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At least 955 records · Page 53

Effect of Electrolyte Ions on Iridium Oxide-Based Water Oxidation Catalysis

The oxygen evolution reaction often limits the efficiency of renewable fuel syntheses due to its sluggish reaction kinetics. Of the factors that have been studied to improve this important reaction is how the choice of the electrolyte may alter the reaction kinetics. Despite its importance, sys-tematic studies of this effect have been relatively rare. Herein, we report an effort toward correcting this deficiency by investigating the effect of nitrate on water oxidation catalyzed by IrO x . The results show that nitrate can suppress the reaction, resulting in a decrease of the rate and an increase in the Tafel slope. The effect was found to be consistent with a microkinetic model incorporating competitive adsorption between reac-tion intermediates and nitrate, suggesting that the reaction mechanism was unaffected by anion identity. Moreover, this blocking effect exhibited dependence on the cations, following a trend Li + ≈ Na + ≈ K + > Cs + > TEA + . The results are expected to find broad applications in electrocatalysis.

Tafel slope analysis↗

Scaling methodologies and similarity analysis for thermal hydraulics test facility development for water-cooled small modular reactor

Small modular reactors (SMRs) represent a promising option for providing clean and sustainable energy due to their potential for enhanced safety, reduced capital costs, and increased siting flexibility. However, new reactor systems require the development and operation of representative scaled-down test facilities to support the verification and validation of system computer codes and models. Here this study reviews the research on scaling methodologies and similarity principles pivotal in developing non-nuclear integral effects test and separate effects test facilities for water-cooled SMRs. The study focuses on a review of the scaling methods, similarity approaches, and possible challenges posed by the unique and compact design features of integral-pressurized water reactor-type SMRs, and their representative test facilities. This study also reviews previous research related to scaling and similarity methodologies and provides insights into design considerations for achieving prototypic conditions in test facilities. The findings and recommendations emphasize the broader impact of appropriate scaling and similarity principles to ensure meaningful and transferable results from non-nuclear test facilities to accelerate the safe and efficient deployment of next-generation water-cooled SMRs.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Instrument for Aircraft-Icing and Cloud-Physics Measurements

The figure shows a compact, rugged, simple sensor head that is part of an instrumentation system for making measurements to characterize the severity of aircraft-icing conditions and/or to perform research on cloud physics. The quantities that are calculated from measurement data acquired by this system and that are used to quantify the severity of icing conditions include sizes of cloud water drops, cloud liquid water content (LWC), cloud ice water content (IWC), and cloud total water content (TWC). The sensor head is mounted on the outside of an aircraft, positioned and oriented to intercept the ambient airflow. The sensor head consists of an open housing that is heated in a controlled manner to keep it free of ice and that contains four hot-wire elements. The hot-wire sensing elements have different shapes and sizes and, therefore, exhibit different measurement efficiencies with respect to droplet size and water phase (liquid, frozen, or mixed). Three of the hot-wire sensing elements are oriented across the airflow so as to intercept incoming cloud water. For each of these elements, the LWC or TWC affects the power required to maintain a constant temperature in the presence of cloud water.

Lilie, Lyle↗

LiCl–Based Aqueous Electrolytes for Efficient Iron Electrodeposition

This study investigates room temperature, aqueous electrolytes for efficient iron electrodeposition. Specifically, a novel lithium chloride-based electrolyte was identified to suppress hydrogen evolution while promoting fast kinetics of iron electrodeposition, achieving high coulombic efficiency (>90%) at high current densities (>400 mA cm −2 ). Electrochemical analysis of the partial current densities of iron deposition and hydrogen co-evolution revealed that water reduction is kinetically suppressed in this electrolyte, resulting in an increase in the measured coulombic efficiency. Furthermore, a detailed investigation of the iron speciation and their complexation was performed, which revealed that, in concentrated LiCl-containing electrolytes, the ferrous (Fe 2+ ) species coordinate with chloride rather than water, enhancing deposition kinetics. The combined effect of enhanced electrodeposition kinetics and suppressed water activity provide elevated coulombic efficiency. Overall, this paper develops an understanding of anion and cation effects on the mechanism of electrodeposition and hydrogen co-evolution in concentrated electrolytes in search of improved aqueous media (e.g., concentrated LiCl) for efficient metal electro-synthesis.

Lvovich, William [Case Western Reserve University,↗

Hydrovolcanism

Hydrovolcanism is a common phenomena produced by the interaction of magma or magmatic heat with an external source of water, such as a surface body, an aquifer, or a glacier. The effects include hydrofracture of existing rock units in the subsurface and the formation of hyaloclastites in a subaqueous environment. Hydroexplosions originate within a few kilometers of the surface. They may be relatively small, phreatic events or devastating complex blasts. Large-scale experiments determined that the optimal mixing ratio of water to basaltic melt (thermite plus silicates) for efficient conversion of thermal energy into mechanical energy is in the range of 0.1 to 0.3. Based on experimental results, eruptions can be classified as dominantly magmatic if the ratio of external water to magma is less than 0.2. Eruptions with water/melt ratios in the range of 0.2 to 1.0 are highly explosive and carry tephra in a hot vapor that contains dominantly superheated (dry) steam.

