potential dependence of the two peak intensities is used to discuss the mechanism of CO oxidation on the catalyst. The in situ approach is extended to the study of FA oxidation on the commercial Pt catalyst. As well as adsorbed CO, two potential-dependent peaks are assigned to adsorbed formate - the first time formate has been observed on a nanoparticle catalyst during electrooxidation. Furthermore, one of the peaks is assigned to an IR surface selection rule-prohibited mode, providing evidence for the previously proposed size-dependence of the selection rule. The effects of concentration, pH, isotope and supporting electrolyte on the adsorbed species are examined and related to the current in order to understand different aspects of the mechanism on nanoparticle catalysts. The results are discussed in the context of previous work on macroscopic electrodes. Overall an approach to in situ IR spectroscopy of nanoparticle electrocatalysts is presented and is used to probe the mechanisms of CO and FA oxidation under conditions relevant to fuel cells.

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Bell, Tamsin Elizabeth. « Stabilisation of metal nanoparticles by confinement on curved supports ». Thesis, University of Cambridge, 2019. https://www.repository.cam.ac.uk/handle/1810/285095.

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Supported metal nanoparticles present unique chemical and physical properties compared to their bulk counterparts. Their high surface energy provides outstanding catalytic activities, opening the door not only to improved catalytic systems but also to new catalytic routes. However, their high surface energy and liquid-like properties are responsible for their instability, usually leading to agglomeration under reaction conditions. This thesis seeks to investigate a novel nanoparticle stabilisation approach by physical confinement on curved supports. Specifically, the project focusses on the stabilisation of cobalt and gold nanoparticles on nanostructured -Al2O3 supports, motivated by the industrial interest of Sasol UK. The research hypothesis is validated by detailed characterisation and catalytic testing of a range of catalysts using different metal loadings and support morphologies. To enable this study, the mechanism of the hydrothermal synthesis of a series of nanostructured -Al2O3 supports with either flat or curved surfaces and differing degrees of curvature has been elucidated, leading to the development of a semi-continuous manufacturing process. Varying the method for loading cobalt onto -Al2O3 supports highlights the implications of method selection on the particle size, reducibility, composition and the tendency to form irreducible cobalt oxides, all of which affect the catalytic activity. The ability to obtain and stabilise small nanoparticles with low loading (1 wt% Co) without the formation of irreducible cobalt oxides exposes the beneficial effect of the support curvature. Specifically, the stabilisation effect is theorised to be effective under the condition where the ratio of the diameter of the nanoparticle (P) and the nanorod (R) is less than one, P:R < 1. In several cases, after cobalt or gold reduction, elongation of the nanoparticles, as opposed to agglomeration, is observed by electron microscopy confirming that the particles are physical confined by the curved surface in all directions except along the nanorod axis. In these cases, highly active Co/-Al2O3 and Au/-Al2O3 catalysts are reported for NH3 decomposition and CO oxidation respectively. For higher metal loadings (> 5 wt% Co), where the particles are the same size or larger than the diameter of the nanorod cross-section, no noticeable stabilisation effect is reported. The results of this thesis are scientifically and industrially important. If applied correctly, this novel nanoparticle stabilisation strategy could be used to design catalysts with improved activity and stability, resulting in lower operational costs and improved resource efficiency.

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McNamara, Nicholas D. « Sonochemical Synthesis and Characterization of Metal Nanoparticle-Decorated Carbon Supports ». University of Dayton / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=dayton1311690542.

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Asara, Gian Giacomo. « Transition metal carbides as active phase and as support in catalysis : Insights from first principles theoretical modelling ». Doctoral thesis, Universitat Rovira i Virgili, 2014. http://hdl.handle.net/10803/454774.

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Els carburs de metalls de transició (TMC) exhibeixen propietats químiques i catalítiques similars a les dels costosos metalls nobles. La conversió d'alcohol, hidrogenació d'olefines i altres reaccions importants han demostrat l'aplicabilitat d'aquests compostos en processos industrials. També se sap que nanopartícules de metalls nobles (NMNPs) mostren una alta activitat catalítica tot i la baixa o nul • la reactivitat del metall sòlid. A més, investigacions recents assenyalen que els suports de TMC polaritzen la densitat electrònica de NMNPs adsorbits i augmenten l'activitat catalítica respecte als suports més tradicionals d'òxid metàl • lic. Aquests descobriments recents han inspirat el treball presentat en aquesta tesi, realitzat mitjançant tècniques actuals de la química quàntica. S'ha estudiat CO, CO2, H2, H2O adsorbits sobre TiC i sobre petits clústers d'or adsorbits en el suport. S'ha considerat la superfície (001), terrasses, esglaons monoatòmics i defectes, i també la reactivitat de les molècules adsorbides sobre la superfície neta de TiC (001) i en dos clústers d'or, Au4 i Au6, adsorbits. Les barreres energètiques calculades per a la formació de metà o formaldehid a partir de gas de síntesi, en TiC (001) resulten ser massa altes i aquests processos són inviables sobre el suport net. Sobre els clústers d'or suportats sobre TiC (001) hi ha una major activitat catalítica, però la reacció continua sent altament impedida. No obstant això, la reacció de desplaçament del gas d'aigua es preveu que sigui ràpida en el sistema Au4/TiC (001), superant els catalitzadors utilitzats normalment en la indústria. Experiments recents mostren que els clústers de Ni, Cu i Au estan fortament deformats un cop adsorbits sobre TMC, donant lloc a catalitzadors molt actius. S'ha investigat la interacció dels àtoms amb la fase delta de MoC. La interacció és més forta pel recobriment més baix considerat, la relaxació de la superfície és important i l'activitat es preveu que augmenti en l'ordre Ni> Cu> Au. Finalment, s'han considerat possibles reconstruccions no polars per a la superfície (001) de Mo2C centrant-se en l'energia d’escissió, la qual és proporcional a l'estabilitat de cada tipus de terminació. Les reconstruccions no polars disminueixen l'energia d’escissió, confirmant l'aplicabilitat dels conceptes clàssics de Tasker per a òxids als TMC.
Los carburos de metales de transición (TMC) exhiben propiedades químicas y catalíticas similares a las de los costosos metales nobles. La conversión de alcohol, hidrogenación de olefinas y otras reacciones importantes han demostrado la aplicabilidad de estos compuestos en procesos industriales. También se sabe que nanopartículas de metales nobles (NMNPs) muestran una alta actividad catalítica a pesar de la baja o nula reactividad del metal sólido. Además, investigaciones recientes señalan que los soportes de TMC polarizan la densidad electrónica de NMNPs adsorbidos y aumentan la actividad catalítica respecto a los soportes más tradicionales de óxido metálico. Estos descubrimientos recientes han inspirado el trabajo presentado en esta tesis, realizado mediante técnicas actuales de la química cuántica. Se ha estudiado CO, CO2, H2, H2O adsorbidos sobre TiC y sobre pequeños clusters de oro adsorbidos sobre el suport. Se ha considerado la superficie (001), terrazas, escalones monoatómicos y defectos y, también, la reactividad de las moléculas adsorbidas sobre la superficie limpia de TiC (001) y en dos clusters de oro, Au4 y Au6, adsorbidos. Las barreras energéticas calculadas para la formación de metano o formaldehído a partir de gas de síntesis en la superficie limpia de TiC (001) resultan ser demasiado altas y esos procesos son inviables sobre el soporte limpio. Sobre los clusters de oro soportados sobre TiC (001) hay una mayor actividad catalítica, pero la reacción continúa siendo altamente impedida. Sin embargo la reacción de desplazamiento del gas de agua se prevé que sea rápida en el sistema Au4/TiC (001), superando los catalizadores utilizados normalmente en la industria. Experimentos recientes muestran que los clusters de Ni, Cu y Au están fuertemente deformados una vez adsorbidos sobre TMC dando lugar en catalizadores muy activos. Se ha investigado la interacción de los átomos con la fase delta del catalizador de MoC. La interacción es más fuerte para el recubrimiento más bajo considerado, la relajación de la superficie es importante y la actividad se prevé que aumente en el orden Ni> Cu> Au. Finalmente, se han considerado posibles reconstrucciones no polares para la superficie (001) de Mo2C centrándose en la energía de escisión, que es proporcional a la estabilidad de cada tipo de terminación. Las reconstrucciones no polares disminuyen la energía de escisión, confirmando la aplicabilidad de los conceptos clásicos de Tasker para óxidos a los TMC.
Carbides of the early transition metals (TMC) exhibit chemical and catalytic properties that in many aspects are very similar to those of expensive noble metals. Alcohol conversion, hydrogenation of olefins and many others important reactions demonstrated the applicability of these compounds for industrial processes. It is also known that small noble metal nanoparticles (NMNPs) show high catalytic activity despite of the poor reactivity or inertness of the bulk metal. Additionally, recent investigations pointed out that supporting TMCs polarize the electron density of adsorbed NMNPs increasing the catalytic activity respect to more traditional metal oxide supports. These recent discoveries inspired the work reported in this thesis using state-of-the-art quantum chemical techniques. We studied CO, CO2, H2, H2O molecules adsorbed on TiC and on small gold clusters adsorbed thereon. We considered the (001) extended surface, terraces, monatomic steps and kink defective sites. The reactivity of adsorbed molecules on the clean TiC (001) surface and on two gold clusters, Au4 and Au6, adsorbed thereon were also studied. Energy barriers calculated for methane or formaldehyde formation from syngas, on the clean TiC (001) surface were by far too high and those processes are unviable on the clean support. Gold clusters supported by TiC (001) show higher catalytic activity but the reaction continues to be highly hindered. However water gas shift reaction is predicted to be fast on the Au4/TiC(001) system, overtaking catalysts normally used in industry. Recent experiments show that Ni, Cu and Au clusters are strongly perturbed upon adsorption on TMC resulting in extremely active catalysts. We investigated the interaction of those atoms with the delta phase of the MoC catalyst. The interaction is stronger for the lowest coverage considered, the relaxation of the surface important and the activity is predicted to increase in the order Ni>Cu >Au. Finally, we have studied possible non-polar reconstructions of the (001) surface of Mo2C focusing on the cleavage energy, proportional to the stability of each type of termination. The non-polar reconstructions decreased the calculated cleavage energy, confirming the applicability of the classical Tasker’s concepts for oxides to TMCs.

