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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Electron Inversion and Tunneling at Silicon Thermal Oxide Interfaces for Solar-Driven Molecular Catalysis to Syngas

Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts to perform solar-driven reduction of CO 2 . Less frequently, molecular catalysts are employed to better control the reactivity toward desired products, yet the development of robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2–3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and a photocurrent density of ∼10 mA/cm 2 for the solar-driven photoelectrochemical reduction of a homogeneous molecular catalyst, producing syngas with an ∼2:1 H 2 to CO ratio. Because of a low defect density, the oxide interface forms an electron inversion layer with metal-like electron density at cathodic potentials. This inversion layer facilitates electron transfer to redox-active molecules via tunneling even if the molecule’s reduction potential is beyond the semiconductor’s conduction band edge. Using an electrolyte solution composed of a homogeneous cobalt bis(terpyridine) catalyst in a water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting an ∼30% Faradaic efficiency for CO that was similar to a glassy carbon electrode under comparable conditions. Furthermore, the results demonstrate that an ultrathin thermal oxide interface is a robust platform for development of aqueous-stable, molecule-driven photoelectrocatalysis.

Catalysts↗
DOE OSTI2024

Development and application of hybrid AIMD/cDFT simulations for atomic-to-mesoscale chemistry

Many important chemical processes involve reactivity and dynamics in complex solutions. Gaining a fundamental understanding of these reaction mechanisms is a challenging goal that requires advanced computational and experimental approaches. However, important techniques such as molecular simulation have limitations in terms of scales of time, length, and system complexity. Furthermore, among the currently available solvation models, there are very few designed to describe the interaction between the molecular scale and the mesoscale. To help address this challenge, here, we establish a novel hybrid approach that couples first-principles plane-wave density functional theory with classical density functional theory (cDFT). In this approach, a region of interest described by ab initio molecular dynamics (AIMD) interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. cDFT is a robust but efficient mesoscopic approach to accurate thermodynamics of bulk electrolyte solutions over a wide concentration range (up to 2M concentrations). Benchmarking against commonly used continuum models of solvation, such as SMD, as well as experiments, demonstrates that our hybrid AIMD–cDFT method is able to produce reasonable solvation energies for a variety of molecules and ions. With this model, we also examined the solvent effects on a prototype S N 2 reaction of the nucleophilic attack of a chloride ion on methyl chloride in the solution. The resulting reaction pathway profile and the solution phase barrier agree well with experiment, showing that our AIMD/cDFT hybrid approach can provide insight into the specific role of the solvent on the reaction coordinate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Mechanistic Study of Controlled Zinc Electrodeposition Behaviors Facilitated by Nanoscale Electrolyte Additives at the Electrode Interface

Nanoparticle organic hybrid materials (NOHMs) are liquid-like materials composed of an inorganic core to which a polymeric canopy is ionically tethered. NOHMs have unique properties including negligible vapor pressure, high oxidative thermal stability, and the ability to bind to reactive species of interest due to the tunability of their polymeric canopy. This makes them promising multifunctional materials for a wide range of energy and environmental technologies, including electrolyte additives for electrochemical energy storage (e.g., flow batteries) and the electrochemical conversion of CO 2 to chemicals and fuels. Due to their unique transport behaviors in fluid systems, an understanding of the near-electrode surface behavior of NOHMs in electrolyte solutions and their effect on electrochemical reactions is still lacking. In this work, the complexation of zinc (Zn) by NOHMs with an ionically tethered polyetheramine canopy (HPE) (NOHM-I-HPE) was studied using attenuated total reflectance Fourier transform infrared and Carbon-13 nuclear magnetic resonance spectroscopy. Additionally, various electrochemical techniques were employed to discern the role of NOHM-I-HPE during zinc electrodeposition, and the results were compared to those of the electrochemical system containing untethered HPE polymers. Our findings confirmed that NOHM-I-HPE and HPE reversibly complex zinc in the aqueous electrolyte. NOHM-I-HPE and HPE were found to block some of the electrode active sites, reducing the overall current density during electrodeposition, while facilitating the formation of smooth zinc deposits, as revealed by surface imaging and diffraction techniques. Observed variations in the current density responses and the degree of passivation created by the NOHM-I-HPE and HPE adsorbed on the electrode surface revealed that their different packing behaviors at the electrode–electrolyte interface influence the zinc deposition mechanism. The presence of the nanoparticle and ordering offered by the NOHMs as well as the structured conformation of the polymeric canopy allowed the formation of void spaces and free volumes for enhanced transport behaviors. Furthermore, these findings provided insights into how structured electrolyte additives such as NOHMs can allow for advancements in electrolyte design for controlled deposition of metal species from energy-dense electrolytes or for other electrochemical reactions.

