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NASA NTRS1992

Convective and morphological instabilities during crystal growth: Effect of gravity modulation

During directional solidification of a binary alloy at constant velocity in the vertical direction, morphological and convective instabilities may occur due to the temperature and solute gradients associated with the solidification process. The effect of time-periodic modulation (vibration) is studied by considering a vertical gravitational acceleration which is sinusoidal in time. The conditions for the onset of solutal convection are calculated numerically, employing two distinct computational procedures based on Floquet theory. In general, a stable state can be destabilized by modulation and an unstable state can be stabilized. In the limit of high frequency modulation, the method of averaging and multiple-scale asymptotic analysis can be used to simplify the calculations.

Coreill, S. R.↗
DOE OSTI2024

DECOVALEX-2023: Task F1 Final Report

DECOVALEX-2023 Task F is a comparison of models and methods for post-closure performance assessment (PA) of a deep geologic repository for radioactive waste. The general aims of Task F are to build confidence in the models, methods, and software used for PA and to stimulate additional research and development in PA methodologies. The task objectives are to motivate development of PA modelling skills and capabilities, to examine the influence of model choices on calculated repository performance, and to compare the uncertainties introduced by model choices to other sources of uncertainty. Task F involves no actual experiment or site. It is a PA modelling exercise that requires the conceptual development of hypothetical repository designs and geologic settings. Because three of the teams were interested in salt and the rest of the teams were interested in crystalline rock, Task F was split into two branches: Task F1 for crystalline rock and Task F2 for salt. This report is for Task F1, crystalline rock. Teams from seven countries (Canada, Czech Republic, Germany, Korea, Sweden, Taiwan, and United States) participated in Task F1. The teams worked together to define the features, events, and processes of the reference case repository and established a set of performance measures. In addition, they defined a set of benchmark problems designed to test and compare modelling capabilities for fracture flow and transport at different scales. The repository design and benchmark problems are documented in a Task Specification that evolved over time as the group honed the specifications. The benchmark problems verified that each team can aptly model flow and transport in fractured media in 1-, 2-, and 3-dimensions. Two general approaches were used for the 3-dimensional benchmarks: discrete fracture network (DFN) and equivalent continuous porous medium (ECPM). DFN modelling involves explicit meshing of each fracture while ECPM modelling aims to capture the effective porosity and directional permeability of each cell in a space-filling mesh as affected by intersecting fractures. In some models, a combination of the two is used, i.e., DFN for large known fractures and ECPM for the rest of the domain. Transport is solved by using either the advection-dispersion equation or particle tracking. Although some variation is observed among model breakthrough curves in the benchmark problems, there is strong agreement in breakthrough behaviour up to at least the 75 th percentile for all benchmarks. At the 90 th percentile, breakthrough results show larger differences, suggesting several models retain substantially higher fractions of tracer in regions of slower moving water. In addition to the flow and transport benchmarks, several teams completed the source term benchmark, verifying capabilities for modelling radionuclide decay and ingrowth, waste package breach, instant release fractions, fuel matrix degradation rates, and radionuclide solubility limitations. The reference case is conceptualized as a generic spent fuel repository at a depth of 450 m in fractured crystalline rock. The repository has 50 parallel backfilled drifts, each with 50 deposition holes 6 m apart. Each deposition hole contains a 4-PWR waste package and bentonite buffer. The rock domain is 5 km in length, 2 km in width, and 1 km in depth. It has 6 deterministic fractured deformation zones and a multitude of stochastic fractures. Teams generally used the ECPM approach for the entire rock or a hybrid approach in which the deterministic fracture zones are modelled with a DFN and the rest of the rock is modelled by ECPM. Of the reference case problems specified, only the results of the initial reference case problem are compared in this report. The initial problem focuses on transport from the deposition holes to the surface, i.e., it neglects waste package performance. Tracers are released at all waste package locations at time zero and tracked for their releases to the near field and ground surface. The water fluxes calculated at the ground surface entry and exit regions of the domain are similar for all models except for two that have considerably lower fluxes. For tracer transport, large differences are observed among models in the magnitude of tracer transported. Much of the difference appears to be due to how the repository is implemented and hence the different degrees of repository simplification. Models that exclude the drifts, buffer, and backfill from the domain tend to show greater release of tracers and radionuclides from the repository. The initial study presented here indicates that major differences in modelling important processes within the repository (e.g., diffusion through buffer and backfill) can produce broadly different release and transport results, especially when those processes are excluded. Even for the models that included all specified features, events, and processes, the results show significant differences and demonstrate the importance of examining multiple modelling approaches in performance assessment. The differences in results observed in this study are expected to motivate teams to either increase complexity in future versions of the reference case models or to improve methods to account for the effects of simplified features and processes. Either way, future improvements in these models are expected to produce results that more closely agree.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1999

