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At least 1,045 records · Page 58

Interactive Effects of Climate Change and Decomposer Communities on the Stabilization of Wood-Derived Carbon Pools: Catalyst for a New Study

Globally, forest soils store ~two-thirds as much carbon (C) as the atmosphere. Although wood makes up the majority of forest biomass, the importance of wood contributions to soil C pools is unknown. Even with recent advances in the mechanistic understanding of soil processes, integrative studies tracing C input pathways and biological fluxes within and from soils are lacking. Therefore, our research objectives were to assess the impact of different fungal decay pathways (i.e., white-rot versus brown-rot)—in interaction with wood quality, soil temperature, wood location (i.e., soil surface and buried in mineral soil), and soil texture—on the transformation of woody material into soil CO 2 efflux, dissolved organic carbon (DOC), and soil C pools. The use of 13 C-depleted woody biomass harvested from the Rhinelander, WI free-air carbon dioxide enrichment (Aspen-FACE) experiment affords the unique opportunity to distinguish the wood-derived C from other soil C fluxes and pools. We established 168 treatment plots across six field sites (three sand and three loam textured soil). Treatment plots consisted of full-factorial design with the following treatments: 1. Wood chips from elevated CO 2 , elevated CO 2 + O 3 , or ambient atmosphere AspenFACE treatments; 2. Inoculated with white rot (Bjerkandera adusta) or brown rot (Gloeophyllum sepiarium) pure fungal cultures, or the original suite of endemic microbial community on the logs; and 3. Buried (15cm in soil as a proxy for coarse roots) or surface applied wood chips. We also created a warming treatment using open-topped, passive warming chambers on a subset of the above treatments. Control plots with no added wood (“no chip control”) were incorporated into the research design. Soils were sampled for initial δ 13 C values, CN concentrations, and bulk density. A subset of plots were instrumented with lysimeters for sampling soil water and temperature data loggers for measuring soil temperatures. To determine the early pathways of decomposition, we measured soil surface CO 2 efflux, dissolved organic C (DOC), and DO 13 C approximately monthly over two growing seasons from a subsample of the research plots. To determine the portion of soil surface CO 2 efflux attributable to wood-derived C, we used Keeling plot techniques to estimate the associated δ 13 C values of the soil CO 2 efflux. We measured the δ 13 CO 2 once during the peak of each growing season. Initial values for soil δ 13 C values and CN concentrations averaged across the six sites were -26.8‰ (standard error = 0.04), 2.46% (se = 0.11), and 0.15% (se = 0.01), respectively. The labeled wood chips from the Aspen FACE treatments had an average δ13C value of -39.5‰ (se 0.10). The >12 ‰ isotopic difference between the soil and wood chip δ 13 C values provides the basis for tracking the wood-derived C through the early stages of decomposition and subsequent storage in the soil. Across our six research sites, average soil surface CO 2 efflux ranged from 1.04 to 2.00 g CO 2 m -2 h -1 for the first two growing seasons. No wood chip controls had an average soil surface CO 2 efflux of 0.67 g CO 2 m -2 h -1 or about half of that of the wood chip treatment plots. Wood-derived CO 2 efflux was higher for loam textured soils relative to sands (0.70 and 0.54 g CO 2 m -2 h -1 , respectively; p = 0.045)), for surface relative to buried wood chip treatments (0.92 and 0.39 g CO 2 m -2 h -1 , respectively; p < 0.001), for warmed relative to ambient temperature treatments (0.99 and 0.78 g CO 2 m -2 h -1 , respectively; 0.004), and for natural rot relative to brown and white rots (0.93, 0.82, and 0.78 g CO 2 m -2 h -1 , respectively; p = 0.068). Our first two growing seasons of soil surface CO 2 efflux data show that wood chip location (i.e., surface vs. buried chip application) is very important, with surface chips loosing twice the wood-derived CO 2 . The DOC data support this trend for greater loss of ecosystem C from surface chips. This has strong implications for the importance of root and buried wood for ecosystem C retention. This strong chip location effect on wood-derived C loss was significantly modified by soil texture, soil temperature, decomposer communities, and wood quality as effected by potential future CO 2 and O 3 levels.

