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Results for “pathway engineering”

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

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At least 1,009 records · Page 56
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Quantitative study of the effect of grain boundary parameters on the slip system level Hall-Petch slope for basal slip system in Mg-4Al

Several theoretical studies have reported that the geometry and structure of grain boundaries in polycrystalline materials could impose a significant effect on the Hall-Petch slope. However, experimental observations are primarily limited by the ability of the techniques to accurately quantify the grain boundary strength and validate these theoretical models. Using high-resolution electron backscatter diffraction (HR-EBSD), the local stress tensor ahead of a slip band blocked by a grain boundary was quantified and coupled with a continuum dislocation pile-up model to assess the barrier strength of specific grain boundaries to specific slip systems, referred to as micro-Hall-Petch coefficient. For basal slip system in a deformed Mg-4Al alloy, the micro-Hall-Petch coefficient ($k^{basal}_{μ}$) varied significantly, from 0.054 to 0.184 MPa - m 1/2 for nine different grain boundaries. These results were correlated with geometric descriptors of the respective grain boundaries, with three-dimensional GB profile additionally measured via focused ion beam milling. It was found that the angle between the two slip plane traces on the grain boundary plane was the most sensitive parameter affecting $k^{basal}_{μ}$, followed by the angle between the slip directions. A functional form for calculation of $k^{basal}_{μ}$ depending on these two angles is proposed to augment crystal plasticity constitutive models with slip resistance dependent on some measure of the grain size. The method allows a new pathway to calibrate grain size strengthening parameters in crystal plasticity models, allowing further computational investigations of the interrelationship between texture, grain morphology, and the Hall Petch effect.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Adaptive mesh based combustion simulations of direct fuel injection effects in a supersonic cavity flame-holder

Here, we present high-fidelity reacting simulations of a supersonic cavity flame-holder configuration. The focus of this work is on flame stabilization brought about by varying the location of fuel injection in a cavity stabilized supersonic flow of air. Central to our approach is a compressible multi-species reacting flow solver that uses adaptive-mesh-refinement (AMR), enabling the resolution of flame, shock-waves, boundary-layers, and small-scale structures in the computational domain. Our analysis indicates that fuel injection closer to the ramp at the aft end of the cavity allows for greater mixing and lower peak temperatures compared to fuel injection upstream that is closer to the backward facing step of the cavity. This difference is mainly due to greater turbulent fluctuations generated from the shear-layer towards the cavity ramp, thereby enhancing the mixing of fuel and air. A low frequency oscillatory behaviour in heat-release and pressure was also observed for the upstream injection case while a much higher-frequency phenomena was observed in the near-ramp injection case. By identifying the important physical determinants of the combustion processes, this study illustrates a promising pathway to design and optimize direct fuel injection strategies in supersonic cavity flame-holders that can improve flame stability, combustion efficiency, and reduce emissions.

42 ENGINEERING↗
DOE OSTI2020

Unraveling the influence of non-fullerene acceptor molecular packing on photovoltaic performance of organic solar cells

In non-fullerene organic solar cells, the long-range structure ordering induced by end-group π–π stacking of fused-ring non-fullerene acceptors is considered as the critical factor in realizing efficient charge transport and high power conversion efficiency. Here, we demonstrate that side-chain engineering of non-fullerene acceptors could drive the fused-ring backbone assembly from a π–π stacking mode to an intermixed packing mode, and to a non-stacking mode to refine its solid-state properties. Different from the above-mentioned understanding, we find that close atom contacts in a non-stacking mode can form efficient charge transport pathway through close side atom interactions. The intermixed solid-state packing motif in active layers could enable organic solar cells with superior efficiency and reduced non-radiative recombination loss compared with devices based on molecules with the classic end-group π–π stacking mode. Our observations open a new avenue in material design that endows better photovoltaic performance.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Rapid atom-efficient polyolefin plastics hydrogenolysis mediated by a well-defined single-site electrophilic/cationic organo-zirconium catalyst

