Matching Items (17)

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Computational Characterization of a Ni Catalyst

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Industrial interest in electrocatalytic production of hydrogen has stimulated considerable research in understanding hydrogenases, the biological catalysts for proton reduction, and related synthetic mimics. Structurally closely related complexes are often

Industrial interest in electrocatalytic production of hydrogen has stimulated considerable research in understanding hydrogenases, the biological catalysts for proton reduction, and related synthetic mimics. Structurally closely related complexes are often synthesized to define structure-function relationships and optimize catalysis. However, this process can also lead to drastic and unpredictable changes in the catalytic behavior. In this paper, we use density functional theory calculations to identify changes in the electronic structure of [Ni(bdt)(dppf)] (bdt = 1,2-benzenedithiolate, dppf = 1,1ʹ-bis(diphenylphosphino)ferrocene) relative to [Ni(tdt)(dppf)] (tdt = toluene-3,4-dithiol) as a means to explain the substantially reduced electrocatalytic activity of the tdt complex. An increased likelihood of protonation at the sulfur sites of the tdt complex relative to the Ni is revealed. This decreased propensity of metal protonation may lead to less efficient metal-hydride production and subsequently catalysis.

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  • 2018-05

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Synthesis and Characterization of Low-Valent Nickel Hydrosilylation Catalysts

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The addition of aminoalkyl-substituted α-diimine (DI) ligands to bis(1,5 cyclooctadiene) nickel (or (COD)2Ni) resulted in the formation of two new nickel complexes with the general formula of (Me2NPrDI)2Ni and (PyEtDI)2Ni.

The addition of aminoalkyl-substituted α-diimine (DI) ligands to bis(1,5 cyclooctadiene) nickel (or (COD)2Ni) resulted in the formation of two new nickel complexes with the general formula of (Me2NPrDI)2Ni and (PyEtDI)2Ni. Investigation of these complexes by 1H NMR spectroscopy revealed diimine coordination but also the absence of amine arm coordination. Using the 1H NMR spectra in conjunction with structures determined through single crystal X-ray diffraction, the electronic structure of both complexes was described as having a Ni(II) metal center that is antiferromagnetically coupled to 2 DI radical monoanions. A greater ligand field was sought by replacing the pendant amines with phosphine groups on the DI ligands. This yielded ligands with the general formula (Ph2PPrDI) and (Ph2PEtDI). Upon addition to (COD)2Ni, each ligand immediately displaced both COD ligands from the Ni0 center to produce new κ4 N,N,P,P complexes, (Ph2PPrDI)Ni and (Ph2PEtDI)Ni, as observed via single crystal X-ray diffraction and NMR spectroscopy. Reduction of the DI backbone was observed in both complexes, with both complexes being described as having a Ni(I) metal center that is antiferromagnetically coupled to a DI radical monoanion. In addition to alkylphosphine substituted DI ligands, the coordination of a pyridine diimine (PDI) ligand featuring pendant alkylphosphines was also investigated. The addition of (Ph2PPrPDI) to (COD)2Ni produced a new paramagnetic (μeff = 1.21 μB), κ4-N,N,N,P complex identified as (Ph2PPrPDI)Ni. Reduction of the PDI chelate was observed through single crystal X-ray diffraction with the electronic structure described as having a low-spin Ni(I) metal center that is weakly coupled to a PDI radical monoanion (SNi = 1/2). The ability of the three Ni complexes to mediate the hydrosilylation of several unsaturated organic substrates was subsequently investigated. Using a range of catalyst loadings, the hydrosilylation of various substituted ketones afforded a mixture of both the mono- and di-hydrosilylated products within 24 hours, while the hydrosilylation of various substituted aldehydes afforded the mono-hydrosilylated product almost exclusively within hours. (Ph2PEtDI)Ni and (Ph2PPrPDI)Ni were identified as the most effective catalysts for the hydrosilylation of aldehydes at ambient temperature using catalyst loadings of 1 mol%.

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  • 2014-05

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A Modelling Approach to Determine Gas and Temperature Profiles during Catalytic Reactions in Environmental Transmission Electron Microscopy

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A scheme has been developed for finding the gas and temperature profiles in an environmental transmission electron microscope (ETEM), using COMSOL Multiphysics and the finite element method (FEM). This model

