Search NASASearch

SEARCH · Search NASA

Results for “Surface Source Banking”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

402 records · Page 13

Cooperative and bifunctional Ga-Ca-Cr 2 O 3 @CaO structured monoliths as versatile platform for reactive capture of CO 2 and its subsequent conversion to ethylene

Cooperative and bifunctional materials (BFMs) that integrate adsorbents and catalysts offer a promising strategy for the reactive capture of CO 2 to produce valuable fuels and chemicals. In this study, we developed structured BFMs via 3D printing that combine CaO as an adsorbent with Ga–Ca–Cr 2 O 3 metal oxides as the catalyst for the reactive capture of CO 2 and its subsequent conversion to C 2 H 4 via the oxidative dehydrogenation of C 2 H 6 (CO 2 -ODHE). Three different Ga–Ca compositions were used to modify the catalyst surface characteristics and enhance C 2 H 4 selectivity. In these formulations, Ga ions stabilize the oxygen lattice of the BFM, while Ca ions interact strongly with Cr to form CaCrO 4 , thereby altering the oxygen species and enhancing the material’s basic properties. Under adsorption–reaction conditions at 600–650 °C, the optimal BFM achieved an excellent C 2 H 4 selectivity of 96.4 %, attributed to a balanced redox process and improved basicity that facilitate efficient C 2 H 6 conversion and rapid desorption of C 2 H 4 without excessive oxidation. Overall, this work provides new insights into the formulation of BFMs monoliths and highlights the critical role of catalytic surface modification in enhancing C 2 H 4 selectivity in the CO 2 -ODHE reactive capture process.

C2H4 production

Field Validation of Thermoelectric Generation System at Holcim Cement Plant in Alpena, Michigan