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Teng, Die. « Computational studies of transition metal nanoclusters on metal-supported graphene moiré ». Diss., Georgia Institute of Technology, 2014. http://hdl.handle.net/1853/51830.

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The graphene moiré superstructure formed on Ru(0001) (g/Ru(0001)) has shown the potential as a template to self-assemble super-lattices of metal nanoparticles as model catalysts. To explore the possibility of rational catalyst design on g/Ru(0001), detailed density functional theory (DFT) calculations have been performed to investigate the adsorption and diffusion of Rh and Au adatoms on g/Ru(0001). The consequences of different hopping rates for cluster nucleation have been explored by performing Monte Carlo-based statistical analysis, which suggests that diffusing species other than adatoms need to be taken into account to develop an accurate description of cluster nucleation and growth on this surface. DFT calculations have also been carried out to investigate the adsorption and diffusion of 18 4d (Y-Ag) and 5d (La-Au) transition metal adatoms on g/Ru(0001). Given the necessity to study larger diffusing species than adatoms, DFT calculations have been performed to study the adsorption and diffusion of Rh and Au dimers and trimers on g/Ru(0001). It was shown that the mobility of Rh clusters decreases with the increase of cluster size, while for Au, dimers diffuse faster than monomers and trimers on the moiré surface. We then used a genetic algorithm combined with DFT calculations to predict the lowest energy structure of a Au8 cluster on g/Ru(0001). Our prediction leads us to propose that Au clusters aggregates through Oswald ripening with Au dimer being the major diffusing species. Finally, we examined the morphology of a Cu19 cluster on g/Cu(111) using MD simulations with COMB3 potential. We also studied the mobility of Cu clusters on g/Cu(111) at elevated temperatures. The analysis suggests that g/Cu(111) may not be a suitable substrate for the formation and growth of isolated Cu clusters. All these calculation results have provided us a better understanding and useful insights into the nucleation and growth mechanism of metal clusters on graphene moiré.

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Liu, Zhe. « New supported metal photocatalysts for synthesis of fine organic chemicals driven by visible light ». Thesis, Queensland University of Technology, 2016. https://eprints.qut.edu.au/95889/1/Zhe%20Liu%20Thesis.pdf.

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This project is to develop a series of new photocatalyst for fine organic synthesis in irradiation of visible light under mild conditions. To achieve this goal, the detailed study of photocatalytic properties of plasmonic metal nanoparticles supported on zirconium dioxide was carried out, including the catalyst synthesis, characterization and application in redox reactions with high activity. The discovery of these new plasmonic metal nanoparticle photocatalyst may inspire further studies on other efficient photocatalysts and enhance the potential to utilize sunlight via a controlled and environmentally friendly process.

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Poupart, Romain. « Nanoparticules métalliques@polymères poreux : matériaux hybrides innovants pour la catalyse supportée ». Thesis, Paris Est, 2017. http://www.theses.fr/2017PESC1174/document.

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Les matériaux poreux basés sur les polymères font l’objet de recherches nombreuses et variées depuis leur découvertes et jusqu’à aujourd’hui encore. Leurs propriétés uniques et remarquables, comme par exemple une fonctionnalisation aisée ou une large gamme de porosité accessibles, couplées à leur faible coût de production les rendent attrayant pour de nombreuses applications. Parmi elles, la catalyse supportée est en plein essor, spécialement depuis l’avènement des nanoparticules. Durant ce travail de thèse, nous avons développé différents matériaux polymères pouvant servir de support, se focalisant majoritairement sur trois types de matériaux : des matériaux polymères massiques, des matrices polymères poreuses en capillaire ainsi que des polystyrènes poreux provenant de la dégradation sélective de copolymères diblocs.Dans un premier temps, différentes stratégies ont été employées pour l’immobilisation et la génération de nanoparticules sur les matériaux massiques. L’un a consisté en la synthèse d’un monomère contenant un pont disulfure qui, après réduction, a permis la libération de groupement thiol permettant l’accrochage de nanoparticules d’or. La seconde a consisté à réduire de manière originale les nanoparticules en utilisant un gaz, l’hydrogène. Dans un seconde partie, la synthèse de différentes matrices polymères dans des capillaires a été réalisée. Tout d’abord, une matrice déjà connue de la littérature à base de N-acryloxysuccinimide a été utilisée, après modification via thiol-ène et substitution nucléophile par différentes amines, pour immobiliser des nanoparticules de cuivre ainsi que d’or, respectivement. D’autre part, une nouvelle matrice à partir de carbonate cyclique aura, elle, été utilisée après modification, pour l’immobilisation de nanoparticules de platine. Enfin à partir de copolymères diblocs possédant différentes jonctions entre chaque bloc (un pont disulfure ainsi qu’un acétal), différents polystyrènes poreux ont été obtenus. Les copolymères possédant une jonction acétal à lui été utilisé pour l’immobilisation de nanoparticules d’or, permettant la mise en place des réactions de réduction de nitro, d’homocouplage boronique ainsi que de la mise en cascade de ces deux réactions
Porous materials based on polymers have been the subject of intense and various researches since their discovery until now. Their unique and remarkable properties, like their easy functionalization or their large porosity range reachable for instance, coupled with their low production cost makes them attractive for numerous applications. Among them, supported catalysis is booming, especially since the rising of nanoparticles. During this Ph.D. contribution, we have developed different polymeric materials, which could be used as support, focusing mainly onto three types: bulky materials, porous polymeric matrixes into capillaries and porous polystyrene arising from the selective degradation of diblocks copolymers.Firstly, different strategies have been employed for the immobilization and the generation of nanoparticles onto bulk materials. On the one hand, the synthesis of a monomer, bearing a disulphide bridge which can, after a reduction step, free a thiol moiety allowing us to anchor gold nanoparticles. On the other hand, a new route to reduce nanoparticle has been employed using gaseous hydrogen. In another part, the syntheses of different polymeric matrixes into capillaries have been made. First, we used an already known matrix, based on N-acryloxysuccinimide -after modification step via thiol-ene reaction and nucleophilic substitution by amines- to anchor copper or gold nanoparticles, respectively. Also, a new matrix based on cyclic carbonates has been used, after modification, to immobilized platinum nanoparticles. Finally, starting from diblocks copolymers possessing different junctions between both blocks (disulphide bridge or acetal), porous polystyrenes have been obtained. The copolymers bearing an acetal have been implemented to immobilized gold nanoparticles, catalysing several reactions like nitro reduction, boronic homocoupling as well as the cascade reaction of both

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Afshani, Parichehr. « Laser Vaporization Methods for the Synthesis of Metal and Semiconductor Nanoparticles ; Graphene, Doped Graphene and Nanoparticles Supported on Graphene ». VCU Scholars Compass, 2013. http://scholarscompass.vcu.edu/etd/569.

