Matching Items (27)
Description
Plastics, when released into the environment, undergo surface weathering due to mechanical abrasion and ultraviolet (UV) exposure that leads to the formation of microplastics. Weathering also introduces oxygen functional groups on the surface, which will affect surface interactions compared to pristine plastics. In this study, the adsorption of selected model contaminants of high environmental relevance was evaluated at different level of abiotic and biotic transformation to understand how microplastics aging influences contaminant adsorption on high density polyethylene (HDPE) and polypropylene (PPE). Microplastics were aged through an accelerated weathering process using UV exposure with or without hydrogen peroxide. The effect of UV aging on the microplastics’ morphology and surface chemistry was characterized by Fourier Transform Infrared Spectroscopy, X-Ray Photoelectron Spectroscopy, streaming Zeta potential, Brunauer–Emmett–Teller Krypton adsorption analyses and Computed X-Ray Tomography. Sorption of organic contaminants was found to be higher on aged microplastics compared to pristine ones for all contaminants investigated. This increase in sorption affinity was found to be associated with a change in the surface chemistry and not in an increase in specific surface area after aging. Biological surface weathering (i.e., biofilm formation) was carried out at a lab-scale setting using model biofilm-forming bacteria followed by adsorption affinity measurement of biofilm-laden microplastics with the model organic contaminants. The amount of microbial biomass accumulated on the surface was also evaluated to correlate the changes in sorption affinity with the change in microplastic biofilm formation. The results of this study emphasize the need to understand how contaminant-microplastics interactions will evolve as microplastics are altered by biotic and abiotic factors in the environment.
ContributorsBhagat, Kartik (Author) / Perreault, Francois (Thesis advisor) / Westerhoff, Paul (Committee member) / Oswald, Jay (Committee member) / Arizona State University (Publisher)
Created2022
Description
Layered chalcogenides are a diverse class of crystalline materials that consist of covalently bound building blocks held together by van der Waals forces, including the transition metal dichalcogenides (TMDCs) and the pnictogen chalcogenides (PCs) among all. These materials, in particular, MoS2 which is the most widely studied TMDC material, have attracted significant attention in recent years due to their unique physical, electronic, optical, and chemical properties that depend on the number of layers. Due to their high aspect ratios and extreme thinness, 2D materials are sensitive to modifications via chemistry on their surfaces. For instance, covalent functionalization can be used to robustly modify the electronic properties of 2D materials, and can also be used to attach other materials or structures. Metal adsorption on the surfaces of 2D materials can also tune their electronic structures, and can be used as a strategy for removing metal contaminants from water. Thus, there are many opportunities for studying the fundamental surface interactions of 2D materials and in particular the TMDCs and PCs.
The work reported in this dissertation represents detailed fundamental studies of the covalent functionalization and metal adsorption behavior of layered chalcogenides, which are two significant aspects of the surface interactions of 2D materials. First, we demonstrate that both the Freundlich and Temkin isotherm models, and the pseudo-second-order reaction kinetics model are good descriptors of the reaction due to the energetically inhomogeneous surface MoS2 and the indirect adsorbate-adsorbate interactions from previously attached nitrophenyl (NP) groups. Second, the covalent functionalization using aryl diazonium salts is extended to nanosheets of other representative TMDC materials MoSe2, WS2, and WSe2, and of the representative PC materials Bi2S3 and Sb2S3, demonstrated using atomic force microscopy (AFM) imaging and Fourier transform infrared spectroscopy (FTIR). Finally, using AFM and X-ray photoelectron spectroscopy (XPS), it is shown that Pb, Cd Zn and Co form nanoclusters on the MoS2 surface without affecting the structure of the MoS2 itself. The metals can also be thermally desorbed from MoS2, thus suggesting a potential application as a reusable water purification technology.
The work reported in this dissertation represents detailed fundamental studies of the covalent functionalization and metal adsorption behavior of layered chalcogenides, which are two significant aspects of the surface interactions of 2D materials. First, we demonstrate that both the Freundlich and Temkin isotherm models, and the pseudo-second-order reaction kinetics model are good descriptors of the reaction due to the energetically inhomogeneous surface MoS2 and the indirect adsorbate-adsorbate interactions from previously attached nitrophenyl (NP) groups. Second, the covalent functionalization using aryl diazonium salts is extended to nanosheets of other representative TMDC materials MoSe2, WS2, and WSe2, and of the representative PC materials Bi2S3 and Sb2S3, demonstrated using atomic force microscopy (AFM) imaging and Fourier transform infrared spectroscopy (FTIR). Finally, using AFM and X-ray photoelectron spectroscopy (XPS), it is shown that Pb, Cd Zn and Co form nanoclusters on the MoS2 surface without affecting the structure of the MoS2 itself. The metals can also be thermally desorbed from MoS2, thus suggesting a potential application as a reusable water purification technology.