54 ENVIRONMENTAL SCIENCES↗

SPRUCE Advanced Molecular Techniques Provide a Rigorous Method for Characterizing Organic Matter Quality in Complex Systems: Supporting Data

This dataset contains Fourier transform ion cyclotron resonance mass spectrometry-based measurements (FTICRMS), gas chromatography, and liquid chromatography data from the Spruce and Peatland Responses Under Changing Environments (SPRUCE) experimental site within the Marcell Experimental Forest in northern Minnesota, USA from 2011 to 2016. Measurement results demonstrate that optical characterization of peatland dissolved organic matter (DOM) may not fully capture classically identified chemical characteristics and may, therefore, not be the best measure of organic matter quality. Analyses show poor regression fits between optical characteristics and Fourier transform ion cyclotron resonance mass spectrometry-based measurements (FTICRMS). These data were used in Wilson and Tfaily (2018) and files are organized by which figure they were used to produce. Data underlying those regression analyses, as shown in Figures 1a and 1b of Wilson and Tfaily (2018), are provided in data files ds01 and ds02, respectively. ds01: Optically-derived specific ultraviolet absorbance method at 254 nm (SUVA254) values and Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) -derived double bond equivalences. ds02: Optically-derived spectral slopes and FTICRMS-derived average molecular weights. Results of analyses of a representative sample by FTICRMS and additional analytical techniques provide a broader picture of the compounds occurring in peatland dissolved organic matter (DOM) as shown in Figure 2 of Wilson and Tfaily (2018). The data underlying Figure 2 in are provided in data files ds03-ds07, organized by the respective analytical technique used to generate the data. ds03: Nitrogen containing compounds identified via FTICRMS. ds04: Compounds identified via FTICRMS which did not have nitrogen. ds05: Nuclear magnetic resonance (NMR) results. ds06: Gas chromatography mass spectrometry (GCMS) results. ds07: Liquid chromatography mass spectrometry (LCMS) results. This dataset contains seven data files in comma-separate values (*.csv) format. Additional metadata are provided: seven data dictionaries and a file-level metadata file in comma-separate values (.csv) format and a user guide in PDF (*.pdf) format.

54 ENVIRONMENTAL SCIENCES↗

Application of GOTHIC to Groundwater Transport Analysis - 20152

Migration of pollutants and hazardous wastes, potentially containing radioactive isotopes, via groundwater transport is a concern at most waste cleanup sites. Predictive analysis can be used to evaluate mitigating actions intended to minimize impact on the environment and public exposure. GOTHIC is a multipurpose thermal hydraulics code that is used extensively in the nuclear industry for design, licensing and operation evaluations. It combines the capabilities of typical one-dimensional system codes and the essential features of Computational Fluid Dynamics (CFD) codes for three-dimensional analysis. There are other codes that are specifically developed for groundwater transport analysis and the results presented here are consistent with prior analyses. However, GOTHIC has some unique features that offer advantages for applications related to nuclear waste. Most importantly, it has been developed and maintained under a Quality Assurance program in compliance with the requirements of 10CFR50 Appendix B [2] and applicable portions of ASME NQA-1 [3] since 1995. Available GOTHIC capabilities that make the code especially useful for groundwater transport of nuclear materials include: - Tracking of any number of tracer elements for contaminants and other species of interest; - Radioactive decay and progeny of tracer elements; - Adsorption/desorption of tracer elements; - Tracking of any number of dissolved gases; - Release and absorption for dissolved gases; - Vapor phase tracking; - Non-Newtonian fluid modeling. The general porous body modeling approach makes GOTHIC well suited to groundwater transport analysis. The multi-region modeling approach used by GOTHIC simplifies model construction for regions of varying hydrologic characteristics and focuses the computational effort on regions of particular interest while simultaneously capturing the macroscopic response and any feedback effects across the larger domain. The applicability of GOTHIC to groundwater transport applications is demonstrated by comparing code results with available analytic or semi-analytic solutions for groundwater behavior. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Pathways of sulfate enhancement by natural and anthropogenic mineral aerosols in China

