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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
Two-dimensional transition metal dichalcogenides (TMDCs) such as
molybdenum disulfide (MoS2), tungsten disulfide (WS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2) are attractive for use in biotechnology, optical and electronics devices due to their promising and tunable electrical, optical and chemical properties. To fulfill the variety of requirements for different applications, chemical treatment methods are developed to tune their properties. In this dissertation, plasma treatment, chemical doping and functionalization methods have been applied to tune the properties of TMDCs. First, plasma treatment of TMDCs results in doping and generation of defects, as well as the synthesis of transition metal oxides (TMOs) with rolled layers that have increased surface-to-volume ratio and are promising for electrochemical applications. Second, chemical functionalization is another powerful approach for tuning the properties of TMDCs for use in many applications. To covalently functionalize the basal planes of TMDCs, previous reports begin with harsh treatments like lithium intercalation that disrupt the structure and lead to a phase transformation from semiconducting to metallic. Instead, this work demonstrates the direct covalent functionalization of semiconducting MoS2 using aryl diazonium salts without lithium treatments. It preserves the structure and semiconducting nature of MoS2, results in covalent C-S bonds on basal planes and enables different functional groups to be tethered to the MoS2 surface via the diazonium salts. The attachment of fluorescent proteins has been used as a demonstration and it suggests future applications in biology and biosensing. The effects of the covalent functionalization on the electronic transport properties of MoS2 were then studied using field effect transistor (FET) devices.
molybdenum disulfide (MoS2), tungsten disulfide (WS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2) are attractive for use in biotechnology, optical and electronics devices due to their promising and tunable electrical, optical and chemical properties. To fulfill the variety of requirements for different applications, chemical treatment methods are developed to tune their properties. In this dissertation, plasma treatment, chemical doping and functionalization methods have been applied to tune the properties of TMDCs. First, plasma treatment of TMDCs results in doping and generation of defects, as well as the synthesis of transition metal oxides (TMOs) with rolled layers that have increased surface-to-volume ratio and are promising for electrochemical applications. Second, chemical functionalization is another powerful approach for tuning the properties of TMDCs for use in many applications. To covalently functionalize the basal planes of TMDCs, previous reports begin with harsh treatments like lithium intercalation that disrupt the structure and lead to a phase transformation from semiconducting to metallic. Instead, this work demonstrates the direct covalent functionalization of semiconducting MoS2 using aryl diazonium salts without lithium treatments. It preserves the structure and semiconducting nature of MoS2, results in covalent C-S bonds on basal planes and enables different functional groups to be tethered to the MoS2 surface via the diazonium salts. The attachment of fluorescent proteins has been used as a demonstration and it suggests future applications in biology and biosensing. The effects of the covalent functionalization on the electronic transport properties of MoS2 were then studied using field effect transistor (FET) devices.
ContributorsChu, Ximo (Author) / Wang, Qing Hua (Thesis advisor) / Sieradzki, Karl (Committee member) / Green, Alexander (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2018
Description
Lithium ion batteries have emerged as the most popular energy storage system, but they pose safety issues under extreme temperatures or in the event of a thermal runaway. Lithium ion batteries with inorganic separators offer the advantage of safer operation. An inorganic separator for lithium ion battery was prepared by an improved method of blade coating α-Al2O3 slurry directly on the electrode followed by drying. The improved separator preparation involves a twice-coating process instead of coating the slurry all at once in order to obtain a thin (~40 µm) and uniform coat. It was also found that α-Al2O3 powder with particle size greater than the pore size in the electrode is preferable for obtaining a separator with 40 µm thickness and consistent cell performance. Unlike state-of-the-art polyolefin separators such as polypropylene (PP) which are selectively wettable with only certain electrolytes, the excellent electrolyte solvent wettability of α-Al2O3 allows the coated alumina separator to function with different electrolytes. The coated α-Al2O3 separator has a much higher resistance to temperature effects than its polyolefin counterparts, retaining its dimensional integrity at temperatures as high as 200ºC. This eliminates the possibility of a short circuit during thermal runaway. Lithium ion batteries assembled as half-cells and full cells with coated α-Al2O3 separator exhibit electrochemical performance comparable with that of polyolefin separators at room temperature. However, the cells with coated alumina separator shows better cycling performance under extreme temperatures in the temperature range of -30°C to 60°C. Therefore, the coated α-Al2O3 separator is very promising for application in safe lithium-ion batteries.
