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164 records · Page 3

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

Adding multiple electrons to helicenes: how they respond?

An overview of structural responses of helicenes with increasing dimensions and complexity to stepwise electron addition reveals charge- and topology-dependent outcomes ranging from reversible to irreversible core transformations and site-specific reactivity.

Chemistry

A holistic platform for accelerating sorbent-based carbon capture

Abstract Reducing carbon dioxide (CO 2 ) emissions urgently requires the large-scale deployment of carbon-capture technologies. These technologies must separate CO 2 from various sources and deliver it to different sinks 1,2 . The quest for optimal solutions for specific source–sink pairs is a complex, multi-objective challenge involving multiple stakeholders and depends on social, economic and regional contexts. Currently, research follows a sequential approach: chemists focus on materials design 3 and engineers on optimizing processes 4,5 , which are then operated at a scale that impacts the economy and the environment. Assessing these impacts, such as the greenhouse gas emissions over the plant’s lifetime, is typically one of the final steps 6 . Here we introduce the PrISMa (Process-Informed design of tailor-made Sorbent Materials) platform, which integrates materials, process design, techno-economics and life-cycle assessment. We compare more than 60 case studies capturing CO 2 from various sources in 5 global regions using different technologies. The platform simultaneously informs various stakeholders about the cost-effectiveness of technologies, process configurations and locations, reveals the molecular characteristics of the top-performing sorbents, and provides insights on environmental impacts, co-benefits and trade-offs. By uniting stakeholders at an early research stage, PrISMa accelerates carbon-capture technology development during this critical period as we aim for a net-zero world.

Science & Technology - Other Topics

Capturing Secondary Kinetic Instabilities in Three‐Dimensional Dayside Reconnection Using an Improved Gradient‐Based Closure

Magnetic reconnection is a highly dynamic process that excites a wide variety of kinetic waves and instabilities. Transverse current sheet instabilities such as the lower-hybrid drift and secondary drift-kink instabilities in particular have been shown by kinetic simulations to modify the reconnection and introduce significant turbulence and mixing to the reconnection layer. Past studies using the ten-moment fluid model to capture important kinetic physics such as the electron inertia and full representation of the pressure tensor proved advantageous to a two-fluid representation of reconnection, but the model struggled when using a local relaxation closure for the heat flux to replicate the current sheet instabilities and subsequent mixing seen in kinetic simulations. This work uses the Gkeyll software framework to perform simulations of asymmetric reconnection based on the 16 October 2015 MMS crossing of a diffusion region, the Burch event. An improved gradient-based heat flux closure is implemented, showing significant improvement in secondary kinetic instabilities that grow in the current sheet. These instabilities generate turbulence which leads to growth of secondary magnetic islands and flux ropes.

Bradshaw, K. [Princeton University, NJ (United Sta

Trace benzene capture by decoration of structural defects in metal–organic framework materials

Abstract Capture of trace benzene is an important and challenging task. Metal–organic framework materials are promising sorbents for a variety of gases, but their limited capacity towards benzene at low concentration remains unresolved. Here we report the adsorption of trace benzene by decorating a structural defect in MIL-125-defect with single-atom metal centres to afford MIL-125-X (X = Mn, Fe, Co, Ni, Cu, Zn; MIL-125, Ti 8 O 8 (OH) 4 (BDC) 6 where H 2 BDC is 1,4-benzenedicarboxylic acid). At 298 K, MIL-125-Zn exhibits a benzene uptake of 7.63 mmol g −1 at 1.2 mbar and 5.33 mmol g −1 at 0.12 mbar, and breakthrough experiments confirm the removal of trace benzene (from 5 to <0.5 ppm) from air (up to 111,000 min g −1 of metal–organic framework), even after exposure to moisture. The binding of benzene to the defect and open Zn(II) sites at low pressure has been visualized by diffraction, scattering and spectroscopy. This work highlights the importance of fine-tuning pore chemistry for designing adsorbents for the removal of air pollutants.

