Matching Items (47)
Description
The colossal global counterfeit market and advances in cryptography including quantum computing supremacy have led the drive for a class of anti-counterfeit tags that are physically unclonable. Dendrites, previously considered an undesirable side effect of battery operation, have promise as an extremely versatile version of such tags, with their fundamental nature ensuring that no two dendrites are alike and that they can be read at multiple magnification scales. In this work, we first pursue a simulation for electrochemical dendrites that elucidates fundamental information about their growth mechanism. We then translate these results into physical dendrites and demonstrate methods of producing a hash from these dendrites that is damage-tolerant for real-world verification. Finally, we explore theoretical curiosities that arise from the fractal nature of dendrites. We find that uniquely ramified dendrites, which rely on lower ion mobility and conductive deposition, are particularly amenable to wavelet hashing, and demonstrate that these dendrites have strong commercial potential for securing supply chains at the highest level while maintaining a low price point.
ContributorsSneh, Tal (Author) / Kozicki, Michael (Thesis director) / Gonzalez-Velo, Yago (Committee member) / School of Molecular Sciences (Contributor) / Department of Physics (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
Description
Electrochemical technologies emerge as a feasible solution to monitor and treat pollutants. Although electrochemical technologies have garnered widespread attention, their commercial applications are still constrained by the use of expensive electrocatalysts, and the bulky and rigid plate design of electrodes that restricts electrochemical reactor design to systems with poor electrode surface/ volume treated ratios. By making electrodes flexible, more compact designs that maximize electrode surface per volume treated might become a reality. This dissertation encompasses the successful fabrication of flexible nanocomposite electrodes for electrocatalysis and electroanalysis applications.First, nano boron-doped diamond electrodes (BDD) were prepared as an inexpensive alternative to commercial boron-doped diamond electrodes. Comparative detailed surface and electrochemical characterization was conducted. Empirical study showed that replacing commercial BDD electrodes with nano-BDD electrodes can result in a cost reduction of roughly 1000x while maintaining the same electrochemical performance.
Next, self-standing electrodes were fabricated through the electropolymerization of conducing polymer, polypyrrole. Surface characterizations, such as SEM, FTIR and XPS proved the successful fabrication of these self-standing electrodes. High mechanical stability and bending flexibility demonstrated the ability to use these electrodes in different designs, such as roll-to-roll membranes. Electrochemical nitrite reduction was employed to demonstrate the viability of using self-standing nanocomposite electrodes for electrocatalytic applications reducing hazardous nitrogen oxyanions (i.e., nitrite) towards innocuous species such as nitrogen gas. A high faradaic efficiency of 78% was achieved, with high selectivity of 91% towards nitrogen gas.
To further enhance the conductivity and charge transfer properties of self-standing polypyrrole electrodes, three different nanoparticles, including copper (Cu), gold (Au), and platinum (Pt), were incorporated in the polypyrrole matrix. Effect of nanoparticle wt% and interaction between metal nanoparticles and polypyrrole matrix was investigated for electroanalytical applications, specifically dopamine sensing. Flexible nanocomposite electrodes showed outstanding performance as electrochemical sensors with PPy-Cu 120s exhibiting a low limit of detection (LOD) of 1.19 µM and PPy-Au 120s exhibiting a high linear range of 5 µM - 300 µM.
This dissertation outlines a method of fabricating self-standing electrodes and provides a pathway of using self-standing electrodes based on polypyrrole and polypyrrole-metal nanocomposites for various applications in wastewater treatment and electroanalytical sensing.
