Dissertations / Theses: 'Oxidation Transition metal halides'

1

Moock, K. H. "Electrochemical studies on transition metal halides." Thesis, University of Glasgow, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.375467.

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Field, Marianne Alice Louise. "Transition metal oxides and oxide-halides." Thesis, University of Southampton, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.401833.

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Ye, Jianjun. "Electronic spectroscopy of transition metal monohalides." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/hkuto/record/B38990167.

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Hodges, Philip J. "Transition metal halides, studied by high-resolution electronic spectroscopy." Thesis, University of Oxford, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.433477.

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5

Rispens, Minze Theunis. "Enantioselective oxidation using transition metal catalysts." [S.l. : [Groningen : s.n.] ; University Library Groningen] [Host], 1996. http://irs.ub.rug.nl/ppn/291237975.

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Orrin, Rachel H. "Photo-oxidation of transition metal carbonyls." Thesis, University of Reading, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.317044.

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Opre, Zsuzsanna. "Catalytic oxidation over transition metal containing hydroxyapatites /." Zürich : ETH, 2007. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=17247.

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Handley, Darren. "Triangulo-trinuclear tmeda complexes of the first transition series." Thesis, University of Sussex, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311347.

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Wilson, Antony. "A matrix isolation study of transition metal halides and their structure." Thesis, University of Hull, 2009. http://hydra.hull.ac.uk/resources/hull:2527.

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The work within this thesis has concentrated on the formation and isolation of titanium, vanadium, palladium, and mercury halides, with emphasis on the fluorides.TiF, TiF2, TiF3, and TiF4 have all been isolated within an argon matrix and infrared spectra obtained. From the titanium isotope splitting pattern a bond angle has been determined for TiF2 for the first time of 165o, or effectively linear. This work is also the first time that TiF has been isolated within an argon matrix. Work has also been conducted with vanadium which has lead to the isolation of VF5, VF4, VF3, and VF2, with VF4 undergoing Fermi Resonance. This is the first time that VF4 and VF2, consistent with a linear structure, have been isolated within a matrix.Work conducted upon palladium led to the isolation of numerous palladium fluorides, identified by the palladium isotope patterns in their IR spectra. Due to the similarity of the calculated stretching frequencies of PdF2, PdF3, PdF4, and PdF6 the assignment was challenging and so identification of these bands was conducted based photolysis and annealing behaviour in conjunction with computational calculations. This has allowed for the assignment of the bands present to PdF6, PdF4, PdF3, PdF2, and PdF.The bond length of molecular HgF2 has also been determined for the first time at 1.94(2) Å using the Hg L3-edge with EXAFS. Although the initial aim of this work was to isolate HgF4, using IR, UV/Vis, and XANES, no evidence could be found for oxidation states of mercury higher that HgII. The work also developed a new clean way of making HgF2 in a matrix. The identification of a new Hg…X2 complex was also discovered which when photolysed forms the HgX2 compound, this has only been proven for HgF2. This was achieved by isolating mercury atoms in an argon matrix doped matrices, photolysis of this matrix the led to the formation of HgF2 in significant amounts.

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Spittle, Peta Jean. "Characterisation of high temperature metal halides by mass spectrometry and matrix isolation infrared spectroscopy." Thesis, University of Southampton, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.242391.

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Rogan, Luke. "Transition metal based catalysts for aerobic alcohol oxidation." Thesis, Queen's University Belfast, 2016. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.709812.

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The selective oxidation of alcohols to the corresponding carbonyl product is an important transformation. Traditionally this reaction has been carried out using stoichiometric oxidants, but such methods are highly undesirable from an environmental viewpoint. In the fine chemical and pharmaceutical industries, oxidative transformations prove problematic, and are often avoided, due to a limited number of existing chemoselective and sustainable oxidation methods. The demand for new, environmentally sustainable and efficient alcohol oxidation methods has driven academic research, and a number of systems have emerged which employ catalytic metal loadings with oxygen as the terminal oxidant. In terms of sustainability, oxygen is the ideal oxidant as it is abundant, and water is the only byproduct formed during aerobic alcohol oxidation catalysis. In spite of the progress made in recent years, the introduction of such systems into industrial processes has not occurred. The aim of this thesis is the development of sustainable and industrially viable catalyst systems for aerobic alcohol oxidation. The research reported in this thesis studies two different catalytic systems. Firstly, the combination of nitroxyl radicals with copper complexes was explored (Chapter 2). The substrate scope was studied, using different nitroxyl radicals, exploring the effect of steric hindrance. The influence of mass transfer and gas pressure was also examined, in order to more efficiently utilise these expensive nitroxyl radicals. In Chapters 3 and 4, research was focused on a zeolite encaged 1,10-phenanthroline-Pd(NO3)2 catalyst system. The aim of these studies was to develop a stable Pd(ll) catalyst which would exhibit longer lifetimes compared to homogeneous systems.

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Zweni, Pumza P. "Dendrimer-transition metal catalyzed oxidation and reduction reactions." Thesis, University of Ottawa (Canada), 2005. http://hdl.handle.net/10393/10529.

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This project was launched with the aim of developing dendrimer catalysts for oxidation and reduction reactions. Poly(amidoamine) (PAMAM) and poly(propyleneimine) (PPI) dendrimers were of interest because of their well-established synthesis. Chapter 1 describes the fundamentals of dendrimers and provides a brief insight of their application in catalysis. In particular, examples of dendritic catalysts that have been previously employed as oxidation and reduction catalysts are presented. Chapter 2 presents the synthesis and characterization of silica-supported PAMAM dendrimers, their phosphomethylation with Ph2 PCH2OH, and their complexation to palladium complexes. Chapter 3 reports the application of the silica-supported PAMAM-Pd complexes to the oxidation of alkenes to methyl ketones under Wacker-type conditions as well as the use of tBuOOH as the oxidant in these reactions. Chapter 4 discusses the use of the above-mentioned complexes to catalyze the selective hydrogenation of dienes to monoolefins in the presence of H2 under mild reaction conditions. Chapter 5 presents our efforts in modifying PPI dendrimers with the salen moiety to give ligands that are coordinated to the metals Ti and V. Attempts at using the former complexes to promote the epoxidation of alkenes and the latter complexes to catalyze the epoxidation of olefinic alcohols are discussed.