25 ENERGY STORAGE↗
DOE OSTI2024

60 Years of Betaine 30–From Solvatochromic Discovery to Future Frontiers

Betaine-30 (B30) was reported by Karl Dimroth and Christian Reichardt et al. in 1963 as a solvatochromic probe that can be easily synthesized, shows good solubility, and remains stable in various organic solvents and solutions. Its strongly negatively solvatochromic behavior arises from differential solvation between its electronic ground and excited states, making it a valuable tool for assessing solvent polarity using the E T (30) polarity scale, also devised by Dimroth and Reichardt. In addition, advancements in femtosecond laser spectroscopy in the 1990s greatly improved the understanding of B30’s relaxation dynamics following photoexcitation. In solvents capable of hydrogen bonding, such as alcohols, intermolecular hydrogen-bond rearrangement contributes to the multiple relaxation components observed. Since the 1990s, the applications of B30 have expanded beyond simple organic solvents to include complex solvent mixtures, such as electrolyte solutions for battery technologies and eutectic solvent mixtures. Furthermore, given the growing importance of these complex solvent mixtures, B30 is becoming an increasingly valuable tool for studying previously unexplored solvation properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Probing the Radial Chemistry of Getter Components in Light Water Reactors via Controlled Electrochemical Dissolution

Getters are among the key functional components in the Tritium Producing Burnable Absorber Rods (TPBARs) of Light Water Reactors, and are used to capture the released tritium gas. They are cylindrical tubes comprised of the alloy zircaloy-4 which is coated with nickel plating both internally and externally. Their exposure to tritium as well as the irradiation environments in the light water reactors changes their structure, chemical composition and chemistry. Understanding the radial tritium distribution is key to gaining insight into the evolution of new chemistry upon irradiation in order to predict getter performance. Consequently, efforts are underway to devise a method that can allow selective probing into the getter core radially to probe the chemistry akin to carefully and selectively peeling of the layers of an onion. We have recently devised an electrochemical dissolution technique for controlled radial dissolution of zirconium based liners; this work describes the first proof-of-concept demonstration of the applicability of this technique on the controlled radial dissolution of nickel plated getters. The technique is complemented with periodic analysis of the electrolyte solution to measure the rates of release of the various elemental components and therefore glean information on their radial distribution across the getter; further complementary microscopy on the exposed surfaces allows us insight into the chemistry at the getter core.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Isolation and conversion of electrolyte components into a value-added product

The overall objective of this work was to develop a process for effectively (i) recycling the electrolyte components from the end-of-life batteries and reduce the environmental hazard, (ii) understand the fundamental differences between pristine and recycled electrolyte components, (iii) electrochemically and analytically evaluate the recycled electrolyte components and (iv) establish deviations from the pristine electrolyte, and effectively separation of value-added product. We focused on determining scaling up the electrolyte recovery process by distillation of end-of-life batteries to get yield enough to use it for electrolyte formulation of reuse in the battery cell. The used cells from the ORNL battery manufacture facility (BMF)as well as received from the industry partner, Austin Elements Inc., was scaled to 10 used multilayered pouch cells in each batch of distillation and systematically separated and identified the electrolyte components of the used cells with FTIR and NMR studies. We were able to recovery 10g of solvent mass from the used pouch cells. NMR spectroscopy showed that the solvent was pure EMC,DMC and the sample was used to make a new battery cell. The end-of-life battery, it was noted that some cells were visually drier than the other cells and were more advanced in aged. In that case, even though the same distillation conditions were utilized, no usable mass of electrolyte solvent was recovered. It is expected that most of the solvent was decomposed during the battery charge-discharge cycling. The solid salt residue was separated by chemical and water treatment processes. Components of resulting solid product was analyzed by XRD and XPS measurements. The solid products are very much related to the salts used in the electrolyte solution.