China, the world’s largest consumer of coal, emits approximately 30 million tons of sulfur dioxide (SO₂) per year. SO₂ is subsequently oxidized to sulfate in the atmosphere. However, large gaps exist between model-predicted and measured sulfate levels in China. Long-term field observations and numerical simulations were integrated to investigate the effect of mineral aerosols on sulfate formation. We found that mineral aerosols contributed a nationwide average of approximately 22% to sulfate production in 2006. The increased sulfate concentration was approximately 2 μg m⁻³ in the entire China. In East China and the Sichuan Basin, the increments reached 6.3 μg m⁻³ and 7.3 μg m⁻³, respectively. Mineral aerosols led to faster SO₂ oxidation through three pathways. First, more SO₂ was dissolved as cloud water alkalinity increased due to water-soluble mineral cations. Sulfate production was then enhanced through the aqueous-phase oxidation of S(IV) (dissolved sulfur in oxidation state +4). The contribution to the national sulfate production was 5%. Second, sulfate was enhanced through S(IV) catalyzed oxidation by transition metals. The contribution to the annual sulfate production was 8%, with 19% during the winter that decreased to 2% during the summer. Third, SO₂ reacts on the surface of mineral aerosols to produce sulfate. The contribution to the national average sulfate concentration was 9% with 16% during the winter and a negligible effect during the summer. The inclusion of mineral aerosols does resolve model discrepancies with sulfate observations in China, especially during the winter. These three pathways, which are not fully considered in most current chemistry-climate models, will significantly impact assessments regarding the effects of aerosol on climate change in China.

Huang, Xin↗

Synchronization of dissolution and precipitation fronts during infiltration‐driven replacement in porous rocks

Abstract Coupled dissolution‐precipitation reactions, where two minerals share a common ion, occur frequently in geological replacement; the reactions are driven by an inflow of precipitating secondary ions and an outflow of dissolved primary ions. Although crystallization pressure is frequently invoked to explain volume‐preserving replacement, it cannot be operative if the chemical reactions lead to a loss of mineral volume; here the host rock that should confine the precipitating mineral is dissolving faster than the grains are growing. In this paper we propose two chemical mechanisms by which a rapid dissolution front and a slower precipitation front can be synchronized, and volume‐for‐volume replacement preserved. We analyze these mechanisms within the framework of reactive transport theory and show that morphological features observed in calcite replacement can be correlated with predictions of the models.

Kondratiuk, Paweł↗

The effect of regional groundwater on carbon dioxide and methane emissions from a lowland rainforest stream in Costa Rica

In the tropical rainforest at La Selva Biological Station in Costa Rica, regional bedrock groundwater high in dissolved carbon discharges into some streams and wetlands, with the potential for multiple cascading effects on ecosystem carbon pools and fluxes. We investigated carbon dioxide (CO 2 ) and methane (CH 4 ) degassing from two streams at La Selva: the Arboleda, where ~1/3 of the streamflow is from regional groundwater, and the Taconazo, fed exclusively by local groundwater recharged within the catchment. The regional groundwater inflow to the Arboleda had no measurable effect on stream gas exchange velocity, dissolved CH 4 concentration, or CH 4 emissions but significantly increased stream CO 2 concentration and degassing. CO 2 evasion from the reach of the Arboleda receiving regional groundwater (lower Arboleda) averaged 5.5 mol C m -2 d -1 , ~7.5x higher than the average (0.7 mol C m -2 d -1 ) from the stream reaches with no regional groundwater inflow (the Taconazo and upper Arboleda). Carbon emissions from both streams were dominated by CO 2 ; CH 4 accounted for only 0.06-1.70% of the total (average of both streams: 5 x10 -3 mol C m -2 d -1 ). Annual stream degassing fluxes normalized by watershed area were 48 and 299 g C m -2 for the Taconazo and Arboleda, respectively. CO 2 degassing from the Arboleda is a significant carbon flux, similar in magnitude to the average net ecosystem exchange estimated by eddy covariance. As a result, examining the effects of catchment connections to underlying hydrogeological systems can help avoid overestimation of ecosystem respiration and advance our understanding of carbon source/sink status and overall terrestrial ecosystem carbon budgets.

