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- Creators: Arizona State University
Description
Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
Titanium oxide (TiO2), an abundant material with high photocatalytic activity and chemical stability is an important candidate for photocatalytic applications. The photocatalytic activity of the TiO2 varies with its phase. In the current project, phase and morphology changes in TiO2 nanotubes were studied using ex-situ and in-situ transmission electron microscopy (TEM). X-ray diffraction and scanning electron microscopy studies were also performed to understand the phase and morphology of the nanotubes. As prepared TiO2 nanotubes supported on Ti metal substrate were amorphous, during the heat treatment in the ex-situ furnace nanotubes transform to anatase at 450 oC and transformed to rutile when heated to 800 oC. TiO2 nanotubes that were heat treated in an in-situ environmental TEM, transformed to anatase at 400 oC and remain anatase even up to 800 oC. In both ex-situ an in-situ case, the morphology of the nanotubes drastically changed from a continuous tubular structure to aggregates of individual nanoparticles. The difference between the ex-situ an in-situ treatments and their effect on the phase transformation is discussed. Metal doping is one of the effective ways to improve the photocatalytic performance. Several approaches were performed to get metal loading on to the TiO2 nanotubes. Mono-dispersed platinum nanoparticles were deposited on the TiO2 nanopowder and nanotubes using photoreduction method. Photo reduction for Ag and Pt bimetallic nanoparticles were also performed on the TiO2 powders.
ContributorsSantra, Sanjitarani (Author) / Crozier, Peter A. (Thesis advisor) / Carpenter, Ray (Committee member) / Buttry, Daniel (Committee member) / Arizona State University (Publisher)
Created2014
Description
A new photocatalytic material was synthesized to investigate its performance for the photoreduction of carbon dioxide (CO2) in the presence of water vapor (H2O) to valuable products such as carbon monoxide (CO) and methane (CH4). The performance was studied using a gas chromatograph (GC) with a flame ionization detector (FID) and a thermal conductivity detector (TCD). The new photocatalytic material was an ionic liquid functionalized reduced graphite oxide (IL-RGO (high conductive surface))-TiO2 (photocatalyst) nanocomposite. Brunauer-Emmett-Teller (BET), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and UV-vis absorption spectroscopy techniques were employed to characterize the new catalyst. In the series of experiments performed, the nanocomposite material was confined in a UV-quartz batch reactor, exposed to CO2 and H2O and illuminated by UV light. The primary product formed was CO with a maximum production ranging from 0.18-1.02 µmol(gcatalyst-hour)-1 for TiO2 and 0.41-1.41 µmol(gcatalyst-hour)-1 for IL-RGO-TiO2. A trace amount of CH4 was also formed with its maximum ranging from 0.009-0.01 µmol(gcatalyst-hour)-1 for TiO2 and 0.01-0.04 µmol(gcatalyst-hour)-1 for IL-RGO-TiO2. A series of background experiments were conducted and results showed that; (a) the use of a ionic liquid functionalized reduced graphite oxide -TiO2 produced more products as compared to commercial TiO2, (b) the addition of methanol as a hole scavenger boosted the production of CO but not CH4, (c) a higher and lower reduction time of IL-RGO as compared to the usual 24 hours of reduction presented basically the same production of CO and CH4, (d) the positive effect of having an ionic liquid was demonstrated by the double production of CO obtained for IL-RGO-TiO2 as compared to RGO-TiO2 and (e) a change in the amount of IL-RGO in the IL-RGO-TiO2 represented a small difference in the CO production but not in the CH4 production. This work ultimately demonstrated the huge potential of the utility of a UV-responsive ionic liquid functionalized reduced graphite oxide-TiO2 nano-composite for the reduction of CO2 in the presence of H2O for the production of fuels.