Environmental Conditions and Threatened and Endangered Species Populations near the Titain, Atlas, and Delta Launch Complexes, Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects. These could occur from direct impacts of launches or indirectly from habitat alterations. This report summarizes a three-year study (1995-1998) characterizing the environment, with particular attention to threatened and endangered species, near Delta, Atlas, and Titan launch facilities. Cape Canaveral has been modified by Air Force development and by 50 years of fire suppression. The dominant vegetation type around the Delta and Atlas launch complexes is coastal oak hammock forest. Oak scrub is the predominant upland vegetation type near the Titan launch complexes. Compositionally, these are coastal scrub communities that has been unburned for greater than 40 years and have developed into closed canopy, low-stature forests. Herbaceous vegetation around active and inactive facilities, coastal strand and dune vegetation near the Atlantic Ocean, and exotic vegetation in disturbed areas are common. Marsh and estuarine vegetation is most common west of the Titan complexes. Launch effects to vegetation include scorch, acid, and particulate deposition. Discernable, cumulative effects are limited to small areas near the launch complexes. Water quality samples were collected at the Titan, Atlas, and Delta launch complexes in September 1995 (wet season) and January 1996 (dry season). Samples were analyzed for heavy metals, chloride, total organic carbon, calcium, iron, magnesium, sodium, total alkalinity, pH, and conductivity. Differences between fresh, brackish, and saline surface waters were evident. The natural buffering capacity of the environment surrounding the CCAS launch complexes is adequate for neutralizing acid deposition in rainfall and launch deposition. Populations of the Florida Scrub-Jay (Aphelocoma coerulescens), a Federally- listed, threatened species, reside near the launch complexes. Thirty-seven to forty-one scrub-jay territories were located at Titan, Atlas, and Delta launch complexes between 1995 and 1997. No direct impacts to scrub-jays were observed as a result of normal launches. The explosion of the Delta rocket in January 1997 caused direct impacts to the habitat of several scrub-jays families, from fire and debris; however, no scrub-jay mortality was observed. Mortality exceeded reproductive output at all areas over the course of the study. Populations of the southeastern beach mouse (Peromyscus polionotus niveiventris) populations, a Federally listed, threatened species, reside near all the launch complexes. Hurricane Erin and several other tropical storms impacted several areas at the inception of the study in 1995 causing coastal habitat alterations as a result of salt-water intrusion. Both the habitat and the beach mice populations recovered during the course of the study. No direct impacts to southeastern beach mice were observed as a result of normal launch operations. Direct impacts were observed to the habitat as a result of the explosion of the Delta rocket in January 1997. This alteration of the habitant resulted in a shift in use with the mice moving on to the newly burned part of the site. Waterbirds use wetlands and aquatic systems near the launch complexes. Species include the Federally-listed, endangered Wood Stork (Mycteria americana) and several state-listed species of special concern including the Snowy Egret (Egretta thula thula), Reddish Egret (Egretta rufescens rufescens), White Ibis (Eudocimus albus), Roseate Spoonbill (Ajaia ajaja), Tricolored Heron (Egretta tricolor ruficolis), and Little Blue Heron (Egretta caerulea). No impacts to these populations resulting from any launch operations were observed. Gopher tortoises (Gopherus polyphemus) also occur around the launch complexes. Most of those observed appeared to be in good condition; however, upper respiratory tract disease is known to occur in the population. Cape Canaveral Air Station, including areas near active launch complexes, remains important habitat for a variety of native plants and animals including threatened and endangered species. Direct negative effects of current launch systems appear limited. Additional monitoring of these populations and habitats is required to determine if subtle, long-term changes are occurring, to determine if new launch systems and facilities cause other effects, and to determine the effects of habitat restoration and management.