54 ENVIRONMENTAL SCIENCES↗

Determining the flux of methane into Hudson Canyon at the edge of methane clathrate hydrate stability: METHANE FLUX INTO HUDSON CANYON

Methane seeps were investigated in Hudson Canyon, the largest shelf-break canyon on the northern U.S. Atlantic Margin. The seeps investigated are located at or updip of the nominal limit of methane clathrate hydrate stability. The acoustic identification of bubble streams was used to guide water column sampling in a 32 km 2 region within the canyon's thalweg. By incorporating measurements of dissolved methane concentration with methane oxidation rates and current velocity into a steady state box model, the total emission of methane to the water column in this region was estimated to be 12 kmol methane per day (range: 6–24 kmol methane per day). These analyses suggest that the emitted methane is largely retained inside the canyon walls below 300 m water depth, and that it is aerobically oxidized to near completion within the larger extent of Hudson Canyon. Based on estimated methane emissions and measured oxidation rates, the oxidation of this methane to dissolved CO 2 is expected to have minimal influences on seawater pH.

58 GEOSCIENCES↗

Influence of Hydrological Perturbations and Riverbed Sediment Characteristics on Hyporheic Zone Respiration of CO 2 and N 2

Rivers in climatic zones characterized by dry and wet seasons often experience periodic transitions between losing and gaining conditions across the river-aquifer continuum. Infiltration shifts can stimulate hyporheic microbial biomass growth and cycling of riverine carbon and nitrogen leading to major exports of biogenic CO 2 and N 2 to rivers. In this study, we develop and test a numerical model that simulates biological-physical feedback in the hyporheic zone. We used the model to explore different initial conditions in terms of dissolved organic carbon availability, sediment characteristics, and stochastic variability in aerobic and anaerobic conditions from water table fluctuations. Our results show that while highly losing rivers have greater hyporheic CO 2 and N 2 production, gaining rivers allowed the greatest fraction of CO 2 and N 2 production to return to the river. Hyporheic aerobic respiration and denitrification contributed 0.1–2 g/m 2 /d of CO 2 and 0.01–0.2 g/m 2 /d of N 2 ; however, the suite of potential microbial behaviors varied greatly among sediment characteristics. We found that losing rivers that consistently lacked an exit pathway can store up to 100% of the entering C/N as subsurface biomass and dissolved gas. Finally, our results demonstrate the importance of subsurface feedbacks whereby microbes and hydrology jointly control fate of C and N and are strongly linked to wet-season control of initial sediment conditions and hydrologic control of seepage direction. These results provide a new understanding of hydrobiological and sediment-based controls on hyporheic zone respiration, including a new explanation for the occurrence of anoxic microzones and large denitrification rates in gravelly riverbeds.

58 GEOSCIENCES↗

Magnesium Recycling of Partially Oxidized, Mixed Magnesium-Aluminum Scrap Through Combined Refining and Solid Oxide Membrane (SOM) Electrolysis Processes

Pure magnesium (Mg) is recycled from 19g of partially oxidized 50.5wt.%Mg-Aluminum (Al) alloy. During the refining process, potentiodynamic scans (PDS) were performed to determine the electrorefining potential for magnesium. The PDS show that the electrorefining potential increases over time as the Mg content inside the Mg-Al scrap decreases. Up to 100% percent of magnesium is refined from the Mg-Al scrap by a novel refining process of dissolving magnesium and its oxide into a flux followed by vapor phase removal of dissolved magnesium and subsequently condensing the magnesium vapors in a separate condenser. The solid oxide membrane (SOM) electrolysis process is employed in the refining system to enable additional recycling of magnesium from magnesium oxide (MgO) in the partially oxidized Mg-Al scrap. The combination of the refining and SOM processes yields 7.4g of pure magnesium; could not collect and weigh all of the magnesium recovered.