Polyolefins comprise a major fraction of single-use plastics, yet their catalytic deconstruction/recycling has proven challenging due to their inert saturated hydrocarbon connectivities. Here a very electrophilic, formally cationic earth-abundant single-site organozirconium catalyst chemisorbed on a highly Brønsted acidic sulfated alumina support and characterized by a broad array of experimental and theoretical techniques, is shown to mediate the rapid hydrogenolytic cleavage of molecular and macromolecular saturated hydrocarbons under mild conditions, with catalytic onset as low as 90 °C/0.5 atm H 2 with 0.02 mol% catalyst loading. For polyethylene, quantitative hydrogenolysis to light hydrocarbons proceeds within 48 min with an activity of > 4000 mol(CH 2 units)·mol(Zr) –1 ·h –1 at 200 °C/2 atm H 2 pressure. Under similar solventless conditions, polyethylene-co–1-octene, isotactic polypropylene, and a post-consumer food container cap are rapidly hydrogenolyzed to low molecular mass hydrocarbons. Regarding mechanism, theory and experiment identify a turnover-limiting C-C scission pathway involving ß-alkyl transfer rather than the more common σ-bond metathesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Ultrafast x-ray scattering of photodissociation dynamics in 2-iodothiophene

Here, a time-resolved x-ray scattering (TRXS) investigation of the photodissociation dynamics of gas-phase 2-iodothiophene molecules following 252 nm excitation is presented. Structural evolution of the molecule and dynamical information on the resulting photofragments were captured using femtosecond x-ray free-electron laser pulses. Two dissociation pathways were identified, arising via excitation to ππ* and (n/π)σ* states, respectively, yielding distinct interfragment recoil velocities of ∼6.4 Åps −1 and 17.0 Åps −1 . A comparison of asymptotic scattering data with simulated patterns indicates that the thiophene ring remains closed following dissociation at this wavelength. Modeling the experimental data yields a branching ratio of ∼3:1 in favor of the high velocity channel. These findings demonstrate the capability of TRXS to disentangle concurrent ultrafast reaction pathways and provide detailed structural insight into energy redistribution during photoinduced bond fission in complex molecular systems.

Razmus, Weronika O. [Univ. of Southampton (United ↗
DOE OSTI2020

Monolithic Two-Terminal All-Perovskite Tandem Solar Cells with Power Conversion Efficiency Exceeding 21%

Monolithic two-terminal (2-T) all-perovskite tandem solar cells are a promising candidate for the next generation solar cells with ultrahigh efficiency and low fabrication cost. Here, we report on the fabrication of 2-T all-perovskite tandem solar cells consisting of solution-processed wide-bandgap and low-bandgap perovskite subcells connected by a vacuum processed interconnection layer. We employed a bulk-passivation strategy to enlarge the grain size, increase carrier mobilities, reduce electronic disorder, and suppress trap-assisted recombination in the low bandgap mixed Sn-Pb perovskite films, which leads to improved performance of low bandgap perovskite solar cells with an absorber thickness over 750 nm. This advance in high-quality low-bandgap perovskite layers enables the fabrication of efficient 2-T all-perovskite solar cells with power conversion efficiencies of more than 21% and decent stability. Our approach provides a suitable pathway to realize ultra-high efficiency 2-T all-perovskite tandem solar cells.

14 SOLAR ENERGY↗
DOE OSTI2022

Integration of physiologically relevant photosynthetic energy flows into whole genome models of light‐driven metabolism

SUMMARY Characterizing photosynthetic productivity is necessary to understand the ecological contributions and biotechnology potential of plants, algae, and cyanobacteria. Light capture efficiency and photophysiology have long been characterized by measurements of chlorophyll fluorescence dynamics. However, these investigations typically do not consider the metabolic network downstream of light harvesting. By contrast, genome‐scale metabolic models capture species‐specific metabolic capabilities but have yet to incorporate the rapid regulation of the light harvesting apparatus. Here, we combine chlorophyll fluorescence parameters defining photosynthetic and non‐photosynthetic yield of absorbed light energy with a metabolic model of the pennate diatom Phaeodactylum tricornutum. This integration increases the model predictive accuracy regarding growth rate, intracellular oxygen production and consumption, and metabolic pathway usage. Through the quantification of excess electron transport, we uncover the sequential activation of non‐radiative energy dissipation processes, cross‐compartment electron shuttling, and non‐photochemical quenching as the rapid photoacclimation strategy in P. tricornutum. Interestingly, the photon absorption thresholds that trigger the transition between these mechanisms were consistent at low and high incident photon fluxes. We use this understanding to explore engineering strategies for rerouting cellular resources and excess light energy towards bioproducts in silico . Overall, we present a methodology for incorporating a common, informative data type into computational models of light‐driven metabolism and show its utilization within the design–build–test–learn cycle for engineering of photosynthetic organisms.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Fatigue Performance of High-Strength Pipeline Steels and Their Welds in Hydrogen Gas Service