Executive Summary Project Background The Industrial Technology Validation (ITV) program aims to identify and demonstrate the performance of new, emerging, and underutilized energy-saving technologies in the industrial sector to help inform decisions to help accelerate their commercialization and deployment, as well as to help make industries more competitive. This ITV demonstration evaluated a thermoelectric generation (TEG) technology at a cement plant, aiming to reduce energy demand in the cement industry. A median cement plant consumes 5.73 million British thermal units per ton of clinker production (resulting in 0.838 metric tons of carbon dioxide [CO₂] emissions per ton of clinker) (Boyd and Zhang 2011, EPA 2021), equivalent to approximately 6.9 trillion British thermal units (TBtu) per year in energy consumption at a cement plant producing 3,300 tons of clinker per day.¹ Collaborating with Holcim, Advanced Thermovoltaic Systems (ATS) developed and deployed a pilot-scale thermoelectric power system to efficiently capture and convert waste heat to electricity. The system leverages the Seebeck effect to convert temperature differences on two sides of semiconductor cartridges into electrical power (ScienceDirect, n.d.). This generation is realized with minimal moving parts compared to existing waste-heat-to-generation solutions and allows capture from heat sources with temperatures as low as 150°C. This project aimed to validate a scalable solution applicable for capturing medium-temperature waste heat, including ambient losses from other high-temperature processes, and high-temperature sources less suitable for other waste-heat-to-power solutions. By recovering this otherwise wasted heat, this project intends to validate improvements to overall process efficiency through reduction in purchased electricity, thereby reducing operational costs while enhancing resiliency and competitiveness. Description and Scope This study evaluated the performance of a TEG system from ATS as a solution to convert waste heat into useful power at a Holcim cement plant in Alpena, Michigan. This plant is a fully integrated cement plant that has been operating since 1907. The facility operates continuously (24/7/365) with approximately 250 employees and five long dry kilns, yielding a total production capacity of 7,852 tons of cement per day (EPA 2023). Currently, the Alpena plant uses waste heat boilers to convert waste heat from the exhaust of each kiln into steam, which drives steam turbine generators. The ATS TEG is being evaluated for its potential to supplement the steam turbines by capturing the remaining lower grade heat. This technology is also being considered for other Holcim plants where steam turbines are not a viable option. ATS installed a pilot-scale TEG unit with an array of 582 individual thermoelectric semiconductor cartridges, of which 573 were operational. The cartridges are sandwiched between 48 hot plates and 49 cold plates. Each cartridge is designed to generate 20 watts (W) of gross power at a hot-side temperature of 240°C and cold-side temperature of 20°C. As such, the total gross generation capacity of the installed system is 11.5 kilowatts (kW) at design conditions. The system configuration for the evaluation was designed to prioritize convenience of installation and minimize disruption to production at the site, while ensuring that the heat required can be obtained for evaluating the TEG system at various operational conditions. To accomplish this, a portion of the steam supplied to Alpena’s steam turbine generation system was diverted to be used as the heat source for the TEG system, while water was supplied to the cold side of the system from nearby Lake Huron. This configuration was designed for the evaluation of the pilot-scale system to assess the performance at different conditions. A commercial-scale system will likely vary from the pilot system depending on typical configurations, including both scale and application. Future commercial applications of the ATS system would involve integrating the system into the exhaust from kiln preheaters, clinker coolers, or radiant heat capture from kiln shells for the heat source. For the cold source, a range of cooling solutions can be considered, including a mechanical cooling system, depending on the location and the application. To increase the generation capacity for commercial applications, the technology provider is working toward developing a commercial-scale TEG system, which would combine multiple TEG units (each similar in design to the pilot system) together. The scope of this evaluation includes the pilot-scale TEG system and all impacted equipment including pumps, controllers, and power handling equipment. Study Objectives The evaluation's goal was to assess the potential of the ATS TEG system to generate useful electrical power by capturing waste heat from cement production kilns. The objectives of this study are to evaluate and verify the following claims made by ATS regarding the pilot-scale system installed at the Holcim Alpena plant. The following design parameters and claims are also outlined in Table ES- 1 and Table ES- 2: • Gross Power: The thermoelectric system converts heat into power to create gross power, the total measured power generated by the system. The 573 active cartridge pilot-scale system is expected to generate 11.5 kW of gross power at the designed hot-side temperature of 240°C and cold-side temperature of 20°C. Power production is dependent on the temperature difference between the heat source (ultimately from the waste heat) and cold temperature supply source. • Net Power: The net power is the total usable power provided to the site by the TEG system after deducting parasitic power loads from the gross generated power. Supplementary equipment is required to operate the TEG system including pumps, controllers, and, in certain anticipated applications, mechanical cooling, which introduce parasitic loads to system operation. After deducting the parasitic loads from the gross power generation, ATS anticipates achieving a net power generation of 7.5 kW from the pilot-scale system. • Thermal Efficiency: The thermal efficiency is the percent of the total heat transferred to the TEG system that is converted to gross power. Historically, TEGs have a thermal efficiency of 2%–5% (DOE 2008). Prior industrial-scale TEG systems, such as the E1 TEG offered by Alphabet Energy, operated at an efficiency of 2.5% (Lamonica, 2014). ATS anticipates achieving an average efficiency of 4.8% or higher in converting heat energy to usable electricity. • Cartridge Performance: The TEG system comprises 573 active individual semiconductor cartridges, each of which generates a portion of the total power. Cartridge optimization and selection is an important design consideration for potential future TEG system design performance. Therefore, understanding the distribution of gross power and efficiency within the pilot system is vital to understanding what is achievable. At a design hot-side temperature of 240°C and cold-side temperature of 20°C, ATS anticipates a cartridge performance of 20 W of gross power per cartridge at an efficiency of 4.8% per cartridge. In addition to evaluating the claimed performance of the TEG pilot-scale unit, the study estimated the potential annual impacts of a scaled-up commercial system used to capture kiln waste heat over annual operations. The evaluation estimated the gross and net annual electric generation achievable by capturing heat from the two proposed tap-in points: the kiln exhaust and the clinker cooler exhaust; see Section 2.1 for details. Two use cases were examined: • Holcim Alpena: The Holcim Alpena site consists of long dry kilns with superheater boilers, which differs from the rest of Holcim’s cement plant portfolio and results in