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Gu, Yanjuan, and 谷艳娟. "Nanostructure of transition metal and metal oxide forelectrocatalysis." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B37774396.

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Tothill, J. N. "An investigation into the magnetic properties of certain Mott insulating transition metal compounds close to delocalization." Thesis, University of Bristol, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.376619.

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Bierenstiel, Matthias. "Transition Metal Catalyzed Selective Oxidation of Sugars and Polyols." Diss., lmu, 2005. http://nbn-resolving.de/urn:nbn:de:bvb:19-37863.

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Loades, Stephen David. "Bonding to transition metal atoms in low oxidation states." Thesis, University of Liverpool, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.333641.

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Ward, Karachie. "Oxidation Chemistry of Some Early Transition-Metal Layered Perovskites." ScholarWorks@UNO, 2005. http://scholarworks.uno.edu/td/143.

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Early transition-metal oxyhalides, (MCl)LaNb2O7 (M = V, Cr) have been prepared by ion exchange of layered perovskite hosts, ALaNb2O7 (A = Li, Rb), with anhydrous metal halides, MCl2. These compounds contain low-valent metals (M2+) that are receptive to oxidation. Thermogravimetric analysis (TGA) shows oxygen uptake at low temperatures (< 500 °C) and subsequent X-ray powder diffraction indicates that the host structure is maintained upon oxidation. Also through EDAX of the starting material and products, it has been found that there is a loss of chlorine upon oxidation. Thorough characterization of oxidation products will be presented and the ramifications of this chemistry on low-temperature topotactic formation of metal-oxide layers within perovskite hosts will be discussed.

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Ravindran, Mythili. "Synthesis and structural studies of N- and O- donor complexes of transition and post-transition metal halides." Thesis, University of Warwick, 1991. http://wrap.warwick.ac.uk/108596/.

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Trimethylamine reacts with MCl2 (M = Mn, Cd, Cu) to give mono adducts of the type MC12Nme3. Recrystallization of MnC12-Nme3 (1) from the polar solvent acetonitrile yields the anionic complexes [NMe3H] [MnCl3] (II) and [Nme3H]2 [MnCl4Δ] (III) both from the same solution. Similarly CuCl2NMe3 (IV) gives lNMe3H][CdCl3\ (V). Recrystallization of CuCliUMe3 (VI) from the chlorinated solvent CH2CI2 yields the anionic complex [Me3NCH2Cl]2 [CuC1Δ] (VII). Compounds (II). (V) and (VII) were further investigated by X-ray crystal structure determinations. The co-ordination chemistry of Group VB trichlorides with the neutral O-donor (crown ether) ligands 1,4,7,10-tetraoxacyclododecane (I2-C-4), 1,4,7,10,13- pentaoxacyclopentadecane (I5-C-5) and 1,4,7,10,13,16-hexaoxacyclooctadecane (18-C- 6) have been investigated. 12-C-4 and 15-C-5 form neutral adducts with the pyramidal MCI3 (M = As, Sb, Bi) where all oxygen atoms of the crown are co-ordinated to the metal atom in a half-sandwich structure. For I8-C-6, AsC13 does not give complex formation, instead the crown ether forms a bis-adduct (18-C-6).2CH3CN with the solvent acetonitrile. SbC13 forms a half-sandwich adduct with I8-C-6 but with an extra molecule of CH3CN trapped in the lattice and BiC13 forms a 2:1 complex which has the ionic formulation 1B2C12(18-C-6)12 + lB12CI312 Here the bismuth cation is eight co-ordinate involving all six oxygen atoms of the crown and the two chlorine atoms. The crown ethers give no simple adducts with the pentahalide SbC15. The crystals obtained from the reactions of I2-C-4 and I8-C-6 with SbC15 are the unexpected hydroniumfcrown) hexachloroantimon(V)ate salts, |H3O(12-C-4)2] (SbC1o1) and [H3O(18-C-6)] [SbC1o) respectively. I5-C-5 gives the neutral Sb(lll) adduct SbC13(l5-C-5) as the major product and the hydroniumfcrown) hexachloroantimon(V)ate salt as the minor product. A plausible mechanism for the formation of hydronium antimon(V)ate salts is presented and discussed. In the preliminary study of sterically crowded aryloxide complexes of Group VB chlorides, the reaction between SbCli and the extremely bulky 2,6-di(tertiary butyl) phenoxide has been investigated. This leads to the formation of 22' .6,6’ -tetra (tertiary butyl) diphenoquinone (A) via a redox reaction. The crystal structure of this oxidation product has been determined via an X-ray study and a plausible mechanism for the formation of (A) is presented and discussed.

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Lakin, Miles T. "Complexation of early- and post-transition metal halides with aza-, oxa-, and thiamacrocyclic ligands." Thesis, University of Warwick, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.357585.

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20

England, Jason. "Multidentate N-donor ligands in transition metal catalysed alkane oxidation." Thesis, Imperial College London, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.424716.

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Schilling, Waldemar [Verfasser]. "Approaches for Transition Metal-Free Photocatalytic Oxidation Reactions / Waldemar Schilling." Göttingen : Niedersächsische Staats- und Universitätsbibliothek Göttingen, 2021. http://d-nb.info/1233009001/34.

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22

Taylor, Mark Stewart. "Wetting and CO oxidation on transition metal and bimetallic surfaces." Thesis, University of Liverpool, 2015. http://livrepository.liverpool.ac.uk/3001403/.