ContributorsCastañeda Flores, Alejandro (Author) / Andino, Jean M (Thesis advisor) / Forzani, Erica (Committee member) / Torres, Cesar (Committee member) / Arizona State University (Publisher)
Created2014
Analysis of photocatalysis for precursor removal and formation inhibition of disinfection byproducts
Description
Disinfection byproducts are the result of reactions between natural organic matter (NOM) and a disinfectant. The formation and speciation of DBP formation is largely dependent on the disinfectant used and the natural organic matter (NOM) concentration and composition. This study examined the use of photocatalysis with titanium dioxide for the oxidation and removal of DBP precursors (NOM) and the inhibition of DBP formation. Water sources were collected from various points in the treatment process, treated with photocatalysis, and chlorinated to analyze the implications on total trihalomethane (TTHM) and the five haloacetic acids (HAA5) formations. The three sub-objectives for this study included: the comparison of enhanced and standard coagulation to photocatalysis for the removal of DBP precursors; the analysis of photocatalysis and characterization of organic matter using size exclusion chromatography and fluorescence spectroscopy and excitation-emission matrices; and the analysis of photocatalysis before GAC filtration. There were consistencies in the trends for each objective including reduced DBP precursors, measured as dissolved organic carbon DOC concentration and UV absorbance at 254 nm. Both of these parameters decreased with increased photocatalytic treatment and could be due in part to the adsorption to as well as the oxidation of NOM on the TiO2 surface. This resulted in lower THM and HAA concentrations at Medium and High photocatalytic treatment levels. However, at No UV exposure and Low photocatalytic treatment levels where oxidation reactions were inherently incomplete, there was an increase in THM and HAA formation potential, in most cases being significantly greater than those found in the raw water or Control samples. The size exclusion chromatography (SEC) results suggest that photocatalysis preferentially degrades the higher molecular mass fraction of NOM releasing lower molecular mass (LMM) compounds that have not been completely oxidized. The molecular weight distributions could explain the THM and HAA formation potentials that decreased at the No UV exposure samples but increased at Low photocatalytic treatment levels. The use of photocatalysis before GAC adsorption appears to increase bed life of the contactors; however, higher photocatalytic treatment levels have been shown to completely mineralize NOM and would therefore not require additional GAC adsorption after photocatalysis.
ContributorsDaugherty, Erin (Author) / Abbaszadegan, Morteza (Thesis advisor) / Fox, Peter (Committee member) / Mayer, Brooke (Committee member) / Arizona State University (Publisher)
Created2011
Description
Intimate coupling of Ti2 photocatalysis and biodegradation (ICPB) offers potential for degrading biorecalcitrant and toxic organic compounds much better than possible with conventional wastewater treatments. This study reports on using a novel sponge-type, Ti2-coated biofilm carrier that shows significant adherence of Ti2 to its exterior and the ability to accumulate biomass in its interior (protected from UV light and free radicals). First, this carrier was tested for ICPB in a continuous-flow photocatalytic circulating-bed biofilm reactor (PCBBR) to mineralize biorecalcitrant organic: 2,4,5-trichlorophenol (TCP). Four mechanisms possibly acting of ICPB were tested separately: TCP adsorption, UV photolysis/photocatalysis, and biodegradation. The carrier exhibited strong TCP adsorption, while photolysis was negligible. Photocatalysis produced TCP-degradation products that could be mineralized and the strong adsorption of TCP to the carrier enhanced biodegradation by relieving toxicity. Validating the ICPB concept, biofilm was protected inside the carriers from UV light and free radicals. ICPB significantly lowered the diversity of the bacterial community, but five genera known to biodegrade chlorinated phenols were markedly enriched. Secondly, decolorization and mineralization of reactive dyes by ICPB were investigated on a refined Ti2-coated biofilm carrier in a PCBBR. Two typical reactive dyes: Reactive Black 5 (RB5) and Reactive Yellow 86 (RY86), showed similar first-order kinetics when being photocatalytically decolorized at low pH (~4-5), which was inhibited at neutral pH in the presence of phosphate or carbonate buffer, presumably due to electrostatic repulsion from negatively charged surface sites on Ti2, radical scavenging by phosphate or carbonate, or both. In the PCBBR, photocatalysis alone with Ti2-coated carriers could remove RB5 and COD by 97% and 47%, respectively. Addition of biofilm inside macroporous carriers maintained a similar RB5 removal efficiency, but COD removal increased to 65%, which is evidence of ICPB despite the low pH. A proposed ICPB pathway for RB5 suggests that a major intermediate, a naphthol derivative, was responsible for most of the residual COD. Finally, three low-temperature sintering methods, called O, D and DN, were compared based on photocatalytic efficiency and Ti2 adherence. The DN method had the best Ti2-coating properties and was a successful carrier for ICPB of RB5 in a PCBBR.
