Matching Items (10)
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- All Subjects: electrochemistry
- Creators: Torres, Cesar
- Creators: Angell, Charles A
Description
This thesis studies three different types of anhydrous proton conducting electrolytes for use in fuel cells. The proton energy level scheme is used to make the first electrolyte which is a rubbery polymer in which the conductivity reaches values typical of activated Nafion, even though it is completely anhydrous. The protons are introduced into a cross-linked polyphospazene rubber by the superacid HOTf, which is absorbed by partial protonation of the backbone nitrogens. The decoupling of conductivity from segmental relaxation times assessed by comparison with conductivity relaxation times amounts to some 10 orders of magnitude, but it cannot be concluded whether it is purely protonic or due equally to a mobile OTf- or H(OTf)2-; component. The second electrolyte is built on the success of phosphoric acid as a fuel cell electrolyte, by designing a variant of the molecular acid that has increased temperature range without sacrifice of high temperature conductivity or open circuit voltage. The success is achieved by introduction of a hybrid component, based on silicon coordination of phosphate groups, which prevents decomposition or water loss to 250ºC, while enhancing free proton motion. Conductivity studies are reported to 285ºC and full H2/O2 cell polarization curves to 226ºC. The current efficiency reported here (current density per unit of fuel supplied per sec) is the highest on record. A power density of 184 (mW.cm-2) is achieved at 226ºC with hydrogen flow rate of 4.1 ml/minute. The third electrolyte is a novel type of ionic liquids which is made by addition of a super strong Brønsted acid to a super weak Brønsted base. Here it is shown that by allowing the proton of transient HAlCl4, to relocate on a very weak base that is also stable to superacids, we can create an anhydrous ionic liquid, itself a superacid, in which the proton is so loosely bound that at least 50% of the electrical conductivity is due to the motion of free protons. The protic ionic liquids (PILs) described, pentafluoropyridinium tetrachloroaluminate and 5-chloro-2,4,6-trifluoropyrimidinium tetrachloroaluminate, might be the forerunner of a class of materials in which the proton plasma state can be approached.
ContributorsAnsari, Younes (Author) / Angell, Charles A (Thesis advisor) / Richert, Ranko (Committee member) / Chizmeshya, Andrew (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
Microbial fuel cells (MFCs) promote the sustainable conversion of organic matter in black water to electrical current, enabling the production of hydrogen peroxide (H2O2) while making waste water treatment energy neutral or positive. H2O2 is useful in remote locations such as U.S. military forward operating bases (FOBs) for on-site tertiary water treatment or as a medical disinfectant, among many other uses. Various carbon-based catalysts and binders for use at the cathode of a an MFC for H2O2 production are explored using linear sweep voltammetry (LSV) and rotating ring-disk electrode (RRDE) techniques. The oxygen reduction reaction (ORR) at the cathode has slow kinetics at conditions present in the MFC, making it important to find a catalyst type and loading which promote a 2e- (rather than 4e-) reaction to maximize H2O2 formation. Using LSV methods, I compared the cathodic overpotentials associated with graphite and Vulcan carbon catalysts as well as Nafion and AS-4 binders. Vulcan carbon catalyst with Nafion binder produced the lowest overpotentials of any binder/catalyst combinations. Additionally, I determined that pH control may be required at the cathode due to large potential losses caused by hydroxide (OH-) concentration gradients. Furthermore, RRDE tests indicate that Vulcan carbon catalyst with a Nafion binder has a higher H2O2 production efficiency at lower catalyst loadings, but the trade-off is a greater potential loss due to higher activation energy. Therefore, an intermediate catalyst loading of 0.5 mg/cm2 Vulcan carbon with Nafion binder is recommended for the final MFC design. The chosen catalyst, binder, and loading will maximize H2O2 production, optimize MFC performance, and minimize the need for additional energy input into the system.