Chemistry

Evaluating Polymer Properties with Different Additives for Carbon Capture and Other Applications

Anthropogenic climate change is one of this generation’s most pressing concerns, with the potential to completely alter the delicate balance we’ve struck with nature. Already, global temperatures have risen 1.29°C, leading to disrupted weather systems, extinctions, increased risks of wildfires, and sea level rise, to name a few effects. Carbon dioxide emission from the combustion of fossil fuels and other industrial activity is a large driver of this phenomenon, as it absorbs heat before it can be radiated away from Earth, trapping it. Carbon dioxide has reached unprecedented levels in our atmosphere, showing a 50% increase from preindustrial averages to a whopping 430 ppm. Thus, reducing the amount of carbon dioxide via carbon capture technology is an important endeavor that serves to benefit everyone. The Microencapsulated CO 2 Sorbent (MECS) team at Lawrence Livermore National Laboratory (LLNL) has turned to microencapsulation to approach this endeavor. Microcapsules provide an attractive approach to carbon capture, combining large surface areas for more efficient mass transfer, regenerative abilities, reduced solvent loss, and improved handling. Additionally, while existing carbon capture technology relies on industrial plants, capsules could present a modular approach to carbon capture, reducing the need for extensive physical infrastructure. The MECS team’s design consists of a polymer membrane that contains a liquid carbon sequestering sorbent, aqueous sodium carbonate. The carbon capturing reaction occurs in three distinct steps, the first of which is the dissolution of carbon dioxide into the sorbent solution and its conversion into carbonic acid (H 2 CO 3 ), shown in equations 1 and 2 respectively. Because this step hinges upon the ability of carbon dioxide to reach the solution inside the capsule, it is necessary that the microcapsule shell is permeable to carbon dioxide gas. The MECS team produces these microcapsules using the in-air droplet encapsulation apparatus (IDEA) shown in figure 1, which can produce uniform micron-scale droplets at speeds much faster than traditional single-dispersal microfluidic-based techniques. The IDEA Is 100 times faster than these current techniques and can reach up to 1000 times their speed when incorporating a multi-nozzle design. Additionally, because droplets are produced in-air via vibration, IDEA can decrease post-processing times and material waste by 99% and can fabricate microgels that are 10 to 100 times more viscous than can be produced via traditional microfluidics. While this design represents a breakthrough in the throughput, efficiency, and tunability of microcapsule production, it imposes a major constraint on the microcapsule curing process. Because microcapsule shells are crosslinked with UV light while falling 30 cm through the air, this gives them a reaction window of approximately 0.2 seconds. Thus, the system and shell formulations must be optimized such that the shells can be fully crosslinked within this very narrow window, prompting investigations into curing behavior.

36 MATERIALS SCIENCE

Mechanistic origin of solvent-dependent thermal stability in sodiated Sn anodes for sodium-ion batteries

Understanding the thermal stability of high-energy density alloy anodes is critical for the safe deployment of sodium-ion batteries (SIBs). Here, accelerating rate calorimetry (ARC), post-mortem characterizations, and density functional theory (DFT) calculations are combined to understand the thermal reactivity of fully sodiated Sn, Sn-hard carbon (HC) blends, and HC anodes in carbonate- and ether-based electrolytes. ARC measurements show that propylene carbonate (PC) causes earlier self-heating rate (SHR) onset and higher reactivity than tetraethylene glycol dimethyl ether (TEGDME), indicating inferior thermal stability. Sodiated Sn exhibits better thermal stability than sodiated HC, while Sn-HC blends show intermediate behavior that improves with increasing Sn content. Post-ARC analyses reveal desodiation of Na15Sn4 to metallic Sn with particle coalescence, whereas Sn-HC blends and HC retain finer morphologies. PC promotes Sn oxidation to SnO, while TEGDME suppresses oxide formation; NaPF6-containing electrolytes additionally form NaF. DFT calculations show that PC adsorption lowers Na extraction energy and enhances interfacial electronic interactions, facilitating Na release and reductive decomposition. These results establish a direct correlation between solvent-dependent reaction pathways and thermal stability in SIB alloy anodes.