Objectives of the project include: Enable the use of high strength steel hydrogen pipelines, as significant cost savings can result by implementing high strength steels as compared to lower strength pipes. Demonstrate that girth welds in high-strength steel pipe exhibit fatigue performance similar to lower-strength steels in high-pressure hydrogen gas. Identify pathways for developing high-strength pipeline steels by establishing the relationship between microstructure constituents and hydrogen-accelerated fatigue crack growth (HA-FCG)

08 HYDROGEN↗
DOE OSTI2025

Enterprise Artificial Intelligence Strategy for Los Alamos National Laboratory

In the 1984 martial arts drama film, The Karate Kid, a young Daniel LaRusso is unexpectedly placed in an adversarial environment unable to eYectively adapt to a series of new threats and limitations. Fortunately for the main character, once placed under the tutelage of a Mr. Miyagi, he finds resiliency not through the adoption of new tools, but a re-focused set of fundamentals. Much in the same way that Daniel learns waxing on and buYing oY car wax by hand has rewards for Karate, LANL is choosing the harder path of self-hosting Large Language Models (LLMs) for enterprise use instead of only relying on buying access to a hosted AI service like Azure’s OpenAI Application Programming Interface (API). We also are not willing to wait for software-as-a-service (SAAS) AI services to meet us where we need to be from a FedRAMP accreditation standpoint. Our operations regularly depend on access at CUI, UCNI, ITAR and other FIPS-199 moderate-impact data levels and hosting our own services gives us the right security and compliance posture to be useful across the broad range of our work at LANL. With the rise in threats to critical infrastructure, cloud service providers (CSPs), and supply chain attacks from both state and non-state actors, we are not placing the bet that SAAS hosted AI services will be available when we need them. Should a major event occur, we do not want our staY and operations left without a pathway for us to fix the problem and resume the use of AI tools.

42 ENGINEERING↗
DOE OSTI2023

Cyanobacteria as cell factories for the photosynthetic production of sucrose

Biofuels and other biologically manufactured sustainable goods are growing in popularity and demand. Carbohydrate feedstocks required for industrial fermentation processes have traditionally been supplied by plant biomass, but the large quantities required to produce replacement commodity products may prevent the long-term feasibility of this approach without alternative strategies to produce sugar feedstocks. Cyanobacteria are under consideration as potential candidates for sustainable production of carbohydrate feedstocks, with potentially lower land and water requirements relative to plants. Several cyanobacterial strains have been genetically engineered to export significant quantities of sugars, especially sucrose. Sucrose is not only naturally synthesized and accumulated by cyanobacteria as a compatible solute to tolerate high salt environments, but also an easily fermentable disaccharide used by many heterotrophic bacteria as a carbon source. In this review, we provide a comprehensive summary of the current knowledge of the endogenous cyanobacterial sucrose synthesis and degradation pathways. We also summarize genetic modifications that have been found to increase sucrose production and secretion. Finally, we consider the current state of synthetic microbial consortia that rely on sugar-secreting cyanobacterial strains, which are co-cultivated alongside heterotrophic microbes able to directly convert the sugars into higher-value compounds (e.g., polyhydroxybutyrates, 3-hydroxypropionic acid, or dyes) in a single-pot reaction. We summarize recent advances reported in such cyanobacteria/heterotroph co-cultivation strategies and provide a perspective on future developments that are likely required to realize their bioindustrial potential.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Addendum 2 to the Closure Report for CAU 577 Area 5 Chromium Containing Waste Disposal Cells, NNSS, Nevada