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The oxidation of carbon monoxide has been investigated in two different systems, Au alloyed with Pd(111) at room temperature and Cu(110) at 90 to 170 K. All experiments were conducted under UHV conditions using mass spectrometry and temperature-programmed desorption to follow the reaction. For the Au/Pd(111) system the intention was to improve the catalytic activity of the pure Pd(111) crystal by alloying with Au, as bimetallic alloys often display enhanced catalytic activities compared to that of the pure metal due to a combination of both ensemble and ligand effects. The ensemble effects being the arrangement of the active atoms and the ligand effects the electronic modifications or charge transfer associated with these active atoms. This was carried out by vapour deposition of various amounts Au on the Pd(111) crystal and annealing to form a surface alloy. Enhanced catalytic activities of up to 27 % was achieved by alloying with Au coverages of 0.2 0.4 ML on the Pd(111) substrate followed by annealing to temperatures 650 – 750 K compared to that of the pure Pd(111) surface. For the Cu(110) system we aimed to assess the catalytic activity of Cu, the objective being to determine the exact kinetic mechanism of the oxidation reaction at 90 to 170 K. This was done initially by pre-adsorbing O2 on the Cu(110) substrate surface at various coverage, followed by CO and monitoring for CO2 production. The experiment was then reversed with CO pre-dosed followed by O2. The catalytic oxidation reaction was found to proceed by a hot-precursor mechanism when O2 was dosed on a CO pre-covered surface above 130 K. Below this temperature any O2 dosed prior to or after the CO uptake would tend to physisorb molecularly and only reacted during dissociation while the O atom remained in a reactive transient. Here, the atomic O reacted directly with adsorbed molecule CO transiently prior to adsorption to the Cu substrate a catalytic reaction akin to that of an Eley-Rideal mechanism. We have studied the wetting properties, autocatalytic dissociative adsorption and the reactivity of the hydroxyl species originating from the co-adsorption of water and oxygen on Cu(110) at 200 to 300 K. Experiments were conducted by two separate methods; using molecular beam uptakes and by varying the static H2O pressures from 1.0 x 10 11 up to 5.0 x 10 7 mbar in conjunction with LEED and TPD. It has been hypothesized that the strong attractive interaction between mixed OH and H2O slows down the desorption kinetics of H2O sufficiently to produce H2O-OH structures that are stable up to RT. As a result the main focal point of the research was to gain some insight into the bonding mechanisms at elevated water pressures and ambient temperatures, whilst assessing the stability of the H2O-OH species. In addition to the 1H2O:1OH chains structures and dimers observed previous at these temperatures we also observed an additional stable structure during the TPD experiments. This structure appeared particularly when H2O was adsorbed with low (0.06 ML) atomic O coverages and became increasingly prominent when the uptake temperature was increased from 200 up to 240 K. The origin of this structure is discussed in the context of the structure proposed by earlier investigators.

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Maule, C. H. "An investigation into the 3d'1 and 3d'2 transition Metal halides and oxyhalides considered as being close to delocalisation." Thesis, University of Bristol, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.379541.

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Pelosin, Primavera. "Molecular water oxidation catalysts based on first row transition metal complexes." Doctoral thesis, Universitat Rovira i Virgili, 2020. http://hdl.handle.net/10803/670969.

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L'objectiu d'aquesta tesi era estudiar el procés d'oxidació de l'aigua mitjançant catalitzadors moleculars basats en metalls de transició de primera fila. En el capítol tres es va demostrar la importància del disseny de lligands en la formació de catalitzadors d’oxidació d’aigües resistents (WOC) basats en coure. Es va demostrar que un lligand tetraamidate macrocicle (TAML) estabilitza el complex durant la catàlisi mitjançant la deslocalització de les càrregues positives generades. A més, l'efecte macrocicle impedeix la desmetal·lació àcida del catalitzador, que era actiu també a pH neutre. En el quart capítol es va descriure un procediment innovador per formar ànodes moleculars. El WOC basat en Cu de TAML descrit anteriorment es va modificar amb restes de pirè, formant dos regioisòmers amb propietats electròniques diferents. Tots dos regioisòmers es van ancorar a la superfície d’elèctrodes d’òxid d’estany d’indi (ITO) mitjançant l’electropolimerització dels fragments de pirè en dissolvents orgànics. L'activitat dels ànodes es va provar mitjançant l'elèctrode de disc d'anell rotatiu (RRDE) a pH 7,5, 9 i 10. El capítol cinc es centra en la determinació de la naturalesa real de la catàlisi. Aquest estudi pren com a exemple un complex de ferro pentanuclear, considerat un WOC molecular, que en realitat es descompon en presència d’aigua i d’alts potencials. Es va confirmar que l’espècie activa era hematita mitjançant diverses anàlisis com EDX, SEM, XPS i XAS.
El objetivo de esta tesis fue estudiar el proceso de oxidación del agua mediante catalizadores moleculares basados en metales de transición de primera fila. En el capítulo tres se demostró la importancia del diseño de ligandos en la formación de catalizadores de oxidación de agua (WOC) resistentes basados en cobre. Se demostró que un ligando tetra-amidate macrociclo (TAML) estabiliza el complejo durante la catálisis mediante la deslocalización de las cargas positivas generadas. Además, el efecto del macrociclo evita la desmetalización ácida del catalizador, que también era activo a pH neutro.En el cuarto capítulo se describió un procedimiento innovador para formar ánodos moleculares. El WOC basado en Cu de TAML descrito anteriormente se modificó con pireno, formando dos regioisómeros con distintas propiedades electrónicas. Ambos regioisómeros se anclaron en la superficie de electrodos de óxido de indio y estaño (ITO) mediante electropolimerización del pireno en disolventes orgánicos. La actividad de los ánodos se evaluó mediante un electrodo de disco de anillo giratorio (RRDE) a pH 7,5, 9 y 10. El capítulo cinco se centra en la determinación de la naturaleza real de la catálisis. Este estudio toma como ejemplo un complejo de hierro pentanuclear, considerado un WOC molecular, que en realidad se descompone en presencia de agua y altos potenciales. Se confirmó que la especie activa era hematita mediante varios análisis como EDX, SEM, XPS y XAS.
The objective of this thesis was to study the process of water oxidation through molecular catalysts based on first row transition metals. In chapter three was proved the importance of ligand design in the formation of rugged water oxidation catalysts (WOCs) based on copper. A tetra-amidate macrocycle ligand (TAML) was proved to stabilize the complex during catalysis through -delocalization of the generated positive charges. Further the macrocycle effect prevents the acidic demetallation of the catalyst, which was active also at neutral pH. In the fourth chapter was described an innovative procedure to form molecular anodes. The previously described TAML Cu-based WOC was modified with pyrene moieties, forming two regio-isomers with distinct electronic properties. Both the regio-isomers were anchored on the surface of indium tin oxide (ITO) electrodes through electropolymerization of the pyrene moieties in organic solvents. The anodes activity was tested through rotating ring disk electrode (RRDE) at pH 7.5, 9 and 10. The Chapter five is focused on the determination of the real nature of the catalysis. This study takes as an example a pentanuclear iron complex, considered a molecular WOC, which actually decomposes in presence of water and high potentials. The active species was confirmed to be hematite through several analysis as EDX, SEM, XPS and XAS.