ContributorsBansal, Rishabh (Author) / Garcia-Segura, Sergio (Thesis advisor) / Westerhoff, Paul (Committee member) / Perreault, Francois (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2023
Description
Over the last decade copper electrodeposition has become the dominant process by which microelectronic interconnects are made. Replacing ultra-high vacuum evaporative film growth, the technology known as the Cu damascene process has been widely implemented in the microelectronics industry since the early 2000s. The transition from vacuum film growth to electrodeposition was enabled by solution chemistries that provide "bottom-up" or superfilling capability of vias and trenches. While the process has been and is used widely, the actual mechanisms responsible for superfilling remain relatively unknown. This dissertation presents and discusses the background and results of experimental investigations that have been done using in situ electrochemical surface stress monitoring techniques to study the evolution of stress on Cu{111} thin film electrodes. Because of its extreme sensitivity to the structure on both the electrode and solution sides of the interface, surface stress monitoring as analytical technique is well suited for the study of electrodeposition. These ultra-high resolution stress measurements reveal the dynamic response of copper electrodes to a number of electrochemical and chemical experimental variables. In the case of constant current pulsed deposition and stripping, the surface stress evolution depends not only on the magnitude of the current pulse, but also shows a marked response to plating bath composition. The plating bath chemistries used in this work include (1) additive free, (2) deposition suppressing solutions that include polyethylene glycol (PEG) and sodium chloride (NaCl) as well as (3) full additive solution combinations which contain PEG, NaCl, and a one of two deposition accelerating species (bis-(sodiumsulfopropyl)disulfide (SPS) or mercaptopropane sulfonic acid (MPS)). The development of thin film stress is further investigated through a series of solution exchange experiments that correlate the magnitude of electrode exchange current density and the stress state of the film. Remarkably, stress changes as large as ~8.5 N/m are observed during solution exchanges at the open circuit potential. Overall, this research demonstrates that solution chemistry can have a large impact on thin film stress evolution, even for very small deposition thicknesses (e.g. <10 ML) or in the absence of net addition or removal of material from the electrode.
ContributorsHeaton, Thomas Stanley (Author) / Friesen, Cody (Thesis advisor) / Buttry, Daniel (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
Description
This work focuses on a novel approach to combine electrical current with cyanobacterial technology, called microbial electrophotosynthesis (MEPS). It involves using genetically modified PSII-less Synechocystis PCC 6803 cells to avoid photoinhibition, a problem that hinders green energy. In the work, a cathodic electron delivery system is employed for growth and synthesis. Photoinhibition leads to the dissipation energy and lower yield, and is a major obstacle to preventing green energy from competing with fossil fuels. However, the urgent need for alternative energy sources is driven by soaring energy consumption and rising atmospheric carbon dioxide levels. When developed, MEPS can contribute to a carbon capture technology while helping with energy demands. It is thought that if PSII electron flux can be replaced with an alternative source photosynthesis could be enhanced for more effective production. MEPS has the potential to address these challenges by serving as a carbon capture technology while meeting energy demands. The idea is to replace PSII electron flux with an alternative source, which can be enhanced for higher yields in light intensities not tolerated with PSII. This research specifically focuses on creating the initiation of electron flux between the cathode and the MEPS cells while controlling and measuring the system in real time.
The successful proof-of-concept work shows that MEPS can indeed generate high-light-dependent current at intensities up to 2050 µmol photons m^‒2 s^‒1, delivering 113 µmol electrons h^‒1 mg-chl^‒1. The results were further developed to characterize redox tuning for electron delivery of flux to the photosynthetic electron transport chain and redox-based kinetic analysis to model the limitations of the MEPS system.
ContributorsLewis, Christine Michelle (Author) / Torres, César I (Thesis advisor) / Fromme, Petra (Thesis advisor) / Woodbury, Neal (Committee member) / Hayes, Mark (Committee member) / Arizona State University (Publisher)
Created2023
Description
This thesis develops molecular models for electron transport in molecular junctions and intra-molecular electron transfer. The goal is to identify molecular descriptors that afford a substantial simplification of these electronic processes.
First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon’s tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer.
Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed.
Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of several intermediates in the catalytic cycle of a model NiFe complex, a hypothetical reaction mechanism, which very well agrees with the observed experimental results, is proffered.
Future work related to this thesis may involve the systematic analysis of chemical reactivity in constrained geometries, a subject of importance if the context of enzymatic activity. Another, more intriguing direction is related to the fundamental issue of reformulating Marcus theory in terms of the molecular dielectric response function.