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The major objective of the research described in this dissertation is the development of new laser vaporization methods for the synthesis of metal and semiconductor nanoparticles, graphene, B- and N-doped graphene, and metal and semiconductor nanoparticles supported on graphene. These methods include the Laser Vaporization Controlled Condensation (LVCC) approach, which has been used in this work for the synthesis of: (1) gold nanoparticles supported on ceria and zirconia nanoparticles for the low temperature oxidation of carbon monoxide, and (2) graphene, boron- and nitrogen-doped graphene, hydrogen-terminated graphene (HTG), metal nanoparticles supported on graphene, and graphene quantum dots. The gold nanoparticles supported on ceria prepared by the LVCC method exhibit high activity for CO oxidation with a 100% conversion of CO to CO2 at about 60 °C. The first application of the LVCC method for the synthesis of these graphene and graphene-based nanomaterials is reported in this dissertation. Complete characterizations of the graphene-based nanomaterials using a variety of techniques including spectroscopic, X-ray diffraction, mass spectrometric and microscopic methods such as Raman, FTIR, UV-Vis, PL, XRD, XPS, TOF-MS, and TEM. The application of B- and N-doped graphene as catalysts for the oxygen reduction reaction in fuel cell applications is reported. The application of Pd nanoparticles supported on graphene for the Suzuki carbon-carbon cross-coupling reaction is reported. A new method is described for the synthesis of graphene quantum dots based on the combination of the LVCC method with oxidation/reduction sequences in solution. The N-doped graphene quantum dots emit strong blue luminescence, which can be tuned to produce different emission colors that could be used in biomedical imagining and other optoelectronic applications. The second method used in the research described in this dissertation is based on the Laser Vaporization Solvent Capturing (LVSC) approach, which has been introduced and developed, for the first time, for the synthesis of solvent-capped semiconductor and metal oxide nanoparticles. The method has been demonstrated for the synthesis of V, Mo, and W oxide nanoparticles capped by different solvent molecules such as acetonitrile and methanol. The LVSC method has also been applied for the synthesis of Si nanocrystals capped by acetonitrile clusters. The acetonitrile-capped Si nanocrystals exhibit strong emissions, which depend on the excitation wavelength and indicate the presence of Si quantum dots with different sizes. The Si and the metal oxide nanoparticles prepared by the LVSC method have been incorporated into graphene in order to synthesize graphene nanosheets with tunable properties depending on graphene-nanoparticle interactions.

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Carew, Alexander Jon. « Fundamental studies into the catalytic properties of metal-oxide supported gold and copper nanoparticles ». Thesis, University of Liverpool, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.367710.

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Xu, Chunbao. « Continuous and batch hydrothermal synthesis of metal oxide nanoparticles and metal oxide-activated carbon nanocomposites ». Diss., Available online, Georgia Institute of Technology, 2006, 2006. http://etd.gatech.edu/theses/available/etd-07302006-231517/.

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Thesis (Ph. D.)--Chemical and Biomolecular Engineering, Georgia Institute of Technology, 2007.
Teja, Amyn, Committee Chair ; Kohl, Paul, Committee Member ; Liu, Meilin, Committee Member ; Nair,Sankar, Committee Member ; Rousseau, Ronald, Committee Member.

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Neumann, Sarah [Verfasser], Sebastian [Akademischer Betreuer] Kunz, Sebastian [Gutachter] Kunz et Marcus [Gutachter] Bäumer. « Heterogeneous Catalysis with supported Nanoparticles : Particle Size Effects and Metal-Support Interactions / Sarah Neumann ; Gutachter : Sebastian Kunz, Marcus Bäumer ; Betreuer : Sebastian Kunz ». Bremen : Staats- und Universitätsbibliothek Bremen, 2019. http://d-nb.info/1203298927/34.

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Zhu, Ju. « Synthesis of precious metal nanoparticles supported on bacterial biomass for catalytic applications in chemical transformations ». Thesis, University of Birmingham, 2014. http://etheses.bham.ac.uk//id/eprint/5009/.

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Bacteria are used to ‘grow’ and scaffold precious metal nanoparticles possessing certain catalytic activities. Focusing on Escherichia coli, this thesis aims to investigate the catalytic behaviours of E. coli-supported palladium (bio-Pd/E. coli) or bimetallic gold-palladium (bio- AuPd/E. coli) in hydrogenations and oxidations operated in laboratory-scale three-phase slurry reactors. A discussion of hydrodynamics, mass transfer, reaction mechanisms and corresponding reaction performance is systematically presented for two major industrially important reactions: soybean oil hydrogenation and benzyl alcohol oxidation. Thermogravimetric analysis indicated a suitable operating temperature of below 175\(^0\)C for the E. coli-supported catalyst. A loading of 5 wt%Pd on E. coli showed an average particle size of 4.31 nm estimated by TEM measurements and a crystallite size of 4.12 nm using Scherrer’s equation from obtained X-ray powder diffraction data. This was smaller than an active particle diameter of 12.77 nm for 5wt%Pd/Al\(_2\)O\(_3\) (determined by CO chemisorption). It is concluded that biomass-supported precious metal catalyst is an environmentally attractive alternative to conventional heterogeneous catalyst for application in industrial catalytic processes.

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Patil, Pratap Tukaram. « Nanoscopic metal fluoride based novel solid catalysts ». Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2009. http://dx.doi.org/10.18452/16021.

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Metallfluoride sind dank ihrer hohen chemischen und thermischen Stabilität, insbesondere bei Reaktionen unter Beteiligung von hoch korrosiven Gasen (HF, HCl, Cl2, F2) den entsprechenden Oxiden überlegen. Über den Sol-Gel Prozess synthetisierte Produkte weisen oft spezifische, zum Teil sehr unterschiedliche Eigenschaften im Vergleich zu klassisch hergestellten Verbindungen auf. In dieser Arbeit wurde der Sol-Gel Prozess zur Herstellung von binären Fluoriden (AlF3, MgF2, CaF2, CuF2 und FeF3) genutzt und zum Teil weiter entwickelt sowie das Synthesepotential dieser Methode als Zugang für komplexe Fluoride (KMgF3, K3AlF6), für Metallfluorid-geträgerte „nano Edelmetall-Systeme (Pd/AlF3, Pt/AlF3, Pd/CaF2, Pd/MgF2) und für Gast–Wirt–Metallfluorid-Systeme (CuF2/AlF3, FeF3/AlF3) untersucht. Die Eigenschaften der als kompakte Materialien hergestellten Metallfluorid Systeme wurden mit Hilfe spektroskopischer Methoden untersucht und dabei insbesondere deren Oberflächeneigenschaften bestimmt. Die neuen Materialien wurden für die Nutzung akademisch und industriell bedeutsamer Katalysereaktionen evaluiert und mit klassischen Katalysatoren verglichen. Es konnte gezeigt werden, dass der Sol-Gel Prozess für Fluoride zu neuartigen Materialien mit außergewöhnlichen Eigenschaften führt. Insbesondere infolge der Synthese-bedingten Vergrößerung der spezifischen Oberflächen um einen bis zu 20-fachen Faktor im Vergleich zu klassisch hergestellten Fluoriden konnten auch eine Reihe von katalytisch interessanten Metallen (Pd, Pt) in die nanoskopischen Festkörperfluoride eingebracht werden. Die TEM Aufnahmen zeigen, dass z. B. 2-5 nm große Palladiumpartikel sehr homogen in ca. 80 nm große CaF2- bzw. 20 nm große AlF3-Matrices in nur einem einzigen Reaktionsschritt eingeführt werden können. Die neuen Materialien wurden in verschiedenen katalytischen Reaktionen getestet und zeigten sich in mehreren Fällen den „Standard Katalysatoren“ überlegen.
Because of their high chemical and thermal stabilities, metal fluorides have found to be advantageous over metal oxides in such cases where reactions involving generation of corrosive acids like HCl and HF are concerned. The Sol-gel method is known for the synthesis of materials with considerably different properties to those prepared by classical routes. In this work, sol-gel route has been employed for the synthesis of binary fluorides (AlF3, MgF2, CaF2, CuF2 and FeF3), hydroxyfluorides [AlF3-x(OH)x, MgF2-x(OH)x] complex fluorides (KMgF3, K3AlF6), metal fluoride supported nanoscopic noble metals (Pd, Pt) and host-guest fluoride systems (CuF2/AlF3, FeF3/AlF3). Besides the successful synthesis of metal fluorides described above, the present thesis deals with investigation of their bulk and surface properties using various analytical and spectroscopic methods (XRD, BET, NH3-TPD FTIR-pyridine adsorption, XPS, microscopic studies) as well as with their catalytic properties for the reactions of academic and industrial interest. Metal fluorides prepared via sol-gel method have shown to possess extraordinary surface properties in terms of surface area, particle size, porosity, Lewis acidity and distortion in their structures as compared to those of classical methods like aqueous synthesis or impregnations. A homogeneous dispersion of Pd nanoparticles supported on high surface area metal fluoride prepared by this method was confirmed by XRD, XPS and TEM imaging. Catalytic properties of these materials have been investigated for dehydrofluorination of hydrofluorocarbons, isomerization of citronellal, hydrodehalogenation of chlorodifluoromethane, Suzuki cross coupling and oxidative fluorination of benzene.