Oddy, Donna M.↗
NASA NTRS1999

Environmental Conditions and Threatened and Endangered Species Populations near the Titan, Atlas, and Delta Launch Complexes, Cape Canaveral Air Station

Launches of Delta, Atlas, and Titan rockets from Cape Canaveral Air Station (CCAS) have potential environmental effects. These could occur from direct impacts of launches or indirectly from habitat alterations. This report summarizes a three-year study (1 995-1 998) characterizing the environment, with particular attention to threatened and endangered species, near Delta, Atlas, and Titan launch facilities. Cape Canaveral has been modified by Air Force development and by 50 years of fire suppression. The dominant vegetation type around the Delta and Atlas launch complexes is coastal oak hammock forest. Oak scrub is the predominant upland vegetation type near the Titan launch complexes. Compositionally, these are coastal scrub communities that has been unburned for > 40 years and have developed into closed canopy, low-stature forests. Herbaceous vegetation around active and inactive facilities, coastal strand and dune vegetation near the Atlantic Ocean, and exotic vegetation in disturbed areas are common. Marsh and estuarine vegetation is most common west of the Titan complexes. Launch effects to vegetation include scorch, acid, and particulate deposition. Discernable, cumulative effects are limited to small areas near the launch complexes. Water quality samples were collected at the Titan, Atlas, and Delta launch complexes in September 1995 (wet season) and January 1996 (dry season). Samples were analyzed for heavy metals, chloride, total organic carbon, calcium, iron, magnesium, sodium, total alkalinity, pH, and conductivity. Differences between fresh, brackish, and saline surface waters were evident. The natural buffering capacity of the environment surrounding the CCAS launch complexes is adequate for neutralizing acid deposition in rainfall and launch deposition. Populations of the Florida Scrub-Jay (Aphelocoma coerulescens), a Federally-listed, threatened species, reside near the launch complexes. Thirty-seven to forty-one scrub-jay territories were located at Titan, Atlas, and Delta launch complexes between 1995 and 1997. No direct impacts to scrub-jays were observed as a result of normal launches. The explosion of the Delta rocket in January 1997 caused direct impacts to the habitat of several scrub-jays families, from fire and debris; however, no scrub-jay mortality was observed. Mortality exceeded reproductive output at all areas over the course of the study. Populations of the southeastern beach mouse (Peromyscus polionotus niveiventris) populations, a Federally listed, threatened species, reside near all the launch complexes. Hurricane Erin and several other tropical storms impacted several areas at the inception of the study in 1995 causing coastal habitat alterations as a result of salt-water intrusion. Both the habitat and the beach mice populations recovered during the course of the study. No direct impacts to southeastern beach mice were observed as a result of normal launch operations. Direct impacts were observed to the habitat as a result of the explosion of the Delta rocket in January 1997. This alteration of the habitat resulted in a shift in use with the mice moving on to the newly burned part of the site. Waterbirds use wetlands and aquatic systems near the launch complexes. Species include the Federally-listed, endangered Wood Stork (Mycferia americana) and several state-listed species of special concern including the Snowy Egret (Egretfa thula fhula), Reddish Egret (Egreffa rufescens rufescens), White Ibis (Eudocimus albus), Roseate Spoonbill (Ajaia ajaja), Tricolored Heron (Egreffa tricolor ruficolis), and Little Blue Heron (Egreffa caerulea). No impacts to these populations resulting from any launch operations were observed. Gopher tortoises (Gopherus polyphemus) also occur around the launch complexes. Most of those observed appeared to be in good condition; however, upper respiratory tract disease is known to occur in the population. Cape Canaveral Air Station, including areas near active launch colexes, remains important habitat for a variety of native plants and animals including threatened and endangered species. Direct negative effects of current launch systems appear limited. Additional monitoring of these populations and habitats is required to determine if subtle, long-term changes are occurring, to determine if new launch systems and facilities cause other effects, and to determine the effects of habitat restoration and management.

Oddy, Donna M.↗
DOE OSTI2024

Agent-Based Model of Combined Community- and Jail-Based Take-Home Naloxone Distribution