First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon’s tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer.
Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed.
Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of several intermediates in the catalytic cycle of a model NiFe complex, a hypothetical reaction mechanism, which very well agrees with the observed experimental results, is proffered.
Future work related to this thesis may involve the systematic analysis of chemical reactivity in constrained geometries, a subject of importance if the context of enzymatic activity. Another, more intriguing direction is related to the fundamental issue of reformulating Marcus theory in terms of the molecular dielectric response function.
ContributorsKhezr Seddigh Mazinani, Shobeir (Author) / Mujica, Vladimiro (Thesis advisor) / Pilarisetty, Tarakeshwar (Committee member) / Angell, Charles A (Committee member) / Jones, Anne K (Committee member) / Arizona State University (Publisher)
Created2015
Description
Oxidoreductases catalyze transformations important in both bioenergetics and microbial technologies. Nonetheless, questions remain about how to tune them to modulate properties such as preference for catalysis in the oxidative or reductive direction, the potential range of activity, or coupling of multiple reactions. Using protein film electrochemistry, the features that control these properties are defined by comparing the activities of five [FeFe]-hydrogenases and two thiosulfate reductases. Although [FeFe]-hydrogenases are largely described as hydrogen evolution catalysts, the catalytic bias of [FeFe]-hydrogenases, i.e. the ratio of maximal reductive to oxidative activities, spans more than six orders of magnitude. At one extreme, two [FeFe]-hdyrogenases, Clostridium pasteuriaunum HydAII and Clostridium symbiosum HydY, are far more active for hydrogen oxidation than hydrogen evolution. On the other extreme, Clostridium pasteurianum HydAI and Clostridium acetobutylicum HydA1 have a neutral bias, in which both proton reduction and hydrogen oxidation are efficient. By investigating a collection of site-directed mutants, it is shown that the catalytic bias of [FeFe]-hydrogenases is not trivially correlated with the identities of residues in the primary or secondary coordination sphere. On the other hand, the catalytic bias of Clostridium acetobutylicum HydAI can be modulated via mutation of an amino acid residue coordinating the terminal [FeS] cluster. Simulations suggest that this change in catalytic bias may be linked to the reduction potential of the cluster.
Two of the enzymes examined in this work, Clostridium pasteurianum HydAIII and Clostridium symbiosum HydY, display novel catalytic properties. HydY is exclusively a hydrogen oxidizing catalyst, and it couples this activity to peroxide reduction activity at a rubrerythrin center in the same enzyme. On the other hand, CpIII operates only in a narrow potential window, inactivating at oxidizing potentials. This suggests it plays a novel physiological role that has not yet been identified. Finally, the electrocatalytic properties of Pyrobaculum aerophilum thiosulfate reductase with either Mo or W in the active site are compared. In both cases, the onset of catalysis corresponds to reduction of the active site. Overall, the Mo enzyme is more active, and reduces thiosulfate with less overpotential.
Two of the enzymes examined in this work, Clostridium pasteurianum HydAIII and Clostridium symbiosum HydY, display novel catalytic properties. HydY is exclusively a hydrogen oxidizing catalyst, and it couples this activity to peroxide reduction activity at a rubrerythrin center in the same enzyme. On the other hand, CpIII operates only in a narrow potential window, inactivating at oxidizing potentials. This suggests it plays a novel physiological role that has not yet been identified. Finally, the electrocatalytic properties of Pyrobaculum aerophilum thiosulfate reductase with either Mo or W in the active site are compared. In both cases, the onset of catalysis corresponds to reduction of the active site. Overall, the Mo enzyme is more active, and reduces thiosulfate with less overpotential.