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Warczinski, Lisa [Verfasser], Christof [Gutachter] Hättig, Robert [Gutachter] Franke et Reinhold [Gutachter] Fink. « Computational study of metal-support interactions for carbon-supported palladium nanoparticles / Lisa Warczinski ; Gutachter : Christof Hättig, Robert Franke, Reinhold Fink ; Fakultät für Chemie und Biochemie ». Bochum : Ruhr-Universität Bochum, 2021. http://d-nb.info/1233484141/34.

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Einakchi, Raha. « Metal Nanoparticles Over Active Ionic-Conductive Supports for the Reverse Water Gas Shift Reaction ». Thesis, Université d'Ottawa / University of Ottawa, 2016. http://hdl.handle.net/10393/34462.

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Increase in carbon dioxide emissions due to economic activity induce global warming. The strong increase in energy demand, mainly based on oil and coal, induces a rapid increase in CO2 in the atmosphere. Within Canada, the amount of human-produced carbon dioxide is considerable because a large portion of energy is supplied by burning of fossil fuels. The Reverse Water Gas Shift (RWGS) reaction is a promising catalytic process for the utilization and subsequent activation of carbon dioxide to carbon monoxide, which can be further converted into fuels such as gasoline. The current thesis studies the development of nano-catalytic systems for the RWGS reaction. Mono- and bi-metallic nanoparticles based on Cu, Fe, Ru and Pt were prepared using a polyol synthesis method. The catalytic performance of three different types of metal oxides (ionically conductive, mixed ionic-electronic conductive and non-conductive) was investigated for the RWGS reaction. Conductive metal oxides including samarium-doped ceria (SDC), ceria (CeO2), yttria-stabilized zirconia (YSZ) and iron III oxide (Fe2O3) were further used as the catalyst supports and the nanoparticles of Cu, Fe, CuxFe1-x (x = 50 and 95 at.%), Ru, Pt, Ru50Pt50 and RuxFe1-x (x = 80 and 90 at.%) were subsequently deposited on them. A stoichiometric mixture of H2 and CO2, i.e. H2/CO2 = 1, was used under atmospheric pressure in the temperature range of 300 - 600°C in order to evaluate the catalyst performance in terms of activity, stability and selectivity. Nanoparticles deposited on ceria-based supports (CeO2 and SDC) showed superior catalytic performance compared to other metal oxides. Among all the catalyst tested, 5 wt.% Ru50Pt50/CeO2 showed the highest CO yield and satisfactory stability for RWGS reaction. The second best catalytic systems were based on Ru90Fe10/CeO2 and Ru80Fe20/CeO2, which are more attractive from the practical point of view.

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Dole, Holly. « Connecting Metal-Support Interaction and Electrochemical Promotion Phenomena for Nano-structured Catalysts ». Thesis, Université d'Ottawa / University of Ottawa, 2016. http://hdl.handle.net/10393/34610.

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Air pollutants can cause poor air quality; however, the use of heterogeneous catalytic oxidation has been shown to be an efficient and cost-effective removal method. Some examples of commercial application of such catalysts include catalytic convertors in automobiles and industrial process exhausts. Research with regards to improving these technologies has included using less-expensive catalyst materials, increasing catalytic performance, and achieving higher efficiency. The concept of metal-support interaction (MSI) is one method of altering catalytic performance through changing the properties of the metal catalyst due to the interaction with the support material. Similarly, the phenomenon of electrochemical promotion of catalysis (EPOC) has also been shown to enhance the catalytic activity, however, through the application of a small electrical stimulus to a catalyst-working electrode deposited on a solid electrolyte (e.g. yttria-stablized zirconia). The properties of the metal catalyst are altered due to the movement of ions (in this case, O2-) from the electrolyte. Since its discovery, several factors were identified that are preventing EPOC from being commercialized, including the use of thick film catalysts. Implementing nano-catalysts makes this method competitive with typical heterogeneous catalysts; however, it has not been studied by many research groups. Furthermore, many heterogeneous catalytic studies have been performed separately for each of these phenomena; however, a connection between EPOC and MSI has yet to be fully understood. The overall objective of this project is to study the concept of EPOC over highly-dispersed nano-catalysts and determine how MSI relates to the change in catalytic activity. Supported nano-catalysts were synthesized, characterized, and evaluated for catalytic performance using model reactions. A reactor was designed to carry out the electrochemical studies, where the EPOC concept was successfully implemented and a relationship with MSI established. Furthermore, additional studies were conducted to determine the role of the O2- in the catalyst support and its relationship to MSI.

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Nguyen, Sorenson Anh Hoang Tu. « Immobilization of Copper Nanoparticles onto Various Supports Applications in Catalysis ». BYU ScholarsArchive, 2020. https://scholarsarchive.byu.edu/etd/8892.

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Copper-based materials are one of the most promising catalysts for performing transformations of important organic compounds in both academic and industrial operations. However, it is challenging to consistently synthesize highly active and stable copper species as heterogeneous catalysts due to their relatively high surface energy. As a result, agglomeration usually occurs, which limits the catalytic activities of the copper species. The work presented in this dissertation shows different synthetic strategies for obtaining active and stable copper-based materials by modifying chemical/physical properties of copper nanoparticles (NPs). Emphasis is placed on discussing specific catalytic systems, including carbon-supported catalysts (monometallic and bimetallic copper-based heterogeneous catalysts) and titania-supported catalysts, and their advantages in terms of catalytic performance. In recent years, there has been increasing interest in using metal-organic frameworks (MOFs) as a sacrificial template to obtain carbon-supported NPs via a thermolysis process. The advantages of using MOFs to prepare carbon supported nanomaterials are a fine distribution of active particles on carbon matrix without post-synthesis treatments and corresponding increased catalytic activity and stability in many reaction conditions. To better understand the potential of this synthetic approach, MOF pyrolyzed products have been characterized. Then, they were applied as heterogeneous catalysts for several chemical reactions. In particular, the high energy copper-based MOF, CuNbO-1, was decomposed to obtain an amorphous copper species supported on carbon (a-Cu@C). This catalyst was found to be highly active for reduction, oxidation, and N-arylation reactions without further tuning or optimization. Higher catalyst turnover numbers for each of these transformations were obtained when comparing a-Cu@C activity to that of similar Cu-based materials. To improve catalyst performance, a secondary metal can be introduced to create synergistic effects with the parent copper species. In order to gain insights into the role of the second metal, a well-known Cu-MOF, HKUST-1, was doped with nickel, cobalt, and silver solutions, followed by a decomposition process with 2,4,6-trinitrotoluene (TNT) as additive. This additive was used to enhance the rapid thermolysis of the bimetallic MOFs. In these bimetallic systems, the addition of a second metal was found to help in dispersing both metals over the carbon composite support and in influencing the particle size and oxidation state of the metals. Catalytic performance showed that even <1% of a secondary metal increased the rate for nitrophenol reduction. Optimal catalytic performance was achieved using a Ni-CuO@C bimetallic catalyst. Another synthetic strategy for Cu-catalyst preparation involves using the deposition-precipitation method, in which a copper catalyst anchored on a titania support was synthesized at low weight % in order to obtain a single atom catalyst (1-Cu/TiO2). The higher copper loading catalyst, 5-Cu/TiO2, was synthesized as a benchmark catalyst for comparison. The copper structure in the synthesized catalysts was investigated by powder X-ray diffraction (PXRD), Raman, scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX), X-ray photoelectron spectroscopy (XPS), N2 physisorption and inductively coupled plasma mass spectrometry (ICP-MS) in order to characterize physical and chemical properties. STEM-EDX observations showed single atom copper species less than 0.75 nm in size, as well as nanoparticles with an average diameter of ~1.31 nm. This catalyst was highly active in the reduction of nitro-aromatic compounds with NaBH4 at room temperature. The small to atomic level sizes of the Cu species and multiple oxidation states of Ti species were found to play a crucial role in the catalytic activity.

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Dong, Hong. « Polymer fiber templates for the preparation of coaxial fibers and tubes, and as metal nanoparticle supports ». Diss., Online access via UMI:, 2005.

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36

Sen, Selda. « Activity Of Carbon Supported Platinum Nanoparticles Catalysts Toward Methanol Oxidation Reaction : Role Of Metal Precursor And A New Surfactant ». Master's thesis, METU, 2008. http://etd.lib.metu.edu.tr/upload/3/12609273/index.pdf.

