Effect of Oxidation Level on the Interfacial Water at the Graphene Oxide-Water Interface: From Spectroscopic Signatures to Hydrogen-Bonding Environment

The interfacial region of the graphene oxide (GO)-water system is nonhomogenous due to the presence of two distinct domains: an oxygen-rich surface and a graphene-like region. The experimental vibrational sum-frequency generation (vSFG) spectra are distinctly different for the fully oxidized GO-water interface as compared to the reduced GO-water case. Computational investigations using ab initio molecular dynamics were performed to determine the molecular origins of the different spectroscopic features. The simulations were first validated by comparing the simulated vSFG spectra to those from the experiment, and the contributions to the spectra from different hydrogen bonding environments and interfacial water orientations were determined as a function of the oxidation level of the GO sheet. The ab initio simulations also revealed the reactive nature of the GO-water interface

Microbial desalination cell with sulfonated sodium (poly(ether ether ketone) as cation exchange membranes for enhancing power generation and salt reduction

© 2018 Microbial desalination cell (MDC) is a bioelectrochemical system capable of oxidizing organics, generating electricity, while reducing the salinity content of brine streams. As it is designed, anion and cation exchange membranes play an important role on the selective removal of ions from the desalination chamber. In this work, sulfonated sodium (Na+) poly(ether ether ketone) (SPEEK) cation exchange membranes (CEM) were tested in combination with quaternary ammonium chloride poly(2,6-dimethyl 1,4-phenylene oxide) (QAPPO) anion exchange membrane (AEM). Non-patterned and patterned (varying topographical features) CEMs were investigated and assessed in this work. The results were contrasted against a commercially available CEM. This work used real seawater from the Pacific Ocean in the desalination chamber. The results displayed a high desalination rate and power generation for all the membranes, with a maximum of 78.6 ± 2.0% in salinity reduction and 235 ± 7 mW m−2 in power generation for the MDCs with the SPEEK CEM. Desalination rate and power generation achieved are higher with synthesized SPEEK membranes when compared with an available commercial CEM. An optimized combination of these types of membranes substantially improves the performances of MDC, making the system more suitable for real applications

Investigation of patterned and non-patterned poly(2,6-dimethyl 1,4-phenylene) oxide based anion exchange membranes for enhanced desalination and power generation in a microbial desalination cell

© 2017 The Authors Quaternary ammonium poly(2,6-dimethyl 1,4-phenylene oxide) (QAPPO) anion exchange membranes (AEMs) with topographically patterned surfaces were assessed in a microbial desalination cell (MDC) system. The MDC results with these QAPPO AEMs were benchmarked against a commercially available AEM. The MDC with the non-patterned QAPPO AEM (Q1) displayed the best desalination rate (a reduction of salinity by 53 ± 2.7%) and power generation (189 ± 5 mW m− 2) when compared against the commercially available AEM and the patterned AEMs. The enhanced performance with the Q1 AEM was attributed to its higher ionic conductivity and smaller thickness leading to a reduced area specific resistance. It is important to note that Real Pacific Ocean seawater and activated sludge were used into the desalination chamber and anode chamber respectively for the MDC – which mimicked realistic conditions. Although the non-patterned QAPPO AEM displayed better performance over the patterned QAPPO AEMs, it was observed that the anodic overpotential was smaller when the MDCs featured QAPPO AEMs with larger lateral feature sizes. The results from this study have important implications for the continuous improvements necessary for developing cheaper and better performing membranes in order to optimize the MDC

Data-mining the Ubuntu Linux Distribution for bug analysis and resolution

textThe Ubuntu Linux Distribution represents a massive investment of time and human effort to produce a reliable computing experience for users. To accomplish these goals, software bugs must be tracked and fixed. However, as the number of users increase and bug reports grow advanced tools such as data mining must be used to increase the effectiveness of all contributors to the project. Thus, this report involved collecting a large amount of bug reports into a database and calculating relevant statistics. Because of the diversity and quantity of bug reports, contributors must find which bugs are most relevant and important to work on. One study in this report created an automatic way to determine who is best fit to solve a particular bug by using classification techniques. In addition, this report explores how to initially classify if a bug report will be eventually marked invalid or not.Electrical and Computer Engineerin