36 MATERIALS SCIENCE↗

Crossover Effects of Transition‐Metal Ions on Lithium‐Metal Anode in Localized High Concentration Electrolytes

Abstract The stability of the solid–electrolyte interphase (SEI) is critical to the cycle life of lithium‐metal batteries (LMBs). While the crossover effect of transition‐metal ions from cathode to anode is extensively studied in lithium‐ion batteries with graphite anodes, its impact on LMBs remains largely unexplored. Herein, this study investigates the electrochemical and chemical properties of SEI layers formed on lithium‐metal anodes in localized high‐concentration electrolytes (LHCEs) containing dissolved transition‐metal ions (Ni 2+ , Mn 2+ , and Co 2+ ). It is demonstrated that transition‐metal ions in LHCEs reduce the coulombic efficiency (CE) and significantly degrade the cycle life of LMBs. Time‐of‐flight secondary‐ion mass spectrometry (ToF‐SIMS) reveals that SEI structures differ depending on the dissolved TM ion, with Mn 2+ and Co 2+ inducing severe destabilization, and Ni 2+ exhibiting a less severe impact. These findings underscore the detrimental effects of transition‐metal crossover effects in LMB systems.

Guo, Zezhou [Materials Science and Engineering Pro↗

Coordination Chemistry as a Universal Strategy for a Controlled Perovskite Crystallization

The most efficient and stable perovskite solar cells (PSCs) are made from complex mixture of precursors, which are practically always dissolved in combinations of the volatile (and toxic) N, N-Dimethylformamide (DMF), and the non-volatile (and green) dimethyl sulfoxide (DMSO) solvents. Typically, to then form a thin film, an extreme oversaturation of the perovskite precursor is initiated to trigger nucleation sites, e.g. by vacuum, an airstream or a so-called antisolvent. Unfortunately, most such oversaturation triggers do not expel the lingering (and highly coordinating) DMSO, which is highly coordinating, from the thin films; this detrimentally affects long-term stability. Here, for the first time, we introduce (the green) dimethyl sulfide (DMS) as a novel nucleation trigger for perovskite films combining, uniquely, high coordination and high vapor pressure. More precisely, DMS coordinates more strongly than all currently used solvents, hence replacing them, including DMSO, effectively during film formation. Crucially, DMS also has among the highest vapor pressures reported in literature, thus effectively leaving the thin film shortly after formation. This gives DMS a universal scope: DMS replaces other solvents by coordinating more strongly and removes itself once the film formation is finished. To demonstrate this novel coordination chemistry approach, we process MAPbI 3 PSCs, typically dissolved in hard-to-remove (and green) DMSO achieving 21.6% efficiency, among the highest reported efficiencies for this system. To confirm the universality of our strategy, we tested DMS for FAPbI 3 as another composition, which showed higher efficiency of 23.5% compared to 20.9% for fabricated device with CB. Finally, this work provides a universal strategy to control perovskite crystallization using coordination chemistry heralding the revival of perovskite compositions with pure DMSO, such as MAPbI 3 .

36 MATERIALS SCIENCE↗

High-Performance High-Loading Lithium-Sulfur Batteries by Low Temperature Atomic Layer Deposition of Aluminum Oxide on Nanophase S Cathodes

This study examines the effects of nanophase S and surface coatings via atomic layer deposition (ALD) on high-loading sulfur cathodes for developing high-performance and high-energy lithium-sulfur (Li-S) batteries. It is first verified that ball milling is an effective and facile route for nanoengineering microsized S powders and the resultant nanoscale S particles exhibit better performance. Using these ball milled nanoscale S cathodes, it is found that ALD Al2O3 performed at 50 degrees C yields deposits that evolve with ALD cycles from dispersed nanoparticles, to porous, connected films, and finally to dense and continuous films. Moreover, this low temperature ALD process suppresses S loss by sublimation. The ALD Al2O3 greatly improves sulfur cathode sustainable capacity and Coulombic efficiency. This study postulates two different mechanisms underlying the effects of ALD Al2O3 surface coatings depending on their morphology. ALD Al2O3 nanoparticles dispersed on the sulfur surface mainly function to adsorb polysulfides, thereby inhibiting S shuttling and improving sustainable capacity and Coulombic efficiency. By contrast, ALD Al2O3 films behave as a physical barrier to prevent polysulfides from contacting the liquid electrolyte and dissolving. The dispersed Al2O3 nanoparticles improve both sustainable capacity and Coulombic efficiency while the closed Al2O3 films improve Coulombic efficiency while decreasing the capacity