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Ding, Zhong Yi. "Catalytic supercritical water oxidation of aromatic compounds on transition metal oxides /." Access abstract and link to full text, 1995. http://0-wwwlib.umi.com.library.utulsa.edu/dissertations/fullcit/9528550.

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Pérez, Inés Monte. "Bioinspired oxidation reactions involving mono- and poly-nuclear transition metal complexes." Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät, 2017. http://dx.doi.org/10.18452/17741.

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Hochvalente Metal-oxo-, -peroxo- und -nitrenzentren später Übergangsmetalle werden als reaktive Intermediate vieler technologisch interessanter und biologischer Transformationsreaktionen wie die Oxidation von Kohlenwasserstoffen, Hydroxylierung, Aminierung, Aziridierung und Sauerstoffreduktion angenommen. Die Isolierung und Charakterisierung solcher Intermediate, wenngleich sie sich schwierig gestaltet, kann wichtige Informationen zum Mechanismus solcher Reaktionen liefern und kann somit zu einer gezielten Optimierung und Herstellung von verbesserten Katalysatoren genutzt werden. In dieser Arbeit wurden drei unterschiedliche Intermediate – Eisenoxo , Kobaltperoxo- und Kupfernitrenkomplexe – näher untersucht. Es konnte in dieser Arbeit gezeigt werden, dass die Reaktivität der hier untersuchten hoch-valenten reaktiven Intermediate maßgeblich abhängig vom Ligandsystem, dem Zentralmetall und dem verwendeten Oxidationsmittel sind.
High-valent metal-oxo, -peroxo and -nitrene cores of late transition metals have been proposed as reactive intermediates in transformations that are both technologically attractive and fundamental for the functioning of biological systems, like the activation of C−H bonds in hydrocarbons and the reduction of dioxygen. The isolation and characterization of such species, despite being challenging, provides valuable information about the mechanisms of the reactions performed and can help in the design of improved catalysts. In this work, three different kinds of intermediates were studied, namely iron-oxo, cobalt-peroxo and copper-nitrenes. Several new reactive species were isolated and spectroscopically characterized, and their reactivity was thoroughly investigated. It was shown that the reactivity patterns of the high-valent reactive intermediates here studied depend greatly on subtle changes in the ligand system, the metal center and the oxidant employed.

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Kim, Minkyu. "Multiscale Modeling of Oxidation and Reduction Chemistry on Transition Metal Oxides." The Ohio State University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=osu1531307161494595.

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Koeckerling, Martin Dr rer nat. "Über metallreiche Halogenide und Chalkogenide früher Übergangsmetalle - Metal-rich halides and chalcogenides of early transition elements." Gerhard-Mercator-Universitaet Duisburg, 2001. http://www.ub.uni-duisburg.de/ETD-db/theses/available/duett-09112001-094019/.

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This habilitation thesis describes the syntheses and characterizations of mostly new metal-rich cluster compounds of early transition elements. It is devided into 4 parts. The first part describes the syntheses and solid-state X-ray structures of a total of 14 mixed-halide (iodide-chloride) zirconium cluster phases, which crystallize in 9 different (some novel) structure types. All these cluster phases contain octahedral Zr6Z-units that are centered by an interstitial atom Z. Phase widths and relations between the differend structure types are discussed. The second part deals with molecular (soluble) zirconium cluster phases which are excised from solid-state precursors. It is shown that liquid mixtures of 1,3-dialkylimidazolium bromide and AlBr3 as well as molten 18-crown-6 are useful solvents for molecular zirconium cluster compounds. The syntheses and single crystal X-ray structures of 3 new materials are detailed. Furthermore, from the reaction of an iron containing Zr-cluster phase with KSCN crystals have been obtained from which a single crystal X-ray structure analysis shows that they contain a high symmetry Fe-cubane cluster. The third part of this thesis is concerned with theoretical investigations (Extended-Hckel band structure calculations) of a series of monoclinic phases which contain double-octahedral chains of rare earth metal clusters of the general formula RE3I3Z (RE = rare-earth metal atoms). The results of the electronic band structure calculations show that the observed structural variations within this series depend largely on the difference of the orbital energies of the rare earth metals and the interstitials. In the last part the phase pure synthesis of Nb21S8 and measurements of physical properties (electrical conductivity and magnetical susceptibility) as well as results from electronic band structure calculations (LMTO) are described. The property measurements show that this metal rich sulfide becomes superconducting below 3.7(2) K. The results from the electronic band structure calculations indicate the existence of an arrangement of electronic levels ("fingerprint") which favors the formation of superconducting Cooper pairs.

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Dixon, Emma Louise. "A matrix isolation study of the vapour phase species of transition metal halides and their reactivity." Thesis, University of Hull, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.411907.

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Ono, Takashi. "Second-Row Transition-Metal Complexes Relevant to CO2." Doctoral thesis, Universitat Rovira i Virgili, 2014. http://hdl.handle.net/10803/276964.