25 ENERGY STORAGE↗
DOE OSTI2025

Complex Dependence of Calcite Crack Kinetics on Salinity: The Role of DLVO and Hydration Forces

Abstract Subcritical crack growth (SCG) plays an important role in many geological processes such as delayed earth rupture and rock weathering. The complex dependency of SCG on the in‐crack fluid chemistry, however, is still poorly understood. In this study, we utilize the newly developed surface force‐based fracture theory (SFFT) to elucidate the relative contributions of surface forces and solute transport to the crack growth kinetics of calcite in NaCl solutions. Expanding on Barenblatt's cohesive crack model, SFFT introduces an effective stress intensity at the crack tip that encompasses all the relevant intermolecular forces across the crack in addition to the external far‐field stresses. The nonlinear system of equations portraying the crack opening profile, the solute distribution in a propagating crack, and the crack growth velocity are numerically solved via an implicit scheme. After carefully calibrating the model for calcite‐water systems, the SFFT is used to predict the SCG response of calcite at different NaCl concentrations, based on various hypotheses. These predictions are then compared to existing SCG data from the literature. We demonstrate that the experimentally observed variation of SCG rate with NaCl concentration cannot be explained solely by DLVO forces (electrostatic and Van der Waals interactions). This can be remediated by introducing an exponentially decaying hydration force with a nonlinear, nonmonotonic dependence on NaCl concentration. Furthermore, we demonstrate that accounting for both diffusive and advective transport of ions is important in explaining the absence of a stage‐II SCG response for calcite in electrolyte solutions. Plain Language Summary Subcritical crack growth (SCG) refers to the slow propagation of cracks in materials under a stress below the threshold for catastrophic failure. SCG is a key process in many geological events, for example, delayed earth ruptures and rock weathering. New initiatives such as underground CO 2 and H 2 storage in carbonate reservoirs further call for better understanding of SCG in carbonate minerals subjected to varying fluid chemistry. This study examines the SCG of calcite, a key mineral found in carbonate rocks, intergranular cement in sandstones, and filling material in mineral veins and faults, determining their deformation and strength. A mathematical model is developed to describe how the crack opens and propagates, how solutes (like salts) distribute within the crack, and how the crack surfaces interact with each other. We used the model to predict calcite SCG in water at different salt concentrations and compared it with experimental data. Our results revealed that the hydration force is the dominating factor in determining the complex, non‐linear dependency of SCG on salinity. We also found that both the movement of ions by diffusion and by bulk water flow are crucial for explaining the SCG rates, especially when the cracks grow quickly. Key Points Surface Force‐Based Fracture Theory predicts the complex subcritical crack growth patterns of calcite crystals immersed in NaCl solutions Results highlight the dominant role of hydration forces in altering the fracture behavior of calcite compared to VdW and electric double‐layer forces Advective solute transport explains the absence of stages‐II and ‐III subcritical crack growth responses in solid‐liquid systems

DLVO↗
DOE OSTI2023

Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces

Proton transfer is critically important to many electrocatalytic reactions, and directed proton delivery could open new avenues for the design of electrocatalysts. However, although this approach has been successful in molecular electrocatalysis, proton transfer has not received the same attention in heterogeneous electrocatalyst design. Here, in this work, we report that a metal oxide proton relay can be built within heterogeneous electrocatalyst architectures and improves the kinetics of electrochemical hydrogen evolution and oxidation reactions. The volcano-type relationship between activity enhancement and pK a of amine additives confirms this improvement; we observe maximum rate enhancement when the pK a of a proton relay matches the pH of the electrolyte solution. Density-functional-theory-based reactivity studies reveal a decreased proton transfer energy barrier with a metal oxide proton relay. These findings demonstrate the possibility of controlling the proton delivery and enhancing the reaction kinetics by tuning the chemical properties and structures at heterogeneous interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Highly swollen ROMP-based gels

In this study, the leakage of organic solvent during the transportation and storage is one of the major threats to the environment. Networks/gels acting as the absorbing materials for organic solvents are the most promising solution for the organic solvent pollution. Here, we report the synthesis of highly swollen networks/gels in high yield (≥95%) via ring opening metathesis polymerization (ROMP) using Grubbs’ first generation catalyst/initiator (G1), a crosslinker (1,1'-(methylenedi-4,1-phenylene)bis-exo-7-oxanorbornenecarboximide) and monofunctional monomer/diluent (exo-N-phenyl-7-oxanorbornenecarboximide). The mesh size of the network was varied by keeping the concentration of monomer constant while changing the concentrations of crosslinker and G1 (initiator). The swelling capacity of the network in N,N-dimethylformamide (DMF) solvent increased from 41 to 53 and to 61 with the increase of theoretical mesh size (molar ratio of monomer to crosslinker) from 20 to 40 and to 60, respectively. By further increasing the mesh size from 60 to 80 there was no significant change in swelling capacities (63). Thus, the gel with the mesh size of 60 was selected for swelling capacity analysis in other polar organic solvents such as dimethyl sulfoxide (DMSO), dichloromethane (DCM), chloroform and lithium-ion battery electrolyte solution (1.0 M LiPF 6 in ethylene carbonate (EC)/diethyl carbonate (DEC) = 50/50 (v/v)). They showed the decreased swelling capacity value from 61 to 57, 40, 31 and 5, respectively. For a controlled mesh size ROMP-based gel, we observed the highest swelling capacity values to date.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Exposure History and its Effect Towards Stabilizing Li Exchange Across Disordered Rock Salt Interfaces

