Physical Sciences and Mathematics Commons^™

Phosphorus Release And Recovery From Simulated Ferric Wastewater Sludge, Aseel Alnimer

Theses and Dissertations (Comprehensive)

Phosphorus (P) is a fundamental element necessary for all life forms and a key component in the fertilizer industry. Meanwhile, the excessive load of P to water bodies due to human activities has the potential to promote eutrophication. Wastewater treatment plants remove P either biologically or chemically and produce P rich sludge which could be a potential renewable source for P. At present, commercial technologies exist for P recovery from biological wastewater sludge. However, P recovery from chemical sludge particularly iron(III)-phosphate (Fe-P) sludge generated in chemical P removal plants that use iron(III) salts remains a challenge.

This study explored, in …

Mechanistic Studies Of Co2 Electrochemical Reduction (Co2er) On Cu And Cuo Nanoparticles With In-Situ Atr-Ftir Spectroscopy, Jason Hsu

Theses and Dissertations (Comprehensive)

Global climate change is a major challenge facing the world in the 21st century. This environmental crisis originated from excess amounts of atmospheric carbon dioxide (CO2) released from burning fossil fuels. One promising remediation method to decrease atmospheric CO2 levels is called carbon dioxide electrochemical reduction (CO2ER). In CO2ER, the CO2 gas undergoes chemical reduction to other hydrocarbon fuels. For CO2ER to take place, an energy source and a catalyst are needed. In this thesis, three aspects of CO2ER were investigated using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy coupled with other surface sensitive characterization tools. First, we studied …

Temperature-Dependent Kinetic Studies Of Arsenicals Adsorption From Solution To Hematite Nanoparticles, Sara Soldoozy

Theses and Dissertations (Comprehensive)

Surface chemistry is the study of the chemical and physical phenomena that transpire at interfaces such as liquid-solid, solid-gas, liquid-gas, and liquid-liquid. To study the reactions occurred at the surfaces, surface sensitive techniques come to play. Adsorption of arsenical compounds (liquid adsorbate), particularly arsenate (iAs) and dimethylarsinic acid (DMA), to the surface of iron bearing materials (solid adsorbent) that frequently are found in geosorbents such as hematite (Fe₂O₃) has been studied in this thesis. Arsenical compounds can pollute the environment through natural sources and anthropogenic activities, and ultimately contaminate water. Absorbing these pollutants to a material …

Size And Shape Control In Metal Nanoparticles And Nanocomposites, Tomendro Subedi

Theses and Dissertations (Comprehensive)

This thesis describes major findings on the shape transformation of the precursor silver decahedral nanoparticles (AgDeNPs) with pentagonal symmetry and twin defects into silver pentagonal prism nanoparticles (AgPPNPs) using Br¯ as a shape selective reagent. Silica-encapsulation of the gold-plated AgDeNPs was also carried out forming ordered arrays of silica encapsulated gold-plated AgDeNPs (SiO₂@Au@AgDeNPs) of different sizes. At first, synthetic procedures for AgDeNPs (pentagonal bipyramids), silver pentagonal rod nanoparticles (AgPRNPs) and gold-plating of AgDeNPs (Au@AgDeNPs) were optimized. Gold plating enhances the chemical stability of AgDeNPs and preserves the superior plasmonic properties of silver. This thesis deals with the transformation …

A Density Functional Theory Study Of Intrinsically Chiral Semiconductor Nanocrystals, Richard Edwards

Theses and Dissertations (Comprehensive)

A plethora of work has been done in the area of nanoparticles of late due to the fact that chemists (and physicists) have discovered that the properties of nanoparticles differ from both those of the bulk material and the atoms themselves. Nanoparticles have become of high interest for the use as catalysts while materials like graphene, being only one atom thick, have been shown to be great electrical conductors in comparison with the 3D structure of diamond. Among these peculiar nanoscale properties is the phenomenon of nanochirality, where a nanoparticle can exhibit chirality that does not extend to the macroscale …

The Role Of Organic Matter In The Surface Chemistry Of Arsenic Compounds On Iron−(Oxyhydr)Oxides Studied By Atr-Ftir, Arthur Situm

Theses and Dissertations (Comprehensive)

The interaction of organic matter with the interfaces of active soil components such as iron oxides is ubiquitous within soil environments. The presence of organics at these interfaces may have implications for other soil constituents whose mobility is controlled by their ability to bind to active soil components. Most of the studies performed to date which look at these interactions are bulk/batch studies performed ex-situ. Attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized within this work to study interactions between select model organics (citrate, oxalate and pyrocatechol) and iron−(oxyhydr)oxides, as well as their effect on the surface …

