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Heterogeneous Catalysis for Organic Reactions

Description

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

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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Construction and Operation of a Hollow Fiber Membrane Spinning Apparatus

Description

This study details the construction and operation of a dry-jet wet spinning apparatus for extruding hollow fiber membranes (HFMs). The main components of the apparatus are a spinneret, a coagulation bath, and an automatic collection reel. Continuous fiber formation was

This study details the construction and operation of a dry-jet wet spinning apparatus for extruding hollow fiber membranes (HFMs). The main components of the apparatus are a spinneret, a coagulation bath, and an automatic collection reel. Continuous fiber formation was achieved using two syringe pumps simultaneously delivering polymer dope and bore fluid to the spinneret. Based on apparatus runs performed with Polysulfone (PSF) dopes dissolved in N,N-Dimethylacetamide and supporting rheological analysis, the entanglement concentration, ce, was identified as a minimum processing threshold for creating HFMs. Similarly, significant increases in the ultimate tensile strength, fracture strain, and Young's modulus for extruded HFMs were observed as polymer dope concentration was increased at levels near ce. Beyond this initial increase, subsequent tests at higher PSF concentrations yielded diminishing changes in mechanical properties, suggesting an asymptotic approach to a point where the trend would cease. Without further research, it is theorized that this point falls on a transition from the semidiute entangled to concentrated concentration regimes. SEM imaging of samples revealed the formation of grooved structures on the inner surface of samples, which was determined to be a result of the low flowrate and polymer dope concentrations used in processing the HFMs during apparatus runs. Based on continued operation of the preliminary apparatus design, many areas of improvement were noted. Namely, these consisted of controlling the collector speed, eliminating rubbing of nascent fibers against the edge of the coagulation bath by installing an elevated roller, and replacing tygon tubing for the polymer line with a luer lock adapter for direct syringe attachment to the spinneret.

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2017-05

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COMBINATORIAL SYNTHESIS OF INTRINSICALLY PHOTOLUMINESCENT POLY(AMINO ETHER)S AND THERMOSET RESINS

Description

Increased investigation into the development of macromolecular fluorophores has resulted in the synthesis and discovery of several potential candidates. These include modified and polymeric based dendritic structures, hyperbranched polymers and linear polymers. Strong inherent blue photoluminescence has been recently described

Increased investigation into the development of macromolecular fluorophores has resulted in the synthesis and discovery of several potential candidates. These include modified and polymeric based dendritic structures, hyperbranched polymers and linear polymers. Strong inherent blue photoluminescence has been recently described in linear polyamine polymers in the absence of any chemical modifications. Here we describe the screening of amine/polyamine compounds for inherent photoluminescence. Several compounds that exhibited strong inherent blue photoluminescence following excitation with UV light were identified. Furthermore we demonstrated successful synthesis of poly(amino ether) polymers as well as chemically cross-linked poly(amino ether) thermosets with the lead Pentaethylenehexamine which was found to have strong inherent blue photoluminescence. The polymers and thermosets were found to retain the photoluminescent properties of the original lead compound. The polymers and thermosets were investigated for their ability to sequester heavy metals from aqueous solutions. An increased decrease in initial photoluminescence was observed as the materials were incubated with increasing metal salt concentration as a result of metal binding sequestration. The poly(amino ether) polymers were found to have higher sensitivity for metal sequestration when compared to equivalent amount of linear 25 kDa polyethylenimine. The strong inherent blue photoluminescence and the ease of synthesis of the poly(amino ether) polymers and thermosets give these materials strong potential for future applications as sensors.

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2015-05

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Photocurable Networks: A Composite Materials Platform that Enables Advances in Additive Manufacturing

Description

This study aims to provide a foundation for future work on photo-responsive polymer composite materials to be utilized in additive manufacturing processes. The curing rate of 2,2-dimethoxy-2-phenyl-acetophenone (DMPA) in thin (<20 µm) and thick (>2 mm) layers of DMPA

