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1,743 records · Page 49

Overcoming the Entropy Penalty of Direct Air Capture for Efficient Gigatonne Removal of Carbon Dioxide

Atmospheric carbon poses an existential threat to civilization via global climate change. Hundreds of gigatonnes of carbon dioxide must be removed from earth’s atmosphere in the next three decades, necessitating a low-cost, energy-efficient process to extract low concentrations of carbon dioxide for conversion to a stable material permanently stored for thousands of years. In this work, the challenge of removing gigatonnes of CO 2 is described via the scale of effort and the thermodynamics of collecting and reducing this diffuse chemical, the accumulation of which imparts a substantial entropy penalty on any atmospheric carbon capture process. The methods of CO 2 reduction combined with upstream direct air capture (DAC) including absorption, membrane separation, and adsorption are compared with biomass torrefaction and permanent burial (BTB). A Monte Carlo model assesses the mass, energy, and economics of the full process of biomass torrefaction from biomass collection and transport to stable carbon burial to determine that 95% of scenarios could remove carbon for less than $200 per CO 2 -tonne-equivalent. Torrefied carbon is further discussed for its long-term stability and availability at the scale required to substantially mitigate the threat of climate change.

biomass

Enzymatic Nylon Deconstruction: Enzyme Discovery, Engineering, and Opportunities

Nylons are widely used synthetic polyamides valued for their strength, versatility, and durability across diverse applications. However, their petrochemical origin and energy-intensive production underscore the need for efficient, circular solutions. Conventional recycling methods remain limited by incomplete recovery, material degradation, and costly sorting requirements. Enzymatic depolymerization offers a selective, low-energy alternative capable of processing mixed waste streams under mild conditions. While significant progress has been achieved for polyesters, enzymatic degradation of polyamides is still at an early stage. The discovery of nylon hydrolases demonstrated the potential of biological systems to evolve catalysts for synthetic polyamides, yet reported depolymerization yields remain low. These limitations reflect both the structural complexity of nylons and the need for improved enzyme discovery and engineering. In conclusion, this review highlights recent advances, key challenges, and future directions for enzymatic nylon recycling, outlining its potential role enabling mixed polymer waste to be used as a green feedstock for remanufacturing.

Amides

Revealing Hidden Quinones Through Diagnostic MS² Fragmentation of Peptide–Quinone Adducts

Quinones are redox-active components of natural organic matter that mediate electron transfer and influence biogeochemical processes, but many quinones in pyrogenic organic matter (PyOM) remain unresolved because they ionize poorly by mass spectrometry. Here, we present a peptide-tagging approach to improve detection of cysteine-reactive electrophiles in PyOM, with quinones expected to be a dominant subset based on reaction chemistry and selectivity experiments. A cysteine-containing peptide was used to form Michael-addition adducts, enhancing electrospray ionization and enabling untargeted screening by high-performance liquid chromatography-high-resolution tandem mass spectrometry. The method was benchmarked with five quinone standards and applied to extracts from charred plant material as a discovery-level screen for cysteine-reactive targets. We identified 98 quinone-candidate adducts (mean neutral mass ~603 Da), of which more than 70% were not detectable in native MS1 data. Among formula-assigned features, hidden quinone candidates had median (O+N)/C of 0.391 and normalized oxidation state of carbon of -0.281, consistent with relatively low polarity and low oxidation state. These results reveal a previously inaccessible pool of hidden redox-active compounds in PyOM and provide a framework for prioritizing quinone-like electrophiles for confirmation and incorporation into models of fire-driven biogeochemical cycling.

