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At least 559 records · Page 31

Developing Novel Electrode Materials for Aqueous Battery

Aqueous rechargeable batteries (ARBs) are particularly interesting for large-scale energy storage due to their inherent safety, superior rate capability and environmental friendliness. However, ARBs are not widely explored as yet, so we proposed designing, preparing, and testing new intercalation materials for ARBs. Development of these electrodes will enrich the electrode chemistry of existing ARBs, open up new avenues for high-performance electrode and system design, offer opportunities to improve energy efficiency of water purification, and inform future development of controls strategies and management systems for stationary aqueous energy storage. Researchers from Bosch and LBNL collaborated on relevant materials to pursue and the general design of experiments to implement. Bosch researchers prepared and fabricated the electrodes and used various characterization facilities at LBNL to evaluate electrode performance in-device. The research collaboration resulted in identifying electrode materials capable of Na + and Ca 2+ intercalation in aqueous systems, and their application for desalination was explored using testing platform available at LBNL. Besides the specific materials and their performance, the data collected during the study was also used to inform a broader techno-economic analysis to compare intercalation-desalination technique to commercially available capacitive desalination approach. Outcomes of this research effort will be published in peer-reviewed journals.

25 ENERGY STORAGE↗

Interaction of Concentrated (68%) Aqueous Nitric Acid Solutions with Cheesecloth: A TGA-DSC-MS Study

The exposure of cotton cheesecloth to concentrated aqueous solutions of nitric acid reduced the onset of combustion by 30-40°C (from ~350°C to ~310°C) relative to that of both unexposed cheesecloth and cheesecloth that was rinsed immediately following exposure to the same solution. Cheesecloth exposed to concentrated (68%) nitric acid underwent three exothermic pre-combustion reactions which onset at 125-135°C, 160- 170°C and 200-210°C. These reactions give off mostly water vapor, with lesser amounts of NO and carbon dioxide. Exposure to concentrated nitric acid damages the cellulose polymers, oxidizing them, reducing them in length, and increasing their reactivity in response to thermal stress. Cheesecloth which was rinsed after exposure behaved similarly to unexposed cheesecloth, indicating that NC was not formed on exposure to the concentrated aqueous nitric acid solution. The addition of a 239Pu – 241Am spike in an aqueous nitric – hydrofluoric solution to the cheesecloth reduced the onset temperature of the first exothermic reaction to 126°C and lowered the onset temperature of combustion from ~310°C to ~275°C. When dried on to cellulose substrates in the presence of excess nitrate, metal ions may act as oxidizers, or may catalyze the oxidation of the carbonaceous material, lowering ignition temperatures. No evidence for the formation of nitrocellulose following the exposure of cheesecloth to nitric acid was observed during this study

36 MATERIALS SCIENCE↗

Non-Equilibrium Nucleation of Rare Earth Metals at Aqueous Interfaces

We conducted mechanical and electrical perturbation experiments on several systems of NdCl 3 aqueous solutions with two phosphonic acids, one as a stable surfactant with high surface activity and another that was fully soluble in aqueous solution. We also conducted experiments with solely the salt in aqueous solution. Our goal was to stimulate surface aggregation at the air/aqueous solution interface that was observable by Brewster angle microscopy, surface tension, and/or surface spectroscopy. We observed changes only with the surface active phosphonic acid. Additional work is needed to further explore confined environments to stimulate surface aggregation events.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interfacial Dark Aging Is an Overlooked Source of Aqueous Secondary Organic Aerosol

In this work, the relative yields of aqueous secondary organic aerosols (aqSOAs) at the air–liquid (a–l) interface are investigated between photochemical and dark aging using in situ time-of-flight secondary ion mass spectrometry (ToF-SIMS). Our results show that dark aging is an important source of aqSOAs despite a lack of photochemical drivers. Photochemical reactions of glyoxal and hydroxyl radicals (•OH) produce oligomers and cluster ions at the aqueous surface. Interestingly, different oligomers and cluster ions form intensely in the dark at the a–l interface, contrary to the notion that oligomer formation mainly depends on light irradiation. Furthermore, cluster ions form readily during dark aging and have a higher water molecule adsorption ability. This finding is supported by the observation of more frequent organic water cluster ion formation. The relative yields of water clusters in the form of protonated and hydroxide ions are presented using van Krevelen diagrams to explore the underlying formation mechanisms of aqSOAs. Large protonated and hydroxide water clusters (e.g., (H2O)nH+, 17 < n ≤ 44) have reasonable yields during UV aging. In contrast, small protonated and hydroxide water clusters (e.g., (H2O)nH+, 1 ≤ n ≤ 17) form after several hours of dark aging. Moreover, cluster ions have higher yields in dark aging, indicating the overlooked influence of dark aging interfacial products on aerosol optical properties. Molecular dynamic simulation shows that cluster ions form stably in UV and dark aging. AqSOAs molecules produced from dark and photochemical aging can enhance UV absorption of the aqueous surface, promote cloud condensation nuclei (CCN) activities, and affect radiative forcing.