This study aims to provide a foundation for future work on photo-responsive polymer composite materials to be utilized in additive manufacturing processes. The curing rate of 2,2-dimethoxy-2-phenyl-acetophenone (DMPA) in thin (<20 µm) and thick (>2 mm) layers of DMPA and poly(ethylene glycol) diacrylate (PEG-DA) mixtures was assessed for 5.0 w/v% (grams per 100 mL) concentrations of DMPA dissolved in PEG-DA. The polymerization rate and quality of curing was found to decrease as the concentration of DMPA increased beyond 1.0 w/v%; thus, confirming the existence of an optimum photo-initiator concentration for a specific sheet thickness. The optimum photo-initiator concentration for a 3-3.1 mm thick sheet of PEG-DA microstructure was determined to be between 0.3 and 0.38 w/v% DMPA. The addition of 1,6-hexanediol or 1,3-butanediol to the optimum photo-initiator concentrated solution of DMPA and PEG-DA was found to increase the Tg of the samples; however, the samples could not fully cure within 40-50 s, which suggested a decrease in polymerization rate. Lastly, the DMPA photo-initiator does not produce gaseous byproducts and is translucent when fully cured, which makes it attractive for infusion with strengthening materials because quality light penetration is paramount to quick polymerization rates. It is recommended that more trials be conducted to evaluate the mechanical properties of the optimum curing rate for DMPA and PEG-DA microstructures as well as a mechanical property comparison following the addition of either of the two alcohols.

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2016-12

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A Model of Nanoparticle Dispersion in Electrospun Nanofibers

Description

Polymer-nanoparticle composites (PNCs) show improved chemical and physical properties compared to pure polymers. However, nanoparticles dispersed in a polymer matrix tend to aggregate due to strong interparticle interactions. Electrospun nanofibers impregnated with nanoparticles have shown improved dispersion of nanoparticles. Currently,

Polymer-nanoparticle composites (PNCs) show improved chemical and physical properties compared to pure polymers. However, nanoparticles dispersed in a polymer matrix tend to aggregate due to strong interparticle interactions. Electrospun nanofibers impregnated with nanoparticles have shown improved dispersion of nanoparticles. Currently, there are few models for quantifying dispersion in a PNC, and none for electrospun PNC fibers. A simulation model was developed to quantify the effects of nanoparticle volume loading and fiber to particle diameter ratios on the dispersion in a nanofiber. The dispersion was characterized using the interparticle distance along the fiber. Distributions of the interparticle distance were fit to Weibull distributions and a two-parameter empirical equation for the mean and standard deviation was found. A dispersion factor was defined to quantify the dispersion along the polymer fiber. This model serves as a standard for comparison for future experimental studies through its comparability with microscopy techniques, and as way to quantify and predict dispersion in polymer-nanoparticle electrospinning systems with a single performance metric.

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2016-12

Rheological Analysis of the Effects of Dopants on the Mechanical Properties of Conjugated Polymers

Description

This honors thesis covers an overview of the the motivation, objectives, and projects of the Xie Research Group, focusing on the mechanical effect of dopants (through p-doping) on the structural domains of conjugated polymers (specifically P3DT). The ability to sustainably

This honors thesis covers an overview of the the motivation, objectives, and projects of the Xie Research Group, focusing on the mechanical effect of dopants (through p-doping) on the structural domains of conjugated polymers (specifically P3DT). The ability to sustainably 3D-print conjugated polymers has the potential to impact a variety of industries (personalized technology, medical treatment, replacement of metals, etc).

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2022-05

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Millman Final Project (Spring 2022)

Description

This honors thesis covers an overview of the the motivation, objectives, and projects of the Xie Research Group, focusing on the mechanical effect of dopants (through p-doping) on the structural domains of conjugated polymers (specifically P3DT). The ability to sustainably

This honors thesis covers an overview of the the motivation, objectives, and projects of the Xie Research Group, focusing on the mechanical effect of dopants (through p-doping) on the structural domains of conjugated polymers (specifically P3DT). The ability to sustainably 3D-print conjugated polymers has the potential to impact a variety of industries (personalized technology, medical treatment, replacement of metals, etc).

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2022-05

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Millman Thesis Defense Presentation (Spring 2022)

Description

This honors thesis covers an overview of the the motivation, objectives, and projects of the Xie Research Group, focusing on the mechanical effect of dopants (through p-doping) on the structural domains of conjugated polymers (specifically P3DT). The ability to sustainably

This honors thesis covers an overview of the the motivation, objectives, and projects of the Xie Research Group, focusing on the mechanical effect of dopants (through p-doping) on the structural domains of conjugated polymers (specifically P3DT). The ability to sustainably 3D-print conjugated polymers has the potential to impact a variety of industries (personalized technology, medical treatment, replacement of metals, etc).

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2022-05