Accelerating rate calorimetry

REDOTHERM (Redox Countercurrent Thermodynamic Limits Model) [SWR-24-88]

REDOTHERM is an open-source, MATLAB-based thermodynamic modeling framework developed to evaluate the performance of redox-active materials for water (H2O) and carbon dioxide (CO2) splitting. It includes models of all major unit operations and supports comparative analysis of different redox-active material candidates. The model is tailored for systems of moving oxide under a parallel/cocurrent flow (PF) and countercurrent flow (CF) configurations. Unvalidated mixed flow reactor (MFR, also known as CSTR) model is also included as an optional addition.

Lidor, Alon [National Renewable Energy Laboratory

H 2 O and CO 2 Sorption in Ion-Exchange Sorbents: Distinct Interactions in Amine Versus Quaternary Ammonium Materials

This article examines how water (H₂O) and carbon dioxide (CO₂) interact with two classes of ion-exchange sorbents — a primary amine sorbent and a quaternary ammonium (QA⁺) sorbent — using calorimetry, thermal gravimetric analysis, gas analysis, and molecular modeling. Here, the QA⁺ sorbent exhibits stronger binding to both H₂O and CO₂ but also shows thermal stability limitations. Mixed-gas experiments reveal that humidity strongly influences CO₂ uptake and that moisture-driven sorbent regeneration enables cyclic moisture swing CO₂ capture, with implications for low-energy CO₂ separation from dilute gas streams.

36 MATERIALS SCIENCE

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

Shakeup and shakeoff spectra in the electron capture decay of atomic 7 Be

The most stringent laboratory-based experimental limits on the existence of submegaelectronvolt sterile neutrinos are currently set by decay spectroscopy of radioactive 7 Be embedded into superconducting sensors. The systematic uncertainties are dominated by the modeling of the electron shakeup and shakeoff spectra that are not based on state-of-the-art atomic theory and do not include electron correlations or relativistic effects. We have used the multiconfiguration Dirac-Fock formalism to obtain correlated wave functions ab initio and compute all single and double shake processes in the electron capture decay of atomic 7 Be . The simulations can explain some but not all of the observed spectral features, likely because the wave functions are modified by the Ta sensor material that the 7 Be is embedded into. The new models also show that the 𝐿/𝐾 electron capture ratio of 7 Be in Ta has previously been slightly underestimated revising the previous value of 0.070(7) to a new value of 0.0756(20).

73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Software Validation Work With The ZPPR-15 Data

The analysis activities for fast reactors involve using many different pieces of software that are relied upon for their predictive capabilities. For this software to be considered reliable, documented proof that the predictions of the software are accurate is required. In this manuscript, the validation work that covers some of the Argonne software used in fast reactor design activities is discussed and displayed. This validation work includes neutron and gamma flux distributions, reaction rate distributions, and reactivity worth. In an ideal world, a reactor development program would have access to a comprehensive set of experimental facilities to help inform the design aspects of the reactor itself. While thermal-hydraulics experiments, and to a limited degree mechanical experiments, can be carried out today for validation needs, neutronics related experimental facilities are rather impractical because of the lack of experimental facilities. Given the desired time table for construction of new reactors, the reconstitution or creation of new neutronic experimental facilities is untenable and thus those reactor development programs must rely upon any available experimental measurements that are qualitatively similar to the design. While a methodology has been proposed to assess the similarity between the past experimental measurements and the reactor itself, that aspect is beyond the scope of this manuscript. In this manuscript, the focus is entirely placed on the analysis results for a series of experiments carried out at the ZPPR facility in Idaho in the mid-1980s. In this regard, this manuscript only shows the validation of the stated neutronics software for specific loadings of the ZPPR reactor. Because of the fuel form, its proposed enrichment, and the material content of the reactor core, the ZPPR-15 experiments were identified as potential validation data for the reactor. The ZPPR-15 experiments were intended as mockups of a 330 MWe Integral Fast Reactor program which was a follow on program to the Clinch River Breeder Reactor. In the ZPPR-15 series of experiments, measurements of the neutron spectrum, control rod worth, sodium void worth, foil reaction rate distributions, Doppler worth of heated samples, gamma dose, and axial expansion worth were all carried out and published. In many cases, these reactivity coefficients are good candidates to validate the reactivity coefficient calculation scheme used by the analysis software and included in the safety analysis activities of fast reactor development projects today. This manuscript discusses the modeling methodology and accuracy of the calculated experimental results using the LANL software MCNP and the ANL software package ARC (Argonne Reactor Codes). As will be shown, for many of the experimental measurements, the two software packages are found to be good predictive analysis tools for those experiments. In other cases, problems with the analysis methodology or underlying cross section data are exposed which indicates where predictive analysis is not as reliable. Finally, in some of the measurements the conclusion is reached that the experimental measurement cannot be reproduced with the analysis software as it is simply too difficult.