Van Krevelen diagram↗

An Overview of Challenges and Strategies for Stabilizing Zinc Anodes in Aqueous Rechargeable Zn-Ion Batteries

Aqueous rechargeable zinc ion batteries (ZIBs) have been revived and are considered a promising candidate for scalable electrochemical energy storage systems due to their intrinsic safety, low cost, large abundance, mature recyclability, competitive electrochemical performance, and sustainability. However, the deployment of aqueous rechargeable ZIBs is still hampered by the poor electrochemical stability and reversibility of Zn anodes, which is a common, inherent issue for most metal-based anodes. This review presents a comprehensive and timely overview of the challenges and strategies of Zn anodes toward durable ZIBs. First, several challenges that significantly reduce the Coulombic efficiency and cycling stability of Zn anodes are briefly discussed including dendrite formation, hydrogen evolution, and corrosion. Then, the mitigation strategies are summarized in terms of modifying the electrode/electrolyte interfaces, designing electrode structures, and optimizing electrolytes and separators. Further, we comprehensively discuss the mechanisms behind these issues and improvement strategies with respect to the anodes, electrolytes, and separators. Lastly, we provide perspectives and critical analyses of remaining challenges, outlook, and future direction for accelerating the practical application of aqueous rechargeable ZIBs.

25 ENERGY STORAGE↗

Electrodes with Electrodeposited Water-excluding Polymer Coating Enable High-Voltage Aqueous Supercapacitors

Aqueous supercapacitors are powerful energy sources, but they are limited by energy density that is much lower than lithium-ion batteries. Since raising the voltage beyond the thermodynamic potential for water splitting (1.23 V) can boost the energy density, there has been much effort on water-stabilizing salvation additives such as Li 2 SO 4 that can provide an aqueous electrolyte capable of withstanding ~1.8 V. Guided by the first-principles calculations that reveal water can promote hydrogen and oxygen evolution reactions, here, we pursue a new strategy of covering the electrode with a dense electroplated polymerized polyacrylic acid, which is an electron insulator but a proton conductor and proton reservoir. The combined effect of salvation and coating expands the electrochemical window throughout pH 3 to pH 10 to 2.4 V for both fast and slow proton-mediated redox reactions. This allows activated carbon to quadruple the energy density, a kilogram of nitrogen-doped graphene to provide 127 Watt-hour, and both to have improved endurance because of suppression of water-mediated corrosion. Therefore, aqueous supercapacitors can now achieve energy densities quite comparable to that of a lithium-ion battery, but at 100 times the charging/discharging speed and cycle durability.

Dong, Wujie↗

Immersion freezing of water and aqueous ammonium sulfate droplets initiated by humic-like substances as a function of water activity