25 ENERGY STORAGE↗

Hybrid Additive Manufacturing and Electric Field-Assisted Sintering of High-temperature Heat Exchangers via Sacrificial Channel Molds

A hybrid manufacturing approach, integrating additive manufacturing (AM) with powder methodology via electric field-assisted sintering (EFAS), was developed for the fabrication of high-temperature compact heat exchangers (CHX) from refractory metals. The methodology employed additively manufactured sacrificial channel molds (SCMs) as shapeholders for CHX channels, which were embedded in metal powders using EFAS. Following embedding, the SCMs were chemically dissolved to form the internal channel network. SCMs were fabricated using both digital light processing (DLP) and direct ink writing (DIW) from chemically reactive, calcium-based ceramic feedstocks with varying ratios of Al2O3 reinforcement. The microstructure, phase composition, and dissolution behavior of both as-printed and embedded SCMs were investigated. The shrinkage behavior of the SCMs embedded in refractory metals, as well as the interfacial characteristics between the SCMs and metal matrix, were studied. The results showed that the SCMs containing sufficient chemical reactive ceramics dissolved effectively before and after embedding. The as-printed SCMs retained the phase composition of their feedstocks, but the embedded SCMs containing calcium-based ceramics and Al2O3 exhibited the formation of calcium aluminates due to high temperature exposure during embedding. Most SCMs exhibited a cellular Al2O3 network filled with Ca-rich ceramics. Shrinkage after embedding was strongly dependent on SCM density, with lower density SCMs exhibiting greater shrinkage. A thin SCM-affected zone was observed at the metal matrix surface, characterized by increased porosity compared to the bulk matrix. This effect was attributed to infiltration of the SCM materials into powder particle boundaries under pressure, followed by their removal during dissolution. This study demonstrates the feasibility of manufacturing CHXs from hard-to-process refractory metals for use in harsh environments.

36 - MATERIALS SCIENCE↗

High Voltage Operation of Ni-Rich NMC Cathodes Enabled by Stable Electrode/Electrolyte Interphases

Lithium (Li) metal battery (LMB) is one of the most promising candidates for the next generation energy storage systems. However, it is still a significant challenge to operate LMBs with high voltage cathode under high rate conditions. In this work, a LMB using nickel-rich layered cathode of LiNi0.76Mn0.14Co0.10O2 (NMC76) and an optimized electrolyte (0.6 M LiTFSI + 0.4 M LiBOB + 0.05 M LiPF6 dissolved in EC: EMC (4:6 by weight)) demonstrate excellent stability under a high charge cutoff voltage of 4.5 V. Remarkably, these Li||NMC76 cells can deliver a high discharge capacity of > 220 mAh g-1 (846 Wh kg-1) and retain more than 80% capacity after 1000 cycles under a high charge/discharge current rates of 2C/2C (1C = 200 mA g-1). These excellent electrochemical performances can be attributed to the highly enhanced structural/interfacial stability of both Ni-rich NMC76 cathode materials and Li metal anode using the optimized electrolyte.

Ni-rich NMC, cathode electrolyte interphase, dual ↗

Mitigating Cyclable Li‐Ion Inventory Loss in Full Cells with Mn‐Rich Disordered Rocksalt Cathodes