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In this thesis, carbon supported platinum nanoparticle catalysts were prepared using PtCl4 and H2PtCl6 as starting materials and 1-heptanethiol, tert-nonyl mercaptan, 1-hexadecanethiol, 1-octadecanethiol as surfactants. These new catalysts were employed for methanol oxidation reaction which are used for direct methanol fuel cells. Tert-nonyl mercaptane was used for the first time in this type of reaction and the other surfactants were used for comparison of the catalysts performance. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used in order to determine the nature of the catalysts. The average platinum crystallite particle sizes of all prepared catalysts were determined by both X-ray diffraction and transmission electron microscopy. It was found that platinum crystallizes in face-centered cubic structure and the surfactant play an important role on the size of platinum nanoparticles, branch surfactant, such as tert-nonyl mercaptane, causes an increase in the size of platinum nanoparticles, about 3 nm, compared to linear surfactant, such as 1-heptanethiol, about 2 nm. The oxidation states of platinum and their ratios were determined by XPS technique. These results indicated that platinum has two different oxidation states, zero and +4, and Pt(0) to Pt(IV) ratio is about 7.5 to 2.5. In addition to this, O 1s region of XPS was also examined and found that the surface of all of the catalysts covered by adsorbed hydroxide except the catalyst which was prepared by PtCl4 and tert-nonyl mercaptane (Catalyst IIa), where adsorption of water were observed and the catalyst which was prepared by H2PtCl6 and tert-nonyl mercaptane (Catalysts IIb), where adsorption of 65% of hydroxide and 35% of water were identified. Electrochemical studies indicated that Catalyst IIa has the maximum activity (&
#61566
342 A/gPt at 0.612 V) towards methanol oxidation reaction while Catalyst IIIb (H2PtCl6 and 1-hexanethiol were used to prepare this catalyst) has the minimum activity (&
#61566
91A/gPt at 0.580V). XRD, TEM and XPS results indicated that the optimum catalyst for methanol oxidation reaction contains about 3 nm of platinum nanoparticles, adsorbed hydroxide and water on the surface of catalyst, but sulphur. These results are in agreement with the proposed mechanism.

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HONEMANN, YVONNE CARINA. « DESIGN, CHARACTERIZATION AND APPLICATION OF HETEROGENEOUS SILICA SUPPORTED CATALYSTS, BASED ON PD NANOPARTICLES AND METAL SINGLE SITES (RH, CU) ». Doctoral thesis, Università degli Studi di Milano, 2013. http://hdl.handle.net/2434/214937.

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The immobilization of metal NPs and metal single sites on silica support materials offers an interesting approach to heterogeneized catalysts for a multitude of different reactions. Selective hydrogenation reactions of prochiral substrates, such as (hetero-)aromatics, can be catalyzed by heterogeneized “hybrid catalysts” of the type RhI-Pd0/SiO2, consisting of silica-supported PdNPs and chiral Rh(I) phosphine single sites. These new “hybrid catalysts” were reported in the recent years, revealing the synergetic effect between Pd and Rh. Regarding the hydrogenation of benzene/toluene, it could be shown that RhI-Pd0/SiO2 are 4 times more active than Pd0/SiO2. In particular, the scope of this work was the extension of the “hybrid catalysts” by the use of chiral phosphine ligands. PdNPs were immobilized onto various mesoporous silica supports, having an ordered (e.g. MCM-41, SBA-15) or a non-ordered (e.g. Davisil B, Davison 62) structure, both in powdery form and as monoliths. Different immobilization methods were tested (impregnation, ionic exchange, CVD), whereupon CVD proved to be a promising procedure, giving high Pd loadings up to 1.95 wt % (expected: 2 wt %). Moreover, this method was suitable for both powdery silica materials and silica monoliths. Silica-supported chiral Cu(I) complexes of the type [CuI(PC-L*)]CF3SO3/SiO2 can be applied in the asymmetric cyclopropanation of -methyl styrene with ethyl diazoacetate (EDA). Regarding the different mesoporous ordered- and non-ordered silica supports (MCM-41, SBA-15, Davisil B, Aerosil, basic silica), SBA-15 turned out to be the most-suitable one, giving excellent Cu loadings up to 1.79 wt %. The application of the [CuI(PC-L*)]CF3SO3/SiO2 catalysts gave the cyclopropanes in high yields (83 %). In this context, the recyclability of [CuI(PC-L*)]CF3SO3/SiO2 could be proven. Silica monoliths are very advantageous and thus gladly used as support material: Besides their easy handling, they allow to work in flow conditions without packing a reactor. Within this work, silica monoliths were grafted and subsequently applied in the dehydration of fructose to 5-hydroxymethylfurfural (HMF). It was shown that the reaction works in batch as well as in flow, both homogeneously (using the sole unsupported grafting agent) and heterogeneously (using blank or grafted silica monoliths).

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Sen, Fatih. « The Preparation And Analysis Of New Carbon Supported Pt And Pt+second Metal Nanoparticles Catalysts For Direct Methanol Fuel Cells ». Phd thesis, METU, 2012. http://etd.lib.metu.edu.tr/upload/12614728/index.pdf.

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In this thesis, firstly, carbon-supported platinum nanoparticle catalysts have been prepared by using PtCl4 and H2PtCl6 as starting materials and 1-hexanethiol, and tert-octanethiol, as surfactants for the first time. Secondly, these prepared catalysts were heated to 200 °
C, 300 °
C, and 400 °
C for 4 h under argon gas. Lastly, PtRu/C catalysts, which have different atomic percent ratios of Pt and Ru (Pt/Ru: 0.8, 2.1 and 3.5), were prepared using PtCl4 and RuCl3 as starting materials and tert-octanethiol as a surfactant. Each was characterized by X-ray diffraction, transmission electron microscopy, energy dispersive analysis, X-ray photoelectron spectroscopy, cyclic voltammetry, and elemental analysis, and their activities were determined toward the methanol oxidation reaction. It has been found that all prepared catalysts are more active toward methanol oxidation reaction compared to the commercial catalysts. It was also found that increasing the temperature during the heat treatment process results in an enlargement of platinum particle size and a decrease in catalytic activity in the methanol oxidation reaction. Transmission electron microscopy shows that platinum nanoparticles are homogeneously dispersed on the carbon support and exhibited a narrow size distribution with an average particle size of about 2-3 nm in diameter. X-ray photoelectron spectra of all catalysts indicated that most of the platinum nanoparticles (>
70 %) have an oxidation state of zero and rest (<
30 %) have a +4 oxidation state with (Pt 4f7/2) binding energies of 71.2-72.2 and 74.3-75.5 eV, respectively.

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Benia, Hadj Mohamed. « Spatially resolved optical measurements on supported metal particles and oxide surfaces with the STM ». Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2008. http://dx.doi.org/10.18452/15862.