LC-MS/MS

Intrinsic even-odd thickness-driven anomalous Hall effect in epitaxial MnBi2⁢Te4 thin films

We demonstrate precise control of magnetism in MnBi2⁢Te4 thin films through careful synthesis by molecular beam epitaxy, achieving minimal defects and accurate layer thickness control. By optimizing Mn-Bi-Te ratios and growth temperatures, we minimize detrimental self-doping effects and accurately target integer-layer films. X-ray diffraction and reflectivity provide quantitative measures of film quality and thickness. When these macroscale probes of structure and thickness are integrated with magnetotransport measurements, a striking even-odd layer dependence of the anomalous Hall effect is revealed. Odd-layer films exhibit a large hysteresis up to the Néel temperature (∼25K), consistent with noncompensated antiferromagnetism, while even-layer films show minimal response, as expected for an antiferromagnet. The sign of the anomalous Hall effect exhibits a sign reversal for intrinsic magnetism versus magnetism associated with defects. This work identifies critical factors for inducing pure, noncompensated ferromagnetism and reveals the characteristics of the intrinsic anomalous Hall effect in MnBi2⁢Te4, which together is a step toward realizing the zero-field quantum anomalous Hall effect in topological materials.

Mallick, Deb [ORNL] (ORCID:000900005806411X)

High-Density Capacitive Energy Storage in Low-Dielectric-Constant Polymer PMMA/2D Mica Nanofillers Heterostructure Composite

The ubiquitous, rising demand for energy storage devices with ultra-high storage capacity and efficiency has drawn tremendous research interest in developing energy storage devices. Dielectric polymers are one of the most suitable materials used to fabricate electrostatic capacitive energy storage devices with thin-film geometry with high power density. In this work, we studied the dielectric properties, electric polarization, and energy density of PMMA/2D Mica nanocomposite capacitors where stratified 2D nanofillers are interfaced between the multiple layers of PMMA thin films using two heterostructure designs of the capacitors, PMMA/2D Mica/PMMA (PMP) and PMMA/2D Mica/PMMA/2D Mica/PMMA (PMPMP). The incorporation of a 2D Mica nanofiller in the low-dielectric-constant PMMA leads to an enhancement in the dielectric constant, with ∆ε ~ 15% and 53% for PMP and PMPMP heterostructures at room temperature. Additionally, a significant improvement in discharged energy density was measured for the PMPMP capacitor (Ud ~ 38 J/cm3 at 825 MV/m) compared to the pristine PMMA (Ud ~ 9.5 J/cm3 at 522 MV/m) and PMP capacitors (Ud ~ 19 J/cm3 at 740 MV/m). This excellent capacitive and energy storage performance of the PMMA/2D Mica heterostructure nanocomposite may inform the fabrication of thin-film, high-density energy storage capacitor devices for potential applications in various platforms.

Biochemistry & Molecular Biology

Evolution of magnetic bubble domains in the uniaxial ferromaget CeRu 2 Ga 2 B inferred from the Hall effect and ac magnetic susceptibility

We study the Hall effect, AC magnetic susceptibility (χ ac ), and magnetic force microscopy of the uniaxial ferromagnet CeRu 2 Ga 2 B with a centrosymmetric crystal structure. We observe a finite topological Hall effect (THE) within the ordered phase, before the magnetization is polarized by applied field. By comparing the field dependences of the area fraction of the magnetic bubbles, the derivative of χ ac , and the THE signal, we deduce that the magnetic bubbles in CeRu 2 Ga 2 B evolve from the trivial to topological spin texture with field. Our findings enable the expansion of the search for magnetic materials hosting topological spin textures to include uniaxial ferromagnets and open a new possibility to tailor the topological spin texture.