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dinucleares de rutenio que contienen ligandospolypyridyl. Estos complejos se han aplicado para las reacciones catalíticas, tales como la reducción de CO2 y la oxidación del agua y sustrato orgánico. En la primera, las actividades catalíticas hacia la reducción de CO2 se han investigado desde el punto de vista de las propiedades electrónicas y estéricas de los catalizadores, así como su nuclearidad. En el segundo, la aplicación de mono-y dinucleares complejos de Ru-aqua que contienen ligando tridentadoaniónico hacia reacción de oxidación se ha estudiado. Además, una reactividad potencial de dianión molibdato, que puede ser considerado como modelo homogéneo de catalizadores de óxido de metal heterogéneos para la transformación de CO2 se ha estudiado.
This thesis has been focused on the synthesis and characterization of a series of new mono- and dinuclear ruthenium complexes containing polypyridyl ligands. These complexes have been applied for the catalytic reactions, such as CO2 reduction and oxidation of water and organic substrate. In the first, the catalytic activities toward CO2 reduction have been investigated from the viewpoint of electronic and steric properties of the catalysts as well as their nuclearity. In the second, the application of mono- and dinuclear Ru-aqua complexes containing anionic tridentate ligand toward oxidation reaction has been studied. Additionally, a potential reactivity of molybdate dianion, which can be considered as homogeneous model of heterogeneous metal oxide catalysts for CO2 transformation has been studied.

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Pan, Li. "First-Principles Studies of the Reactivity of Transition Metal Oxide Surfaces." The Ohio State University, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=osu1448910602.

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Lamb, David J. "The oxidation of low density lipoprotein by cells and transition metal ions." Thesis, University of Reading, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.358450.

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McMorn, Paul. "Oxidation of selected organic compounds using transition metal containing silicates and aluminophosphates." Thesis, University of Liverpool, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.266048.

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Tarnai, Máté. "Oxidation of transition metal complexes with 3,7-diazabicyclo[3.3.1]nonane-derived ligands." [S.l. : s.n.], 2006. http://nbn-resolving.de/urn:nbn:de:bsz:16-opus-66199.

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35

Sharninghausen, Liam S. "Transition Metal Complexes for Glycerol Dehydrogenation and Study of Water Oxidation Catalysis." Thesis, Yale University, 2018. http://pqdtopen.proquest.com/#viewpdf?dispub=10957339.

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This dissertation describes the study of transition metal complexes in relation to two types of oxidation catalysis, namely dehydrogenation and water oxidation.

Chapters 1 and 2 explore dehydrogenation catalysis as a means of glycerol valorization. Glycerol is the major byproduct of biodiesel production (~10%), and there is thus intense interest in developing methods to convert this waste glycerol to more valuable products. One such product is lactic acid, which is commonly used in the food and detergent industries, and is a platform chemical that is seeing increasing demand. All prior methods for convening glycerol to lactic acid employed heterogeneous catalysts, which often require high temperatures and give generally poor selectivity and catalytic activity. In this work, I describe our study of homogeneous catalysts for glycerol conversion to lactic acid. Our Ir bis-NHC (NHC = N-heterocyclic carbene) precatalysts are superior to the previous systems in terms of selectivity and activity, and function in neat glycerol without the need for a co-solvent. These complexes can convert samples of crude glycerol from the biodiesel industry without the need for prior purification, suggesting their possible industrial application. Additionally, hydrogen is produced as a valuable byproduct. Chapter 2, carried out in collaboration with Professor Nilay Hazari (Yale), describes the study of catalysts based on non-precious metals for this reaction. A family of Fe precatalysts with bifunctional PNP pincer ligands give excellent selectivity and activity, and represent the first examples of homogeneous base-metal catalysts for glycerol conversion to lactic acid. In studies of Ir species formed from our Ir bis-NHC precatalysts during glycerol dehydrogenation, we isolated a series of unusual NHC-rich Ir polyhydride clusters (Chapter 3). These compounds are unprecedented in terms of their high NHC content, and were fully characterized using a variety of methods.

Chapters 4 and 5, carried out in collaboration with Shashi Sinha and Dimitar Shopov, joint BrudvigCrabtree students, describe the study of model complexes related to resting states and high oxidation state intermediates in water oxidation catalysis. Water oxidation has garnered intense interest because of its potential application in the production of solar fuels, but effective catalysts are needed to carry out the reaction with low overpotentials. Our group previously found that upon oxidative activation, the Cp*Ir(pyalk)OH precatalyst (pyalk = 2-pyridyl-2-propanolate) generates one of the most active and robust water oxidation catalysts reported to date. Previous spectroscopic characterization and DFT studies revealed that the Cp* ligand is oxidatively degraded, and the catalyst resting state likely consists of a mixture of related species with a (pyalk)₂Ir^IV-O-Ir^IV(pyalk) core. However, these species completely resisted purification and crystallization by standard methods. Therefore, we developed a protocol to more selectively prepare related CI(pyalk)₂Ir^IV-O-Ir^IV(pyalk)₂CI complexes, which can be isolated and crystallographically characterized. These complexes are unusual examples of well-defined Ir(IV,IV) mono-μ-oxo dimers, and are stable under ambient conditions, in contrast to previous examples of Ir(IV,IV) mono-μ-oxo dimers containing organometallic ligands. Our study of these complexes sheds light on the resting state of our Ir water oxidation catalyst, and opens the door to future development of well-defined Ir-oxo dimers for water oxidation catalysis.

In a related study (Chapter 5), we use techniques and insights that build on our Ir oxo-dimer study to synthesize unprecedented Ir(V) coordination complexes with organic ligands. Study of such well-defined high oxidation state complexes is of interest in relation to oxidation catalysis, where Ir(V) species have been proposed as key intermediates. In order to access Ir(V), we developed the ligand dpyp, an N,O,Odonor analogue of pyalk. Importantly, dpyp forms coordination complexes with four coplanar alkoxogroups, an arrangement that favors attainment of high oxidation states based on our previous work. Indeed, oxidation of Ir^IV(dpyp)₂gives Ir^V(dpyp)_⁺2+, which was fully characterized including by X-ray crystallography and DFT methods.