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In der vorliegenden Arbeit wurde mit Hilfe eines Photon-STM die Korrelation zwischen optischen Eigenschaften und der lokalen Morphologie an zwei unterschiedlichen Systemen untersucht. Hierfür wurden zum einem oxidgetragene Ensemble von Silber-Partikeln präpariert, wobei sowohl die Partikelform (Kuppel- und Scheibenform) als auch die deponierte Partikeldichte variiert werden konnte. Neben der Präparation solcher Partikel auf Al10O13/NiAl, konnten sphärische Silber-Kolloide geordnet, als auch ungeordnet auf HOPG aufgebracht und untersucht werden. Dabei zeigte sich, dass das Verhältnis von Höhen zu Breiten nicht nur einen signifikanten Einfluss auf die Mie-Resonanz des einzelnen Partikels hat, sondern auch die elektromagnetische Kopplung der Partikel in einem Ensemble stark kontrolliert. Die energetische Lage der Mie-Resonanz zeigt im Fall der kuppelförmigen Ag-Partikel eine starke Abhängigkeit vom Intepartikel-Abstand, was sich in einer Verschiebung zu höheren Energien für eine steigende Partikeldichte äußert. Eine solche Abhängigkeit konnte bei den Ensembles der scheibenförmigen Partikel nicht beobachtet werden. Des weiteren zeigte sich, dass, verglichen mit den ungeordneten Ensembles, die selbstorganisierte langreichweitige Ordnung der Silber-Kolloide auf HOPG nur einen schwachen Einfluss auf die energetische Position der Mie Resonanz hat.Das zweite hier untersuchte System sind dünne MgO Filme unterschiedlicher Dicken auf einem Mo(001) Substrat. Diese zeigen ein reichhaltiges Wachstumsverhalten, welches durch eine Differenz in den Gitterkonstanten von 5.3% begründet ist und erst ab etwa 25 ML zu einem flachen und defektarmen Film führt. Die so induzierte Spannung relaxiert bis zu einer Dicke von etwa 7 ML in einer periodischen Überstruktur die aus abwechselnd flachen und verkippten Ebenen an der MgO-Mo Grenzschicht hervorgeht. Für MgO Filme mit einer Dicke von etwa 12 ML werden dann Schraubenversetzungen, ausgedehnte verkippte Ebenen und Stufenkanten mit einer Orientierung entlang der Richtung beobachtet. Die optische Charakterisierung durch Feldemission von Elektronen aus der STM-Spitze in den MgO-Film wird dominiert von zwei Emissionsmaxima bei Energien von 3.1 eV und 4.4 eV. Die kontrollierte Nukleation von Gold Partikeln und die Erzeugung von Farbzentren im MgO Film erlaubten eine Zuordnung dieser Emissionen zu strahlenden Zerfällen von Exitonen an Ecken, Kinken bzw. Stufen des Magnesiumoxids. Solche Emissionsprozesse konnten allerdings nur unter Einstellungen beobachtet werden, bei denen ein gleichzeitiges Rastern der Oberfläche unmöglich ist. Bei moderaten Einstellungen war auch eine ortsaufgelösten Spektroskopie möglich, wobei dann neue Emissionsmechanismen beobachtet wurden. Dabei sind zwei Prozesse wesentlich; zum einen die Ausbildung von sog. Spitzen-induzierten Plasmonen im Bereich zwischen Spitze und dem Mo-Substrat, zum anderen strahlende Elektronenübergänge zwischen sog. Feldemissionsresonanzen, die sich im Spitze/MgO-Film System ausbilden.
In this thesis, the correlation between the optical properties and the local morphology of supported silver nanoparticle ensembles and MgO thin films deposited on Mo(001) systems is explored by means of Photon-STM. In the first section, dome and disk shaped Ag nanoparticle ensembles with increasing density on an alumina film on NiAl(110) were analyzed as well as ordered and disordered ensembles of Ag nanocolloids on HOPG. The aspect ratio of the Ag nanoparticles was found to have a significant influence not only on the Mie plasmon resonance of a single particle, but also on the electromagnetic coupling within the nanoparticle ensembles. The Mie resonance in the ensemble of dome shaped Ag nanoparticles shows a strong dependence on the interparticle distance, where it shifts to higher energies with increasing particle density, due to destructive interference effects. In the disk-like Ag ensembles, however, the plasmon energy is independent of particle-particle separation. The long-range lateral ordering of size-selected Ag nanocolloids is found to induce a high dipole-dipole coupling within the ensemble. This is mainly reflected by the enhancement of the spectral intensity of the in-plane Mie mode, due to constructive coupling. However, ensembles with either well-ordered or disordered arrangements reveal no important difference in their optical properties, reflecting the weak influence of the long-range order in the particle ensemble. Thin MgO films with different thicknesses were grown on a Mo(001) surface. The stress resulting from the 5.3% lattice mismatch between the MgO(001) and the Mo(001) lattice parameters is found to control the surface morphology of the MgO film until thicknesses of around 25ML at which flat and defect-poor films are obtained. The relaxation of the stress induces a periodic network in the first 7ML of the MgO film, consisting of alternated flat and tilted mosaics. The presence of screw dislocations, steps oriented along the MgO directions, and tilted planes is observed when the MgO films are approximately 12ML thick. In addition, an increase of the MgO work function around these new surface features is revealed from STM spectroscopy. The photon emission induced by field-emitted electron injection from the STM tip into the MgO films is dominated by two emission bands located at 3.1eV and 4.4eV. To check the origin of these bands, further experiments, namely, nucleation of Au particles and creation of F-centers on the MgO surface, have been performed. The nucleation of Au particles at the low coordinated sites is found to quench the MgO optical signal, while the creation or annihilation of F-centers does not alter the MgO emission bands. The 3.1eV and the 4.4eV bands are therefore assigned to the radiative decay of MgO excitons at corner and kink sites, and step sites, respectively. Besides, spatially resolved optical measurements in the tunneling mode of the STM revealed different light emission mechanisms. These radiative processes are mainly related to tip-induced plasmons that form between the tip and the Mo support and to electron transitions between field-emission-resonance states in the STM tip-MgO film junction. The signal from exciton decays at corners and kinks of the MgO surface is however only observed at excitation conditions where the spatial resolution is already strongly reduced.

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Wyrzgol, Sonja Agnes [Verfasser], Johannes A. [Akademischer Betreuer] Lercher et Moniek [Akademischer Betreuer] Tromp. « Controlled Catalysis by the Electronic Charge Transfer at Metal-Support Interfaces : A Study of Gallium Nitride Supported Platinum Nanoparticles / Sonja Agnes Wyrzgol. Gutachter : Johannes A. Lercher ; Moniek Tromp. Betreuer : Johannes A. Lercher ». München : Universitätsbibliothek der TU München, 2013. http://d-nb.info/1043802223/34.

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Saoud, Khaled Mohammad Eqab. « Carbon Monoxide Oxidation on Nanoparticle Catalysts and Gas Phase Reactions of Small Molecules and Volatile Organics with Metal Cations ». VCU Scholars Compass, 2005. http://scholarscompass.vcu.edu/etd/1372.

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This dissertation demonstrates the application of a vapor phase method to synthesize supported and unsupported nanoparticle catalysts for CO oxidation. The method is based on the Laser Vaporization/Controlled Condensation (LVCC) technique. The first part of this dissertation presents the vapor phase synthesis and characterization of gold nanoparticles supported on a variety of oxide supports such as CeO2, TiO2, CuO and MgO.The results indicate that Au nanoparticles supported on CeO2 exhibit higher catalytic activity than Au supported on other oxides. The high activity of the Au/CeO2 catalyst is attributed to the strong interaction of Au with CeO2. The results also indicate that 5% Au loading on CeO2 has higher activity than 2% Au or 10% Au. When comparing the catalytic activity of Au/CeO2 prepared by physical (LVCC) and chemical (deposition-precipitation)methods, it was found that the catalytic activity is higher for Au/CeO2 prepared by the deposition-precipitation method.The effect of alloying Au and Cu nanoparticles on the catalytic activity for low temperature CO oxidation was also investigated. The unsupported Au-Cu alloy nanoparticle catalyst exhibits higher catalytic activity than the activities of the individualcomponents and their physical mixtures. The XRD data of Au-Cu alloy taken after the catalysis test indicates the formation of CuO within the bimetallic nanoparticles, whichimproves the catalytic activity of Au-Cu alloy nanoparticle.The second part of this dissertation investigates the gas phase reactions of Au+ and Cu+ with CO, O2 and H2O molecules using the Laser Vaporization ionization, High-Pressure Mass Spectrometry (LVI-HPMS) technique. The gas phase reactions resulting from the interactions of Au+ with CO and O2 molecules are investigated. Although multiple additions of CO and O2 molecules on Au+ have been observed at room temperature, no evidence was found of the production of CO2. This is attributed to the presence of water molecules which effectively replace the oxygen molecules on Au+ at room temperature.Finally, the role of the metal cations Au+ and Cu+ in initiating the gas phase polymerization of butadiene and isoprene vapors was investigated.

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Vijwani, Hema. « Hierarchical Porous Structures with Aligned Carbon Nanotubes as Efficient Adsorbents and Metal-Catalyst Supports ». Wright State University / OhioLINK, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=wright1433350549.

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Hong, Jingping. « Novel preparation techniques and reactivity of cobalt metal nanoparticles for synthesis of clean fuels using Fischer-Tropsch reaction ». Thesis, Lille 1, 2009. http://www.theses.fr/2009LIL10018/document.

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La synthèse Fischer-Tropsch permet de produire des carburants propres à partir du gaz naturel, de la biomasse ou du charbon. Les carburants issus d’une synthèse Fischer-Tropsch sont totalement exempts de soufre et de composés aromatiques. Cette thèse présente de nouvelles approches de conception des catalyseurs Fischer-Tropsch à base de cobalt supportés par des silices mésoporeuses. Ces approches sont fondées sur la promotion de catalyseurs par le ruthénium et la zircone, sur l’utilisation de la technique plasma pour la décomposition du précurseur de cobalt, ainsi que sur l’étude cinétique des étapes élémentaires de la réaction Fischer-Tropsch dans des conditions transitoires dont la méthode TAP. La structure des catalyseurs a été caractérisée à chaque étape de leur synthèse et de leur activation par des techniques physico-chimiques dont certaines techniques in-situ. Il a été démontré que la promotion des catalyseurs avec le ruthénium et l’oxyde de zirconium dépendait fortement de la texture du support. La promotion améliore la performance catalytique de façon plus importante pour les catalyseurs supportés par les silices qui possèdent des pores plus étroits. L’utilisation de la technique plasma pour la décomposition du cobalt permet de contrôler efficacement la taille des nanoparticules de cobalt et donc d’améliorer de façon significative les performances catalytiques. Les études transitoires et la modélisation des étapes élémentaires ont fourni des informations fondamentales sur la nature des sites actifs des catalyseurs à base de cobalt pour la réaction Fischer-Tropsch
Fischer-Tropsch synthesis produces clean hydrocarbon fuels from natural gas, biomass or coal. These synthetic fuels are totally free of sulfur and aromatics. This thesis addresses novel approaches to the design of cobalt Fischer-Tropsch catalysts supported by mesoporous silicas. These approaches involve catalyst promotion with ruthenium and zirconium oxide, use of plasma technology for the decomposition of cobalt precursors and kinetic studies of the elementary steps of the Fischer-Tropsch by transient kinetic methods including TAP. The structure of catalysts was characterized at each stage of their synthesis and their activation by physico-chemical techniques including in-situ methods. It was shown that the promotion of catalysts with ruthenium and zirconium oxide strongly depended on the texture of the support. The promotion improved the catalytic performance more importantly for the catalysts supported by narrow pore silicas. Use of plasma technology for the decomposition of cobalt precursors allowed efficient control of the size of cobalt nanoparticles and thus resulted in the enhanced catalytic performance. Transient kinetic studies and modeling of the elementary reaction steps have provided fundamental information on the nature of active sites in the supported cobalt catalysts for Fischer-Tropsch reaction