lower waste heat temperatures. The study estimates gross and net annual generation using the superheater boiler exhaust and clinker cooler exhaust, based on 2023 operational data. • Typical Installation: Common cement plants have preheater kilns with higher exhaust temperatures than Holcim Alpena across a range of production rates. The study estimates gross and net annual generation using the preheater exhaust and clinker cooler exhaust, with a sensitivity analysis to account for the typical range of preheater exhaust temperatures, clinker cooler exhaust temperatures, and clinker production rates. Methodology The evaluation methodology followed a measurement and verification (M&V) strategy based on the International Performance Measurement and Verification Protocol Option B through comprehensive measurements and analyses of the affected systems. Evaluation data was collected from March 9 to March 11, 2024, the test period of the pilot TEG system. During the test period, in coordination with the ITV team, the ATS team adjusted system operations to capture the range of variability expected for each of the variables pertinent to performance of the system. The methodology consisted of two parts: evaluating the performance of the pilot unit's TEG system and estimating the annual TEG impact in terms of gross and net power based on a given waste heat profile. First, the evaluation of the thermoelectric generation performance of the pilot unit relative to the claims was performed by analyzing the collected test data. Gross power of the pilot TEG system was directly measured. Net power was determined by deducting the measured parasitic power from the gross power. The gross power generation was compared to heat transferred to the system by the working fluid (which was heated by steam generated from the kiln waste heat) to calculate the thermal efficiency achieved by the system. Performance of individual semiconductor cartridges within the pilot array was also assessed in terms of measured gross cartridge power and calculated cartridge thermal efficiency. The second part of the evaluation estimated the annual TEG impacts in terms of gross power and net power (calculated from the difference between gross power and parasitic power). This analysis comprised development of mathematical regression models for gross power and parasitic power, with assessment of each model’s goodness-of-fit characteristics to ensure satisfaction of statistical requirements. The models predicted the gross power generation, the parasitic load based on the temperature difference between the hot working fluid and the cold-side fluid (cold water from Lake Huron) entering the system, the volumetric flow rate of the cold-side fluid at the inlet, and the volumetric flow rate of the hot working fluid at the inlet. The annual impact analysis considered a theoretical commercial-scale system sized to capture the available waste heat at a cement plant, consisting of linked pilot-scale units that receive heat from a theoretical gas-to-working-fluid heat exchanger. To estimate annual impacts at the Alpena plant, the gross power and parasitic power regression models were applied to the arrays in the theoretical commercial-scale system. The heat supplied to the unit was calculated based on the kiln run time, annual production, kiln exhaust waste heat, and clinker cooler waste heat derived from 2023 Holcim Alpena kiln operational data. Net power impacts were calculated by deducting the resulting parasitic power from the estimated gross power. Inputs for the model were generated from a combination of hourly data, assumed design considerations for TEG system scale-up from the pilot-scale unit, and assumptions regarding TEG system operations. This analysis was then used as the basis for estimating annual impacts of typical TEG installation at cement plants, by applying sensitivity analyses to key kiln operational characteristics including kiln preheater exhaust temperatures, cooler clinker exhaust temperatures, and plant daily production rates across a range of expected values. Project Results/Findings Table ES- 2 and Table ES- 2 provide a summary of the operating conditions and evaluation results compared to the stated claims from the technology provider. Key takeaways include: • Gross Power: The peak gross power achieved during the testing period was 10.0 kW, compared to the 11.5 kW expected for 573 active cartridges. The claimed gross power was associated with a target hot side of 240°C; however, the system only received a maximum hot-side mean plate temperature of 212°C during the testing period. • Net Power: The pilot-scale unit exceeded the claims for net power, achieving a peak of 7.7 kW net compared to a claim of 7.5 kW. One factor contributing to the higher achieved net power is the relatively high water pressure available through Lake Huron. The pilot TEG system did not require cold-side pumps during the test, whereas most installations would. This reduced the parasitic loads on the system, ultimately contributing to higher net power relative to the gross power. • Thermal Efficiency: The pilot-scale unit outperformed the claimed efficiency, achieving a peak system efficiency of 5.0% thermal efficiency compared to the stated 4.8%. • Cartridge Performance: To compare cartridge performance against claims, the study focused on the third day of testing, which aimed for conditions closest to the design specifications, with a hot side of 240°C and cold-side exit temperature of 6.4°–30°C. On this day, the mean gross power observed in the cartridges within the TEG array was 18.1 W/cartridge, and the peak performance was 34.7 W/cartridge. The estimated mean cartridge efficiency was 5.2%, and the estimated efficiency at peak gross cartridge power was 10%. The regression models developed for gross power generation and parasitic loads were used to estimate the generation impact for given heat input to the TEG from the working fluid (captured from the waste heat) and from the cold loop (Lake Huron) on an hourly basis for a year of operation. Based on this analysis, installation of a commercial-scale TEG system at the Holcim cement plant in Alpena, Michigan, with a waste heat exchanger of 0.85 effectiveness, would generate up to 391 kW of net power, translating to between 920,000 and 1,800,000 kilowatt-hours (kWh) in net electricity per year. Based on typical grid emissions for Alpena, this would avoid estimated net emissions by 752 metric tons of CO₂ annually.² The sensitivity analysis estimated that typical TEG system installations at cement plants could generate an average of 56–1,040 kW of net power, or between 488,000 and 9,110,000 kWh of net energy. This generation potential is most significantly affected by plant production rates and also influenced by preheater and clinker cooler exhaust temperatures. Applying the national average emission rate, typical commercial-scale installations at Holcim plants are projected to avoid between 182 and 3,401 metric tons of CO₂ annually per site. Table ES- 3 shows a summary of the estimated annual impacts.³ While parasitic loads are significant and vary by application, this analysis assumed the use of heating loop pumps and access to Lake Huron as a cold sink. This setup assumed no need for cooling loop pumps due to the available water pressure at the test site. Applications that require cooling towers or additional equipment are likely to experience higher parasitic loads. Therefore, the study’s estimates are most applicable to scenarios with similar parasitic load configurations—namely, access to a high-pressure cold sink. Applicability to other locations may be limited, as differing conditions could necessitate additional pumps and cooling systems, potentially impacting performance significantly.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI