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36

To, Wai-pong, and 杜偉邦. "Transition metal catalysed photo-induced oxidative C-H bond functionalization and water oxidation." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2012. http://hdl.handle.net/10722/193012.

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A series of cyclometalated gold(III) complexes with N-heterocyclic carbine (NHC) or alkynyl as auxiliary ligand were synthesized and characterized. Complexes [AuIII(R1 –C^N^C)(NHC)](OTf) and [AuIII(C^N^C)(C≡CR2)] (HC^N^CH = 2,6-di(naphthalene-2-yl)pyridine; R1 = H or 4-methoxyphenyl; R2 =aryl) are emissive in solution at room temperature with quantum yields in the range of 0.65–11.4% and lifetimes ranging from 98 to 506 s. [AuIII(4-(4-OMePh)–C^N^C)(NHC)](OTf) showed prominent photochemical properties. This complex effectively catalyses photo-induced oxidation of secondary amines (to the corresponding imines) and -functionalization of tertiary amines in good to excellent yields; it also acts as a photosensitizer for hydrogen generation in a water/acetonitrile mixture, producing more than 350 turnovers of hydrogen after 4 hours of irradiation. Palladium(II) meso-tetrakis(pentafluorophenyl)porphyrin was found to be an efficient and robust catalyst for the photo-induced oxidative C–H bond functionalization reactions. Several kinds of -functionalized tertiary amines were obtained in good to excellent yields by irradiating a mixture of palladium(II) catalyst, corresponding tertiary amine and nucleophile under aerobic conditions. The nucleophiles for these reactions include cyanide, nitromethane, dimethyl malonate, diethyl phosphite and acetone. Two examples of novel intramolecularly cyclized amines were also described. Comparison of the UV-vis absorption spectra before and after reaction indicated that the palladium catalyst was highly robust. The practical potential of this catalyst was shown by the success in reactions at a low catalyst loading and on a large scale. The palladium(II) catalyst could also sensitize photo-induced oxidation of sulfide to sulfoxide and photo-induced hydrogen production in a water/acetonitrile mixture with up to 240 turnovers. [FeIII(L-N4Me2)Cl2][FeCl4] (L-N4Me2 = N,N’-dimethyl-2,11-diaza[3,3] (2,6)pyridinophane) was demonstrated to be an active catalyst for water oxidation. When cerium ammonium nitrate (CAN) was used as the oxidant, the iron(III) catalyst oxidized water to oxygen with up to 93 turnovers after 30 minutes in 0.1 M nitric acid, whereas changing the oxidant to sodium periodate (NaIO4) resulted in only 44 turnovers of oxygen after 30 minutes. The mechanism of the reaction was explored by high resolution electrospray ionization mass spectrometry (ESI-MS), 18O labeling, UV-vis absorption spectroscopy, kinetic plots and DFT calculations. In the case of using CAN, an FeIV-oxo species was detected by ESI-MS and UV-vis absorption spectroscopy. The rate of oxygen evolution was found to be linearly dependent on both concentrations of catalyst and oxidant. 18O labeling studies confirmed that the origin of oxo ligands was from water and was irrespective of the choice of oxidant. This reaction was proposed to involve a coupling between an FeIV-oxo species and a hydroxocerium(IV) radical. In the case of using NaIO4, an FeV-dioxo species was detected by ESI-MS as a major species, and a small amount of FeIV-oxo species was detected by UV-vis absorption spectroscopy. As the rate of oxygen evolution was found to be linearly dependent on the concentration of catalyst only, the reaction was proposed to involve a cis-FeV-dioxo species. DFT calculations showed that the cis-FeV-dioxo species was capable of oxidizing water to oxygen through the formation of an [FeIII(L-N4Me2)(OO?)(OH)]+ intermediate.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy

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37

Williams, Dara Bridget. "Tridentate, dianionic ligands for alkane functionalization with platinum(II) and oxidation of iridium(III) hydrides with dioxygen /." Thesis, Connect to this title online; UW restricted, 2007. http://hdl.handle.net/1773/8545.

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38

Lyvik, Amanda. "Design criteria for transition metal catalysts for water oxidation : Comparison of a catalyst with diﬀerent metal centers." Thesis, Uppsala universitet, Institutionen för kemi - BMC, 2018. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-358394.

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39

Li, Lin [Verfasser]. "Matrix Isolation and IR Spectroscopic Study on Late-Transition Fluorides, Metal Oxo Complexes and Actinide Halides / Lin Li." Berlin : Freie Universität Berlin, 2021. http://d-nb.info/1232726710/34.

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40

Shrestha, Sweta. "Application of Transition Metal Coordination for Energy Efficient Processes: Catalysis and Separation." The Ohio State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=osu1502975499629018.

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41

Najafian, Ahmad. "Activation of Small Molecules by Transition Metal Complexes via Computational Methods." Thesis, University of North Texas, 2020. https://digital.library.unt.edu/ark:/67531/metadc1703353/.