Importance Opioid-related overdose accounts for almost 80 000 deaths annually across the US. People who use drugs leaving jails are at particularly high risk for opioid-related overdose and may benefit from take-home naloxone (THN) distribution. Objective To estimate the population impact of THN distribution at jail release to reverse opioid-related overdose among people with opioid use disorders. Design, Setting, and Participants This study developed the agent-based Justice-Community Circulation Model (JCCM) to model a synthetic population of individuals with and without a history of opioid use. Epidemiological data from 2014 to 2020 for Cook County, Illinois, were used to identify parameters pertinent to the synthetic population. Twenty-seven experimental scenarios were examined to capture diverse strategies of THN distribution and use. Sensitivity analysis was performed to identify critical mediating and moderating variables associated with population impact and a proxy metric for cost-effectiveness (ie, the direct costs of THN kits distributed per death averted). Data were analyzed between February 2022 and March 2024. Intervention Modeled interventions included 3 THN distribution channels: community facilities and practitioners; jail, at release; and social network or peers of persons released from jail. Main Outcomes and Measures The primary outcome was the percentage of opioid-related overdose deaths averted with THN in the modeled population relative to a baseline scenario with no intervention. Results Take-home naloxone distribution at jail release had the highest median (IQR) percentage of averted deaths at 11.70% (6.57%-15.75%). The probability of bystander presence at an opioid overdose showed the greatest proportional contribution (27.15%) to the variance in deaths averted in persons released from jail. The estimated costs of distributed THN kits were less than $\$$15 000 per averted death in all 27 scenarios. Conclusions and Relevance This study found that THN distribution at jail release is an economical and feasible approach to substantially reducing opioid-related overdose mortality. Training and preparation of proficient and willing bystanders are central factors in reaching the full potential of this intervention.

Tatara, Eric [Argonne National Laboratory (ANL), A↗
DOE OSTI2021

Interfacial-Strain-Controlled Ferroelectricity in Self-Assembled BiFeO 3 Nanostructures

Self-assembled BiFeO 3 -CoFe 2 O 4 (BFO-CFO) vertically aligned nanocomposites are promising for logic, memory, and multiferroic applications, primarily due to the tunability enabled by strain engineering at the prodigious epitaxial vertical interfaces. However, local investigations directly revealing functional properties in the vicinity of such critical interfaces are often hampered by the size, geometry, microstructure, and concomitant experimental artifacts. Ferroelectric switching in the presence of lateral distributions of vertical strain thus remains relatively unexplored, with broader implications for all strain-engineered functional devices. Additionally, by implementing tomographic atomic force microscopy, 3D domain orientation mapping, and spatially-resolved ferroelectric switching movies, local tensile strain significantly impacts the ferroelectric switching, principally by retarding domain nucleation in the BFO nearest to the vertically epitaxial tensile-strained interfaces. The relaxed centers of the BFO pillars become preferred domain nucleation and growth sites for low biases, with up to an order of magnitude change in the edge:center switching ratio for high biases. The new, multi-dimensional imaging approach—and its corresponding insights especially for directly strained interface effects on local properties—thereby advances the fundamental understanding of polarization switching and provides design principles for optimizing functional response in confined nanoferroic systems.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Scalable Substitutional Re‐Doping and its Impact on the Optical and Electronic Properties of Tungsten Diselenide

Abstract Reliable, controlled doping of 2D transition metal dichalcogenides will enable the realization of next‐generation electronic, logic‐memory, and magnetic devices based on these materials. However, to date, accurate control over dopant concentration and scalability of the process remains a challenge. Here, a systematic study of scalable in situ doping of fully coalesced 2D WSe 2 films with Re atoms via metal–organic chemical vapor deposition is reported. Dopant concentrations are uniformly distributed over the substrate surface, with precisely controlled concentrations down to <0.001% Re achieved by tuning the precursor partial pressure. Moreover, the impact of doping on morphological, chemical, optical, and electronic properties of WSe 2 is elucidated with detailed experimental and theoretical examinations, confirming that the substitutional doping of Re at the W site leads to n‐type behavior of WSe 2 . Transport characteristics of fabricated back‐gated field‐effect‐transistors are directly correlated to the dopant concentration, with degrading device performances for doping concentrations exceeding 1% of Re. The study demonstrates a viable approach to introducing true dopant‐level impurities with high precision, which can be scaled up to batch production for applications beyond digital electronics.

Kozhakhmetov, Azimkhan↗
DOE OSTI2025

Floatable Protective Layers: a Strategy to Minimize Solid Electrolyte Interphase Growth and Maximize the Lithium Utilization

Abstract Maximizing lithium (Li) utilization is crucial for enhancing the long‐term stability of Li‐based batteries. In anode‐free Li batteries (AFLBs), although the initial formation of solid electrolyte interphase (SEI) is beneficial on limiting further reaction between Li and electrolyte, large volume change of Li metal anode (LMA) during cycling often leads to continuous breakdown and re‐formation of SEI and formation of inactive Li, hindering its efficiency. In this study, a novel strategy is presented to protect Li metal by applying a floatable protection layer (FPL) on a copper substrate, enabling large Li particles to be primarily deposited below FPL, but SEI to be primarily formed above FPL. This approach effectively minimizes the direct contact between electrolyte and freshly deposited Li, therefore mitigating the continuous side reactions and early failure of AFLBs. As a result, Li consumption is minimized, and the overall stability of the battery is significantly enhanced. Further development of this approach can also be used to improve the performance of other Li‐based batteries for large‐scale applications.