AC magnetic susceptibility

Comparing Thermal Neutron Scintillators for Use With SiPM-Readout Detectors

Scintillator-based thermal neutron detectors for scientific scattering facilities offer an effective combination of large-area coverage and good spatial resolution. At Oak Ridge National Laboratory, silicon photomultiplier (SiPM)-readout Anger cameras using 6 Li glass scintillators have been developed, but the spatial resolution of these detectors is limited by the relatively low light yield of the glass. Recently, several brighter scintillator compositions with sufficient 6 Li concentration have emerged as promising candidates for higher-resolution imaging. Here, in this work, we evaluate five scintillator materials: GS20, LiF/ZnS:Ag, LiF/ZnO:Zn, LiI:Eu, and Cs 2 LiYCl 6 :Ce, each mounted on a SiPM Anger camera. For each scintillator, the neutron detection efficiency, spatial resolution, and count rate capabilities were measured and compared. Each of the new compositions achieved a spatial resolution better than 0.5 mm, compared to 0.66 mm for GS20, with LiI:Eu reaching the best value of 0.32 mm. Although these compositions improve the spatial resolution of the Anger camera, their longer pulse decay times limit their use in high count rate applications, and the camera’s hardware must be optimized for the different properties of the new scintillators.

Neutron detectors

Synthesis and application of thermally responsive nanofiber coatings for overtemperature monitoring

This study presents a one-pot synthesis route to organometallic nanofibers based on copper thiolate, exhibiting distinctive chemical and physical characteristics. Electron microscopy analysis of morphology and composition revealed 2-10 μm-long, 50-90 nm-diameter hollow and non-hollow fibers composed of copper, sulfur, oxygen, hydrocarbon, and chlorine. Thermogravimetric analysis showed a pronounced mass loss within 120°C-135°C. To elucidate the thermal responsive pathways, the nanofibers were characterized before and after heating. X-ray photoelectron spectroscopy indicates that an initially mixed Cu(I)/Cu(II) oxidation states transition to predominantly Cu(I) upon heating. A layer of nanofiber was coated on battery pouch foil and evaluated as a candidate thermally sensitive coating. At elevated temperature (100-130°C), nanofiber coating released volatile organic compounds, sulfide and sulfur dioxide as detected using multiple gas sensors. This thermally responsive gas release/sensing approach provides a potential large-area temperature monitoring strategy, which is particularly relevant where direct temperature measurements of individual batteries is impractical. The results established proof of concept for nanofiber-coated battery pouch foil as overtemperature warning platform that can provide alerts when surface temperatures exceed a critical threshold. More broadly, the ability to form interconnected fiber networks positions copper thiolate nanofiber coatings as promising materials for advanced applications.

Ihala Gamaralalage, Chanaka [ORNL] (ORCID:00000002

Taking three-dimensional x-ray diffraction (3DXRD) from the synchrotron to the laboratory scale

Three-dimensional x-ray diffraction (3DXRD), a rotating x-ray diffraction technique, is a powerful tool for studying the micromechanical behavior of polycrystalline materials, capable of measuring the volume, position, orientation, and strain of thousands of grains simultaneously. However, its application has been historically limited to synchrotron facilities. Here, we present the first demonstration of laboratory-scale 3DXRD (Lab-3DXRD) using a liquid-metal-jet source. Lab-3DXRD achieves accuracy comparable to synchrotron-based 3DXRD, as validated against laboratory diffraction contrast tomography (LabDCT) and synchrotron-3DXRD. Over 96% of the grains detected with Lab-3DXRD are cross-validated, particularly for coarse grains (> ~60 μm), while the results suggest that finer grains should be accessible by taking advantage of high-efficiency detectors. We further demonstrate that its sensitivity to finer grains is enhanced by incorporating pre-characterization into the analysis. This study establishes Lab-3DXRD as a practical alternative to synchrotron techniques, making 3DXRD accessible to a wider range of academic and industrial researchers.

characterization and analytical techniques

Fracture Analysis of Cohesive Zone Models for Modeling Residual Stress Induced Delamination in Composite Structures