Immersion freezing of water and aqueous (NH 4 ) 2 SO 4 droplets containing leonardite (LEO) and Pahokee peat (PP) serving as surrogates for humic-like substances (HULIS) has been investigated. Organic aerosol containing HULIS are ubiquitous in the atmosphere; however, their potential for ice cloud formation is uncertain. Immersion freezing has been studied for temperatures as low as 215K and solution water activity, a w , from 0.85 to 1.0. The freezing temperatures of water and aqueous solution droplets containing LEO and PP are 5–15 K warmer than homogeneous ice nucleation temperatures. Heterogeneous freezing temperatures can be represented by a horizontal shift of the ice melting curve as a function of solution aw by Δ a w = 0.2703 and 0.2466, respectively. Corresponding heterogeneous ice nucleation rate coefficients, Jhet, are (9.6 ± 2.5) × 10 4 and (5.4 ± 1.4) × 10 4 cm -2 s -1 for LEO and PP containing droplets, respectively, and remain constant along freezing curves characterized by Δ a w . Consequently predictions of freezing temperatures and kinetics can be made without knowledge of the solute type when relative humidity and ice nuclei (IN) surface areas are known. The acquired ice nucleation data are applied to evaluate different approaches to fit and reproduce experimentally derived frozen fractions. In addition, we apply a basic formulation of classical nucleation theory (α( T )-model) to calculate contact angles and frozen fractions. Contact angles calculated for each ice nucleus as a function of temperature, α( T )-model, reproduce exactly experimentally derived frozen fractions without involving free-fit parameters. However, assigning the IN a single contact angle for the entire population (single-α model) is not suited to represent the frozen fractions. Application of α-PDF, active sites, and deterministic model approaches to measured frozen fractions yield similar good representations. Furthermore, when using a single parameterization of α-PDF or active sites distribution to fit all individual a w immersion freezing data simultaneously, frozen fraction curves are not reproduced. This implies that these fitting formulations cannot be applied to immersion freezing of aqueous solutions, and suggests that derived fit parameters do not represent independent particle properties. Thus, from fitting frozen fractions only, the underlying ice nucleation mechanism and nature of the ice nucleating sites cannot be inferred. In contrast to using fitted functions obtained to represent experimental conditions only, we suggest to use experimentally derived J het as a function of temperature and a w that can be applied to conditions outside of those probed in laboratory. Finally, this is because J het (T) is independent of time and IN surface areas in contrast to the fit parameters obtained by representation of experimentally derived frozen fractions.

54 ENVIRONMENTAL SCIENCES↗

Source apportionment of soot particles and aqueous-phase processing of black carbon coatings in an urban environment

Abstract. The impacts of soot particles on climate and human health depend on the concentration of black carbon (BC) as well as the thickness and composition of the coating material, i.e., organic and inorganic compounds internally mixed with BC. In this study, the size-resolved chemical composition of BC-containing aerosol was measured using a high-resolution soot particle aerosol mass spectrometer (SP-AMS) during wintertime in Fresno, California, a location influenced by abundant combustion emissions and frequent fog events. Concurrently, particle optical properties were measured to investigate the BC absorption enhancement. Positive matrix factorization (PMF) analysis was performed on the SP-AMS mass spectral measurements to explore the sources of soot particles and the atmospheric processes affecting the properties of BC coatings. The analysis revealed that residential woodburning and traffic are the dominant sources of soot particles. Alongside primary soot particles originating from biomass burning (BBOABC) and vehicles (HOABC) two distinct types of processed BC-containing aerosol were identified: fog-related oxidized organic aerosol (FOOABC) and winter-background OOABC (WOOABC). Both types of OOABC showed evidence of having undergone aqueous processing, albeit with differences. The concentration of FOOABC was substantially elevated during fog events, indicating the formation of aqueous secondary organic aerosol (aqSOA) within fog droplets. On the other hand, WOOABC was present at a relatively consistent concentration throughout the winter and was likely related to the formation of secondary organic aerosol (SOA) in both the gas phase and aerosol liquid water. By comparing the chemical properties and temporal variations in FOOABC and WOOABC, we gain insights into the key aging processes of BC aerosol. It was found that aqueous-phase reactions facilitated by fog droplets had a significant impact on the thickness and chemical composition of BC coatings, thereby affecting the light absorption and hygroscopic properties of soot particles. These findings underscore the important role of chemical reactions occurring within clouds and fogs and influencing the climate forcing of BC aerosol in the atmosphere.

54 ENVIRONMENTAL SCIENCES↗

Photoaging of phenolic secondary organic aerosol in the aqueous phase: evolution of chemical and optical properties and effects of oxidants