Sheridan, M. F.↗

High-Temperature Alkaline Water Electrolysis

Hydrogen production for mobile and energy storage applications from water electrolysis is attractive due to its high efficiency, fast ramp rates, and potential for the clean energy economy. However, current hydrogen production from electrolysis comprises only a small fraction of the global hydrogen market due to the high cost associated with expensive stack materials (membrane, catalyst, and bipolar plates) and electricity consumption of the commercial electrolysis systems. In this project, we aimed to develop a high temperature alkaline water electrolyzer (HTAWE) that can simultaneously reduce the electrolyzer cost (by adopting cheap material) and improve energy efficiency (by enabling high-temperature operation).

08 HYDROGEN↗

Elevator deflections on the icing process

The effect of elevator deflection of the horizontal stabilizer for certain icing parameters is investigated. Elevator deflection can severely change the lower and upper leading-edge impingement limits, and ice can accrete on the elevator itself. Also, elevator deflection had practically no effect on the maximum local collection efficiency. It is shown that for severe icing conditions (large water droplets), elevator deflections that increase the projected height of the airfoil can significantly increase the total collection efficiency of the airfoil.

Britton, Randall K.↗

A GCM Recent History of the Northern Martian Polar Layered Deposits

The polar layered deposits are thought to contain alternate layers of water and dust in different proportions resulting from the astronomical forcing of the martian climate. In particular, longterm variations in the orbital and axial elements of Mars are presumed to generate variations of the latitudes of surface water ice stability and of the amount of water exchanged in the polar areas. At high obliquity, simplified climate models and independent general circulation simulations suggest a transfer of water ice from the north polar region to tropical areas, whereas at lower and present obliquities, water ice is expected to be stable only at the poles. If so, over obliquity cycles, water ice may be redistributed between the surface water reservoirs leading to their incremental building or disintegration depending on the rates of water transfer. If only a relative limited amount of the available water is exchanged on orbital timescales, this may provide an efficient mechanism for the formation of the observed polar deposits. Within this context, GCM simulations of the martian water cycle have been performed for various obliquities ranging from 15 degrees to 45 degrees and for a large set of initial water ice locations to determine the rate of water exchange between the surface water reservoirs as a function of the obliquity. Propagating these rates over the last 10 Ma orbital history gives a possible recent evolution of these reservoirs.

Levrard, B.↗

Intensified atomic utilization efficiency of single-atom catalysts for nitrate conversion via electrified nanoporous membrane

Conventional electrochemical reactors for nitrate reduction typically suffer from limited reaction efficiency when applied for real-world water treatment due to poor utilization of electrocatalytic active sites. Here, we applied nanoporous electrofiltration to intensify atomic utilization by incorporating single-atom catalysts into an electrified membrane for reducing low-concentration nitrate to ammonia under realistic water conditions. We enhance the exposure of single atoms in nanopores by coating the catalysts on a carbon nanotube–interwoven membrane framework. Electrofiltration intensifies the transport and adsorption of nitrate in confined nanopores with highly exposed single-atom active sites to enhance reduction. The membrane enables a superior ammonia turnover frequency of 15.1 grams of nitrogen per gram of metal per hour, up to four orders of magnitude higher than that reported in the literature, under both high removal efficiency and Faradaic efficiency of over 86% when treating influents with a low nitrate concentration of 100 milligrams of nitrogen per liter in a residence time on the order of seconds.

Science & Technology - Other Topics↗

Strategies for Semiconductor/Electrocatalyst Coupling toward Solar‐Driven Water Splitting

Abstract Hydrogen (H 2 ) has a significant potential to enable the global energy transition from the current fossil‐dominant system to a clean, sustainable, and low‐carbon energy system. While presently global H 2 production is predominated by fossil‐fuel feedstocks, for future widespread utilization it is of paramount importance to produce H 2 in a decarbonized manner. To this end, photoelectrochemical (PEC) water splitting has been proposed to be a highly desirable approach with minimal negative impact on the environment. Both semiconductor light‐absorbers and hydrogen/oxygen evolution reaction (HER/OER) catalysts are essential components of an efficient PEC cell. It is well documented that loading electrocatalysts on semiconductor photoelectrodes plays significant roles in accelerating the HER/OER kinetics, suppressing surface recombination, reducing overpotentials needed to accomplish HER/OER, and extending the operational lifetime of semiconductors. Herein, how electrocatalyst coupling influences the PEC performance of semiconductor photoelectrodes is outlined. The focus is then placed on the major strategies developed so far for semiconductor/electrocatalyst coupling, including a variety of dry processes and wet chemical approaches. This Review provides a comprehensive account of advanced methodologies adopted for semiconductor/electrocatalyst coupling and can serve as a guideline for the design of efficient and stable semiconductor photoelectrodes for use in water splitting.