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El, Sayed Sami Verfasser], Walter [Akademischer Betreuer] [Leitner et Andrij [Akademischer Betreuer] Pich. « Metal nanoparticles immobilized on molecularly modified supports as multifunctional catalysts for the selective hydrogenation of aromatic substrates / Sami El Sayed ; Walter Leitner, Andrij Pich ». Aachen : Universitätsbibliothek der RWTH Aachen, 2021. http://d-nb.info/1233734989/34.

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Behafarid, Farzad. « Structure, stability, vibrational, thermodynamic, and catalytic properties of metal nanostructures : size, shape, support, and adsorbate effects ». Doctoral diss., University of Central Florida, 2012. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/5121.

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Recent advances in nanoscience and nanotechnology have provided the scientific community with exciting new opportunities to rationally design and fabricate materials at the nanometer scale with drastically different properties as compared to their bulk counterparts. In this dissertation, several challenges have been tackled in aspects related to nanoparticle (NP) synthesis and characterization, allowing us to make homogenous, size- and shape-selected NPs via the use of colloidal chemistry, and to gain in depth understanding of their distinct physical and chemical properties via the synergistic use of a variety of ex situ, in situ, and operando experimental tools. A variety of phenomena relevant to nanosized materials were investigated, including the role of the NP size and shape in the thermodynamic and electronic properties of NPs, their thermal stability, NP-support interactions, coarsening phenomena, and the evolution of the NP structure and chemical state under different environments and reaction conditions.
Ph.D.
Doctorate
Physics
Sciences
Physics

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Bernsmeier, Denis Robert [Verfasser], Ralph [Akademischer Betreuer] Krähnert, Ralph [Gutachter] Krähnert, Peter [Gutachter] Strasser et Christina [Gutachter] Roth. « Noble metal nanoparticles supported in ordered mesoporous carbon coatings as efficient electrocatalysts for the hydrogen evolution reaction / Denis Robert Bernsmeier ; Gutachter : Ralph Krähnert, Peter Strasser, Christina Roth ; Betreuer : Ralph Krähnert ». Berlin : Technische Universität Berlin, 2017. http://d-nb.info/1156014301/34.

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Xu, Zhenxin. « Development of new macroscopic carbon materials for catalytic applications ». Thesis, Strasbourg, 2019. http://www.theses.fr/2019STRAF005/document.

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De nos jours, les matériaux carbonés macroscopiques font face à un nombre croissant d'applications en catalyse, soit en tant que supports, soit directement en tant que catalyseurs sans métal. Cependant, il reste difficile de développer un support de catalyseur hiérarchisé à base de. carbone ou un catalyseur utilisant un procédé de synthèse beaucoup plus simple. À la recherche de nouveaux matériaux carbonés structurés pour la catalyse hétérogène, nous avons exploré le potentiel du feutre de carbone / graphite du commerce (FC / FG). Le but du travail décrit dans cette thèse a été le développement du monolithe FG et FC en tant que catalyseur sans métal pour les réactions d’oxydation en phase gazeuse et en tant que support de catalyseur, notamment pour le palladium, pour les réactions d’hydrogénation en phase liquide, et leur rôle dans la performance de réaction de ces catalyseurs. En raison de leur surface de chimie inerte avec une mouillabilité inappropriée, une telle étude avait pour condition d'activer celles d'origine. Par conséquent, des FG et des FC modifiés bien arrondis ont été synthétisés avec des propriétés physico-chimiques adaptées par une série de procédés de traitement chimique, tels que l'oxydation, l'amination, la thiolation, le dopage à l'azote et au soufre. L’oxydation partielle du sulfure d’hydrogène en soufre élémentaire et l’hydrogénation sélective du cinnamaldéhyde α, β-insaturé, en tant que réactions sensibles à l’effet des propriétés du catalyseur sur l’activité et la sélectivité, combinées à des techniques de caractérisation, ont été choisis pour étudier l’effet de la matériaux carbonés sur le comportement catalytique
Nowadays, macroscopic carbon materials are facing an increasing number of applications in catalysis, either as supports or directly as metal-free catalysts on their own. However, it is still challenging to develop hierarchical carbon-based catalyst support or catalyst using a much simple synthesis process. In the quest for novel structured carbon materials for heterogeneous catalysis we explored the potential of commercial carbon/graphite felt (CF/GF). The aim of the work described in this thesis has been the development of GF and CF monolith as metal-free catalyst for gas-phase oxidation reactions and as catalyst support, notably for palladium, for liquid-phase hydrogenation reactions, and their roles in the reaction performance of these catalysts. Due to their inert chemistry surface with inappropriate wettability, a prerequisite for such a study was to activate the origin ones. Therefore, well-rounded modified GFs and CFs were synthesized with tailored physic-chemical properties by a series of chemical treatment processes, such as oxidation, amination, thiolation, nitrogen- and sulfur-doping. The partial oxidation of hydrogen sulfide into elemental sulfur and selective hydrogenation of α, β-unsaturated cinnamaldehyde, as the sensitive test reactions to the influence of the catalyst properties on activity and selectivity, combined with characterization techniques, were chosen to investigate the effect of functionalized carbon materials on the catalytic behavior

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Mazilu, Irina. « Nanoparticules métalliques déposées sur des matériaux poreux multifonctionnels pour des applications catalytiques ». Thesis, Poitiers, 2017. http://www.theses.fr/2017POIT2268.

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L’objectif de cette thèse est le développement de nouveaux systèmes catalytiques à base de nanoparticules métalliques non nobles (Cu et/ou Co MNPs) déposées sur des supports mésostructurés multifonctionnels. Plusieurs supports ont été préparés par dopage de silices SBA-15 avec des hétéroatomes de type Al, Ga et Fe en utilisant la méthode de saut de pH ou par recouvrement de la surface de la SBA-15 par les oxydes correspondants en utilisant l’infiltration des sels fondus. Egalement, des supports SBA-15 hybrides organique-silice sont synthétisés par élimination partielle du porogène, et ont été utilisés pour la dispersion des phases métalliques. Les caractérisations et les résultats catalytiques démontrent que la fonctionnalisation des supports SBA-15 avec des hétéroatomes ou avec des groupements polyéthers permettent d’obtenir un contrôle amélioré de l’environnement local des MNPs hébergées, permettant d’ajuster à la fois l'interaction métal-support et la taille des nanoparticules, pour finalement affiner les performances catalytiques en termes d'activité et de chimiosélectivité pour l'hydrogénation en phase liquide d'aldéhydes insaturés tels que le cinnamaldéhyde. De plus, les matériaux SBA-15 dopés par l’oxyde de fer, isolé et/ou fortement dispersé, présentent d’excellentes propriétés catalytiques pour la dégradation de polluants dans l’eau (Reactive Red 120)
The objective of the Ph.D. thesis is the development of new catalytic systems based on non-noble metal nanoparticles (Cu and/or Co MNPs) hosted in functional mesostructured hosts. To this aim, various supports are prepared by doping SBA-15 with Al, Ga and Fe heteroatoms using the two-step pH-adjustment method or by coating the SBA-15 surface with Al, Ga and Fe oxides using the melt infiltration approach. Likewise, hybrid organic-silica SBA-15 supports are obtained by partial extraction of the Pluronic P123 surfactant. The characterization and catalytic results show that the functionalization of SBA-15 supports with heteroatoms or with polyether groups originating from the native surfactant represents new strategic lines to achieve an enhanced control on the local environments of hosted MNPs and to engineer both the metal-support interaction and nanoparticle size, ultimately to fine tuning the performances of Cu and/or Co-based nanocatalysts in terms of activity and chemoselectivity for the liquid-phase hydrogenation of unsaturated aldehydes, such as cinnamaldehyde. Furthermore, SBA-15 materials containing Fe species in isolated and/or highly dispersed states are evaluated for the Fenton-type peroxidation of Reactive Red 120 azo dye, exhibiting excellent catalytic properties for the dye degradation

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Wang, Changlong. « Nanomatériaux à base de métaux de transition pour la catalyse ». Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30106/document.