ContributorsStadie, Mikaela Johanna (Author) / Torres, Cesar (Thesis director) / Popat, Sudeep (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2015-05
Description
Diabetes mellitus is a disease characterized by many chronic and acute conditions. With the prevalence and cost quickly increasing, we seek to improve on the current standard of care and create a rapid, label free sensor for glycated albumin (GA) index using electrochemical impedance spectroscopy (EIS). The antibody, anti-HA, was fixed to gold electrodes and a sine wave of sweeping frequencies was induced with a range of HA, GA, and GA with HA concentrations. Each frequency in the impedance sweep was analyzed for highest response and R-squared value. The frequency with both factors optimized is specific for both the antibody-antigen binding interactions with HA and GA and was determined to be 1476 Hz and 1.18 Hz respectively in purified solutions. The correlation slope between the impedance response and concentration for albumin (0 \u2014 5400 mg/dL of albumin) was determined to be 72.28 ohm/ln(mg/dL) with an R-square value of 0.89 with a 2.27 lower limit of detection. The correlation slope between the impedance response and concentration for glycated albumin (0 \u2014 108 mg/dL) was determined to be -876.96 ohm/ln(mg/dL) with an R-squared value of 0.70 with a 0.92 mg/dL lower limit of detection (LLD). The above data confirms that EIS offers a new method of GA detection by providing unique correlation with albumin as well as glycated albumin. The unique frequency response of GA and HA allows for modulation of alternating current signals so that several other markers important in the management of diabetes could be measured with a single sensor. Future work will be necessary to establish multimarker sensing on one electrode.
ContributorsEusebio, Francis Ang (Author) / LaBelle, Jeffrey (Thesis director) / Pizziconi, Vincent (Committee member) / Barrett, The Honors College (Contributor) / Harrington Bioengineering Program (Contributor)
Created2014-05
Description
In this Honors thesis, direct flame solid oxide fuel cells (DFFC) were considered for their feasibility in providing a means of power generation for remote powering needs. Also considered for combined heat and fuel cell power cogeneration are thermoelectric cells (TEC). Among the major factors tested in this project for all cells were life time, thermal cycle/time based performance, and failure modes for cells. Two types of DFFC, anode and electrolyte supported, were used with two different fuel feed streams of propane/isobutene and ethanol. Several test configurations consisting of single cells, as well as stacked systems were tested to show how cell performed and degraded over time. All tests were run using a Biologic VMP3 potentiostat connected to a cell placed within the flame of a modified burner MSR® Wisperlite Universal stove. The maximum current and power output seen by any electrolyte supported DFFCs tested was 47.7 mA/cm2 and 9.6 mW/cm2 respectively, while that generated by anode supported DFFCs was 53.7 mA/cm2 and 9.25 mW/cm2 respectively with both cells operating under propane/isobutene fuel feed streams. All TECs tested dramatically outperformed both constructions of DFFC with a maximum current and power output of 309 mA/cm2 and 80 mW/cm2 respectively. It was also found that electrolyte supported DFFCs appeared to be less susceptible to degradation of the cell microstructure over time but more prone to cracking, while anode supported DFFCs were dramatically less susceptible to cracking but exhibited substantial microstructure degradation and shorter usable lifecycles. TECs tested were found to only be susceptible to overheating, and thus were suggested for use with electrolyte supported DFFCs in remote powering applications.
ContributorsTropsa, Sean Michael (Author) / Torres, Cesar (Thesis director) / Popat, Sudeep (Committee member) / Barrett, The Honors College (Contributor) / Chemical Engineering Program (Contributor)
Created2014-05
Description
Microbial fuel cells (MFCs) facilitate the conversion of organic matter to electrical current to make the total energy in black water treatment neutral or positive and produce hydrogen peroxide to assist the reuse of gray water. This research focuses on wastewater treatment at the U.S. military forward operating bases (FOBs). FOBs experience significant challenges with their wastewater treatment due to their isolation and dangers in transporting waste water and fresh water to and from the bases. Even though it is theoretically favorable to produce power in a MFC while treating black water, producing H2O2 is more useful and practical because it is a powerful cleaning agent that can reduce odor, disinfect, and aid in the treatment of gray water. Various acid forms of buffers were tested in the anode and cathode chamber to determine if the pH would lower in the cathode chamber while maintaining H2O2 efficiency, as well as to determine ion diffusion from the anode to the cathode via the membrane. For the catholyte experiments, phosphate and bicarbonate were tested as buffers while sodium chloride was the control. These experiments determined that the two buffers did not lower the pH. It was seen that the phosphate buffer reduced the H2O2 efficiency significantly while still staying at a high pH, while the bicarbonate buffer had the same efficiency as the NaCl control. For the anolyte experiments, it was shown that there was no diffusion of the buffers or MFC media across the membrane that would cause a decrease in the H2O2 production efficiency.