ContributorsLi, Duo, Ph.D (Author) / Wang, Qing Hua (Thesis advisor) / Green, Alexander A. (Committee member) / Chan, Candace K. (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2019
Description
Global warming resulted from greenhouse gases emission has received widespread attention. Meanwhile, it is required to explore renewable and environmentally friendly energy sources due to the severe pollution of the environment caused by fossil fuel combustion. In order to realize a substantial adsorption process to resolve the environmental issues, the development of new adsorbents with improved properties has become the most critical issue. This dissertation presents the work of four individual but related studies on systematic characterization and process simulations of novel adsorbents with superior adsorption properties.
A perovskite oxide material, La0.1Sr0.9Co0.9Fe0.1O3-δ (LSCF1991), was investigated first for high-temperature air separation. The oxygen sorption/desorption behavior of LSCF1991 was studied by thermogravimetric analysis (TGA) and fixed-bed breakthrough experiments. A parametric study was performed to design and optimize the operating parameters of the high-temperature air separation process by pressure swing adsorption (PSA). The results have shown great potential for applying LSCF1991 to the high-temperature air separation due to its excellent separation performance and low energy requirement.
Research on using nanostructured zeolite NaX (NZ) as adsorbents for CO2 capture was subsequently conducted. The CO2/N2 adsorption characterizations indicated that the NZ samples lead to enhanced adsorption properties compared with the commercial zeolites (MZ). From the two-bed six-step PSA simulation, NZ saved around 30% energy over MZ for CO2 capture and recovery while achieving a higher CO2 purity and productivity.
A unique screening method was developed for efficient evaluation of adsorbents for PSA processes. In the case study, 47 novel adsorbents have been screened for coal bed methane (CBM) recovery. The adsorbents went through scoring-based prescreening, PSA simulation, and optimization. The process performance indicators were correlated with the adsorption selectivity and capacities, which provides new insights for predicting the PSA performance.
A new medium-temperature oxygen sorbent, YBaCo4O7+δ (YBC114), was investigated as an oxygen pumping material to facilitate solar thermochemical fuel production. The oxygen uptake and release attributes of YBC114 were studied by both TGA and a small-scale evacuation test. The study proved that the particle size has a significant effect on the oxygen pumping behavior of YBC114, especially for the uptake kinetics.
A perovskite oxide material, La0.1Sr0.9Co0.9Fe0.1O3-δ (LSCF1991), was investigated first for high-temperature air separation. The oxygen sorption/desorption behavior of LSCF1991 was studied by thermogravimetric analysis (TGA) and fixed-bed breakthrough experiments. A parametric study was performed to design and optimize the operating parameters of the high-temperature air separation process by pressure swing adsorption (PSA). The results have shown great potential for applying LSCF1991 to the high-temperature air separation due to its excellent separation performance and low energy requirement.
Research on using nanostructured zeolite NaX (NZ) as adsorbents for CO2 capture was subsequently conducted. The CO2/N2 adsorption characterizations indicated that the NZ samples lead to enhanced adsorption properties compared with the commercial zeolites (MZ). From the two-bed six-step PSA simulation, NZ saved around 30% energy over MZ for CO2 capture and recovery while achieving a higher CO2 purity and productivity.
A unique screening method was developed for efficient evaluation of adsorbents for PSA processes. In the case study, 47 novel adsorbents have been screened for coal bed methane (CBM) recovery. The adsorbents went through scoring-based prescreening, PSA simulation, and optimization. The process performance indicators were correlated with the adsorption selectivity and capacities, which provides new insights for predicting the PSA performance.
A new medium-temperature oxygen sorbent, YBaCo4O7+δ (YBC114), was investigated as an oxygen pumping material to facilitate solar thermochemical fuel production. The oxygen uptake and release attributes of YBC114 were studied by both TGA and a small-scale evacuation test. The study proved that the particle size has a significant effect on the oxygen pumping behavior of YBC114, especially for the uptake kinetics.