ContributorsLi, Guozheng (Author) / Rittmann, Bruce E. (Thesis advisor) / Halden, Rolf (Committee member) / Krajmalnik-Brown, Rosa (Committee member) / Arizona State University (Publisher)
Created2011
Description
Over the past years, an interest has arisen in resolving two major issues: increased carbon dioxide (CO2) emissions and depleting energy resources. A convenient solution would be a process that could simultaneously use CO2 while producing energy. The photocatalytic reduction of CO2 to fuels over the photocatalyst titanium dioxide (TiO2) is such a process. However, this process is presently inefficient and unsuitable for industrial applications. A step toward making this process more effective is to alter TiO2 based photocatalysts to improve their activity. The interactions of CO2 with oxygen-deficient and unmodified (210) surfaces of brookite TiO2 were studied using first-principle calculations on cluster systems. Charge and spin density analyses were implemented to determine if charge transfer to the CO2 molecule occurred and whether this charge transfer was comparable to that seen with the oxygen-deficient and unmodified anatase TiO2 (101) surfaces. Although the unmodified brookite (210) surface provided energetically similar CO2 interactions as compared to the unmodified anatase (101) surface, the unmodified brookite surface had negligible charge transfer to the CO2 molecule. This result suggests that unmodified brookite is not a suitable catalyst for the reduction of CO2. However, the results also suggest that modification of the brookite surface through the creation of oxygen vacancies may lead to enhancements in CO2 reduction. The computational results were supported with laboratory data for CO2 interaction with perfect brookite and oxygen-deficient brookite. The laboratory data, generated using diffuse reflectance Fourier transform infrared spectroscopy, confirms the presence of CO2- on only the oxygen-deficient brookite. Additional computational work was performed on I-doped anatase (101) and I-doped brookite (210) surface clusters. Adsorption energies and charge and spin density analyses were performed and the results compared. While charge and spin density analyses showed minute charge transfer to CO2, the calculated adsorption energies demonstrated an increased affinity for CO2adsorption onto the I-doped brookite surface. Gathering the results from all calculations, the computational work on oxygen-deficient, I-doped, and unmodified anatase and brookite surface structures suggest that brookite TiO2 is a potential photocatalysts for CO2 photoreduction.
ContributorsRodriguez, Monique M (Author) / Andino, Jean M (Thesis advisor) / Nielsen, David R (Committee member) / Dai, Lenore (Committee member) / Arizona State University (Publisher)
Created2012
Description
A system for illuminating a sample in situ with visible and UV light inside a transmission electron microscope was devised to study photocatalysts. There are many factors which must be considered when designing and building such a system. These include both mechanical, optical, and electron optical considerations. Some of the restrictions posed by the electron microscope column are significant, and care must be taken not to degrade the microscope's electron optical performance, or to unduly restrict the other current capabilities of the microscope. The nature of these various design considerations is discussed in detail. A description of the system that has been added to the microscope at ASU, an FEI Tecnai F20 environmental transmission electron microscope is also given. The system includes a high brightness broadband light source with optical filters, a fiber to guide the light to the sample, and a system for precisely aligning the fiber tip. The spatial distribution and spectrum of the light reaching the sample has been characterized, and is described in detail.