ContributorsThompson, Julia (Author) / Torres, Cesar (Thesis director) / Popat, Sudeep (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
The removal of support material from metal 3D printed objects is a laborious necessity for the post-processing of powder bed fusion printing (PBF). Supports are typically mechanically removed by machining techniques. Sacrificial supports are necessary in PBF printing to relieve thermal stresses and support overhanging parts often resulting in the inclusion of supports in regions of the part that are not easily accessed by mechanical removal methods. Recent innovations in PBF support removal include dissolvable metal supports through an electrochemical etching process. Dissolvable PBF supports have the potential to significantly reduce the costs and time associated with traditional support removal. However, the speed and effectiveness of this approach is inhibited by numerous factors such as support geometry and metal powder entrapment within supports. To fully realize this innovative approach, it is necessary to model and understand the design parameters necessary to optimize support structures applicable to an electrochemical etching process. The objective of this study was to evaluate the impact of block additive manufacturing support parameters on key process outcomes of the dissolution of 316 stainless steel support structures. The parameters investigated included hatch spacing and perforation, and the outcomes of interests included time required for completion, surface roughness, and effectiveness of the etching process. Electrical current was also evaluated as an indicator of process completion. Analysis of the electrical current throughout the etching process showed that the dissolution is diffusion limited to varying degrees, and is dependent on support structure parameters. Activation and passivation behavior was observed during current leveling, and appeared to be more pronounced in non-perforated samples with less dense hatch spacing. The correlation between electrical current and completion of the etching process was unclear, as the support structures became mechanically removable well before the current leveled. The etching process was shown to improve surface finish on unsupported surfaces, but support was shown to negatively impact surface finish. Tighter hatch spacing was shown to correlate to larger variation in surface finish, due to ridges left behind by the support structures. In future studies, it is recommended current be more closely correlated to process completion and more roughness data be collected to identify a trend between hatch spacing and surface roughness.
ContributorsAbranovic, Brandon (Author) / Hildreth, Owen (Thesis director) / Torres, Cesar (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
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
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
Optimizing cathodes for microbial fuel cells is important to maximize energy harvested from wastewater. Cathodes were made by modifying a recipe from previous literature and testing the current of the cathode using linear sweep voltammetry. The cathodes contained an Fe-N-C catalyst combined with a Polytetrafluoroethylene binder. Optimizing the power resulting from the microbial fuel cells will help MFCs be an alternative energy source to fossil fuels. The new cathodes did improve in current production from −16 𝐴/𝑚 to −37 𝐴/𝑚 at -0.4 V. When fitted using a Butler-Volmer model, the cathode linear-sweep voltammograms did not follow the expected exponential trend. These results show a need for more research on the cathodes and the Butler-Volmer model, and they also show that the cathode is ready for further and longer application in a microbial fuel cell.
ContributorsRussell, Andrea Christine (Author) / Torres, Cesar (Thesis director) / Young, Michelle (Committee member) / School of Sustainable Engineering & Built Envirnmt (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
Description
Energy can be harvested from wastewater using microbial fuel cells (MFC). In order to increase power generation, MFCs can be scaled-up. The MFCs are designed with two air cathodes and two anode electrodes. The limiting electrode for power generation is the cathode and in order to maximize power, the cathodes were made out of a C-N-Fe catalyst and a polytetrafluoroethylene binder which had a higher current production at -3.2 mA/cm2 than previous carbon felt cathodes at -0.15 mA/cm2 at a potential of -0.29 V. Commercial microbial fuel cells from Aquacycl were tested for their power production while operating with simulated blackwater achieved an average of 5.67 mW per cell. The small MFC with the C-N-Fe catalyst and one cathode was able to generate 8.7 mW. Imitating the Aquacycl cells, the new MFC was a scaled-up version of the small MFC where the cathode surface area increased from 81 cm2 to 200 cm2. While the MFC was operating with simulated blackwater, the peak power produced was 14.8 mW, more than the smaller MFC, but only increasing in the scaled-up MFC by 1.7 when the surface area of the cathode increased by 2.46. Further long-term application can be done, as well as operating multiple MFCs in series to generate more power and improve the design.
ContributorsRussell, Andrea (Author) / Torres, Cesar (Thesis advisor) / Garcia Segura, Sergio (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2022