ContributorsXu, Mai (Author) / Deng, Shuguang (Thesis advisor) / Lind, Marylaura (Committee member) / Lin, Jerry Y.S. (Committee member) / Green, Matthew D. (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2020
Description
Per- and polyfluoroalkyl substances (PFAS) are a group of man-made chemicals that are detected ubiquitously in the aquatic environment, biota, and humans. Human exposure and adverse health of PFAS through consuming impacted drinking water is getting regulatory attention. Adsorption using granular activated carbon (GAC) and ion exchange resin (IX) has proved to be efficient in removing PFAS from water. There is a need to study the effectiveness of commercially available sorbents in PFAS removal at the pilot-scale with real PFAS contaminated water, which would aid in efficient full-scale plant design. Additionally, there is also a need to have validated bench-scale testing techniques to aid municipalities and researchers in selecting or comparing adsorbents to remove PFAS. Rapid Small-Scale Column Tests (RSSCTs) are bench-scale testing to assess media performance and operational life to remove trace organics but have not been validated for PFAS. Different design considerations exist for RSSCTs, which rely upon either proportional diffusivity (PD) or constant diffusivity (CD) dimensionless scaling relationships.
This thesis aims to validate the use of RSSCTs to simulate PFAS breakthrough in pilot columns. First, a pilot-scale study using two GACs and an IX was conducted for five months at a wellsite in central Arizona. PFAS adsorption capacity was greatest for a commercial IX, and then two GAC sources exhibited similar performance. Second, RSSCTs scaled using PD or CD relationships, simulated the pilot columns, were designed and performed. For IX and the two types of GAC, the CD–RSSCTs simulated the PFAS breakthrough concentration, shape, and order of C8 to C4 compounds observed pilot columns better than the PD-RSSCTs. Finally, PFAS breakthrough and adsorption capacities for PD- and CD-RSSCTs were performed on multiple groundwaters (GWs) from across Arizona to assess the treatability of PFAS chain length and functional head-group moieties. PFAS breakthrough in GAC and IX was dictated by chain length (C4>C6>C8) and functional group (PFCAs>PFSAs) of the compound. Shorter-chain PFAS broke through earlier than the longer chain, and removal trends were related to the hydrophobicity of PFAS. Overall, single-use IX performed superior to any of the evaluated GACs across a range of water chemistries in Arizona GWs.
This thesis aims to validate the use of RSSCTs to simulate PFAS breakthrough in pilot columns. First, a pilot-scale study using two GACs and an IX was conducted for five months at a wellsite in central Arizona. PFAS adsorption capacity was greatest for a commercial IX, and then two GAC sources exhibited similar performance. Second, RSSCTs scaled using PD or CD relationships, simulated the pilot columns, were designed and performed. For IX and the two types of GAC, the CD–RSSCTs simulated the PFAS breakthrough concentration, shape, and order of C8 to C4 compounds observed pilot columns better than the PD-RSSCTs. Finally, PFAS breakthrough and adsorption capacities for PD- and CD-RSSCTs were performed on multiple groundwaters (GWs) from across Arizona to assess the treatability of PFAS chain length and functional head-group moieties. PFAS breakthrough in GAC and IX was dictated by chain length (C4>C6>C8) and functional group (PFCAs>PFSAs) of the compound. Shorter-chain PFAS broke through earlier than the longer chain, and removal trends were related to the hydrophobicity of PFAS. Overall, single-use IX performed superior to any of the evaluated GACs across a range of water chemistries in Arizona GWs.
ContributorsVenkatesh, Krishishvar (Author) / Westerhoff, Paul (Thesis advisor) / Sinha, Shahnawaz (Committee member) / Lind, Marylaura (Committee member) / Arizona State University (Publisher)
Created2020
Description
Desorption processes are an important part of all processes which involve utilization of solid adsorbents such as adsorption cooling, sorption thermal energy storage, and drying and dehumidification processes and are inherently energy-intensive. Here, how those energy requirements can be reduced through the application of ultrasound for three widely used adsorbents namely zeolite 13X, activated alumina and silica gel is investigated. To determine and justify the effectiveness of incorporating ultrasound from an energy-savings point of view, an approach of constant overall input power of 20 and 25 W was adopted. To measure the extent of the effectiveness of using ultrasound, the ultrasonic-power-to-total power ratios of 0.2, 0.25, 0.4 and 0.5 were investigated and the results compared with those of no-ultrasound (heat only) at the same total power. Duplicate experiments were performed at three nominal frequencies of 28, 40 and 80 kHz to observe the influence of frequency on regeneration dynamics. Regarding moisture removal, application of ultrasound results in higher desorption rate compared to a non-ultrasound process. A nonlinear inverse proportionality was observed between the effectiveness of ultrasound and the frequency at which it is applied. Based on the variation of desorption dynamics with ultrasonic power and frequency, three mechanisms of reduced adsorbate adsorption potential, increased adsorbate surface energy and enhanced mass diffusion are proposed. Two analytical models that describe the desorption process were developed based on the experimental data from which novel efficiency metrics were proposed, which can be employed to justify incorporating ultrasound in regeneration and drying processes.