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The first study project is based on modeling Earth abundant 3d transition-metal methoxide complexes with potentially redox-noninnocent ligands for methane C–H bond activation to form methanol (LnM-OMe + CH4 → LnM–Me + CH3OH). Three types of complex consisting of tridentate pincer terpyridine-like ligands, and different first-row transition metals (M = Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) were modeled to elucidate the reaction mechanism as well as the effect of the metal identity on the thermodynamics and kinetics of a methane activation reaction. The calculations showed that the d electron count of the metal is a more significant factor than the metal's formal charge in controlling the thermodynamics and kinetics of C–H activation. These researches suggest that late 3d-metal methoxide complexes that favor σ-bond metathesis pathways for methane activation will yield lower barriers for C–H activation, and are more profitable catalyst for future studies. Second, subsequently, on the basis of the first project, density functional theory is used to analyze methane C−H activation by neutral and cationic nickel-methoxide complexes. This study identifies strategies to further lower the barriers for methane C−H activation through evaluation of supporting ligand modifications, solvent polarity, overall charge of complex, metal identity and counterion effects. Overall, neutral low coordinate complexes (e.g. bipyridine) are calculated to have lower activation barriers than the cationic complexes. For both neutral and cationic complexes, the methane C−H activation proceed via a σ-bond metathesis rather than an oxidative addition/reductive elimination pathway. Neutralizing the cationic catalyst models by a counterion, BF4-, has a considerable impact on reducing the methane activation barrier free energy. Third, theoretical studies were performed to explore the effects of appended s-block metal ion crown ethers upon the redox properties of nitridomanganese(V) salen complexes, [(salen)MnV(N)(Mn+-crown ether)]n+, where, M = Na+, K+, Ba2+, Sr2+ for 1Na, 1K, 1Ba, 1Sr complexes respectively; A = complex without Mn+-crown ether and B = without Mn+). The results of the calculations reveal that ΔGrxn(e ̶ ) and thus reduction potentials are quite sensitive to the point charge (q) of the s-block metal ions. Methane activation by A, 1K and 1Ba complexes proceeds via a hydrogen atom abstraction (HAA) pathway with reasonable barriers for all complexes with ~ 4 kcal/mol difference in energy, more favorable free energy barrier for the complexes with higher point charge of metal ion. Changes in predicted properties as a function of continuum solvent dielectric constant suggest that the primary effect of the appended s-block ion is via "through space" interactions. Finally, a comprehensive DFT study of the electrocatalytic oxidation of ammonia to dinitrogen by a ruthenium polypyridyl complex, [(tpy)(bpy)RuII(NH3)]2+ (complex a), and its NMe2-substituted derivative (b), is presented. The thermodynamics and kinetics of electron (ET) and proton transfer (PT) steps and transition states are calculated. NMe2 substitution on bpy reduces the ET steps on average 8 kcal/mol for complex b as compared to a. The calculations indicate that N–N formation occurs by ammonia nucleophilic attack/H-transfer via a nitrene intermediate, rather than a nitride intermediate. Comparison of the free energy profiles of Ru-b with its first-row Fe congener reveals that the thermodynamics are less favorable for the Fe-b model, especially for ET steps. The N-H bond dissociation free energies (BDFEs) for NH3 to form N2 show the following trend: Ru-b

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42

Grill, Joseph Michael. "The design of new ligands and transition metal compounds for the oxidation of organic compounds." [College Station, Tex. : Texas A&M University, 2006. http://hdl.handle.net/1969.1/ETD-TAMU-1746.

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43

Acuña-Parés, Ferran. "Theoretical study of water oxidation and reduction mechanisms by aminopyridine first row transition metal catalysts." Doctoral thesis, Universitat de Girona, 2016. http://hdl.handle.net/10803/398411.

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One of the major current scientific goals is the development of renewable energy sources. An effective alternative to fossil fuels consists in the conversion of the sunlight energy into chemical fuels. The molecular hydrogen from water is considered the most promising energy carrier. In the natural photosynthesis the solar energy is stored into the carbohydrate chemical bonds derived from water and CO2. The key step of this process is the photo-oxidation of H2O molecules into O2, which provides the protons and electrons needed to produce H2. A detailed knowledge of the reaction mechanisms results essential to enhance the catalytic performance and to ensure the compatibility of the water oxidation and proton reduction catalysts. In this thesis, the key steps of the water oxidation and proton reduction reactions catalyzed by a group of metal complexes and the catalysts structural features that benefit both processes are studied using computational tools
Un dels grans reptes actuals consisteix en el desenvolupament de fonts d'energia renovables. Una alternativa eficaç als combustibles fòssils consisteix en la conversió de l'energia solar en combustibles químics. L’hidrogen molecular provinent de l’aigua és considerat el portador d’energia més prometador. En la fotosíntesi natural l’energia solar és emmagatzemada en els enllaços químics dels carbohidrats obtinguts a partir d’aigua i CO2. L’etapa clau del procés és la foto-oxidació de l'aigua en O2, que aporta els protons i electrons necessaris per produir H2. El coneixement detallat del mecanisme de reacció resulta essencial per millorar el rendiment catalític i assegurar la compatibilitat dels catalitzadors d’oxidació de l’aigua i reducció de protons. En aquesta tesi, les etapes fonamentals del mecanisme de les reaccions d’oxidació de l’aigua o la reducció de protons catalitzades per un grup de complexos metàl·lics i les característiques estructurals dels catalitzadors que beneficien ambdues reaccions són estudiades utilitzant eines computacionals

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44

Cuzan, Olesea. "Synthesis and characterization of new transition metal complexes for catalytic oxidation and electrolytic proton reduction." Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4356/document.

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De nos jours, la capacité à synthétiser de nouveaux catalyseurs métallique bioinspirés pour améliorer et élargir le spectre d'activité catalytique est d’une importance capitale pour une chimie respectueuse de notre environnement.Cette thèse se concentre sur la conception de nouveaux complexes de métaux de transition (cuivre et palladium) basés sur deux classes différentes de ligands organiques : les benzotriazolyle-phénolates et les phosphonates. La synthèse et la caractérisation de nouveaux composés a été réalisée par différentes méthodes physico-chimiques (électrochimie, EPR, UV-vis, IR, cristallographie aux rayons X) et la chimie théorique. La génération et la caractérisation des différentes espèces réduites et oxydées nous ont aidés dans la détermination des mécanismes possible. Les composés obtenus ont été utilisés avec succès comme catalyseurs dans divers procédés tels que: la production d'hydrogène, l'oxydation d'alcool et le clivage d'ADN
Nowadays, the ability to synthesize new bioinspired metal catalysts to improve and broaden the spectrum of catalytic activity is of paramount importance for sustainable chemistry respectful for our environment. This thesis is focused on the design of transition metal complexes (copper and palladium) based on two different classes of organic ligands: benzotriazolyl-phenolates and phosphonates.Different original complexes based on palladium and copper were synthetized from benzotriazolyl-phenolate and phosphonates ligands. The characterization of the new compounds was performed by different physical and physico-chemical methods (electrochemistry, EPR, UV-vis, IR, X-ray crystallography) and quantum chemistry. The generation and characterization of different reduced and oxidized species helped us in the possible mechanisms determination. The obtained compounds were successfully employed as catalysts in different processes as: hydrogen production, alcohol oxidation and DNA cleavage

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45

Trotochaud, Lena. "Structure-Composition-Activity Relationships in Transition-Metal Oxide and Oxyhydroxide Oxygen-Evolution Electrocatalysts." Thesis, University of Oregon, 2014. http://hdl.handle.net/1794/18312.