Lithium (Li)- and manganese (Mn)-rich disordered rock salt (DRX) materials are promising cathode materials for next-generation Li-ion batteries. Although these cathode materials are Li-ions rich in their pristine state, their incorporation into full cells results in challenges with maintaining Li-ion inventory during cycling. Herein, the degradation mechanisms of DRX materials in different DRX||Graphite full cells are reported. It is found that DRX electrodes contain Li impurities, primarily due to the environmental sensitivity of mechanochemically synthesized DRX materials during sample transfer and storage. In addition, the structural instability of DRX triggers Mn dissolution. Dissolved Mn ions react with exposed Li x C y compounds and induce electrolyte decomposition on the anode, further depleting Li-ion inventory. Control experiments involving the pre-addition of Mn 2+ provide clear evidence of the impact of Mn dissolution on Li-ion inventory. The electrochemical activation process can stabilize DRX, alleviate Mn dissolution and thus mitigate the loss of Li-ion inventory. These mechanistic insights inform the development of chemical pre-lithiation and electrolyte additive strategies to collectively passivate interfaces, mitigate the effects of trace dissolved Mn ions, and preserve Li-ion inventory. Ultimately, the DRX||Graphite full cell achieves highly reversible electrochemical reactions with a high capacity retention. This study fills a research gap in DRX-based full cells and provides insights into degradation mechanisms and optimization strategies for their practical use.

36 MATERIALS SCIENCE↗

Responsive Interfacial Assemblies Based on Charge‐Transfer Interactions

Abstract Charge transfer (CT) interactions have been widely used to construct supramolecular systems, such as functional nanostructures and gels. However, to date, there is no report on the generation of CT complexes at the liquid–liquid interface. Here, by using an electron‐deficient acceptor dissolved in water and an electron‐rich donor dissolved in oil, we present the in situ formation and assembly of CT complex surfactants (CTCSs) at the oil–water interface. With time, CTCSs can assemble into higher‐order nanofilms with exceptional mechanical properties, allowing the stabilization of liquids and offering the possibility to structure liquids into nonequilibrium shapes. Moreover, due to the redox‐responsiveness of the electron‐deficient acceptor, the association and dissociation of CTCSs can be reversibly manipulated in a redox process, leading to the switchable assembly and disassembly of the resultant constructs.

Sun, Shuyi↗

Speciation of Transition Metal Dissolution in Electrolyte from Common Cathode Materials

Abstract Significant capacity loss has been observed across extended cycling of lithium‐ion batteries cycled to high potential. One of the sources of capacity fade is transition metal dissolution from the cathode active material, ion migration through the electrolyte, and deposition on the solid‐electrolyte interphase on the anode. While much research has been conducted on the oxidation state of the transition metal in the cathode active material or deposited on the anode, there have been limited investigations of the oxidation state of the transition metal ions dissolved in the electrolyte. In this work, X‐ray absorption spectroscopy has been performed on electrolytes extracted from cells built with four different cathode active materials (LiMn 2 O 4 (LMO), LiNi 0.5 Mn 1.5 O 4 (LNMO), LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), and (x Li 2 MnO 3 *(1‐x) LiNi a Mn b Co c O 2 , with a+b+ c =1) (LMRNMC)) that were cycled at either high or standard potentials to determine the oxidation state of Mn and Ni in solution. Inductively coupled plasma‐mass spectrometry has been performed on the anodes from these cells to determine the concentration of deposited transition metal ions. While transition metal ions were found dissolved in all electrolytes, the oxidation state(s) of Mn and Ni were determined to be dependent on the cathode material and independent of cycling potential.

Rynearson, Leah↗

Nondisruptive Dissolution of Hyperpolarized 129 Xe into Viscous Aqueous and Organic Liquid Crystalline Environments

Studies of hyperpolarized xenon-129 (hp- 129 Xe) in media such as liquid crystals and cell suspensions are in demand for applications ranging from biomedical imaging to materials engineering but have been hindered by the inability to bubble Xe through the desired media as a result of viscosity or perturbations caused by bubbles. In this paper a device is reported that can be reliably used to dissolve hp- 129 Xe into viscous aqueous and organic samples without bubbling. This method is robust, requires small sample volumes (<60 μL), is compatible with existing NMR hardware, and is made from readily available materials. Experiments show that Xe can be introduced into viscous and aligned media without disrupting molecular order. We detected dissolved xenon in an aqueous liquid crystal that is disrupted by the shear forces of bubbling, and we observed liquid-crystal phase transitions in (MBBA). This tool allows an entirely new class of samples to be investigated by hyperpolarized-gas NMR spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