Abstract. While gas-phase reactions are well established to have significant impacts on the mass concentration, chemical composition, and optical properties of secondary organic aerosol (SOA), the aqueous-phase aging of SOA remains poorly understood. In this study, we performed a series of long-duration photochemical aging experiments to investigate the evolution of the composition and light absorption of the aqueous SOA (aqSOA) from guaiacyl acetone (GA), a semivolatile phenolic carbonyl that is common in biomass burning smoke. The aqSOA was produced from reactions of GA with hydroxyl radical (•OH-aqSOA) or a triplet excited state of organic carbon (3C∗-aqSOA) and was then photoaged in water under conditions that simulate sunlight exposure in northern California for up to 48 h. The effects of increasing aqueous-phase •OH or 3C∗ concentration on the photoaging of the aqSOA were also studied. High-resolution aerosol mass spectrometry (HR-AMS) and UV–Vis spectroscopy were utilized to characterize the composition and the light absorptivity of the aqSOA and to track their changes during aging. Compared to •OH-aqSOA, the 3C∗-aqSOA is produced more rapidly and shows less oxidation, a greater abundance of oligomers, and higher light absorption. Prolonged photoaging promotes fragmentation and the formation of more volatile and less light-absorbing products. More than half of the initial aqSOA mass is lost, and substantial photobleaching occurs after 10.5 h of prolonged aging under simulated sunlight illumination for 3C∗-aqSOA and 48 h for •OH-aqSOA. By performing positive matrix factorization (PMF) analysis of the combined HR-AMS and UV–Vis spectral data, we resolved three generations of aqSOA with distinctly different chemical and optical properties. The first-generation aqSOA shows significant oligomer formation and enhanced light absorption at 340–400 nm. The second-generation aqSOA is enriched in functionalized GA species and has the highest mass absorption coefficients in 300–500 nm, while the third-generation aqSOA contains more fragmented products and is the least light absorbing. These results suggest that intermediately aged phenolic aqSOA is more light absorbing than other generations, and that the light absorptivity of phenolic aqSOA results from a competition between brown carbon (BrC) formation and photobleaching, which is dependent on aging time. Although photoaging generally increases the oxidation of aqSOA, a slightly decreased O/C of the •OH-aqSOA is observed after 48 h of prolonged photoaging with additional •OH exposure. This is likely due to greater fragmentation and evaporation of highly oxidized compounds. Increased oxidant concentration accelerates the transformation of aqSOA and promotes the decay of BrC chromophores, leading to faster mass reduction and photobleaching. In addition, compared with •OH, photoaging by 3C∗ produces more low-volatility functionalized products, which counterbalances part of the aqSOA mass loss due to fragmentation and evaporation.

54 ENVIRONMENTAL SCIENCES↗

Specular reflectance of aqueous solutions.

Description of two laboratory instruments for measuring the specular reflectance of aqueous solutions. The instruments are an organic-dye-laser spectrophotometer for the 360- to 650-nm wavelength region and a reflectometer accessory for a Perkin-Elmer E-system spectrophotometer which will operate in the 0.2- to 20-micron wavelength region. The reflectometer accessory has been used to measure the relative infrared specular reflectance in limited spectral regions for aqueous solutions of NaCl, K2SO4, ZnSO4, (NH4)2SO4, and NH4H2PO4 with radiant flux incident at about 70 deg and polarized perpendicular to the plane of incidence. The laser spectrometer has been used to measure the absolute reflectance of aqueous solutions of NaCl in the wavelength region from 575 to 610 nm for light incident at angles of about 60, 65, and 70 deg and polarized parallel to the plane of incidence.

Querry, M. R.↗

Aqueous chloride stress corrosion cracking of titanium - A comparison with environmental hydrogen embrittlement

The physical characteristics of stress corrosion cracking of titanium in an aqueous chloride environment are compared with those of embrittlement of titanium by a gaseous hydrogen environment in an effort to help contribute to the understanding of the possible role of hydrogen in the complex stress corrosion cracking process. Based on previous studies, the two forms of embrittlement are shown to be similar at low hydrogen pressures (100 N/sq m) but dissimilar at higher hydrogen pressures. In an effort to quantify this comparison, tests were conducted in an aqueous chloride solution using the same material and test techniques as had previously been employed in a gaseous hydrogen environment. The results of these tests strongly support models based on hydrogen as the embrittling species in an aqueous chloride environment.

Nelson, H. G.↗

Aqueous-phase source of formic acid in clouds

The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

Chameides, W. L.↗

The role of aqueous chemistry in determining the composition and cloud structure of the upper troposphere on Uranus

Aqueous chemistry on Uranus affects the atmospheric abundances of NH3 and H2S below the methane cloud base. Here a complete thermochemical equilibrium model for the H2O-NH3-H2S system is presented. Inclusion of H2S increases the aqueous removal of NH3 to 20-30 percent, but aqueous chemistry alone cannot account for the depletion of NH3 in the 150-200-K region of the atmosphere required to fit microwave observations. Formation of NH4SH clouds can account for the observed depletion provided the H2S/NH3 ratio is enhanced by a factor of 4 relative to solar. Perturbations to the chemical balance between N and S, for example by the general circulation on Uranus, would then produce regions with either NH3 or H2S aloft.