ContributorsMiller, Benjamin (Author) / Crozier, Peter A. (Thesis advisor) / McCartney, Martha (Committee member) / Rez, Peter (Committee member) / Arizona State University (Publisher)
Created2012
Description
The mitigation and conversion of carbon dioxide (CO2) to more useful carbon chemicals is a research topic that is at the forefront of current engineering and sustainability applications. Direct photocatalytic reduction of CO2 with water (H2O) vapor to C1-C4 hydrocarbons has significant potential in setting substantial groundwork for meeting the increasing energy demands with minimal environmental impact. Previous studies indicate that titanium dioxide (TiO2) containing materials serve as the best photocatalyst for CO2 and H2O conversion to higher-value products. An understanding of the CO2-H2O reaction mechanism over TiO2 materials allows one to increase the yield of certain products such as carbon monoxide (CO) and methane (CH4). The basis of the work discussed in this thesis, investigates the interaction of small molecules (CO, CH4,H2O) over the least studied TiO2 polymorph - brookite. Using the Gaussian03 computational chemistry software package, density functional theory (DFT) calculations were performed to investigate the adsorption behavior of CO, H2O, and CH4 gases on perfect and oxygen-deficient brookite TiO2 (210) and anatase TiO2 (101) surfaces. The most geometrically and energetically favorable configurations of these molecules on the TiO2 surfaces were computed using the B3LYP/6-31+G(2df,p) functional/basis set. Calculations from this theoretical study indicate all three molecules adsorb more favorably onto the brookite TiO2 (210) surface. Diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) was used to investigate the adsorption and desorption behavior of H2O and CH4 on Evonik P25 TiO2. Results from the experimental studies and theoretical work will serve as a significant basis for reaction prediction on brookite TiO2 surfaces.
ContributorsRollins, Selisa F (Author) / Andino, Jean M (Thesis advisor) / Dai, Lenore L (Committee member) / Forzani, Erica S (Committee member) / Arizona State University (Publisher)
Created2012
Description
Photocatalytic water splitting has been proposed as a promising way of generating carbon-neutral fuels from sunlight and water. In one approach, water decomposition is enabled by the use of functionalized nano-particulate photocatalyst composites. The atomic structures of the photocatalysts dictate their electronic and photonic structures, which are controlled by synthesis methods and may alter under reaction conditions. Characterizing these structures, especially the ones associated with photocatalysts’ surfaces, is essential because they determine the efficiencies of various reaction steps involved in photocatalytic water splitting. Due to its superior spatial resolution, (scanning) transmission electron microscopy (STEM/TEM), which includes various imaging and spectroscopic techniques, is a suitable tool for probing materials’ local atomic, electronic and optical structures. In this work, techniques specific for the study of photocatalysts are developed using model systems.
Nano-level structure-reactivity relationships as well as deactivation mechanisms of Ni core-NiO shell co-catalysts loaded on Ta2O5 particles are studied using an aberration-corrected TEM. It is revealed that nanometer changes in the shell thickness lead to significant changes in the H2 production. Also, deactivation of this system is found to be related to a photo-driven process resulting in the loss of the Ni core.
In addition, a special form of monochromated electron energy-loss spectroscopy (EELS), the so-called aloof beam EELS, is used to probe surface electronic states as well as light-particle interactions from model oxide nanoparticles. Surface states associated with hydrate species are analyzed using spectral simulations based on a dielectric theory and a density of states model. Geometry-induced optical-frequency resonant modes are excited using fast electrons in catalytically relevant oxides. Combing the spectral features detected in experiments with classical electrodynamics simulations, the underlying physics involved in this excitation process and the various influencing factors of the modes are investigated.
Finally, an in situ light illumination system is developed for an aberration-corrected environmental TEM to enable direct observation of atomic structural transformations of model photocatalysts while they are exposed to near reaction conditions.
Nano-level structure-reactivity relationships as well as deactivation mechanisms of Ni core-NiO shell co-catalysts loaded on Ta2O5 particles are studied using an aberration-corrected TEM. It is revealed that nanometer changes in the shell thickness lead to significant changes in the H2 production. Also, deactivation of this system is found to be related to a photo-driven process resulting in the loss of the Ni core.
In addition, a special form of monochromated electron energy-loss spectroscopy (EELS), the so-called aloof beam EELS, is used to probe surface electronic states as well as light-particle interactions from model oxide nanoparticles. Surface states associated with hydrate species are analyzed using spectral simulations based on a dielectric theory and a density of states model. Geometry-induced optical-frequency resonant modes are excited using fast electrons in catalytically relevant oxides. Combing the spectral features detected in experiments with classical electrodynamics simulations, the underlying physics involved in this excitation process and the various influencing factors of the modes are investigated.
Finally, an in situ light illumination system is developed for an aberration-corrected environmental TEM to enable direct observation of atomic structural transformations of model photocatalysts while they are exposed to near reaction conditions.