Abstract The application of lithium rich disordered rock salts (DRX) as cathode materials has greatly expanded the materials space for high energy density cathodes. These materials are able to consistently achieve capacities higher than via a complex percolation based intercalation mechanism. Most current DRX materials face significant capacity fade when cycled over an extended period. One of the factors responsible for this could be deleterious side effect of interface reactions between the electrode and electrolyte at high voltage. We aim to focus on one aspect of this interaction, i.e the effect of exposure to electrolyte on the surface and its effect on the electrochemical properties of (LMNOF) powder. LMNOF was systematically treated in an electrolyte solution for varying periods of time at an elevated temperature. Treated samples exhibit surface layer modification (removal of F rich surface layer), leading to a 10 % improvement in the capacity retention behavior of LMNOF. Surface and bulk based measurements indicate an increase in disorder and gradual removal of F and Li. All of these processes mimic an aging process similar to cycling. This a priori formed interface allows for increased stability with respect to retention of capacity and oxygen loss.

Satish, Rohit↗
DOE OSTI2025

Experimental Evaluation of Interfacial Bonding Strength Between 304 Stainless Steel Substrate and Electrodeposited Nickel Coating Using Mesoscale Mechanical Testing Methods

Electrodeposition is a commonly used method for depositing a metal layer on a metallic substrate, to provide a decorative finish or for functional purposes including wear and corrosion resistance. The interfacial bonding strength is a critical factor in determining the quality of electrodeposition, as it ensures the adhesion of the deposited layer to the substrate. Despite its importance, there has not previously been a suitable mechanical testing method to quantitatively characterize the bonding strength between the electrodeposited layers and the substrate, due to the high strength of the materials and to restrictions imposed by the geometry (due to the small thickness of the plating layer) to manufacture tensile bars. In this study, we introduce a novel mesoscale mechanical testing method to overcome these limitations. This technique was applied to assess the bonding strength between a 304 stainless steel (SS) substrate and electrodeposited nickel with three different plating formulae (nickel sulfamate, Watts bath, and hard nickel). The thickness of the pure nickel coatings achieved for each of the three electrolyte solutions was approximately 1 mm on each side of the substrate. Mesoscale tensile bars of 1 mm length were manufactured by a femtosecond laser, with the material interface at the center of the gauge section, and then tensile-tested with digital image correlation. Further, the results proved that the electrodeposition technique is able to produce a very high bonding strength that is close to the yield strength of both the substrate material and the electrodeposited nickel layer. Additionally, in the case of the Watts bath formula, the interfacial bonding strength between the SS 304 and electrodeposited nickel can exceed that of the nickel layer. This method is expected to be useful for quantifying the interfacial bonding strength in numerous applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Thermodynamic modeling with uncertainty quantification using the modified quasichemical model in quadruplet approximation: Implementation into PyCalphad and ESPEI

The modified quasichemical model in the quadruplet approximation (MQMQA) considers the first- and the second-nearest-neighbor coordination and interactions, particularly useful in describing short-range ordering (SRO) in complex liquids such as molten salts, slag in metal processing, and electrolytic solutions. Here, the present work implements the MQMQA into the Python based open-source software PyCalphad for thermodynamic calculations. This endeavor facilitates the development of MQMQA-based thermodynamic database with uncertainty quantification (UQ) and propagation (UP) using the open-source software ESPEI. A new database structure based on Extensible Markup Language (XML) is proposed for ESPEI evaluation of MQMQA model parameters. Using the KF-NiF 2 , KCl-NaCl-MgCl 2 , and CaCl 2 -CaF 2 -LiCl-LiF salt systems as examples, we demonstrate the successful implementation of MQMQA in PyCalphad through thermodynamic calculations of Gibbs energy, equilibrium quadruplet fractions, and phase diagram, as well as database development with UQ and UP using ESPEI. Furthermore, as an application of the present implementation, both the LiF–TbF 3 and LiF-HoF 3 systems have been modeled by MQMQA for the first time, which are in good agreement with experiments. The present implementation hence offers an open-source capability for performing CALPHAD modeling for complex liquids with SRO using MQMQA plus a new XML database structure.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tree-inspired lignin microrods-based composite heterogeneous nanochannels for ion transport and osmotic energy harvesting