Aliberti, Gerardo

A fully light-driven approach to separate carbon dioxide from emission streams

Carbon capture from industrial point sources is an essential component of the global effort to mitigate climate risks. However, traditional approaches require significant energy input—often provided, counterproductively, by fossil fuel combustion. Using sunlight directly as the energy source would significantly improve the energy efficiency of carbon capture processes. Herein, we report the first fully visible-light-driven CO 2 separation system, in which carbon capture is achieved via the photoenolization/addition reaction of inexpensive 2-methylbenzophenone with CO 2 , and CO 2 release is realized through an intramolecular photodecarboxylation reaction. Finally, this system operates isothermally, works with natural sunlight, and facilitates CO 2 removal from natural gas flue emissions, providing a blueprint for other non-thermal chemical separations.

Ahmad, Bayu I. Z. [Cornell Univ., Ithaca, NY (Unit

Smart Droplets Stabilized by Designer Surfactants: From Biomimicry to Active Motion to Materials Healing

The science and technologies of emulsion droplets have been a long‐term focus of extensive research endeavors for their practical utility across a breadth of industries, including pharmaceutical products, oil recovery processes, and the food sciences. However, with advances in materials chemistry and characterization tools, new emerging areas are arising with a focus on “smart droplets”. The versatility of emulsion droplets across is based on their ability to partition and create isolated systems with properties defined by the liquid–liquid interface, while preparative routes allow manipulation of droplet size, stability, and encapsulated contents. As described in this article, significant efforts are being devoted to creating new types of droplets by “activating” this interface through the incorporation of reactive structures that trigger droplet response to applied or environmental stimuli (e.g., pH, temperature, salt, or external fields). Moreover, parallels between droplets and live cells inspire efforts to conceive systems that resemble biological motifs or that can produce cellular behaviors that imitate biology (e.g., swarming, communication, or motion). Here, the authors highlight recent advances in smart droplets, with emphasis on organic, polymer, and/or particle surfactants that give rise to inter‐droplet communication (via aggregation, fusion, division, or mass transfer), droplet vehicles for controlled delivery, autonomous droplet motion, and tunable emulsion inversion. Especially emphasized is the macromolecular design to produce reactive and functional surfactants, which are crucial to responsive droplet behavior and their underlying mechanisms. More generally, the exquisite interplay between materials science and biology inspires the review of this research area that provides unique opportunities for insight and inspiration into the capabilities of new droplet designs.

36 MATERIALS SCIENCE

Direct observation of diamond formation in a shock-compressed high explosive

Understanding the formation timescale and structure of carbonaceous reaction products is critical for modeling the high-pressure equation-of-state of organic materials. We use the National Ignition Facility to shock-compress polycrystalline TATB (C 6 H 6 N 6 O 6 ) samples to ~70–130 GPa and ~4000–5500 K, employing in situ nanosecond X-ray diffraction to probe reaction products and velocimetry to measure transmitted compression wave profiles. Our diffraction data is consistent with the formation of diamond over timescales less than ~60 ns. This represents carbon condensation from a molecular explosive on timescales three times faster than previously reported and the earliest observation of diamond produced from reacting TATB. Reactive flow simulations with explicit chemistry reproduce the observed temporal structure within wave profiles to inform the distribution of P-T states. These findings provide direct evidence of ultrafast diamond formation in a reactive system at extreme conditions and provide new constraints for models of shock and detonation chemistry.