A fracture study of coupon-scale composite cylinders with embedded defects was conducted with an objective to assess and validate a modeling approach using two available cohesive material models. The study included experimental and simulation evaluations of initiation of crack growth and progression. Interrupted thermal experiments used acoustic emissions monitoring to identify the onset of crack progression during each cooling interval and ultrasonic scanning provided images of defect growth. Verification, validation, and uncertainty quantification (VVUQ) processes were performed in the assessment of the simulation predicted temperature at which crack propagation begins (quantity of interest). The Sobol sensitivity analysis identified the hoop direction elastic modulus in the carbon fiber reinforced polymer (CFRP) plies as the most influential parameter for simulations using both cohesive models, accounting for at least 70% of the variation in the temperature at crack propagation. The UQ temperature range for the Tvergaard-Hutchinson model was higher (more conservative) than the experimental acoustic measurement indicators of crack progression, while the temperature range for the Thouless-Parmigiani model enveloped the experimental data points for the primary defect size of 0.75 x 1 in. The simulations could not capture the stable crack growth indicated in the experiments. This is likely due to the models’ inability to represent anisotropic fracture toughness attributed to the structure of the orthotropic fiber weave in a woven composite laminate.

42 ENGINEERING

Preliminary Assessment for the Electric Load Shifting Potential of Integrating Thermal Energy Storage with Heat Pumps in Residential Buildings in Texas of United States

The widespread adoption of electric-driven heat pumps for heating and cooling is expected to significantly increase electric demand. Cooling electric demand will result in an increase in peak hours electric loads, placing additional strain on the grid during peak hours. This challenge, combined with the current rapidly increasing demand from data centers, exacerbates the electric demand duck curve problem. Integrating thermal energy storage (TES) with heat pump can shift electric use for heating and cooling from peak to off-peak hours of the electric grid, which can help flatten the daily electric demand profile of a building. This paper presents a novel design that integrates heat pump with TES (HP-TES), which uses phase change materials (PCM). Heat pump charges TES by melting or freezing PCM during off-peak hours when there is no thermal demand from the building. TES is then discharged (i.e., by freezing or melting PCM) during peak hours to provide a more favorable heat source or heat sink for the heat pump to meet the thermal demand of the building with lower electricity use than conventional air-source heat pumps. Computer simulations were developed to predict the performance of HP-TES applied to a typical single-family house in the US. The building-level simulation results were scaled up to preliminarily assess the aggregated impacts of deploying HP-TES across all single-family houses in Texas of the United States, including reduction of peak demand of the electric grid.

Anees, Fady [ORNL]

Dynamic Oscillation and Motion of Oil‐in‐Water Emulsion Droplets

The interplay of interfacial tensions on droplets results in a range of self‐powered motions that mimic those of living systems and serve as a tunable model to understand their complex non‐equilibrium behavior. Spontaneous shape deformations and oscillations are crucial features observed in nature but difficult to incorporate in synthetic artificial systems. Here, we report sessile oil‐in‐water emulsions that exhibit rapid oscillating behavior. The oscillations depend on the nature and concentration of the surfactant, the chemical composition of the oil, and the wettability of the solid substrate. The rapid changes in the contact angle per oscillation are observed using side‐view optical microscopy. We propose that the changes in the interfacial tension of the oil droplets is due to the partitioning of the surfactant into the oil phase and the movement of self‐emulsified oil out of the parent droplets giving rise to the rhythmic variation in droplet contact‐line. The ability to control and understand droplet oscillation can help model similar oscillations in out‐of‐equilibrium systems in nature and reproduce biomimetic behavior in artificial systems for various applications, such as microfluidic lab‐on‐a‐chip and adaptive materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Thermodynamics of Tritium Trapping by Point Defects at Interfacial Cr-based Phases of the Al Coating