ContributorsDaghooghi Mobarakeh, Hooman (Author) / Phelan, Patrick (Thesis advisor) / Wang, Liping (Committee member) / Wang, Robert (Committee member) / Calhoun, Ronald (Committee member) / Deng, Shuguang (Committee member) / Arizona State University (Publisher)
Created2021
Description
The objective of this research was to develop Aluminophosphate-five (AlPO4-5, AFI) zeolite adsorbents for efficient oxygen removal from a process stream to support an on-going Department of Energy (DOE) project on solar energy storage. A molecular simulation study predicted that substituted AlPO4-5 zeolite can adsorb O2 through a weak chemical bond at ambient temperature. Substituted AlPO4-5 zeolite was successfully synthesized via hydrothermal crystallization by following carefully designed procedures to tailor the zeolite for efficient O2 adsorption. Synthesized AlPO4-5 in this work included Sn/AlPO-5, Mo/AlPO-5, Pd/AlPO-5, Si/AlPO-5, Mn/AlPO-5, Ce/AlPO-5, Fe/AlPO-5, CuCe/AlPO-5, and MnSnSi/AlPO-5. While not all zeolite samples synthesized were fully characterized, selected zeolite samples were characterized by powder x-ray diffraction (XRD) for crystal structure confirmation and phase identification, and nitrogen adsorption for their pore textural properties. The Brunauer-Emmett-Teller (BET) specific surface area and pore size distribution were between 172 m2 /g - 306 m2 /g and 6Å - 9Å, respectively, for most of the zeolites synthesized. Samples of great interest to this project such as Sn/AlPO-5, Mo/AlPO-5 and MnSnSi/AlPO-5 were also characterized using x-ray photoelectron spectroscopy (XPS) and energy-dispersive x-ray spectroscopy (EDS) for elemental analysis, scanning electron microscopy (SEM) for morphology and particle size estimation, and electron paramagnetic resonance (EPR) for nature of adsorbed oxygen. Oxygen and nitrogen adsorption experiments were carried out in a 3-Flex adsorption apparatus (Micrometrics) at various temperatures (primarily at 25℃) to determine the adsorption properties of these zeolite samples as potential adsorbents for oxygen/nitrogen separation. Experiments showed that some of the zeolite samples adsorb little-to-no oxygen and nitrogen at 25℃, while other zeolites such as Sn/AlPO-5, Mo/AlPO-5, and MnSnSi/AlPO-5 adsorb decent but inconsistent amounts of oxygen with the highest observed values of about 0.47 mmol/ g, 0.56 mmol/g, and 0.84 mmol/ g respectively. The inconsistency in adsorption is currently attributed to non-uniform doping of the zeolites, and these findings validate that some substituted AlPO4-5 zeolites are promising adsorbents. However, more investigations are needed to verify the causes of this inconsistency to develop a successful AlPO4-5 zeolite-based adsorbent for oxygen/nitrogen separation.
ContributorsBuyinza, Allan Smith (Author) / Deng, Shuguang (Thesis advisor) / Varman, Arul M (Committee member) / Jin, Kailong (Committee member) / Arizona State University (Publisher)
Created2021
Description
Utilizing DFT calculations, various substitutions on the AlPO-5 zeolite were screened for adsorption of common air molecules. Furthermore, free energy analyses using the Helmholtz free energy equation were performed to determine candidates for selective adsorption of one specific air molecule, and their operating temperature range. Through this study, it was found that Cerium- (92-542 K), Germanium- (69-370 K), Chromium- (35-293 K), and Praseodymium- (0-420 K) substituted AlPO-5 selectively adsorbs to O2 molecules for the given temperature ranges. In addition, Palladium-substituted AlPO-5 selectively adsorbs to CO within 430-755 K.
ContributorsIrudaya Pious Suresh, Enosh (Author) / Muhich, Christopher (Thesis director) / Emady, Heather (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2022-05