ContributorsSharma, Gaurav (Author) / Lin, Jerry Y.S. (Thesis advisor) / Chan, Candace (Committee member) / Kannan, Arunachala (Committee member) / Arizona State University (Publisher)
Created2016
Description
Zinc oxide nanowires ( NWs) have broad applications in various fields such as nanoelectronics, optoelectronics, piezoelectric nanogenerators, chemical/biological sensors, and heterogeneous catalysis. To meet the requirements for broader applications, the growth of high-quality ZnO NWs and functionalization of ZnO NWs are critical. In this work, specific types of functionalized ZnO NWs have been synthesized and correlations between specific structures and properties have been investigated. Deposition of δ-Bi2O3 (narrow band gap) epilayers onto ZnO (wide band gap) NWs improves the absorption efficiency of the visible light spectrum by 70%. Furthermore, the deposited δ-Bi2O3 grows selectively and epitaxially on the {11-20} but not on the {10-10} facets of the ZnO NWs. The selective epitaxial deposition and the interfacial structure were thoroughly investigated. The morphology and structure of the Bi2O3/ZnO nanocomposites can be tuned by controlling the deposition conditions.
Various deposition methods, both physical and chemical, were used to functionalize the ZnO NWs with metal or alloy nanoparticles (NPs) for catalytic transformations of important molecules which are relevant to energy and environment. Cu and PdZn NPs were epitaxially grown on ZnO NWs to make them resistant to sintering at elevated temperatures and thus improved the stability of such catalytic systems for methanol steam reforming (MSR) to produce hydrogen. A series of Pd/ZnO catalysts with different Pd loadings were synthesized and tested for MSR reaction. The CO selectivity was found to be strongly dependent on the size of the Pd: Both PdZn alloy and single Pd atoms yield low CO selectivity while Pd clusters give the highest CO selectivity.
By dispersing single Pd atoms onto ZnO NWs, Pd1/ZnO single-atom catalysts (SACs) was synthesized and their catalytic performance was evaluated for selected catalytic reactions. The experimental results show that the Pd1/ZnO SAC is active for CO oxidation and MSR but is not desirable other reactions. We further synthesized ZnO NWs supported noble metal (M1/ZnO; M=Rh, Pd, Pt, Ir) SACs and studied their catalytic performances for CO oxidation. The catalytic test data shows that all the fabricated noble metal SACs are active for CO oxidation but their activity are significantly different. Structure-performance relationships were investigated.
Various deposition methods, both physical and chemical, were used to functionalize the ZnO NWs with metal or alloy nanoparticles (NPs) for catalytic transformations of important molecules which are relevant to energy and environment. Cu and PdZn NPs were epitaxially grown on ZnO NWs to make them resistant to sintering at elevated temperatures and thus improved the stability of such catalytic systems for methanol steam reforming (MSR) to produce hydrogen. A series of Pd/ZnO catalysts with different Pd loadings were synthesized and tested for MSR reaction. The CO selectivity was found to be strongly dependent on the size of the Pd: Both PdZn alloy and single Pd atoms yield low CO selectivity while Pd clusters give the highest CO selectivity.
By dispersing single Pd atoms onto ZnO NWs, Pd1/ZnO single-atom catalysts (SACs) was synthesized and their catalytic performance was evaluated for selected catalytic reactions. The experimental results show that the Pd1/ZnO SAC is active for CO oxidation and MSR but is not desirable other reactions. We further synthesized ZnO NWs supported noble metal (M1/ZnO; M=Rh, Pd, Pt, Ir) SACs and studied their catalytic performances for CO oxidation. The catalytic test data shows that all the fabricated noble metal SACs are active for CO oxidation but their activity are significantly different. Structure-performance relationships were investigated.
