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Catalysis

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Articles 31 - 41 of 41

Full-Text Articles in Inorganic Chemistry

Synthesis, Kinetic And Catalytic Studies Of Manganese Complexes With Corrole And Porphyrin Ligands, Haleh Jeddi Apr 2017

Synthesis, Kinetic And Catalytic Studies Of Manganese Complexes With Corrole And Porphyrin Ligands, Haleh Jeddi

Masters Theses & Specialist Projects

High-valent transition metal-oxo intermediates play a significant role in the catalytic cycle of the ubiquitous cytochrome P450 enzymes and in biomimetic catalytic systems. In this work, manganese(III) porphyrin and corrole systems (2) were synthesized and characterized by UV-vis absorbance and 1H-NMR, matching literaturereported spectroscopic data. Manganese(V)-oxo corroles (3) and a manganese(IV)-oxo porphyrin (4) were successfully generated by chemical oxidation using mchloroperoxybenzoic acid (m-CPBA), and their oxidation reactions with organic reductants were comparatively investigated. Results from single-turnover kinetic studies indicate that in the tris(pentafluorophenyl)corrole system (3a), the active oxidizing intermediate differs in different solvents. The active oxidizing intermediate in acetonitrile is …


Synthesis And Catalytic Applications Of Non-Metal Doped Mesoporous Titania, Syed Z. Islam, Suraj R. Nagpure, Doo Young Kim, Stephen E. Rankin Mar 2017

Synthesis And Catalytic Applications Of Non-Metal Doped Mesoporous Titania, Syed Z. Islam, Suraj R. Nagpure, Doo Young Kim, Stephen E. Rankin

Chemical and Materials Engineering Faculty Publications

Mesoporous titania (mp-TiO2) has drawn tremendous attention for a diverse set of applications due to its high surface area, interfacial structure, and tunable combination of pore size, pore orientation, wall thickness, and pore connectivity. Its pore structure facilitates rapid diffusion of reactants and charge carriers to the photocatalytically active interface of TiO2. However, because the large band gap of TiO2 limits its ability to utilize visible light, non-metal doping has been extensively studied to tune the energy levels of TiO2. While first-principles calculations support the efficacy of this approach, it is challenging to …


Decarbonylative Cross Coupling Of Phthalimides With Diorganozinc Reagents—Efforts Toward Catalysis, Kimberly S. Deglopper, Sarah K. Fodor, Thomas Bd Endean, Jeffrey B. Johnson Jan 2016

Decarbonylative Cross Coupling Of Phthalimides With Diorganozinc Reagents—Efforts Toward Catalysis, Kimberly S. Deglopper, Sarah K. Fodor, Thomas Bd Endean, Jeffrey B. Johnson

Faculty Publications

The decarbonylative coupling of phthalimides with diorganozinc reagents to form o-substituted benzamides has been previously demonstrated as a viable process, but only with stoichiometric nickel(0). Investigations into a number of reaction variables, including solvent, ligand, and substrate substitution, have yielded multiple sets of conditions capable of achieving up to 10 catalyst turnovers, most successfully with the use of electron withdrawing nitrogen substituents on the phthalimide. In addition, these investigations have provided insight into the intermediates within the catalytic cycle and have revealed new approaches to the development of a general catalytic methodology.


Sol-Gel Assembly Of Metal Nanostructures Into Metallic Gel Frameworks And Their Applications, Xiaonan Gao Jan 2016

Sol-Gel Assembly Of Metal Nanostructures Into Metallic Gel Frameworks And Their Applications, Xiaonan Gao

Theses and Dissertations

The advent of nanoscience and nanotechnology has sparked many research forefronts in the creation of materials with control over size, shape, composition, and surface properties.1,2 However, for most of the applications, nanoscale materials need to be assembled into functional nanostructures that exhibit useful and controllable physical properties. Therefore, numerous efforts on the assembly of nanoparticles (NPs) using organic ligands, polymers and polyelectrolytes have been reported.3,4 However, the interactions between NPs are mediated by intervening ligands, which are detrimental to charge transport and limit the thermal stability. Hence, developing a new method to produce solid …


Towards Catalytic Oxidative Depolymerization Of Lignin, Justin K. Mobley Jan 2016

Towards Catalytic Oxidative Depolymerization Of Lignin, Justin K. Mobley

Theses and Dissertations--Chemistry

Lignin is one of the most abundant and underutilized biopolymers on earth. Primarily composed on three monolignol units (sinapyl, coniferyl, and p-coumaryl alcohol), lignin is formed through a radical pathway resulting in an assortment of linkages, of which the β-O-4 linkage is the most prevalent (up to 60% in some hardwood species). In planta, lignin plays an important role in water transport and in protecting plants from chemical and biological attack. Traditional attempts to depolymerize lignin have focused on the cleavage of β-O-4 linkages via thermal or reductive routes. However these pathways lead to low-value, unstable product mixtures. Moreover, …