ContributorsLiu, Qianlang (Author) / Crozier, Peter A. (Thesis advisor) / Chan, Candace (Committee member) / Buttry, Daniel (Committee member) / Liu, Jingyue (Committee member) / Nemanich, Robert (Committee member) / Arizona State University (Publisher)
Created2018
Description
There is a fundamental attractiveness about harnessing renewable energy in an age when sustainability is an ethical norm. Lithium ion batteries and hydrogen fuels are considered the most promising energy source instead of fossil fuels. This work describes the investigation of new cathode materials and devices architectures for lithium ion batteries, and photocatalysts for their usage in water splitting and waste water treatment.
LiCoO2 and LiNi1/3Mn1/3Co1/3O2 were exfoliated into nanosheets using electrochemical oxidation followed by intercalation of tetraethylammonium cations. The nanosheets were purified using dialysis and electrophoresis. The nanosheets were successfully restacked into functional cathode materials with microwave hydrothermal assistance, indicating that new cathodes can be obtained by reassembling nanosheets. This method can pave the way for the synthesis of materials with novel structures and electrochemical properties, as well as facilitate the fabrication of hybrid and composite structures from different nanosheets as building blocks.
Paper folding techniques are used in order to compact a Li-ion battery and increase its energy per footprint area. Full cells were prepared using Li4Ti5O12 and LiCoO2 powders deposited onto current collectors consisting of paper coated with carbon nanotubes. Folded cells showed higher areal capacities compared to the planar versions. Origami lithium-ion battery made in this method that can be deformed at an unprecedented high level, including folding, bending and twisting.
Spray pyrolysis was used to prepare films of AgInS2 with and without Sn as an extrinsic dopant. The photoelectrochemical performance of these films was evaluated after annealing under a N2 or S atmosphere with different amounts of the Sn dopant. Density Function Theory (DFT) was used to calculate the band structure of AgInS2 and understand the role of Sn doping in the observed properties.
Cr(VI) removal was investigated using multiple oxide photocatalyst and additives. The efficiency for Cr(VI) removal using these photocatalysts was investigated in synthetic neutral and alkaline water, as well as in cooling tower blowdown water. While sulfite alone can chemically reduce Cr(VI), sulfite in combination with a photocatalyst resulted in faster and complete removal of Cr(VI) in 10 min using a SO32−/Cr(VI) ratio >35 in pH ∼ 8 solutions.
LiCoO2 and LiNi1/3Mn1/3Co1/3O2 were exfoliated into nanosheets using electrochemical oxidation followed by intercalation of tetraethylammonium cations. The nanosheets were purified using dialysis and electrophoresis. The nanosheets were successfully restacked into functional cathode materials with microwave hydrothermal assistance, indicating that new cathodes can be obtained by reassembling nanosheets. This method can pave the way for the synthesis of materials with novel structures and electrochemical properties, as well as facilitate the fabrication of hybrid and composite structures from different nanosheets as building blocks.
Paper folding techniques are used in order to compact a Li-ion battery and increase its energy per footprint area. Full cells were prepared using Li4Ti5O12 and LiCoO2 powders deposited onto current collectors consisting of paper coated with carbon nanotubes. Folded cells showed higher areal capacities compared to the planar versions. Origami lithium-ion battery made in this method that can be deformed at an unprecedented high level, including folding, bending and twisting.
Spray pyrolysis was used to prepare films of AgInS2 with and without Sn as an extrinsic dopant. The photoelectrochemical performance of these films was evaluated after annealing under a N2 or S atmosphere with different amounts of the Sn dopant. Density Function Theory (DFT) was used to calculate the band structure of AgInS2 and understand the role of Sn doping in the observed properties.
Cr(VI) removal was investigated using multiple oxide photocatalyst and additives. The efficiency for Cr(VI) removal using these photocatalysts was investigated in synthetic neutral and alkaline water, as well as in cooling tower blowdown water. While sulfite alone can chemically reduce Cr(VI), sulfite in combination with a photocatalyst resulted in faster and complete removal of Cr(VI) in 10 min using a SO32−/Cr(VI) ratio >35 in pH ∼ 8 solutions.
ContributorsCheng, Qian (Author) / Chan, Candace Kay (Thesis advisor) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016