Adaptive Scalpel Scanning Probe Microscopy for Enhanced Volumetric Sensing in Tomographic Analysis

Controlling nanoscale tip‐induced material removal is crucial for achieving atomic‐level precision in tomographic sensing with atomic force microscopy (AFM). While advances have enabled volumetric probing of conductive features with nanometer accuracy in solid‐state devices, materials, and photovoltaics, limitations in spatial resolution and volumetric sensitivity persist. This work identifies and addresses in‐plane and vertical tip‐sample junction leakage as sources of parasitic contrast in tomographic AFM, hindering real‐space 3D reconstructions. Novel strategies are proposed to overcome these limitations. First, the contrast mechanisms analyzing nanosized conductive features are explored when confining current collection purely to in‐plane transport, thus allowing reconstruction with a reduction in the overestimation of the lateral dimensions. Furthermore, an adaptive tip‐sample biasing scheme is demonstrated for the mitigation of a class of artefacts induced by the high electric field inside the thin oxide when volumetrically reduced. This significantly enhances vertical sensitivity by approaching the intrinsic limits set by quantum tunneling processes, allowing detailed depth analysis in thin dielectrics. The effectiveness of these methods is showcased in tomographic reconstructions of conductive filaments in valence change memory, highlighting the potential for application in nanoelectronics devices and bulk materials and unlocking new limits for tomographic AFM.

36 MATERIALS SCIENCE

Impacts of Multidimensional Progenitor Perturbations on Core-collapse Supernova Explosions

Numerical studies of core-collapse supernovae have demonstrated the importance of nonradial motions in precollapse progenitors on the explosion outcome. We use the Chimera neutrino radiation hydrodynamics code running seven two-dimensional simulations of 15 M⊙ progenitors with different progenitor structures introduced by different one- and two-dimensional precollapse stellar evolution environments to examine the impacts of stellar structure and nonspherical motion in the precollapse progenitor on the development of explosions. We compare the explosion evolution of these models in terms of shock dynamics, diagnostic energy, neutrino heating, accretion, explosion geometry, nuclear abundances, and turbulent convection. We also analyze how stochastic variation impacts our simulations. Contrary to results reported in prior studies examining the impacts of multidimensional progenitors, we observe similar shock revival times and explosion development in our simulations despite differences in initial compositions and structures. We find no discernible impact from the accretion of nonradial perturbations from a multi-D progenitor onto the stalled shock in the revival and strength of explosion, as fully developed neutrino-driven convection behind the stalled shock is similar for all our models. For models with physically sourced noise in the iron core, a strong oscillation of the shock occurs after bounce and deflects infall laterally, and accelerates the saturation of the lateral turbulent kinetic energy. An examination of model stochasticity shows that any prior expected impacts on explosive outcome due to convection-related perturbations lie below the detectable threshold of numerical variation.

Chen, Chien-Hui [North Carolina State University]

Probing and Tuning Spatiotemporal pH Evolution in Aqueous Zinc Ion Batteries

Aqueous zinc-ion batteries (AZIBs) offer a combination of safety and low cost, but they suffer from dynamic pH fluctuations that drive parasitic reactions and capacity fading. In this review, we report the current mechanistic understanding of the dynamic pH evolution across the electrolyte-electrode interface and its role in triggering interphase instability. We summarize advanced strategies to regulate pH, including electrolyte engineering, electrode surface modification, and interphase construction. We further discuss current methods for probing pH dynamics and outline potential future approaches for gaining deeper mechanistic and design insights.

Zheng, Xueli [SLAC]

Cation valency in water-in-salt electrolytes alters the short- and long-range structure of the electrical double layer

Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI) 2 ], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI) 2 ], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.