Corrective Action Unit (CAU) 577, “Area 5 Chromium Containing Waste Disposal Cells,” includes five low-level waste cells at the Nevada National Security Site Area 5 Radioactive Waste Management Site where buried waste received from Nuclear Fuel Services, Inc., was subsequently determined to contain chromium that exceeded the toxicity characteristic leaching procedure regulatory limit, which would require the waste to carry hazardous waste code D007. CAU 577 was created to satisfy the requirements of the Settlement Agreement (SA) executed between the Nevada Division of Environmental Protection (NDEP) and the U.S. Department of Energy, National Nuclear Security Administration Nevada Field Office (NNSA/NFO) on April 25, 2019 (NDEP 2019). The SA required that the chromium-containing waste received from NFS would be addressed following the closure process laid out in the Federal Facility Agreement and Consent Order (FFACO). The FFACO process ensures proper closure of the chromium-containing waste and documentation of that closure through FFACO-type documents. The following three Corrective Action Sites (CASs) were closed, and their closure was documented in the Closure Report for Corrective Action Unit 577: Area 5 Chromium Containing Waste Disposal Cells, Nevada National Security Site, Nevada, DOE/EMNV--0030, dated September 2021 (U.S. Department of Energy [DOE] Environmental Management [EM] Nevada Program 2021a): • CAS 05-21-02, Waste Disposal Cell 12 • CAS 05-21-03, Waste Disposal Cell 15 • CAS 05-21-04, Waste Disposal Cell 17 Closure of the following CAS was previously documented in the Addendum to the Closure Report for Corrective Action Unit 577: Area 5 Chromium Containing Waste Disposal Cells, Nevada National Security Site, Nevada, DOE/EMNV--0030-ADD, dated September 2022 (DOE EM Nevada Program 2022): • CAS 05-21-05, Waste Disposal Cell 20 This second addendum to the Closure Report documents the closure activities that have occurred for CAS 05-21-06, Waste Disposal Cell 21. This is the last CAS in CAU 577. The final waste shipment was placed in the waste disposal cell on November 21, 2022. Following this, closure activities began on November 28, 2022, and were conducted according to the Corrective Action Decision Document/Corrective Action Plan (CADD/CAP) for CAU 577 (DOE EM Nevada Program 2021b). The following closure activities were performed: • Constructing an engineered evapotranspiration cover • Installing two subsidence monuments and vadose zone monitoring equipment • Seeding the cover with a mixture of native plant species • Installing four concrete monuments on the corners of the cover and placing two use restriction (UR) warning signs on each monument These activities fulfill applicable federal and state regulations for closure of CAS 05-21-06 and minimize potential future exposure pathways to buried waste. Completed closure activities are also consistent with closure of the nine historical Resource Conservation and Recovery Act (RCRA) units included in Section 10.2.2 of the RCRA Permit that governs hazardous waste management activities at the Nevada National Security Site (Permit NEV HW0101) (NDEP 2023). UR documentation for this CAS is included in Appendix B of this report. The post-closure plan is presented in detail in the CADD/CAP for CAU 577 (DOE EM Nevada Program 2021b), and the requirements are summarized in Section 5.2 of this document. In accordance with paragraph 5D of the SA, a request to incorporate the requirements for post-closure monitoring of CAU 577 was included with the permit application for RCRA Permit NEV HW0101 that was submitted in January 2022 (NNSA/NFO 2022). The request included the post-closure requirements for the three CASs that had been closed at the time of submittal of the application as well as requirements that would be implemented upon future approval of closure of the remaining two CASs. All CAU 577 post-closure monitoring requirements have been captured in the April 4, 2023, Revision 7 of the RCRA Permit (NDEP 2023). As the RCRA Permit NEV HW0101 has been revised since the submittal of the original CAU 577 Closure Report (DOE EM Nevada Program 2021a) and Addendum 1 (DOE EM Nevada Program 2022), the post-closure requirements in this Addendum 2 report do not align with the previous documents. Specific changes resulting from the issuance of Revision 7 of the RCRA Permit are discussed in Section 5.2 of this report. The requirements in this report are consistent with the current permit (NDEP 2023) and supersede all requirements listed in the CAU 577 Closure Report and Addendum 1. All CAU 577 post-closure requirements should be conducted in accordance with the version of the RCRA Permit that is current at the time of the activities being performed. The DOE EM Nevada Program is requesting a Notice of Completion from NDEP for closure of CAU 577. Although CAU 577 is not a legacy site, the FFACO process is being followed to ensure proper closure of the chromium-containing waste. Therefore, transfer of CAU 577 from Appendix III of the FFACO to Appendix IV, Closed Corrective Action Units, is requested, as all closure activities have been completed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Cradle-to-Grave Lifecycle Analysis of U.S. Medium- and Heavy-Duty Vehicle-Fuel Pathways: A Greenhouse Gas Emissions Assessment of Current (2021) and Future (2035) Technologies