Thalluri, Sitaramanjaneya Mouli↗

Elucidating the Role of Hydroxide Electrolyte on Anion-Exchange-Membrane Water Electrolyzer Performance

Many solid-state devices, especially those requiring anion conduction, often add a supporting electrolyte to enable efficient operation. The prototypical case is that of anion-exchange-membrane water electrolyzers (AEMWEs), where addition of an alkali metal solution improves performance. However, the specific mechanism of this performance improvement is currently unknown. This work investigates the functionality of the alkali metal solution in AEMWEs using experiments and mathematical models. The results show that additional hydroxide plays a key role not only in ohmic resistance of the membrane and catalyst layer but also in the reaction kinetics. The modeling suggests that the added liquid electrolyte creates an additional electrochemical interface with the electrocatalyst that provides ion-transport pathways and distributes product gas bubbles; the total effective electrochemical active surface area in the cell with 1 M KOH is 5 times higher than that of the cell with DI water. In the cell with 1 M KOH, more than 80% of the reaction current is associate with the liquid electrolyte. These results indicate the importance of high pH of electrolyte and catalyst/electrolyte interface in AEMWEs. The understanding of the functionality of the alkali metal solution presented in this study should help guide the design and optimization of AEMWEs.

25 ENERGY STORAGE↗

Characterizing Rocky and Gaseous Exoplanets with 2 m Class Space-based Coronagraphs

Several concepts now exist for small, space-based missions to directly characterize exoplanets in reflected light. While studies have been performed that investigate the potential detection yields of such missions, little work has been done to understand how instrumental and astrophysical parameters will affect the ability of these missions to obtain spectra that are useful for characterizing their planetary targets. Here, we develop an instrument noise model suitable for studying the spectral characterization potential of a coronagraph-equipped, space-based telescope. We adopt a baseline set of telescope and instrument parameters appropriate for near-future planned missions like WFIRST-AFTA, including a 2 m diameter primary aperture, an operational wavelength range of 0.4–1.0 μm, and an instrument spectral resolution of λ/Δλ =70, and apply our baseline model to a variety of spectral models of different planet types, including Earth twins, Jupiter twins, and warm and cool Jupiters and Neptunes. With our exoplanet spectral models, we explore wavelength-dependent planet–star flux ratios for main-sequence stars of various effective temperatures and discuss how coronagraph inner and outer working angle constraints will influence the potential to study different types of planets. For planets most favorable to spectroscopic characterization—cool Jupiters and Neptunes as well as nearby super-Earths—we study the integration times required to achieve moderate signal-to-noise ratio spectra. We also explore the sensitivity of the integration times required to either detect the bottom or presence of key absorption bands (for methane, water vapor, and molecular oxygen) to coronagraph raw contrast performance, exozodiacal light levels, and the distance to the planetary system. Decreasing detector quantum efficiency at longer visible wavelengths makes the detection of water vapor in the atmospheres of Earth-like planets extremely challenging, and also hinders detections of the 0.89 μm methane band. Additionally, most modeled observations have noise dominated by dark currents, indicating that improving CCD performance could substantially drive down requisite integration times. Finally, we briefly discuss the extension of our models to a more distant future Large UV-Optical-InfraRed (LUVOIR) mission.

Astrobiology↗

Highly reversible Zn metal anode enabled by sustainable hydroxyl chemistry

Rechargeable Zn metal batteries (RZMBs) may provide a more sustainable and lower-cost alternative to established battery technologies in meeting energy storage applications of the future. However, the most promising electrolytes for RZMBs are generally aqueous and require high concentrations of salt(s) to bring efficiencies toward commercially viable levels and mitigate water-originated parasitic reactions including hydrogen evolution and corrosion. Electrolytes based on nonaqueous solvents are promising for avoiding these issues, although full cell performance demonstrations with solvents other than water have been very limited. To address these challenges, we investigated MeOH as an alternative electrolyte solvent. These MeOH-based electrolytes exhibited exceptional Zn reversibility over a wide temperature range, with a Coulombic efficiency > 99.5% at 50% Zn utilization without cell short-circuit behavior for > 1,800 h. More important, this remarkable performance translates well to Zn || metal-free organic cathode full cells, supporting < 6% capacity decay after > 800 cycles at –40°C.