Science & Technology - Other Topics

Symmetry‐Breaking Strategy Yields Dopant‐Free Small Molecule Hole Transport Materials for Inorganic Perovskite Solar Cells with 20.58% Efficiency and Outstanding Stability

Abstract Inorganic perovskites are known for their excellent photothermal stability; however, the photothermal stability of all‐inorganic n‐i‐p perovskite solar cells (PSCs) is compromised due to ion diffusion and free radical‐induced degradation caused by the use of doped spiro‐OMeTAD hole transport materials (HTMs). In this study, two isomeric donor–acceptor–donor (D–A–D) type small molecules, namely HBT and HiBT, were developed and used as dopant‐free HTMs, using 2,1,3‐benzothiadiazole or benzo[d][1,2,3]thiadiazole as acceptor moieties. The HiBT molecule, with its symmetry‐breaking features, exhibits a large dipole moment, enhanced coordination‐active sites, and a well‐aligned energy level structure, all of which contribute to passivating perovskite surface defects and improving free charge separation. As a result, inorganic CsPbI 3 PSCs with HiBT HTM achieved an impressive power conversion efficiency (PCE) of 20.58%, the highest reported for dopant‐free HTM‐based inorganic PSCs. Moreover, the enhanced hydrophobic properties of HiBT molecules, coupled with their ability to passivate perovskite surface defects, contribute to significantly improved device stability. The unencapsulated devices based on HiBT HTM retained over 83% and 80% of their initial efficiency after being stored at 85 °C for 50 days and undergoing maximum power point (MPP) tracking at 85 °C for 1100 h, respectively. These results highlight that the symmetry‐breaking strategy is an exceptionally effective approach for designing efficient, dopant‐free small molecule HTMs, significantly contributing to both the high efficiency and enhanced stability of all‐inorganic PSCs.

Chemistry

Pivotal role of organic adsorbates for the creation of catalytic sites during dry reforming of methane

Inadvertent factors can sometimes be crucial for synthesis of catalysts. The use of polyalcohols is common in the synthesis of heterogeneous catalysts. Interactions between alcohols and heterogeneous catalysts have been shown to induce surface reconstructions that greatly impact catalytic performance. Thus, traces of these alcohol functionalities on the as-synthesized catalysts, combined with heat treatment, could be critical in the generation of catalytic sites. Here, we show that during the synthesis of a Ni–Mo/MgO catalyst using a polyol process, residual ethylene glycol (EG) on the surface plays a significant role in the generation of catalytic sites for dry reforming of methane (DRM). The as-synthesized catalyst presents dispersed cationic Ni. Under DRM reaction conditions, the presence of EG, and H2 generated in situ, promote the generation of co-localized Ni–Mo nanoparticles (NPs). Greater amount of EG in the as-synthesized catalyst prevented sintering, leading to better catalyst stability and higher rates. If the residual EG remaining post-synthesis is removed through calcination, before conducting DRM, NiO NPs are formed and the material is completely inactive for catalyzing the reaction. When using a different support, denoted MgO*, EG also proved indispensable to generate active sites, although Ni–Mo co-localization was not evident, and a combination of DRM-related species was needed to activate the catalyst, not just H2. This work systematically uncovers how the interactions between organic adsorbates, the supported metals and the catalyst support dictate the creation of catalytic active sites.

Polo Garzon, Felipe [ORNL] (ORCID:0000000265076183

Update on Radiochemical Assessment of High Burnup Commercially Irradiated Fuel

This work documents an effort to collect burnup measurements on a high burnup rod, designated 6XV, and first cycle accident tolerant fuel (ATF) rod, designated 47I, to enable benchmarking of fuel performance codes and neutronics codes. In addition to measurements, Virtual Environment for Reactor Applications (VERA) full-core-depletion analysis was also performed for the rods that were experimentally analyzed to provide an opportunity for code validation. This effort focuses on collecting data from rods irradiated at Byron Generating Station and shipped to the Oak Ridge National Laboratory (ORNL) hot-cells. This data will also anchor non-destructive examination evaluations of burnup of the various fuel rods undergoing postirradiation examination (PIE) at ORNL. Previous PIE of these fuel rods provides some guidance on the burnup trend across the fuel. Axial gamma spectroscopy scans provide a measure of relative changes in burnup across a fuel pin. Mass spectrometry based burnup measurements performed for this work at specific axial locations in the fuel are fully quantitative. By combining the mass spectrometry data with the gamma scans it is possible to more quantitatively evaluate axial variations in burnup across the entire fuel pin [1]. The combined set of burnup evaluations will be made available to other organizations that have an interest in high burnup radiochemistry data for validation of neutronic simulations and source term evaluation such as the Nuclear Regulatory Commission (NRC).