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Solar water-splitting is a potentially transformative renewable energy technology. Slow kinetics of the oxygen evolution reaction (OER) limit the efficiency of solar-water-splitting devices, thus constituting a hurdle to widespread implementation of this technology. Catalysts must be stable under highly oxidizing conditions in aqueous electrolyte and minimally absorb light. A grand goal of OER catalysis research is the design of new materials with higher efficiencies enabled by comprehensive understanding of the fundamental chemistry behind catalyst activity. However, little progress has been made towards this goal to date. This dissertation details work addressing major challenges in the field of OER catalysis. Chapter I introduces the current state-of-the-art and challenges in the field. Chapter II highlights work using ultra-thin films as a platform for fundamental study and comparison of catalyst activity. Key results of this work are (1) the identification of a Ni0.9Fe0.1OOH catalyst displaying the highest OER activity in base to date and (2) that in base, many transition-metal oxides transform to layered oxyhydroxide materials which are the active catalysts. The latter result is critical in the context of understanding structure-activity relationships in OER catalysts. Chapter III explores the optical properties of these catalysts, using in situ spectroelectrochemistry to quantify their optical absorption. A new figure-of-merit for catalyst performance is developed which considers both optical and kinetic losses due to the catalyst and describes how these factors together affect the efficiency of composite semiconductor/catalyst photoanodes. In Chapter IV, the fundamental structure-composition-activity relationships in Ni1-xFexOOH catalysts are systematically investigated. This work shows that nearly all previous studies of Ni-based catalysts were likely affected by the presence of Fe impurities, a realization which holds significant weight for future study of Ni-based catalyst materials. Chapter V discusses the synthesis of tin-titanium oxide nanoparticles with tunable lattice constants. These materials could be used to make high-surface-area supports for thin layers of OER catalysts, which is important for maximizing catalyst surface area, minimizing the use of precious-metal catalysts, and optimizing 3D structure for enhanced mass/bubble transport. Finally, Chapter VI summarizes this work and outlines directions for future research. This work contains previously published and unpublished co-authored material.
2015-03-29

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46

Cecchini, Chiara. "Late Transition Metal-Oxo complexes: Synthesis, and Biorelevant Reactivity." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2016. http://amslaurea.unibo.it/11249/.

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High-valent terminal metal-oxygen adducts are supposed to be potent oxidising intermediates in enzymatic catalyses. In contrast to those from groups 6-8, oxidants that contain late transition metals (Co, Ni, Cu) are poorly understood. Because of their high reactivity, only a few examples of these compounds have been observed. The aim of this project was to investigate the reactivity of high-valent Ni(III) complexes, containing a monodentate oxygen-donor ligands, in hydrogen atom abstraction (HAA) and oxygen atom transfer (OAT) reactions which are typical of biological high-valent metal-oxygen species. Particularly, the Ni(III) complexes were generated in situ, at low temperature, from the oxidation of the Ni(II) species.The nickel complexes studied during this work were supported by tridentate ligands, with a strong σ-donating ability and exceedingly resistant to several common degradation pathways. These complexes vary based on the monodentate group in the fourth coordination position site, which can be neutral or anionic. In particular, we prepared four different Ni(III) complexes [NiIII(pyN2Me2)(OCO2H)] (12), [NiIII(pyN2Me2)(ONO2)] (14), [NiIII(pyN2Me2)(OC(O)CH3)] (18) and [NiIII(pyN2Me2)(OC(O)H)] (25). They feature a bicarbonate (-OCO2H), nitrate (-ONO2), acetate (-OC(O)CH3) and formate (-OC(O)H) group, respectively.HAA and OAT reactions were performed by adding 2,6-di-tert-butylphenol (2,6-DTBP) at -40°C, and triphenylphosphine (PPh3) at -80°C, to the in situ generated Ni(III) complexes, respectively. These reactions were carried out by adding 7 to 500 equivalents of substrate, in order to ensure pseudo-first order conditions. Since, the reactivity of the Ni(III) complex featured by the bicarbonate group has been studied in a previous work, we only investigated that of the species bearing the nitrate, acetate and formate ligand. Finally we compared the value of the reaction rate of all the four species in the HAA and OAT reactions.

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47

Fugate, Elizabeth Anne. "Investigation of Electronic Structure Effects of Transition Metal Oxides toward Water Oxidation and CO2 Reduction Catalysis." The Ohio State University, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=osu1462868623.

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48

Mitchell, Michael S. "Oxidation of biological molecules with bicarbonate-activated hydrogen peroxide and the decomposition of hydrogen peroxide catalyzed by manganese(II) and bicarbonate." [Gainesville, Fla.] : University of Florida, 2004. http://purl.fcla.edu/fcla/etd/UFE0004948.

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49

Shang, Hongyu SHANG. "Investigating Electronic Structure Effects in Transition Metal Oxides Used as Catalysts for Water Oxidation and CO2 Reduction." The Ohio State University, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=osu1525451894252362.

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50

Kuwata, Shigemasa. "Transition metal complexes of 3,7-diazabicyclo[3.3.1]nonane derivatives complex stabilities and oxidation reactivity of cobalt (II) and vanadium (IV) /." [S.l. : s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=974319856.

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Dissertations / Theses on the topic 'Oxidation Transition metal halides'

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