25 ENERGY STORAGE↗

Defect engineering of porous aromatic frameworks via end capping improves dioxane removal from water

Amorphous porous organic polymers show promise for energy-efficient adsorptive separations, but it is difficult to understand or improve their performance through intentional structural modification. Herein, we report the synthesis of porous aromatic frameworks (PAFs) with pore structures tailored by the incorporation of a monofunctionalized end-capping monomer that disrupts framework topology. Combining experimental characterization with molecular simulations, we show that this defect engineering strategy yields less densely crosslinked networks, which leads to pore collapse and the presence of unique adsorption sites. These defect-engineered PAFs exhibit enhanced removal of 1,4-dioxane, an important environmental pollutant, from water. Increasing the concentration of end-capping monomers produces PAFs with narrower pore size distributions and improved 1,4-dioxane uptake. These results illustrate that defect engineering can effectively modulate polymer connectivity and porosity for applications in selective adsorptive separations. In conclusion, this technique avoids post-synthetic treatments and presents another approach to tailor amorphous polymeric adsorbents.

36 MATERIALS SCIENCE↗

Use of Renewable Alcohols in Autocatalytic Production of Aspen Organosolv Lignins

This study aimed to investigate the intrinsic efficiency of renewable alcohols, applied under autocatalytic conditions, for removing lignin from aspen and hot-water-extracted aspen while substantially preserving the lignin structure so as to facilitate various valorization strategies. Ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol (BDO), ethanol (EtOH), and tetrahydrofurfuryl alcohol (THFA) were evaluated based on their lignin solubilization ability, expressed as the relative energy difference (RED) following the principles of the Hansen solubility theory. The findings indicate that alcohols with a higher lignin solubilization potential lead to increased delignification, almost 90%, and produce a lignin with a higher content of β-O-4 bonds, up to 68% of those found in aspen milled wood lignin, thereby indicating their potential for valorization through depolymerization. However, these alcohols also produce lignin with a higher content of β-β and β-5 bonds, resulting in a higher molecular weight and polydispersity, due to readily occurring homolytic reactions. Hot-water extraction (HWE) conducted prior to alcohol treatment reduced the delignification efficiency and resulted in a lignin with a lower β-O-4 bond content. The lignins produced in these experiments exhibited a superior UV-A absorption capacity compared with synthetic benzophenone, as well as a greater radical quenching ability than synthetic butylated hydroxytoluene, indicating their potential for use in the protection of polymers against degradation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Parameterizing Single Scattering Properties Across the Electromagnetic Spectrum for Water Cloud Retrieval

Water clouds are composed of spherical water droplets, to which the Mie solution applies for their electromagnetic scattering. The essential variable of Mie solutions is ξ ≡ 𝑚𝑘𝐷 (or equivalently 𝑚𝑘𝑟), where 𝑚 is the complex index of refraction of water, 𝑘 = 2π/λ the angular wavenumber, λ the wavelength, and 𝐷 (𝑟) the diameter (radius) of the water droplet. Consequently, all water-droplet single-scattering properties, such as extinction and scattering efficiencies, i.e., 𝑄 and , are functions of , 𝑒 𝑄𝑠 ξ which provides a convenient pathway to parameterize water-droplet single-scattering properties across the electromagnetic spectrum or spectrum segments. In this paper, we first demonstrate that the numerical Mie solution indeed depends only on ξ. We then present our first attempt to parameterize extinction efficiency across the visible-infrared spectrum.

Kwo-Sen Kuo↗

Honeywell Cascade Distiller System Performance Testing Interim Results

The ability to recover and purify water through physiochemical processes is crucial for realizing long-term human space missions, including both planetary habitation and space travel. Because of their robust nature, distillation systems have been actively pursued as one of the technologies for water recovery. The Cascade Distillation System (CDS) is a vacuum rotary distillation system with potential for greater reliability and lower energy costs than existing distillation systems. The CDS was previously under development through Honeywell and NASA. In 2009, an assessment was performed to collect data to support down-selection and development of a primary distillation technology for application in a lunar outpost water recovery system. Based on the results of this testing, an expert panel concluded that the CDS showed adequate development maturity, TRL-4, together with the best product water quality and competitive weight and power estimates to warrant further development. The Advanced Exploration Systems (AES) Water Recovery Project (WRP) worked to address weaknesses identified by The Panel; namely bearing design and heat pump power efficiency. Testing at the NASA-JSC Advanced Exploration System Water Laboratory (AES Water Lab) using a prototype Cascade Distillation Subsystem (CDS) wastewater processor (Honeywell International, Torrance, Calif.) with test support equipment and control system developed by Johnson Space Center was performed to evaluate performance of the system with the upgrades. The CDS will also have been challenged with ISS analog waste streams and a subset of those being considered for Exploration architectures. This paper details interim results of the AES WRP CDS performance testing.

Callahan, Michael R.↗