This study presents a cradle-to-grave lifecycle analysis of energy use and greenhouse gas (GHG) emissions for U.S. medium- and heavy-duty vehicles across current (2021) and future (2035) technologies using the Greenhouse gas, Regulated Emissions, and Energy use in Technologies (GREET) model with industry-vetted assumptions. Results vary across vehicle classes but point to common trends: today, battery electric vehicles (BEVs) offer significant (10–60%) GHG emissions reduction compared to diesel internal combustion engine vehicles and are the lowest emissions option per ton-mile of cargo movement, followed by hydrogen fuel cell electric vehicles (FCEVs) (5–50% emissions reduction). Emissions savings depend largely on the duty cycle and fuel economy of the vehicle type. Future vehicle technology advancements result in comparable emission reductions associated with BEVs and hydrogen FCEVs. Weight-limited BEV trucks see less per-ton-mile emissions reduction due to the impact of battery weight on increased vehicle weight and reduced payload capacity. By 2035, improvements in vehicle efficiency can reduce emissions across all powertrains. However, very low levels of emissions require switching vehicles’ use-phase fuel/energy to low-carbon fuels and electricity. Renewable diesel, e-fuels, hydrogen produced from natural gas with carbon capture and storage or renewables, and use of low-carbon electricity can all achieve over 70% reduction in GHG emissions from the current day diesel-based internal combustion engine vehicle.

alternative fuels↗
DOE OSTI2022

Techno-economic performances and life cycle greenhouse gas emissions of various ammonia production pathways including conventional, carbon-capturing, nuclear-powered, and renewable production

Ammonia (NH 3 ) is conventionally produced using fossil natural gas (NG) for hydrogen production through steam reformation and synthesis in the Haber–Bosch (HB) process. The global conventional ammonia production contributes more than 420 million tons of CO 2 emissions annually. Here, in this work, we investigated the techno-economics and well-to-plant-gate (WTG) greenhouse gas (GHG) emissions of conventional NG-based, carbon-capturing, nuclear-powered, and renewable ammonia production by developing an engineering process model for each. Carbon-capturing ammonia production refers to the NG-based ammonia production while capturing CO 2 and transporting it via pipelines for storage or utilization. Nuclear-powered and renewable ammonia production represents an alternative ammonia production through water electrolysis, air separation, and the HB process using carbon-free energy sources. Nuclear and renewable energy sources are assumed to be used for nuclear-powered and renewable ammonia production, respectively. Sensitivity analyses are performed for CO 2 pipeline transport distances, potential carbon capture tax credits, and clean H 2 production cost. Carbon-capturing ammonia production reduces WTG GHG emissions by 55–70% compared to conventional NG-based ammonia production methods. Nuclear-powered and renewable ammonia production almost eliminate GHG emissions since energy supply is either zero carbon or near-zero carbon. However, when $4.16–4.83 per kg is the cost assumed for clean H 2 production using state-of-the-art electrolysis technologies, the levelized costs of nuclear-powered and renewable ammonia are calculated to be $0.92–1.06 per kg NH 3 , which are approximately four times higher than the conventional NG-based ammonia production cost. The cost of CO 2 emission avoidance is estimated in the range of $266–318 per metric ton of CO 2 for nuclear-powered and renewable ammonia production. The clean H 2 production cost is the major contributor to the levelized costs of nuclear-powered and renewable ammonia production. A lower production cost, near $1 per kg H 2 , for clean H 2 is required for nuclear-powered and renewable ammonia production to be cost-competitive with conventional NG-based ammonia production.