One of the key processes of tree lignification is that lignin penetrates into the cell wall and fills in the cell wall framework, thereby increasing the hardness and hydrophobic of the tree channels, which is beneficial to consolidate and support the tree cell wall and water transport. Inspired by this natural process, we demonstrated a lignin-based nanofluidic heterogeneous membrane that closely mimics the channels in tree, which can realize ion transport function and effectively capture reverse electrodialysis. The membrane was synthesized by heating dealkaline lignin and PVA at 200 °C and this formed fusiform microrods and a closed-packed membrane. Simultaneously, this membrane composited with anodized aluminum (AAO) channels membrane at 200 °C to form asymmetric heterogeneous nanochannels membrane, which can transport counter-ions and harvest osmotic energy. This membrane implements ion current rectification in 0.1 M KCl electrolyte solution at pH 3 due to the confinement of pores and opposite surface charges in lignin-based heterogeneous nanochannel. An output power density of 0.97 W m- 2 is obtained under a 50-fold salinity gradient, which can be further improved to 1.19 W m -2 by increasing the salinity gradient from 50-fold to 500-fold. Accordingly, this nanofluidic membranes were prepared by using lignin, the key component in tree, which not only mimicked a crucial process of the water and ionic transport process of channels in tree, but also had the prospect in the field of osmotic energy harvesting.

09 BIOMASS FUELS↗
DOE OSTI2021

Quantifying the chemical, electrochemical heterogeneity and spatial distribution of (poly) sulfide species using Operando SANS

In-situ and operando measurements are done to gain a better understanding of the precipitation mechanisms during charge and discharge in lithium sulfur batteries. A carbon felt networked with microfibers consisting of pores, 2 nm and smaller, is used as a freestanding sulfur host. Three different methods of sulfur infiltration are explored in order to determine the best one to fill most of the pores. It was identified to be a melt infiltration method in a vacuum oven, where the pores including the ultra-micropores, are successfully filled. In-situ electrochemical impedance spectroscopy measurements show a solid product formation occurring at the sulfur cathode, both during the high voltage plateau and at the end of discharge. In a 3-electrode EIS measurement, a similar solid product formation on the Li counter electrode due to its reaction with polysulfides is also observed. Operando small angle neutron scattering measurements show the solid product formation, in the carbon, both near the beginning and at the end of discharge, confirming the precipitation data via contrast changes as a function of charge and discharge. It is shown that Li 2 S precipitates in the pores at the beginning and the end of discharge, whereas S8 precipitates on the surface of the carbon felt. Finally, this lithium sulfur system shows both the quasi-solid-state and the solid-liquid-solid reactions in a typical ethereal electrolyte solution with a two-plateau discharge profile.

25 ENERGY STORAGE↗
DOE OSTI2020

Co-ion specific effect on sodium halides sorption and transport in a cross-linked poly(p-styrene sulfonate-co-divinylbenzene) for membrane applications

Here, sodium halide sorption and transport in a cation exchange membrane based on cross-linked poly(p-styrene sulfonate-co-divinylbenzene) (CR61) were investigated experimentally and theoretically. At fixed co-ion valence, sodium halide partitioning between aqueous electrolyte solutions and ion exchange polymers is only minimally sensitive to co-ion chemical identity. NaCl, NaF and NaI exhibit similar solubility coefficients in CR61, which agrees reasonably well with predictions of the Donnan-Manning model, especially at high external salt concentrations. Ion activity coefficients in the membrane were evaluated and ion sorption thermodynamics were investigated. Ion diffusion coefficients in CR61 were predicted using a recently developed framework based on the Manning diffusion model, which accounts for electrostatic effects on ion diffusion, and the Mackie-Meares model, which accounts for tortuosity/area effects on ion diffusion in swollen polymers. Model predictions agree reasonably well with the experimental data, especially at high external salt concentrations. The observed decrease in salt diffusion coefficients in CR61 relative to values in aqueous solutions is due primarily to tortuosity/area effects. Salt diffusion coefficients correlate with co-ion hydrated radius and membrane water content. Finally, salt permeability coefficients predicted using the solution-diffusion model exhibit good agreement with experimental data, especially at external salt concentration greater than 0.1 mol/L.