STRUCTURE-PROPERTY RELATIONSHIPS IN ANION EXCHANGE MEMBRANES FOR ELECTROCHEMICAL ENERGY CONVERSION AND STORAGE

Polymer electrolyte membrane (PEM) fuel cells are promising candidates for powering automotive vehicles, but their advancement has been hindered by the costs associated with their platinum-based electrocatalysts. One strategy to resolve this problem is to replace the conventional acidic PEM with an alkaline anion exchange membrane (AEM) because fuel cells operated in alkaline media do not require platinum group metal catalysts. A significant challenge to realizing this concept is to design and implement an AEM that is chemically robust under alkaline conditions and that facilitates high ionic conductivity. This dissertation presents a scientific approach to address the aforementioned problems through investigation of alternative cations, beyond quaternary trimethylammonium, to understand what chemical features influence ion conductivity and alkaline stability. It was postulated that selecting cations with larger free base conjugate pKA values (i.e., greater basicity) would yield improved AEM alkaline stability and ionic conductivity. The pKA value accounts for the steric hindrance, inductive, and resonance features of an organic cation and these features influence a cation’s interaction with hydroxide. Udel® polysulfone (PSF) and poly(2,6-dimethyl 1,4-phenylene) oxide (PPO) were selected as the model polymer backbones because they can be tailored with different cation groups. The types of cations assessed were of the quaternary ammonium and phosphonium types and 1-methylimidazolium. The prepared AEMs demonstrated a direct correlation between the cation’s free base conjugate pKA and anion conductivity for most cations assessed. Alkaline stability was assessed through multi-dimensional NMR to determine the degradation products in AEMs. NMR confirmed that the cation groups x xxii degraded through fundamentally different degradation mechanisms dependent upon their chemical make-up. Because the degradation mechanisms were different, the rate of degradation of the cation groups did not demonstrate a correlation to the cation’s free base conjugate pKA. If the cations did proceed through the same degradation mechanism, then a correlation was observed. Additionally, it was discovered that the cation groups in PSF and PPO triggered polymer backbone degradation in alkaline despite the resiliency of both these pristine polymers in alkaline solutions. The AEMs prepared were successfully demonstrated in several electrochemical energy storage and conversion technologies (including alkaline fuel cell, alkaline water electrolyzer, and the all-vanadium redox flow battery).PH.D in Chemical Engineering, December 201

Computational Investigations of the Water Structure at α-Al2O3(0001)-Water Interfaces

The α-Al2O3(0001)-water interface is investigated using ab initio molecular dynamics (AIMD) simulations. The spectral signatures of the vibrational sum frequency generation (vSFG) spectra of OH stretching mode for water molecules at the interface was related to the interfacial water orientation, hydrogen bond network, and water dissociation process at different water/alumina interfaces. Significant differences are found between alumina surfaces at different hydroxylation levels, namely, Al-terminated and O-terminated α-Al2O3(0001). By calculating the vibrational sum frequency generation spectra and its imaginary component from AIMD results, the structure of interfacial waters as well as the termination of the alumina slab were related to the spectral signatures of vSFG data

Bipolar membrane capacitive deionization for pH-assisted ionic separations

Selective ionic separations represent an increasingly important technical area for the strategic interests of the U.S. economy - e.g., securing critical minerals and materials and circular economy aspirations that include recovering organic acids from processed biomass. This work disseminates bipolar membrane (BPM) capacitive deionization for selective ionic separations from multi-component, ionic species mixtures. The selective separations are guided by the Pourbaix diagram and acid-base equilibria principles. BPM capacitive deionization was demonstrated to generate alkaline or acidic process streams depending upon the location of the BPM in the electrochemical cell. Prior to assessing BPM-membrane capacitive deionization (BPM-MCDI) for selective ionic separations, the role of system operating parameters on effluent stream pH was studied. pH adjustment in BPM-CDI/MCDI was more sensitive to cell voltage when compared to process stream residence time and salt feed concentration. The BPM-MCDI gave about 6x or greater higher copper(II) removal efficiency when compared to sodium ion removal efficiency from brine mixtures. Finally, BPM-MCDI demonstrated over 1.4x greater removal efficiency for copper ions from brine mixtures and 5x greater removal efficiency for itaconic acid from brine mixtures when benchmarked against a traditional flow-by-MCDI setup

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Extended-surface thin film platinum electrocatalysts with tunable nanostructured morphologies.

Reducing platinum-group metal (PGM) loadings in fuel cells and electrolyzers is paramount for cost reductions and getting hydrogen to scale to help decarbonize the global economy. Conventional PGM nanoparticle-based ink-cast electrocatalysts lose performance at high current densities owing to mass transport resistances that arise due to the use of ionomer binders. Herein, we report the development of binder-free extended surface thin film platinum electrocatalysts with tunable nanoscale morphology and periodic spacing. The electrocatalysts are prepared by sputtering various loadings of platinum on Al2O3 nanostructures templated from block copolymer (BCP) thin films self-assembled on glassy carbon substrates via sequential infiltration synthesis. Testing for oxygen reduction on a rotating disk electrode setup with ultra-low PGM loadings (5.8 µgPt cm-2) demonstrates electrocatalyst performance that rivals commercial platinum electrocatalysts in terms of mass activity (380 mA mgPt-1 at 0.9 V vs RHE), whilst surpassing commercial catalysts in terms of stability (mass activity loss: 11.45% at after 20,000 potential cycles). Moreover, catalyst performance probed as a function of nanoscale feature size and morphology reveals an inverse correlation between particle size and electroactivity, as well as the superiority of cylindrical morphologies over lamellae, presenting BCP templating as a fabrication pathway towards stable, tunable catalyst geometries