Carlson, Barbara E.↗

Computer modeling of the mineralogy of the Martian surface, as modified by aqueous alteration

Mineralogical constraints can be placed on the Martian surface by assuming chemical equilibria among the surface rocks, atmosphere and hypothesized percolating groundwater. A study was made of possible Martian surface mineralogy, as modified by the action of aqueous alteration, using the EQ3/6 computer codes. These codes calculate gas fugacities, aqueous speciation, ionic strength, pH, Eh and concentration and degree of mineral saturation for complex aqueous systems. Thus, these codes are also able to consider mineralogical solid solutions. These codes are able to predict the likely alteration phases which will occur as the result of weathering on the Martian surface. Knowledge of the stability conditions of these phases will then assist in the definition of the specifications for the sample canister of the proposed Martian sample return mission. The model and its results are discussed.

Zolensky, M. E.↗

Cell separations and the demixing of aqueous two phase polymer solutions in microgravity

Partition in phase separated aqueous polymer solutions is a cell separation procedure thought to be adversely influenced by gravity. In preparation for performing cell partitioning experiments in space, and to provide general information concerning the demixing of immiscible liquids in low gravity, a series of phase separated aqueous polymer solutions have been flown on two shuttle flights. Fluorocarbon oil and water emulsions were also flown on the second flight. The aqueous polymer emulsions, which in one g demix largely by sedimentation and convection due to the density differences between the phases, demixed more slowly than on the ground and the final disposition of the phases was determined by the wetting of the container wall by the phases. The demixing behavior and kinetics were influenced by the phase volume ratio, physical properties of the systems and chamber wall interaction. The average domain size increased linearly with time as the systems demixed.

Brooks, Donald E.↗

Cathodoluminescence observations of in situ aqueous destruction of chondrules in the Murchison CM chondrite

A low-power cathodoluminescence (CL) mosaic of a 1x2 cm section of the Murchison CM chondrite contains chondrules of two types: one contains olivines with red CL and is thought to be the equivalent of group A chondrules of Sears et.; and one without observable CL, which is probably equivalent to their group B chondrules. Both types of chondrule contain dust mantles with a characteristic uniform red CL due to very fine-grained forsterites, but the mantles of group A chondrules have a complex internal structure and are much thicker than the relatively thin rims on the group B chondrules. The variety of internal textures and the progressive integration of the objects with the surrounding matrix suggests to us that these features are large group A chondrules in the process of being destroyed by aqueous alteration. Prior to aqueous alteration, group A chondrules in CM chondrites were larger than group B chondrules, which is contrary to the situation in ordinary chondrites and were apparently destroyed more rapidly than group B chondrules by aqueous alteration.

Sears, Derek W. G.↗

Non-aqueous cleaning solvent substitution

A variety of environmental, safety, and health concerns exist over use of chlorinated and fluorinated cleaning solvents. Sandia National Laboratories, Lawrence Livermore National Laboratories, and the Kansas City Division of AlliedSignal have combined efforts to focus on finding alternative cleaning solvents and processes which are effective, environmentally safe, and compliant with local, state, and federal regulations. An alternative solvent has been identified, qualified, and implemented into production of complex electronic assemblies, where aqueous and semi-aqueous cleaning processes are not allowed. Extensive compatibility studies were performed with components, piece-parts, and materials. Electrical testing and accelerated aging were used to screen for detrimental, long-term effects. A terpene, d-limonene, was selected as the solvent of choice, and it was found to be compatible with the components and materials tested. A brief history of the overall project will be presented, along with representative cleaning efficiency results, compatibility results, and residual solvent data. The electronics industry is constantly searching for proven methods and environmentally-safe materials to use in manufacturing processes. The information in this presentation will provide another option to consider on future projects for applications requiring high levels of quality, reliability, and cleanliness from non-aqueous cleaning processes.

Meier, Gerald J.↗

Fiber-Optic Chemiluminescent Biosensors for Monitoring Aqueous Alcohols and Other Water Quality Parameters

A "reagentless" chemiluminescent biosensor and method for the determination of hydrogen peroxide, ethanol and D-glucose in water is disclosed. An aqueous stream is basified by passing it through a solid phase base bed. Luminol is then dissolved in the basified effluent at a controlled rate. Oxidation of the luminol is catalyzed by the target chemical to produce emitted light. The intensity of the emitted light is detected as a measure of the target chemical concentration in the aqueous stream. The emitted light can be transmitted by a fiber optic bundle to a remote location from the aqueous stream for a remote reading of the target chemical concentration.

Verostko, Charles E.↗