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

Mn(III)-mediated bisphenol a degradation: Mechanisms and products

Bisphenol A (BPA) is a high production volume chemical with potential estrogenic effects susceptible to abiotic degradation by MnO 2 . BPA transformation products and reaction mechanisms with MnO 2 have been investigated, but detailed process understanding of Mn(III)-mediated degradation has not been attained. Rapid consumption of BPA occurred in batch reaction vessels with 1 mM Mn(III) and 63.9 ± 0.7% of 1.76 ± 0.02 μmol BPA was degraded in 1 hour at circumneutral pH. BPA was consumed at 1.86 ± 0.09-fold higher rates in vessels with synthetic MnO 2 comprising approximately 13 mol% surface-associated Mn(III) versus surface-Mn(III)-free MnO 2 , and 10–35% of BPA transformation could be attributed to Mn(III) during the initial 10-min reaction phase. High-resolution tandem mass spectrometry (HRMS/MS) analysis detected eight transformation intermediates in reactions with Mn(III), and quantum calculations proposed 14 BPA degradation products, nine of which had not been observed during MnO 2 -mediated BPA degradation, suggesting mechanistic differences between Mn(III)- versus MnO 2 -mediated BPA degradation. Finally, the findings demonstrate that both Mn(III) and Mn(IV) can effectively degrade BPA and indicate that surface-associated Mn(III) increases the reactivity of synthetic MnO 2 , offering opportunities for engineering more reactive oxidized Mn species for BPA removal.

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

Programmable soft valves for digital and analog control

In soft devices, complex actuation sequences and precise force control typically require hard electronic valves and microcontrollers. Existing designs for entirely soft pneumatic control systems are capable of either digital or analog operation, but not both, and are limited by speed of actuation, range of pressure, time required for fabrication, or loss of power through pull-down resistors. Using the nonlinear mechanics intrinsic to structures composed of soft materials—in this case, by leveraging membrane inversion and tube kinking—two modular soft components are developed: a piston actuator and a bistable pneumatic switch. These two components combine to create valves capable of analog pressure regulation, simplified digital logic, controlled oscillation, nonvolatile memory storage, linear actuation, and interfacing with human users in both digital and analog formats. Three demonstrations showcase the capabilities of systems constructed from these valves: 1) a wearable glove capable of analog control of a soft artificial robotic hand based on input from a human user’s fingers, 2) a human-controlled cushion matrix designed for use in medical care, and 3) an untethered robot which travels a distance dynamically programmed at the time of operation to retrieve an object. This work illustrates pathways for complementary digital and analog control of soft robots using a unified valve design.

42 ENGINEERING↗
DOE OSTI2021

Additive Manufacturing of Corrosion Resistant UHTC Materials for Chloride Salt-to-sCO2 Brayton Cycle Heat Exchangers

The objectives of the project include: (1) screen high-purity, high density ultra-high-temperature ceramics (UHTCs) for chloride salt corrosion resistance, (2) develop binder-jet additive manufacturing and sintering for ZrB 2 -MoSi 2 blends using literature and experiments to demonstrate feasibility, and (3) evaluate chloride salt corrosion resistance of additively manufactured ZrB 2 -MoSi 2 . These initial objectives support the development of a durable and reliable ultra-compact high-efficiency salt-to-sCO 2 heat exchanger for closed-loop Brayton power cycles based on corrosion resistant, high-strength, thermally conductive UHTC materials and novel designs enabled by additive manufacturing. The UHTC materials are also abrasion resistant so that they could be applicable to all three thermal carrier media pathways identified in the CSP Gen3 Roadmap.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Investigation of the iodate sorption mechanism by CoAl LDH through experiments and ab initio molecular dynamics simulations

Radioiodine released during the nuclear-fuel cycle constitutes a persistent radiological hazard. In this study, the IO 3 – uptake mechanism of CoAl LDH was resolved by combining pH-controlled sorption experiments, synchrotron XAFS, and DFT-based AIMD simulations. At pH close to 6, approximately 90% of IO 3 – was removed, and the equilibrium distribution coefficient reached about 1.7 × 10 4 mL g –1 . EXAFS analysis indicated an average iodine–oxygen bond length of 1.81 Å and a coordination number near 3, with the fit R-factor equal to 0.002. The simulations faithfully reproduced the experimental spectrum and revealed transient proton hopping events that generated metastable I–O–H species inside the interlayer, thereby confirming nitrate-to-iodate exchange as the controlling capture pathway. Atomic density profiles and radial distribution functions further showed that IO 3 – adopt an end-on orientation perpendicular to the hydroxide sheets, while water molecules mediate proton migration without disturbing the host lattice. In conclusion, the integrated experimental–computational evidence demonstrates that CoAl LDH can rapidly and selectively sequester IO 3 – under near-neutral conditions, offering atomic scale guidance for the rational engineering of layered sorbents for advanced radioactive-waste treatment.

Kang, Jaehyuk [Jeju National Univ. (Korea, Republi↗