Density functional theory (DFT) simulations have been carried out to evaluate the potential for tritium trapping by metal vacancies in four phases Cr-containing phases (i.e., Cr3Si, Al0.3Cr0.7, Al8Cr5-HT, and Al8Cr5) identified near the interface between the Al coating and 316 stainless steel (316 SS) cladding. In addition, an ab initio thermodynamics approach has been employed to predict the temperature and T2-partial pressure dependence on the thermodynamics of singly tritiated defects. Key results in this work suggest that metal vacancies in the four phases have the potential to favorably trap tritium species, especially Si vacancies in Cr3Si phase. This overall thermodynamic trend can be correlated to the energy cost of having an interstitial tritium in the lattice, which has been calculated to range from 0.17 eV in Al8Cr5-HT to 0.89 eV in Cr3Si. A comparison of the results from this study with previous theoretical works investigating tritium behavior in other Fe-Al phases identified in the aluminide coating, suggests that metal vacancies are generally able to trap tritium in various Fe-Al aluminide phases. Especially, it was found that Si and Al vacancies would be the most efficient to trap for tritium, followed by Cr vacancies, then Fe and Ni vacancies. In the four Cr-based material phases investigated in this work, it is interesting to note that, in the absences of Fe or Ni species, strong interactions between tritium and the metal vacancies are always occurring by the formation of preferential Cr—T bonds (i.e., no Si—T or Al—T bonds were formed).

Sassi, Michel J.

In situ studies on heavy ion irradiation and partial oxidation induced stacking faults and nanograins in tungsten nanolaminates

Understanding the microstructural evolution of tungsten (W) under extreme irradiation environments is critical for its application as a plasma-facing material in future fusion reactors. Heavy ion irradiation study offers expedited damage accumulation and thus allows irradiation tolerance property prediction in a short period of time. In this study we explore in situ Kr ion irradiation of W nanolaminates at 800 °C and uncover a complex interplay of irradiation-induced transformations, including the emergence of stacking faults, nanograin formation, and generation of thickened grain boundaries defined as GB regions with the thickness of up to 15 nm. High-resolution transmission electron microscopy studies reveal the formation of extended planar faults and a metastable hexagonal close-packed (hcp) phase within the body-centered cubic (bcc) matrix. These structural transitions are facilitated by irradiation-induced shear. They are further stabilized by the presence of oxygen, which promotes stacking fault formation and vacancy trapping. Elevated temperatures enhance defect mobility, enabling dynamic recrystallization into ultrafine grains and the thickening of GBs due to defect absorption and impurity segregation. These findings unravel non-equilibrium phase transformation pathways in heavy ion irradiated W and highlight the critical role of impurity-mediated defect dynamics in governing its radiation tolerance properties.

Wazeer, Adil [Purdue University]

Intrinsically Conductive {pi}‑d Conjugated Layers with Co–N4 Active Sites for Efficient Nitrate Electrocatalysis and Zinc-Nitrate Batteries

Electrochemical synthesis of ammonia from nitrate has been extensively investigated as a potential alternative to the energy-intensive Haber-Bosch process. This approach not only operates under ambient conditions but also simultaneously removes nitrate contaminants while producing ammonia as a value-added product. However, the ongoing quest lies in designing an efficient electrocatalyst that achieves a high ammonia yield rate, high selectivity, and long-term stability. Herein, we report the outstanding performance of a Co–N4 coordinated π-d layered Co3(HITP)2 (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) in nitrate electrocatalysis. The unique combination of abundant Co–N4 active sites and superior electrical conductivity enables significant electrocatalytic activity, delivering a maximum ammonia yield rate of 56.8 mg cm–2 h–1 at −0.8 V vs RHE and a Faradaic efficiency of ∼91% at −0.4 V vs RHE. Mechanistic analysis reveals that alkaline conditions accelerate water dissociation to generate adsorbed hydrogen intermediates (H*), which are utilized by Co–N4 sites to drive the stepwise hydrogenation of nitrate to ammonia while suppressing competing hydrogen evolution reaction (HER) pathways. Furthermore, integration of this catalyst into a zinc-nitrate battery resulted in a maximum power density of 5.3 mW cm–2 and an open-circuit potential of ∼1.45 V. These results highlight the potential of π-d conjugated Co–N4 materials as an efficient catalyst for both environmental remediation and energy conversion.