ContributorsWilliams, Samuel Garrett (Author) / Jones, Anne K (Thesis advisor) / Hayes, Mark A. (Committee member) / Trovitch, Ryan J (Committee member) / Arizona State University (Publisher)
Created2020
Description
Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals used for a wide variety of products and industrial processes, including being an essential class of chemicals in the fabrication of semiconductors. Proven concerns related to bioaccumulation and toxicity across multiple species have resulted in health advisory and regulatory initiatives for PFAS in drinking and wastewaters. Among impacted users of PFAS, the semiconductor industry is in urgent need of technologies to remove PFAS from water. Specifically, they prefer technologies capable of mineralizing PFAS into inorganic fluoride (F-). The goal of this thesis is to compare the effectiveness of photo- versus electrocatalytic treatment in benchtop reactor systems PFAS in industrial wastewater before selecting one technology to investigate comprehensively. First, a model wastewater was developed based upon semiconductor samples to represent water matrices near where PFAS are used and the aggregate Fab effluent, which were then used in batch catalytic experiments. Second, batch experiments with homogenous photocatalysis (UV/SO32-) were found to be more energy-intensive than heterogeneous catalysis using boron-doped diamond (BDD) electrodes, and the latter approach was then studied in-depth.
During electrocatalysis, longer chain PFAS (C8; PFOA & PFOS) were observed to degrade faster than C6 and C4 PFAS. This study is the first to report near-complete defluorination of not only C8- and C6- PFAS, but also C4-PFAS, in model wastewaters using BDD electrocatalysis, and the first to report such degradation in real Fab wastewater effluents. Based upon differences in PFAS degradation rates observed in single-solute systems containing only C4 PFAS versus multi-solute systems including C4, C6, and C8 PFAS, it was concluded that the surfactant properties of the longer-chain PFAS created surface films on the BDD electrode surface which synergistically enhanced removal of shorter-chain PFAS. The results from batch experiments that serve as the basis of this thesis will be used to assess the chemical byproducts and their associated bioaccumulation and toxicity. This thesis was aimed at developing an efficient method for the degradation of perfluoroalkyl substances from industrial process waters at realistic concentrations.
ContributorsNienhauser, Alec Brockway (Author) / Westerhoff, Paul (Thesis advisor) / Garcia-Segura, Sergi (Committee member) / Thomas, Marylaura (Committee member) / Green, Matthew (Committee member) / Arizona State University (Publisher)
Created2021
Description
Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for
future energy storage devices. Electrode materials that alloy with Li, such as Si, are one
of the most promising alternatives for Li-ion battery anodes due to their high capacities.
Tetrel (Si, Ge, Sn) clathrates are a class of host-guest crystalline structures in which
Tetrel elements form a cage framework and encapsulate metal guest atoms. These
structures can form with defects such as framework/guest atom substitutions and
vacancies which result in a wide design space for tuning materials properties. The goal of
this work is to establish structure property relationships within the context of Li-ion
battery anode applications. The type I Ba 8 Al y Ge 46-y clathrates are investigated for their
electrochemical reactions with Li and show high capacities indicative of alloying
reactions. DFT calculations show that Li insertion into the framework vacancies is
favorable, but the migration barriers are too high for room temperature diffusion. Then,
guest free type I clathrates are investigated for their Li and Na migration barriers. The
results show that Li migration in the clathrate frameworks have low energy barriers (0.1-
0.4 eV) which suggest the possibility for room temperature diffusion. Then, the guest
free, type II Si clathrate (Na 1 Si 136 ) is synthesized and reversible Li insertion into the type
II Si clathrate structure is demonstrated. Based on the reasonable capacity (230 mAh/g),
low reaction voltage (0.30 V) and low volume expansion (0.21 %), the Si clathrate could
be a promising insertion anode for Li-ion batteries. Next, synchrotron X-ray
measurements and pair distribution function (PDF) analysis are used to investigate the
lithiation pathways of Ba 8 Ge 43 , Ba 8 Al 16 Ge 30 , Ba 8 Ga 15 Sn 31 and Na 0.3 Si 136 . The results
show that the Ba-clathrates undergo amorphous phase transformations which is distinct
from their elemental analogues (Ge, Sn) which feature crystalline lithiation pathways.