Harp, Jason [Oak Ridge National Laboratory (ORNL),

First Principles Study of Aluminum Doped Polycrystalline Silicon as a Potential Anode Candidate in Li‐ion Batteries

Addressing sustainable energy storage remains crucial for transitioning to renewable sources. While Li‐ion batteries have made significant contributions, enhancing their capacity through alternative materials remains a key challenge. Micro‐sized silicon is a promising anode material due to its tenfold higher theoretical capacity compared to conventional graphite. However, its substantial volumetric expansion during cycling impedes practical application due to mechanical failure and rapid capacity fading. A novel approach is proposed to mitigate this issue by incorporating trace amounts of aluminum into the micro‐sized silicon electrode using ball milling. Density functional theory (DFT) is employed to establish a theoretical framework elucidating how grain boundary sliding, a key mechanism involved in preventing mechanical failure is facilitated by the presence of trace aluminum at grain boundaries. This, in turn, reduces stress accumulation within the material, reducing the likelihood of failure. To validate the theoretical predictions, capacity retention experiments are conducted on undoped and Al‐doped micro‐sized silicon samples. In conclusion, the results demonstrate significantly reduced capacity fading in the doped sample, corroborating the theoretical framework and showcasing the potential of aluminum doping for improved Li‐ion battery performance.

25 ENERGY STORAGE

Interfacial Adhesion Mechanism of Anionic Polyelectrolyte Brushes Induced by Oppositely Charged Macromolecular Counterions

Abstract Polyelectrolyte brushes are widely used as model systems for investigating electrostatic interactions at soft interfaces and to achieve exceptional lubrication properties. Previous studies have primarily focused on their behavior in the presence of multivalent counterions, which induce brush collapse, ionic crosslinking, and pronounced changes in interfacial structures. However, interactions between polyelectrolyte brushes and oppositely charged macromolecular counterions, such as polycations, remain poorly understood. Here, we prepare well-defined polystyrene sulfonate (PSS) brushes fabricated via surface-initiated grafting and employ surface forces apparatus measurements to investigate their interactions with oppositely charged polycations. In contrast to multivalent ions, polycations do not induce noticeable brush collapse, but instead generate significant adhesion between symmetric PSS brush layers. This adhesion increases with both contact time and applied load, eventually reaching a steady plateau, indicating that the interaction is governed not simply by electrostatic screening but by the gradual formation of polycation-mediated bridging under confinement. Furthermore, the introduction of monovalent Na+ ions disrupts the adhesive interaction even at very low concentrations, suggesting that the bridging function of the adsorbed polycation is highly sensitive to competitive ionic screening. In comparison, measurements with trivalent counterions reveal the expected brush collapse behavior but minimal dependence of adhesion on contact time, highlighting a clear mechanistic distinction from the polymeric counterion case. Collectively, these results demonstrate that molecular size, configurational restriction, and confinement-induced rearrangement, rather than charge valency alone, govern the interaction behavior of macromolecular counterions at brush interfaces. This work provides new insight into the molecular origins of adhesion and the regulation of interfacial interactions in charged polymer brush systems.

Park, Jinwoo [Argonne National Laboratory , , , ,;

Robustness of inertial fusion energy relevant implosions to low-mode asymmetries

Inertial confinement fusion implosions for power production need to be robust. Degradation sources need to be understood and considered for an economic power plant. In this work, the impact of low-mode asymmetries on yield is studied using 2D radiation hydrodynamics simulations for inertial fusion energy relevant implosions. First, a high-gain indirectly driven capsule design is developed. This design is subsequently degraded with low-mode drive asymmetries. The results show that yield is constant with increasing amounts of asymmetry until a cliff is reached where the yield quickly drops below ignition. Robustness arises because the degraded hotspot still has enough time to get to ignition before capsule decompression. This robustness occurs even though the asymmetry couples less energy to the hotspot and causes decompression to occur sooner. The robustness is linked to the generalized Lawson parameter, χ⁠. The value of χ steadily decreases with increasing asymmetry. Once χ is close to one, the hotspot is no longer able to ignite before the capsule decompresses. A simple piston model is used to predict where the robustness cliff is for any design. The trade-off between yield and robustness is also demonstrated.