ContributorsXu, Jia, Ph.D (Author) / Liu, Jingyue (Thesis advisor) / Smith, David (Committee member) / Chan, Candace (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2017
Description
Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and a cathode immersed in an aqueous electrolyte where charge separation takes place in the bulk of the semiconducting material on light absorption, leading to water oxidation/reduction at the surface of the photoelectrodes/cathode. It is imperative to develop materials that demonstrate high light absorption in the wide spectrum along with photoelectrochemical stability. N-type Monoclinic scheelite bismuth vanadate (BiVO4) is selected due to its incredible light absorption capabilities, direct bandgap (Eg ∼ 2.4-2.5 eV) and relatively better photoelectrochemical stability. However, BiVO4 encounters huge electron-hole recombination due to smaller diffusion lengths and positive conduction bands that cause slow charge dynamics and sluggish water oxidation kinetics. In order to improve the illustrated drawbacks, four strategies were discussed. Chapter 1 describe the fundamental understanding of photoelectrochemical cell and BiVO4. Chapter 2 illustrates details of the experimental procedure and state-of-the-art material characterization. Chapter 3 provide the impact of alkali metal placement in the crystal structure of BiVO4 systematically that exhibited ~20 times more performance than intrinsic BiVO4, almost complete bulk charge separation and enhancement in the diffusion length. Detailed characterization determined that the alkali metal getting placed in the interstitial void of BiVO4 lattice and multiple interbands formation enhanced the charge dynamics. Chapter 4 contains stoichiometric doping of Y3+ or Er3+ or Yb3+ at the Bi3+ site, leading to an extended absorption region, whereas non-stoichiometric W6+ doping at the V5+ site minimizes defects and increased charge carriers. To further enhance the performance, type-II heterojunction with WO3 along p-n junction with Fe:NiO enhance light absorption and charge dynamics close to the theoretical performance. Chapter 5 provides a comprehensive study of a uniquely developed sulfur modified Bi2O3 interface layer to facilitate charge dynamics and carrier lifetime improvement by effectively passivating the WO3/BiVO4 heterojunction interface. Finally, chapter 6 summarized the major findings, conclusion and outlook in developing BiVO4 as an efficient photoanode material.
ContributorsPrasad, Umesh (Author) / Kannan, Arunachala Mada (Thesis advisor) / Azeredo, Bruno (Committee member) / Chan, Candace (Committee member) / Segura, Sergio Garcia (Committee member) / Arizona State University (Publisher)
Created2021
Description
Heavy metals such as selenium can be especially important to limit because they can cause serious health problems even at relatively low concentrations. In an effort to selectively remove selenium from solution, a PAABA (poly(aniline-co-p-aminobenzoic acid) conductive copolymer was synthesized in a selenic acid solution, and its ability to remove selenium was studied. Analysis of the Raman spectra confirmed the hypothesized formation of PAABA polymer. Constant voltage cycles showed success in precipitating the selenium out of solution via electroreduction, and ICP-MS confirmed the reduction of selenium concentrated in solution. These results indicate the PAABA synthesized in selenic acid shows promise for selective water treatment.
ContributorsSulzman, Serita Lynne (Author) / Wang, Qing Hua (Thesis director) / Chan, Candace (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-05
Description
Delamination of solar module interfaces often occurs in field-tested solar modules after decades of service due to environmental stressors such as humidity. In the presence of water, the interfaces between the encapsulant and the cell, glass, and backsheet all experience losses of adhesion, exposing the module to accelerated degradation. Understanding the relation between interfacial adhesion and water content inside photovoltaic modules can help mitigate detrimental power losses. Water content measurements via water reflectometry detection combined with 180° peel tests were used to study adhesion of module materials exposed to damp heat and dry heat conditions. The effect of temperature, cumulative water dose, and water content on interfacial adhesion between ethylene vinyl acetate and (1) glass, (2) front of the cell, and (3) backsheet was studied. Temperature and time decreased adhesion at all these interfaces. Water content in the sample during the measurement showed significant decreases in adhesion for the Backsheet/Ethylene vinyl acetate interface. Water dose showed little effect for the Glass/ Ethylene vinyl acetate and Backsheet/ Ethylene vinyl acetate interfaces, but there was significant adhesion loss with water dose at the front cell busbar/encapsulant interface. Initial tensile test results to monitor the effects of the mechanical properties ethylene vinyl acetate and backsheet showed water content increasing the strength of ethylene vinyl acetate during plastic deformation but no change in the strength of the backsheet properties. This mechanical property change is likely inducing variation along the peel interface to possibly convolute the adhesion measurements conducted or to explain the variation seen for the water saturated and dried peel test sample types.
ContributorsTheut, Nicholas (Author) / Bertoni, Mariana (Thesis advisor) / Holman, Zachary (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2020