Based on the high capacities and solid-solution reaction mechanism, guest-filled
clathrates could be promising precursors to form alloying anodes with novel
electrochemical properties. Finally, several high temperature (300-550 °C)
electrochemical synthesis methods for Na-Si and Na-Ge clathrates are demonstrated in a
cell using a Na β’’-alumina solid electrolyte.
ContributorsDopilka, Andrew (Author) / Chan, Candace K (Thesis advisor) / Zhuang, Houlong (Committee member) / Peng, Xihong (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021
Description
Corrosion is one of the key failure modes for stainless steel (SS) piping assets handling water resources managed by utility companies. During downtime, the costs start to incur as the field engineer procures its replacement parts. The parts may or may not be in stock depending on how old, complex, and common the part model is. As a result, water utility companies and its resilience to operate amid part failure are a strong function of the supply chain for replacement piping. Metal additive manufacturing (AM) has been widely recognized for its ability to (a) deliver small production scales, (b) address complex part geometries, (c) offer large elemental metal and alloy selections, (d) provide superior material properties. The key motive is to harvest the short lead time of metal AM to explore its use for replacement parts for legacy piping assets in utility-scale water management facilities. In this paper, the goal was to demonstrate 3D printing of stainless steel (SS) 316L parts using selective laser melting (SLM) technology. The corrosion resistance of 3D printed SS 316L was investigated using (a) Chronoamperometry (b) Cyclic Potentiodynamic Polarization (CPP) and Electrochemical Impedance Spectroscopy (EIS) and its improved resistance from wrought (conventional) part was also studied. Then the weldability of 3D printed SS 316L to wrought SS 316L was illustrated and finally, the mechanical strength of the weld and the effect of corrosion on weld strength was investigated using uniaxial tensile testing. The results show that 3D printed part compared to the wrought part has a) lower mass loss before and after corrosion, (b) higher pitting potential, and (c) higher charge transfer resistance. The tensile testing of welded dog bone specimens indicates that the 3D printed parts despite being less ductile were observed to have higher weld strength compared to the wrought part. On this basis, metal AM holds great value to be explored further for replacement piping parts owing to their better corrosion resistance and mechanical performance.
ContributorsSampath, Venkata Krishnan (Author) / Azeredo, Bruno (Thesis advisor) / Torres, Cesar (Committee member) / Mu, Bin (Committee member) / Arizona State University (Publisher)
Created2021
Description
Tin (Sn) has a high-specific capacity (993 mAhg-1) as an anode material for Li-ion batteries. To overcome the poor cycling performance issue caused by its large volume expansion and pulverization during the charging and discharging process, many researchers put efforts into it. Most of the strategies are through nanostructured material design and introducing conductive polymer binders that serve as matrix of the active material in anode. This thesis aims for developing a novel method for preparing the anode to improve the capacity retention rate. This would require the anode to have high electrical conductivity, high ionic conductivity, and good mechanical properties, especially elasticity. Here the incorporation of a conducting polymer and a conductive hydrogel in Sn-based anodes using a one-step electrochemical deposition via a 3-electrode cell method is reported: the Sn particles and conductive component can be electrochemically synthesized and simultaneously deposited into a hybrid thin film onto the working electrode directly forming the anode. A well-defined three dimensional network structure consisting of Sn nanoparticles coated by conducting polymers is achieved. Such a conductive polymer-hydrogel network has multiple advantageous features: meshporous polymeric structure can offer the pathway for lithium ion transfer between the anode and electrolyte; the continuous electrically conductive polypyrrole network, with the electrostatic interaction with elastic, porous hydrogel, poly (2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) (PAMPS) as both the crosslinker and doping anion for polypyrrole (PPy) can decrease the volume expansion by creating porous scaffold and softening the system itself. Furthermore, by increasing the amount of PAMPS and creating an interval can improve the cycling performance, resulting in improved capacity retention about 80% after 20 cycles, compared with only 54% of that of the control sample without PAMPS. The cycle is performed under current of 0.1 C.
ContributorsGao, Tianxiang (Author) / He, Ximin (Thesis advisor) / Sieradzki, Karl (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2015