Physics - Plasma physics

Adsorptive behavior of poly (vinylidene fluoride) membranes for the recovery of lignin-derived hydrophobic deep eutectic solvents

Abstract Recently, membrane technology has gained significant traction as an energy-efficient alternative to traditional thermal processes for solvent recovery. Deep eutectic solvents (DESs) have emerged as sustainable alternatives to conventional organic solvents, yet a systematic methodology for selecting compatible membrane materials for their recovery remains underdeveloped. This study established a predictive framework for membrane material selection in hydrophobic DES applications using Hansen Solubility Parameters (HSP) with inverted criteria targeting materials with relative energy difference (RED) values greater than 1.0. Flat sheet membranes were fabricated via the non-solvent induced phase separation (NIPS) technique. Four NIPS fabricated polymer membranes were evaluated: polysulfone, cellulose acetate, polyvinylidene fluoride (PVDF) fabricated with polyethylene glycol (PEG) as a pore-forming agent, and polybenzimidazole (PBI). The HSP approach successfully predicted membrane-solvent compatibility, with polysulfone (RED = 0.6) and cellulose acetate (RED = 0.9) dissolving completely within 24 h, while PVDF (RED = 1.9) and PBI (RED = 1.1) maintained structural integrity throughout a 7-day exposure period. Furthermore, PVDF demonstrated superior performance with minimal weight gain (3.0%), hydrophobic surface characteristics (122° water contact angle), and enhanced mechanical properties following DES exposure. Comprehensive chemical and morphological characterization confirmed PVDF’s chemical stability and revealed a surface-selective interaction mechanism involving simultaneous PEG (pore-forming agent) extraction and DES component adsorption. Adsorption kinetics followed pseudo-first-order behavior with reversible characteristics, best described by the Temkin isotherm model (R² = 0.9987). PVDF membranes-maintained separation functionality with average lignin rejection (75.2 ± 7.69%) and demonstrated filtration permeability of 2.0 ± 0.34 LMH/bar. This methodology provides a rational approach for membrane selection in emerging solvent systems, contributing to the advancement of sustainable separation technologies for DES-based biomass processing applications.

Science & Technology - Other Topics

The high-valent vanadium chemistry of isoindoline chelates

Isoindoline-based chelates, in particular bis(arylimino)isoindolines, have shown extensive metal binding chemistry. Although this chemistry has been explored for the middle and late transition metal ions, little work has been carried out on early transition metal complexes. In this article, we present the first examples of vanadium coordinated using four bis(arylimino)isoindolines, in which the aryl groups are pyrazole, indazole, benzimidazole, and pyridine (ligands 1–4 , respectively). We isolated five complexes using vanadyl sulfate or vanadyl acetylacetonate as the vanadium source. In all cases, the ligands bound in a meridional mode, and for four of the complexes, the vanadium ion was observed in the V(v) oxidation state. Three of the ligands ( 1–3 ) formed VO 2 complexes with vanadyl sulfate and vanadyl acetylacetonate, but the bis(pyridylimino)isoindoline (ligand 4 ) formed a V(v) oxosulfonato complex with the former starting material and a vanadyl V(iv) acetylacetonate with the latter starting material. All metal compounds were structurally elucidated by X-ray crystallographic methods, and we probed their electronic structures using DFT methods.

Bore, Joan C. [Univ. of Akron, OH (United States)]

Spin‐Polarized Interfaces Redirect CO 2 Reduction From CO to Formate

Achieving high product selectivity in electrocatalytic carbon dioxide reduction (CO 2 RR) remains a critical challenge due to competition between multiple proton-coupled electron-transfer pathways on catalyst surfaces. Meanwhile, chirality-induced spin selectivity (CISS), which enables spin-polarized electron transport through chiral interfaces, has recently emerged as a promising strategy to modulate interfacial electrochemical reactions. Although the CISS effect has been shown to enhance selectivity and efficiency in the spin-sensitive oxygen evolution reaction (OER), its role in regulating CO 2 RR pathways and in stabilizing intermediates remains largely unexplored. Here, chiral molecules (R- and S-1,1′-bi-2-naphthyl-2,2′-diyl hydrogen phosphate, BNP) were integrated with SnO 2 to construct chiral-modified catalysts (R-BNP/SnO 2 and S-BNP/SnO 2 ). Compared with bare SnO 2 and racemic BNP-modified SnO 2 (Rac-BNP/SnO 2 ), the chiral catalysts exhibited a pronounced shift in product selectivity from CO toward formate production. Importantly, in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals that the chiral interface selectively stabilizes the O-bound *OCHO intermediate associated with the formate pathway and modulates interfacial water structure and hydrogen-bonding dynamics. These findings demonstrate that spin-polarized interfacial electron transfer can regulate CO 2 RR pathway selectivity by modulating the stabilization of key intermediates. More broadly, this work establishes chiral spin-selective interfaces as a new strategy for regulating competitive electrocatalytic reaction pathways.