42 ENGINEERING↗
DOE OSTI2026

The effect of hydroxyl spacing in diols on the solvation structure, dynamics, and transport properties of choline chloride-based deep eutectic solvents

Deep eutectic solvents (DESs) are a class of liquids that offer great potential in alleviating some of the challenges present in today's long-term energy storage methods because they have physical properties that are favorable for storable electrolyte solutions. In this work, a series of glycols (ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol) were studied as potential hydrogen bond donors (HBD) with a common choline chloride (ChCl) as the hydrogen bond acceptor (HBA). The solvation dynamics of the prepared systems were studied by measuring the solvent reorganization response using femtosecond transient absorption spectroscopy (fs-TA). Conductivity, viscosity, density, ET(30) polarity, and dynamics of the prepared DESs were analyzed, with a particular interest in determining the effect of HBD chain length on these parameters. Here, classical molecular dynamics simulations were employed to investigate how the local liquid structure, solvent dynamics, and bulk solvent properties vary with changes in glycol chain length.

Conductivity↗
DOE OSTI2020

Microbial potentiometric sensor array measurements in unsaturated soils

The overarching goal of this study is to demonstrate a novel technology for monitoring changes in electrical potential of unsaturated soils using biofilm-populated electrodes. The novelty of the study stems from the fact that it demonstrates a method for measuring open-circuit potentials (OCP) in environments without the presence of an electrolyte solution. This study also reveals that using a biofilm-populated electrode as a reference in stable environments could successfully be employed to assess and monitor the electrochemical potential generated by plants and microorganisms. The findings imply that long-term (months to years) and real-time measurements of the open-circuit potential in unsaturated soils are possible. Because MPS arrays can directly measure open-circuit potential from the biofilm, the challenges related to locally induced electrochemical changes caused by microorganisms in the soil to achieve optimum physiological levels are eliminated. The simplicity of the technology, which allows for multiple indicator electrodes to be referenced against an “internal” reference electrode, enables spatial-temporal monitoring of the changes in the soil and the generation of 2D- or 3D-signal patterns. Once a signal pattern, generated by an array of sensors, develops (usually after 30 to 90 days), it does not significantly change unless the soil is exposed to external stimuli. The observed OCP phenomena, however, suggests that the change in OCP signal is independent of changes in soil conductivity resulting from the addition of water. In brief, findings suggest that the proposed technology can enable multidimensional profiling and long-term monitoring of changes occurring in unsaturated soils without direct implications of presence of water. The changes in the 2D or 3-D signal patterns, however, can be correlated to other important parameters that characterize soil health.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Decoding the Effect of Anion Identity on the Solubility of N -(2-(2-Methoxyethoxy)ethyl)phenothiazine (MEEPT)

Variations in the solubility of redox-active organic molecules (ROM) of interest for nonaqueous redox flow batteries (RFB), especially as the ROM state-of-charge changes during charge-discharge cycling, present significant molecular design challenges. The situation is further complicated as ROM solubility can be regulated by the choice of electrolyte salt and solvent that together with the ROM comprise the catholyte or anolyte (redox electrolyte) formulation, presenting materials design challenges. The ROM N-(2-(2-methoxyethoxy)ethyl)phenothiazine (MEEPT) is a viscous liquid at room temperature and is miscible in several organic solvents, including acetonitrile and propylene carbonate. The MEEPT radical cation (MEEPT +· ) paired with tetrafluoroborate (BF 4 - ) in acetonitrile presents a 0.5 M solubility, a dramatic decrease when compared to the viscous liquid of neutral MEEPT. Here, in this study, we present a joint experimental, regression modeling, and molecular dynamics (MD) simulations investigation to explore MEEPT-X (where X represents the counteranion) salt solubility variability as a function of concentration and counteranion chemistry in acetonitrile. We find a strong dependence of the salt solubility on the counteranion and relate these findings to explicit intermolecular interactions between MEEPT +· and the counteranion in the electrolyte solution.

Perera, Anton S. [Univ. of Kentucky, Lexington, KY↗