Surface Complexation Of Monosubstituted Organoarsenicals On Hematite: Atr-Ftir Investigations, Md Abdus Sabur

Theses and Dissertations (Comprehensive)

Little is known about the surface chemistry of organoarsenic compounds with iron-containing materials commonly found in geosorbents and arsenic removal technologies. In this thesis, these organoarsenicals include aliphatic and aromatic arsenicals that historically have been used as herbicides, pesticides and in the poultry feed industry, respectively. Attenuated total internal reflectance Fourier transform infrared spectroscopy has been used to study the surface interactions of organoarsenicals at the molecular level under various environmentally-relevant conditions. Kinetic and thermodynamic parameters extracted from these molecular level experiments provide trends that are not observed in any published bulk experiments. Apparent initial rates of adsorption and desorption …

A Computational Study Of Small Gold Clusters With H2s, Thiols, H2o, And Alcohols, Silvija C. Smith

Theses and Dissertations (Comprehensive)

Alkane thiols, RSH, are commonly used in aqueous solution to stabilize and prevent aggregation of gold clusters, Au_n. Initially a RSH-Au_n complex is formed and, subsequently, there is hydrogen atom transfer to form a RSAu_nH complex. We examine the rate of this reaction for small neutral gold clusters, with n=1-2 and short-chain thiols with R = H, CH₃, and CH₃CH₂, using transition state theory. The comparison of DFT (with the functionals, BP86 and M06-2X), and MP2 was performed. A pseudopotential was employed to account for the large relativisitic effects …

Controlled Transformation Of Nanoparticles With Tunable Surface Plasmon Resonance, Nimer Murshid

Theses and Dissertations (Comprehensive)

This thesis reports key findings in the synthesis and transformation of silver nanoparticles (AgNPs) with pentagonal symmetries. The main focus of the thesis work is on the synthesis of silver decahedral nanoparticles (AgDeNPs) and their transformation into larger AgDeNPs and silver pentagonal rod nanoparticles (AgPRNPs). In another direction, produced AgNPs were stabilized by gold plating. In a one-stage photochemical synthesis of AgDeNPs (pentagonal bipyramid, J₁₃ solid), oxidative etching by hydrogen peroxide was implemented to achieve complete conversion of the small silver platelet precursor NPs. For convenient laboratory synthesis of high-purity size-selected AgDeNPs, we have also adapted LEDs as a …

Atr-Ftir Studies On The Kinetics Of Dimethylarsinic Acid (Dma) Surface Complexation With Iron(Oxyhydr)Oxides, Julia Tofan-Lazar Miss

Theses and Dissertations (Comprehensive)

Dimethylarsinic acid (DMA) is an organoarsenical compound that, along with monomethylarsonic acid, poses a health and an environmental risk, and a challenge to the energy industry. Little is known about the surface chemistry of DMA at the molecular level with materials relevant to geochemical environments and industrial sectors. The surface chemistry of phosphorus and arsenic compounds in their organic and inorganic forms is of great interest due to its role in controlling their transport, bioaccessibility and speciation. This thesis reports the first in-situ and surface-sensitive rapid kinetic studies on the adsorption and desorption of DMA to and from Fe-(oxyhydr)oxide films …

Density Functional Theory Calculations On Hydrated Dimethylarsinic Acid And Iron Oxide Clusters, Adrian Adamescu

Theses and Dissertations (Comprehensive)

Dimethylarsinic Acid (DMA) or (CH₃)₂AsO₂H is an important organoarsenical compound detected in arsenic speciation studies of environmental samples and synthesized during pyrolysis of oil shale. DMA was used historically as a herbicide on large agricultural fields and can be detected in the leachates of landfills rich in waste containing arsenic such as glass, alloys, and semiconductors, as well as biologically pre-treated municipal solid waste. Under certain soil conditions DMA can become bio-available and has the potential to be recycled to more toxic inorganic forms of arsenic. Bioavailability of DMA is largely controlled by the …

Synthesis And Investigation Of The Liquid Crystalline Properties Of Polycyclic Aromatic Hydrocarbons, Joseph A. Paquette

Theses and Dissertations (Comprehensive)

In this thesis, the synthesis and liquid crystalline properties of a series of novel substituted dibenz[a,c]anthracenes is reported. Specifically, a series of hexaalkoxydibenz[a,c]anthracenes were prepared and found not to exhibit a mesophase. In contrast, when substituents are introduced on the aromatic core, columnar mesophases are observed over broad temperature ranges. A series substituted derivatives was prepared and their mesomorphic properties compared. In general, electron-withdrawing substituents promote broad mesophase temperature ranges, as do larger substituents. The liquid crystalline phase is a result of the electronic effects, size and shape of the substituents in the 10 and 13 positions.

We also synthesized …