Namvar, shahrirar

Development of an Amine Oxide Polyzwitterion Brush Martini Model with Polarizable Water and Ions

Abstract In order to accurately simulate the fouling process of proteins onto polyzwitterion brushes, models that accurately capture the hydration properties and chain conformations of such brushes must first be established. We developed a Martini coarse-grained (CG) model for amine oxide polyzwitterion (PNOMA) brushes, a promising class of antifouling materials, in polarizable water and ions by fitting to all-atom bond and angle distributions, monomer hydration free energy, monomer–monomer distance potential of mean force (PMF), and monomer–salt radial distribution functions (RDFs). Martini 2.2P was selected for compatibility with the established polarizable water and ion models. For comparison with PNOMA, we also constructed models for conventional sulfobetaine (PSBMA) and phosphorylcholine (PMPC) polyzwitterions and the polycation PMETAC using established nonbonded bead types from the literature and refitting bond and angle potentials. We simulated each polymer brush chemistry for varying grafting density and chain length, validating brush height scaling relations against experimental data. The CG models captured the relative hydration strengths among different polyzwitterion chemistries, and brush heights extrapolated to higher molecular weights are in agreement with experimental ellipsometry data. We find that chain swelling of the superhydrophilic PNOMA brushes lies between that of the traditional polyzwitterions PSBMA/PMPC and the polycation PMETAC. For PNOMA brushes in NaCl solution, simulated brush height decreases with salt concentration due to the selectively strong interactions between amine oxide and sodium ions.

Walker, Christopher C. [Oak Ridge National Laborat

Echo state network for coarsening dynamics of charge density waves

An echo state network (ESN) is a type of reservoir computer that uses a recurrent neural network with a sparsely connected hidden layer. Compared with other recurrent neural networks, one great advantage of ESN is the simplicity of its training process. Yet, despite the seemingly restricted learnable parameters, ESN has been shown to successfully capture the spatial-temporal dynamics of complex patterns. Here we build an ESN to model the coarsening dynamics of charge-density waves (CDWs) in a semiclassical Holstein model, which exhibits a checkerboard electron density modulation at half-filling stabilized by a commensurate lattice distortion. The inputs to the ESN are local CDW order parameters in a finite neighborhood centered around a given site, while the output is the predicted CDW order of the center site at the next time step. Special care is taken in the design of couplings between hidden layer and input nodes to ensure lattice symmetries are properly incorporated into the ESN model. Since the model predictions depend only on CDW configurations of a finite domain, the ESN is scalable and transferrable in the sense that a model trained on dataset from a small system can be directly applied to dynamical simulations on larger lattices. Furthermore, our work opens avenues for efficient dynamical modeling of pattern formations in functional electron materials.

2-dimensional systems

Fingerprinting Uranium Oxides with Electron Energy Loss Spectroscopy Supported by Theoretical Computations

Uranium oxides occur in a variety of phases that differ in crystal structure and uranium oxidation states. Electron energy loss spectroscopy (EELS) is one of the few techniques that has sufficient spatial resolution and sensitivity to electronic structure to distinguish amongst phases at the nanoscale. However, beam-sensitive materials such as uranium oxides are subject to spectral modification due to interactions with the electron beam. Therefore, theory support is essential to reliably exclude the impact of beam damage and generate true reference datasets. Here we use a comparison of theoretical and experimental spectra to probe the impact of beam damage on O K-edge and U N-edge (N6,7 and N4,5) EELS spectra of various single-valent and mixed-valence uranium oxide bulk phases. Using a low-dose experimental set-up, we show that the O K-edge theoretical spectra are in excellent agreement with experiment for both peak positions and relative intensities of respective peaks. In contrast, U N-edge features are less distinguishing due to the partially localized nature of the U 5f orbitals and overlapping multiplet and spin–orbit coupling effects. This work demonstrates that O K-edge EELS is sufficiently diagnostic to distinguish a wide range of uranium oxides and that the experimental approach used here minimizes beam damage and allows valence state discrimination across the U(IV), U(V) and U(VI) series. When combined with imaging modes available in electron mi-croscopy, the work enables detailed investigation and characterization of uranium redox transformations at the nanoscale.

Carbone, Jacopo