Synthesis, Characterization, And Catalytic Applications Of Porous Transition-Metal Oxide Systems For The Conversion Of Biomass, Anton Gudz May 2015

Synthesis, Characterization, And Catalytic Applications Of Porous Transition-Metal Oxide Systems For The Conversion Of Biomass, Anton Gudz

Honors Scholar Theses

The development of innovative strategies and environmentally-friendly resources for the sustainable production of fuels and chemicals from renewable materials has recently received much interest in the scientific world. Among such resources, biomass has enormous potential as a raw material for generation of green fine chemicals to replace the petroleum feedstocks currently in place. Biomass derived carbohydrates can be converted into such valuable platform chemicals as levulinates, 5-hydroxymethyl furfural (HMF), and lactates. In order to catalyze the biomass conversion process, porous transition-metal oxide catalytic systems have been developed in this study. High catalytic activities and potential for reusability of such systems …


Utilization Of Biomass Derived Furans In Value-Added Organics And Heterogeneous Oxorhenium Catalysts For Deoxydehydration Of Diols, Benjamin L. Wegenhart Oct 2013

Utilization Of Biomass Derived Furans In Value-Added Organics And Heterogeneous Oxorhenium Catalysts For Deoxydehydration Of Diols, Benjamin L. Wegenhart

Open Access Dissertations

As fossil fuels are depleted, there is a growing focus on renewable chemicals based on biomass materials, including both fuels and chemical feedstocks. Current methods for biomass utilization include biological conversion to produce ethanol and various thermochemical routes (gasification, pyrolysis, liquefaction, hydrothermal treatment, etc.). Furfural is one particular chemical that can be obtained from lignocellulosic biomass in good yields through the dehydration of sugar residues. It can be used as a feedstock for chemicals such as furan and THF, or as a platform molecule for making liquid fuels. The objective of this research is to investigate new pathways for the …


Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee Jan 2013

Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee

Applied Research Center Publications

Brust–Schiffrin reduction of Pd and Pt precursors in the presence of resorcinarene amine surfactant led to the formation of substantially Pt rich, PdPt bimetallic nanoparticles of a V-shape or variants on the V-shape. New insights into this reaction are provided on the basis of reversed Brust–Schiffrin syntheses, DLS, UV-vis, and NMR analysis. Based on our experiments we conclude that the resorcinarene amine surfactant is part of the inverse micelle formed from TOABr and it also selectively complexes with the Pd salts prior to their reduction. Remarkably, the composition of the bipodal nanoparticles could be varied substantially by varying the reaction …


Synthetic And Mechanistic Studies Of Coupling Reactions Involving C-H Bond Activation, Ki Hyeok Kwon Jul 2011

Synthetic And Mechanistic Studies Of Coupling Reactions Involving C-H Bond Activation, Ki Hyeok Kwon

Dissertations (1934 -)

Transition metal-catalyzed C-C bond forming reactions involving C-H bond activation have been shown to be effective methods for functionalization of unreactive compounds. Since Murai's pioneering work on ruthenium-catalyzed regioselective arene-to-alkene coupling reactions, a number of well-defined, late transition metal catalysts have been shown to mediate regioseletive C-C bond forming reaction involving C-H bond activation. Recently, late transition metal complexes have also been found to catalyze the regioselective coupling reaction of nitrogen containing compounds with alkenes as well as sp3 bond insertions and oxidative coupling reaction of aimdes. The catalytic C-C bond forming reaction involving C-H bond activation would provide simple …


Synthesis And Catalytic Activity Of Nanostructured Cerium Oxide, Neil J. Lawrence Dec 2010

Synthesis And Catalytic Activity Of Nanostructured Cerium Oxide, Neil J. Lawrence

Department of Chemistry: Dissertations, Theses, and Student Research

Cerium oxide (ceria, CeO2-x where x is 0 to 0.5) has been one of the most widely used heterogeneous catalysts particularly in three way catalytic converters. Most of the catalytic traits can be attributed to two properties of ceria: first, the high mobility and storage capacity of oxygen within the lattice; second, the ease with which cerium changes between Ce3+ and Ce4+ states. These properties, combined with the abundance of cerium on earth, make ceria a low-cost highly effective alternative to noble metal catalysts. Recent research has been focused on the nanoscale properties of ceria.

The effect …


Synthesis Of Meta-Terphenyl Scaffolded Molecules For Catalysis And Sensor Applications, Brad Morgan May 2010

Synthesis Of Meta-Terphenyl Scaffolded Molecules For Catalysis And Sensor Applications, Brad Morgan

All Dissertations

The utility of the m-terphenyl has been observed in a wide variety of applications since its first discovery. The tunable conformational flexibility contributes to the unique properties and resulting applications thereof. Chapter 1 goes into detail about the concepts used throughout and defines the tools needed to understand the chemistry in the
resulting chapters.
The primary use of the m-terphenyl herein is as a canopy that shields a pocket created underneath the central ring. Functionalization within this pocket allows metal binding in defined coordination environments. with the use of donor ligands attached to the flanking rings. The applications of these …