14 SOLAR ENERGY

Patchy nanoparticles by atomic stencilling

Stencilling, in which patterns are created by painting over masks, has ubiquitous applications in art, architecture and manufacturing. Modern, top-down microfabrication methods have succeeded in reducing mask sizes to under 10 nm, enabling ever smaller microdevices as today’s fastest computer chips. Meanwhile, bottom-up masking using chemical bonds or physical interactions has remained largely unexplored, despite its advantages of low cost, solution-processability, scalability and high compatibility with complex, curved and three-dimensional (3D) surfaces. Here we report atomic stencilling to make patchy nanoparticles (NPs), using surface-adsorbed iodide submonolayers to create the mask and ligand-mediated grafted polymers onto unmasked regions as ‘paint’. We use this approach to synthesize more than 20 different types of NP coated with polymer patches in high yield. Polymer scaling theory and molecular dynamics (MD) simulation show that stencilling, along with the interplay of enthalpic and entropic effects of polymers, generates patchy particle morphologies not reported previously. These polymer-patched NPs self-assemble into extended crystals owing to highly uniform patches, including different non-closely packed superlattices. We propose that atomic stencilling opens new avenues in patterning NPs and other substrates at the nanometre length scale, leading to precise control of their chemistry, reactivity and interactions for a wide range of applications, such as targeted delivery, catalysis, microelectronics, integrated metamaterials and tissue engineering.

36 MATERIALS SCIENCE

The effect of gamma ray irradiation on few layered MoSe2: A material for nuclear and space applications

In recent years, emerging two-dimensional (2D) materials, such as molybdenum diselenide (MoSe2), have been at the center of attention for many researchers. This is due to their unique and fascinating physicochemical properties that make them attractive in space and defense applications that include shielding harsh irradiation environments. In this study, we examined the effects of gamma (γ) rays at various doses on the structural, chemical, and optical properties of MoSe2 layers. After the samples were exposed to intense gamma radiation (from a 60Co source) with various exposure times to vary the total accumulated dosage (up to 100 kGy), Raman and photoluminescence spectroscopies were used to study and probe radiation-induced changes to the samples. When compared to pristine materials, very few changes in optical properties were typically observed, indicating good robustness with little sensitivity, even at relatively high doses of gamma radiation. The imaging using scanning electron microscopy revealed a number of nano-hillocks that were connected to substrate alterations. X-ray photoelectron spectroscopies revealed that Mo’s binding energies remained the same, but Se’s binding energies blueshifted. We associated this shift with the decrease in Se vacancies that occurred after irradiation as a result of Mo atoms creating adatoms next to Se atoms. When compared to pristine materials, very few changes in optical, chemical, and structural properties were typically observed. These findings highlight the inherent resilience of MoSe2 in hostile radioactive conditions, which spurs additional research into their optical, electrical, and structural characteristics as well as exploration for potential space, energy, and defense applications.

Materials Science

Dark Energy Survey Year 6 results: Clustering redshifts and importance sampling of self-organized-maps 𝑛⁡(𝑧) realizations for 3 × 2 ⁢pt samples

This work is part of a series establishing the redshift framework for the 3 × 2 ⁢pt analysis of the Dark Energy Survey Year 6 (DES Y6). For DES Y6, photometric redshift distributions are estimated using self-organizing maps (SOMs), calibrated with spectroscopic and many-band photometric data. To overcome limitations from color-redshift degeneracies and incomplete spectroscopic coverage, we enhance this approach by incorporating clustering-based redshift constraints (clustering-z, or WZ) from angular cross-correlations with BOSS and eBOSS galaxies and eBOSS quasar samples. We define a WZ likelihood and apply importance sampling to a large ensemble of SOM-derived 𝑛⁡(𝑧) realizations, selecting those consistent with the clustering measurements to produce a posterior sample for each lens and source bin. The analysis uses angular scales corresponding to 1.5–5 Mpc to optimize signal-to-noise ratio while mitigating modeling uncertainties and marginalizes over redshift-dependent galaxy bias and other systematics informed by the N-body simulation CARDINAL . While a sparser spectroscopic reference sample limits WZ constraining power at 𝑧 >1.1, particularly for source bins, we demonstrate that combining SOM with WZ improves redshift accuracy and enhances the overall cosmological constraining power of DES Y6. As a result, we estimate an improvement in 𝑆 8 of approximately 10% for cosmic shear and 3 ×2⁢pt analysis, primarily due to the WZ calibration of the source samples.

Cosmological parameters