A scheme has been developed for finding the gas and temperature profiles in an environmental transmission electron microscope (ETEM), using COMSOL Multiphysics and the finite element method (FEM). This model should permit better correlation between catalyst structure and activity, by providing a more accurate understanding of gas composition than the assumption of homogeneity typically used. While more data is needed to complete the model, current progress has identified several details about the system and its ideal modeling approach.
It is found that at the low pressures and flowrates of catalysis in ETEM, natural and forced convection are negligible forms of heat transfer. Up to 250 °C, radiation is also negligible. Gas conduction, being enhanced at low pressures, dominates.
Similarly, mass transport is dominated by diffusion, which is most accurately described by the Maxwell-Stefan model. Bulk fluid flow is highly laminar, and in fact borders the line between continuum and molecular flow. The no-slip boundary condition does not apply here, and both viscous slip and thermal creep must be considered. In the porous catalyst pellet considered in this work, Knudsen diffusion dominates, with bulk flow being best described by the Darcy-Brinkman equation.
With these physics modelled, it appears as though the gas homogeneity assumption is not completely accurate, breaking down in the porous pellet where reactions occur. While these results are not yet quantitative, this trend is likely to remain in future model iterations. It is not yet clear how significant this deviation is, though methods are proposed to minimize it if necessary.
Some model-experiment mismatch has been found which must be further explored. Experimental data shows a pressure dependence on the furnace temperature at constant power, a trend as-yet unresolvable by the model. It is proposed that this relates to the breakdown of the assumption of fluid continuity at low pressures and small dimensions, though no compelling mathematical formulation has been found. This issue may have significant ramifications on ETEM and ETEM experiment design.

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  • 2017-05

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Effect of Defects on Calculation of Electron Energy Loss Spectra of Ceria and Titania

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Climate change is one of the biggest challenges facing today's society.Since the late 19th century, the global average temperature has been rising. In order to minimize the temperature increase of

Climate change is one of the biggest challenges facing today's society.Since the late 19th century, the global average temperature has been rising. In order to minimize the temperature increase of the earth, it is necessary to develop alternative energy technologies that do not depend on fossil fuels. Solar fuels are one potential energy source for the future. Solar fuel technologies use catalysts to convert low energy molecules into fuels via artificial photosynthesis. TiO2, or titania, is an important model photocatalyst for studying these reactions. It is also important to use remaining fossil fuel resources efficiently and with the lowest possible greenhouse gas emissions. Fuel cells are electrochemical devices that aim to accomplish this goal and CeO2, or ceria, is an important material used in these devices. One way to observe the atomic structure of a material is with a transmission electron microscope (TEM). A traditional transmission electron microscope employs a beam of fast electrons to form atomic resolution images of a material. While imaging gives information about the positions of the atoms in the material, spectroscopy gives information about the composition and bonding of the material. A type of spectroscopy that can be performed inside the transmission electron microscope is electron energy loss spectroscopy (EELS), which provides a fundamental understanding of the electronic structure of a material. The energy loss spectrum also contains information on the chemical bonding in the material, and theoretical calculations that model the spectra are essential to correctly interpreting this bonding information. FEFF is a software that performs EELS calculations. Calculations of the oxygen K edges of TiO2 and CeO2 were made using FEFF in order to understand the changes that occur in the spectrum when oxygen vacancies are introduced as well as the changes near a grain boundary.

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  • 2013-12

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社交網站對於國際經濟的影響

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隨著全球一體化,社交網絡在國際平台上擁有了相當出色的表現,影響全球人民的生活,特別有助於國際經濟發展,因此引起了各國的關注。雖然如此,它們具體的效果是難以去評估的。本文在前人研究的基礎上探討社交網絡的經營模式以及它對於國際經濟的影響。在微觀層面可以看到社交網的存在對市場有著直接的影響。在宏觀層面上,社交網站通過其網站設計推銷其他公司產品,提高廣告商的知名度,刺激消費。這兩方面,本文討論社交網的影響為何跟傳統公司有差別。

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  • 2013-12

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Investigation of Amorphous Photocatalysts for Applications in Solar Water Splitting

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The purpose of this thesis was to investigate the properties of amorphous and crystalline NaTaO3 to determine what makes amorphous NaTaO3 a suitable photocatalyst for water splitting applications. Amorphous and

The purpose of this thesis was to investigate the properties of amorphous and crystalline NaTaO3 to determine what makes amorphous NaTaO3 a suitable photocatalyst for water splitting applications. Amorphous and nanocrystalline NaTaO3 were synthesized and characterized using X-Ray Diffraction (XRD), Raman Spectroscopy, and Fourier Transform Infrared Spectroscopy (FT-IR). The photocatalytic activity of the materials was analyzed using methylene blue degradation as an indicator of photocatalytic activity. The amorphous material showed significant photocatalytic activity in methylene blue degradation experiments, removing 100% of a 0.1 mmol methylene blue solution in 20 minutes, compared to the monoclinic crystalline NaTaO3, which showed negligible photocatalytic activity. Additional electrochemical characterization studies were carried out with methyl viologen (MV2+) to determine the band structure of the materials. Performing these synthesis and characterization has provided insight into further investigation of amorphous NaTaO3 and what makes the material an effective and inexpensive photocatalyst.

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  • 2014-05

Heterogeneous Catalysis for Organic Reactions

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This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium

This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel phosphide catalysts. This work is the subject of a publication of which I am a co-author, as cited below.

Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.

Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.

This work is the subject of a publication of which I am a co-author, as cited below.

D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430

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  • 2019-05

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Hydrothermal organic reduction and deoxygenation

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Organic reactions in natural hydrothermal settings have relevance toward the deep carbon cycle, petroleum formation, the ecology of deep microbial communities, and potentially the origin of life. Many reaction

Organic reactions in natural hydrothermal settings have relevance toward the deep carbon cycle, petroleum formation, the ecology of deep microbial communities, and potentially the origin of life. Many reaction pathways involving organic compounds under geochemically relevant hydrothermal conditions have now been characterized, but their mechanisms, in particular those involving mineral surface catalysis, are largely unknown. The overall goal of this work is to describe these mechanisms so that predictive models of reactivity can be developed and so that applications of these reactions beyond geochemistry can be explored. The focus of this dissertation is the mechanisms of hydrothermal dehydration and catalytic hydrogenation reactions. Kinetic and structure/activity relationships show that elimination occurs mainly by the E1 mechanism for simple alcohols via homogeneous catalysis. Stereochemical probes show that hydrogenation on nickel occurs on the metal surface. By combining dehydration with and catalytic reduction, effective deoxygenation of organic structures with various functional groups such as alkenes, polyols, ketones, and carboxylic acids can be accomplished under hydrothermal conditions, using either nickel or copper-zinc alloy. These geomimetic reactions can potentially be used in biomass reduction to generate useful fuels and other high value chemicals. Through the use of earth-abundant metal catalysts, and water as the solvent, the reactions presented in this dissertation are a green alternative to current biomass deoxygenation/reduction methods, which often use exotic, rare-metal catalysts, and organic solvents.

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  • 2018

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Design of Redox Proteins as Catalysts for Fuel Production

Description

Redox enzymes represent a big group of proteins and they serve as catalysts for

biological processes that involve electron transfer. These proteins contain a redox center

that determines their functional properties, and

Redox enzymes represent a big group of proteins and they serve as catalysts for

biological processes that involve electron transfer. These proteins contain a redox center

that determines their functional properties, and hence, altering this center or incorporating

non-biological redox cofactor to proteins has been used as a means to generate redox

proteins with desirable activities for biological and chemical applications. Porphyrins and

Fe-S clusters are among the most common cofactors that biology employs for electron

transfer processes and there have been many studies on potential activities that they offer

in redox reactions.

In this dissertation, redox activity of Fe-S clusters and catalytic activity of porphyrins

have been explored with regard to protein scaffolds. In the first part, modular property of

repeat proteins along with previously established protein design principles have been

used to incorporate multiple Fe-S clusters within the repeat protein scaffold. This study is

the first example of exploiting a single scaffold to assemble a determined number of

clusters. In exploring the catalytic activity of transmetallated porphyrins, a cobalt-porphyrin

binding protein known as cytochrome c was employed in a water oxidation

photoelectrochemical cell. This system can be further coupled to a hydrogen production

electrode to achieve a full water splitting tandem cell. Finally, a cobalt-porphyrin binding

protein known as cytochrome b562 was employed to design a whole cell catalysis system,

and the activity of the surface-displayed protein for hydrogen production was explored

photochemically. This system can further be expanded for directed evolution studies and

high-throughput screening.

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Date Created
  • 2019

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Potential materials for fuel cells

Description

Proton exchange membrane fuel cells have attracted immense research activities from the inception of the technology due to its high stability and performance capabilities. The major obstacle from commercialization is

Proton exchange membrane fuel cells have attracted immense research activities from the inception of the technology due to its high stability and performance capabilities. The major obstacle from commercialization is the cost of the catalyst material in manufacturing the fuel cell. In the present study, the major focus in PEMFCs has been in reduction of the cost of the catalyst material using graphene, thin film coated and Organometallic Molecular catalysts. The present research is focused on improving the durability and active surface area of the catalyst materials with low platinum loading using nanomaterials to reduce the effective cost of the fuel cells. Performance, Electrochemical impedance spectroscopy, oxygen reduction and surface morphology studies were performed on each manufactured material.

Alkaline fuel cells with anion exchange membrane get immense attention due to very attractive opportunity of using non-noble metal catalyst materials. In the present study, cathodes with various organometallic cathode materials were prepared and investigated for alkaline membrane fuel cells for oxygen reduction and performance studies. Co and Fe Phthalocyanine catalyst materials were deposited on multi-walled carbon nanotubes (MWCNTs) support materials. Membrane Electrode Assemblies (MEAs) were fabricated using Tokuyama Membrane (#A901) with cathodes containing Co and Fe Phthalocyanine/MWCNTs and Pt/C anodes. Fuel cell performance of the MEAs was examined.

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  • 2014