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La nanocatalyse à base de métaux de transition constitue un domaine prometteur pour lequel l'efficacité accrue, le caractère de chimie verte et le recyclage sont activement recherchés. Dans cet esprit, cette thèse a été dédiée à la synthèse, la caractérisation et les applications catalytiques de nouveaux nanomatériaux à base de métaux de transition. D'une part, en catalyse homogène colloïdale, des nanoparticules de métaux de transition stabilisées par des ligands amphiphiles ont procuré d'excellentes performances catalytiques en terme d'activité, stabilité et recyclabilité pour la réduction du nitro-4-phénol, le couplage de Suzuki-Miyaura, le transfert d'hydrogéné et la cyclo-addition entre un alcyne et un azoture dans l'eau. D'autre part, en catalyse hétérogène, le design, la synthèse et les applications catalytiques de nano-catalyseurs basés sur les supports de type graphène ou architectures moléculaires organiques ont également été conduits. Leurs excellentes propriétés catalytiques ont été démontrées pour la réduction du nitro-4-phénol, le couplage de Sonogashira, la cyclo-addition des alcynes avec les azotures et l'hydrolyse d'ammonia-borane avec génération d'hydrogène dans l'eau dans les conditions ambiantes
Transition metal nanocatalysis is a promising area, where increased efficiency, greenness and reusability are actively sought. In this spirit, the thesis has been devoted to the synthesis, characterization and catalytic applications of new transition metal nanomaterials. Amphiphilic ligand stabilized transition metal nanoparticles catalysts have provided excellent catalytic performances in terms of activity, stability and recyclability in the 4-nitrophenol reduction, Suzuki-Miyaura coupling, transfer hydrogenation and alkyne-azide cycloaddition reactions with low amounts of metal loadings. Moreover, an efficient amphiphilic "click" CuI catalyst was also designed for part-per-million levels of alkyne-azide cycloaddition reaction in water. The design, synthesis and catalytic application of heterogeneous nanocatalysts based on graphene and metal organic framework supports have also been carried out, and their excellent catalytic properties in 4-nitrophenol reduction, Sonogashira coupling, alkyne-azide cycloaddition and hydrolysis of ammonia-borane for hydrogen generation in water under ambient conditions have been disclosed

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Favaro, Marco. « A rational approach to the optimization of efficient electrocatalysts for the next generation Fuel Cells ». Doctoral thesis, Università degli studi di Padova, 2014. http://hdl.handle.net/11577/3424667.

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The PhD project has been performed in the Surfaces and Catalysts group active in the Department of Chemical Sciences, within the frame of the grant “A rational approach to the optimization of efficient electrocatalysts for the next generation Fuel Cells”, funded by CARIPARO foundation. The project has been focused on the preparation and characterization of new carbon-based materials for applications in Polymer Electrolyte Membrane Fuel Cells (PEMFCs), also known as oxygen-hydrogen FCs. The preparation of the materials has been performed using different techniques, depending on the type of the target material and on the possible applications that these materials can offer. With reference to the studied model systems (Highly Oriented Pyrolytic Graphite (HOPG) and Glassy Carbon (GC)), the introduction of doping heteroatoms has been performed by ion implantation, while the study of new chemical functionalities has been allowed by the use of Wet Chemistry techniques, in particular derived from the electrochemical synthesis. The deposition of thin films or nanoparticles (metal or oxides of transition metals) on the ion-modified materials has been carried out in-situ by using advanced techniques under Ultra High Vacuum conditions (UHV), such as Physical Vapor Deposition (PVD). Within the study of the model systems, PVD was chosen because of its ability to provide an atomic scale control of the metal deposition. In a second time, conventional deposition techniques such as chemical or electrochemical reduction of suitable metal precursors have been performed, in a synergistic combination between Surface Science and Electrochemistry-derived techniques. The characterization of these materials has been performed using the facilities of the Surface Science group, such as the X-ray and Ultraviolet Photoelectron Spectroscopy (XPS - UPS), Scanning Tunneling and Atomic Force Microscopy (STM - AFM), Scanning Electron Microscopy (SEM), Energy Dispersive X-ray spectroscopy (EDX) and Low Energy Electron Diffraction (LEED). To get a deeper insight in the chemistry/structure/properties of the prepared systems, synchrotron light-based techniques such as HR-XPS, NEXAFS, ARPES, ResPES and PEEM have been extensively used. The study of the electro-catalytic activity has been performed using conventional Electrochemistry techniques, in particular Cyclic and Linear Sweep Voltammetry (CV - LSV), as well as electro-dynamic techniques such as Rotating Disk Electrode (RDE). Finally, in order to support the experimental data or to bring their understanding at a deeper level, simulations using Density Functional Theory (DFT) have been performed in collaboration with the group coordinated by Prof. Cristiana Di Valentin (University of Milano Bicocca). During the course of the doctorate, several collaborations have been pursued with other research groups operating in the Department of Chemical Sciences or abroad, such as the "Interfaces and Energy Conversion E19" research unit, Technical University of Munich (TUM, Germany), coordinated by Profs. O. Schneider and J. Kunze-Liebhäuser.
Il progetto di dottorato nasce all’interno del gruppo di ricerca di Superfici e Catalizzatori operante nel dipartimento di Scienze Chimiche, nell’ambito della borsa a titolo vincolato “Un approccio razionale alla ottimizzazione di elettrocatalizzatori efficienti per le celle a combustibile di nuova generazione”, finanziata da fondazione CARIPARO. Le tematica è stata focalizzata sulla preparazione e caratterizzazione di nuovi materiali a base di carbonio utilizzabili per applicazioni in celle a combustibile di tipo PEMFCs (Polymer Electrolyte Membrane Fuel Cells) ad ossigeno-idrogeno. La preparazione dei materiali è avvenuta facendo uso di differenti tecniche, in relazione al tipo di materiale oggetto di studio ed alle applicazioni che tali materiali possono offrire. Con riferimento allo studio dei sistemi modello (grafite pirolitica altamente orientata, HOPG, e carbonio vetroso, GC), il drogaggio degli stessi mediante l’introduzione di eteroatomi (in particolare azoto) è avvenuto ricorrendo alla tecnica dell’impiantazione ionica, mentre lo studio di nuove funzionalità chimiche è stato permesso dall’utilizzo di tecniche di Wet Chemistry, in particolare mutuate dalla sintesi elettrochimica. La deposizione di film sottili o di nanoparticelle (metalliche o a base di ossidi di metalli di transizione) su tali materiali modificati è stata effettuata facendo uso di tecniche avanzate come la deposizione fisica da fase vapore (PVD) in condizioni controllate di Ultra Alto Vuoto (UHV), in grado di offrire un controllo su scala atomica della deposizione di tali film. Sono state utilizzate anche tecniche di deposizione tradizionali quali la riduzione chimica o elettrochimica di opportuni precursori metallici: l‘utilizzazione di una siffatta combinazione sinergica tra tali differenti tecniche di preparazione ha permesso di ottenere materiali caratterizzati da strutture e proprietà peculiari. La caratterizzazione di tali materiali è svolta utilizzando le facilities del gruppo di Scienza delle Superfici, come la spettroscopia di fotoelettroni (XPS) o della banda di valenza (UPS), la microscopia ad effetto tunnel o a forza atomica (STM - AFM), la microscopia elettronica e la dispersione energetica dei raggi X indotta dagli elettroni (SEM-EDX), la diffrazione di elettroni lenti (LEED). Allo scopo di caratterizzare maggiormente in dettaglio la struttura e le proprietà chimiche dei materiali preparati sono state usate estensivamente le tecniche di indagine offerte dalla luce di sincrotrone (HR-XPS, NEXAFS, ARPES, ResPES, PEEM), mentre lo studio della reattività catalitica si basa su tecniche derivate dall’analisi elettrochimica, in particolare la voltammetria ciclica ed a scansione lineare del potenziale applicato, nonchè tecniche elettro-dinamiche come la voltammetria su elettrodo rotante. Infine, allo scopo di supportare i dati sperimentali o portare la comprensione delle proprietà dei materiali ad un livello più profondo, simulazioni mediante teoria del funzionale densità (DFT) sono state adottate per un approccio critico allo studio dei materiali preparati (in collaborazione con il gruppo coordinato dalla prof. Cristiana Di Valentin, Università di Milano Bicocca). Durante il corso del dottorato, diverse collaborazioni sono state perseguite con gruppi interni al Dipartimento di Scienze Chimiche o anche Esteri, come l’unità di ricerca “Interfaces and Energy Conversion E19”, dell’università tecnica di Monaco di Baviera (TUM, Technische Universität München, Germania), coordinata dai proff. O. Schneider e J. Kunze-Liebhäuser.

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