Clarke, Samantha M. [Lawrence Livermore National L

FY26 Progress on Demonstration of a Multiphysics Steady State Capability for Modeling Core Radial Expansion in SFRs

Under the U.S. Department of Energy Office of Nuclear Energy Advanced Modeling and Simulation (NEAMS) Program, an integrated multiphysics approach is being developed to model the core bowing phenomena important to liquid metal-cooled fast reactors. Core bowing is an important passive safety mechanism in liquid metal-cooled fast reactors and involves multiphysics effects including radiation transport, fluid flow, heat transfer, and mechanical response to temperature and flux gradients. This report summarizes recent progress on developing a multiphysics, MOOSE-based workflow to predict core bowing and associated reactivity feedback. Significant new capabilities in the reactor physics code Griffin - sodium backfill and pin power reconstruction for deformed geometries - were applied in this effort. This year’s work included verification, code comparisons, sensitivity studies, and coupled demonstrations that advance the state of MOOSE-based core bowing workflow. Griffin’s sodium backfill capability was verified by demonstrating that its automated treatment of geometry expansion and material-density updates reproduces manual calculations exactly, confirming solid mass conservation and proper coolant backfilling in expanded geometries. Reconstructed pin powers were compared for Griffin’s ductheterogeneous and ring-heterogeneous treatments in single-, seven-, and nineteen-assembly cases, with best agreement observed in lower-leakage configurations and the duct-heterogeneous approach offering substantially lower computational cost. Thermal-hydraulic sensitivity sensitivities showed that MOOSE SCM, SAM, and CFD are expected to produce similar deformation predictions despite variances in their temperature predictions, and that explicit treatment of inter-assembly flow becomes increasingly important as gap flow rate increases. Finally, coupled demonstrations on small multi-assembly configurations using Griffin, MOOSE Solid Mechanics, MOOSE SCM, and Heat Conduction produced physically consistent reactivity feedback from thermal expansion and bowing. The coupled demonstrations simulated grid plate expansion as well as resultant core bowing at full power conditions. Simplifications were made in current workflow, namely the assumption of instantaneous full power conditions following hot zero power, and pre-expanding the Griffin geometry axially due to lack of an axial fuel pin expansion model and temperature feedback to Griffin.

Wozniak, Nicholas

Method of tuning physical properties of thermosets

Polymerization-induced phase separation enables fine control over thermoset network morphologies, yielding heterogeneous structures with domain sizes tunable over 1-100 nm. However, the controlled chain-growth polymerization techniques exclusively employed to regulate morphology at these length scales are unsuitable for most thermoset materials typically formed through step-growth mechanisms. By employing binary mixtures in place of the classic constituents of phase-separating thermosets—resin, curing agent, and secondary polymer—facile tunability over morphology can be achieved through a single compositional parameter. Indeed, this method yields morphologies spanning nano-scale to macro-scale, controlled by the relative reactivities and thermodynamic compatibility of the network components. Due to the connection between chain dynamics and microstructure in these materials, the tunable morphology enables exquisite control over glass transition and other physical and mechanical properties.

Jones, Brad Howard

Enhanced Recovery of Critical Minerals and Geological Hydrogen in The Mine of the Future

invited perspective article: The rapid demand for critical minerals (CMs) and hydrogen (H2) necessitates innovative solutions beyond conventional mining. This study explores enhanced mineral recovery (EMR) and geological hydrogen production (GeoH2) by leveraging the Earth’s subsurface as a reactive platform. Using ultramafic rocks and engineered fluids, the approach simultaneously mobilizes critical resources and produces H2 through natural processes like serpentinization. This paradigm offers a transformative pathway to secure essential materials and diversify energy resources, setting a foundation for the Terrestrial Mine of the Future

Yan, Keju