Lim, Hyung‐Seok [Energy and Environment Directorat↗
DOE OSTI2023

A Review of Factors Affecting the Susceptibility of Juvenile Salmonids to Avian Predation

Abstract We reviewed studies of piscivorous colonial waterbird predation on juvenile salmonids to synthesize current knowledge of factors affecting fish susceptibility to avian predators. Specifically, we examined peer-reviewed publications and reports from academic, governmental, and nongovernmental agencies to identify commonalities and differences in susceptibility of salmonids to avian predation, with a focus on mark–recovery studies in the Columbia River basin. Factors hypothesized to influence salmonid susceptibility to avian predation were grouped into four general categories: (1) salmonid species and populations, (2) environmental factors, (3) prey density, predator density, and migration timing, and (4) prey characteristics. Our review focused on predation by Caspian terns Hydroprogne caspia, double-crested cormorants Nannopterum auritum, and gull species Larus spp. as these are the most well-studied avian predators of salmonids. Results indicated that predator–prey interactions varied across salmonid species and populations and species of avian predator. Inferences across studies supported multiple hypotheses regarding predator–prey dynamics, including environmental factors that influence prey exposure to predators (e.g., river flows, turbidity, alternative prey), variation in predator and prey abundances, predator characteristics (e.g., foraging behavior, colony location), and prey characteristics (e.g., fish length, condition). Mark–recovery studies of avian predation on fish populations have greatly improved our understanding of the factors affecting fish susceptibility to avian predation, the relative contributions of abiotic and biotic factors to predation susceptibility, and the extent to which avian predation affects fish survival and the viability of prey populations. Future studies that jointly model predation and survival and the factors affecting those processes will further broaden our understanding of predator–prey dynamics and directly evaluate the effects of predation on prey population dynamics.

Hostetter, Nathan J. (ORCID:0000000160752157)↗
DOE OSTI2020

Mechanistic Models as Framework for Understanding Biomarker Disposition: Prediction of Creatinine‐Drug Interactions

Creatinine is widely used as a biomarker of glomerular filtration, and, hence, renal function. However, transporter‐mediated secretion also contributes to its renal clearance, albeit to a lesser degree. Inhibition of these transporters causes transient serum creatinine elevation, which can be mistaken as impaired renal function. The current study developed mechanistic models of creatinine kinetics within physiologically based framework accounting for multiple transporters involved in creatinine renal elimination, assuming either unidirectional or bidirectional‐OCT2 transport (driven by electrochemical gradient). Robustness of creatinine models was assessed by predicting creatinine‐drug interactions with 10 perpetrators; performance evaluation accounted for 5% intra‐individual variability in serum creatinine. Models showed comparable predictive performances of the maximum steady‐state effect regardless of OCT2 directionality assumptions. However, only the bidirectional‐OCT2 model successfully predicted the minimal effect of ranitidine. The dynamic nature of models provides clear advantage to static approaches and most advanced framework for evaluating interplay between multiple processes in creatinine renal disposition.

Scotcher, Daniel↗
DOE OSTI2020

Direct nanoscale mapping of open circuit voltages at local back surface fields for PERC solar cells

The open circuit voltage (V OC) is a critical and common indicator of solar cell performance as well as degradation, for panel down to lab-scale photovoltaics. Detecting V OC at the nanoscale is much more challenging, however, due to experimental limitations on spatial resolution, voltage resolution, and/or measurement times. Accordingly, in this work an approach based on Conductive Atomic Force Microscopy is implemented to directly detect the local V OC , notably for monocrystalline Passivated Emitter Rear Contact (PERC) cells which are the most common industrial-scale solar panel technology in production worldwide. This is demonstrated with cross-sectioned monocrystalline PERC cells around the entire circumference of a poly-Aluminum-Silicide via through the rear emitter. The V OC maps reveal a local Back Surface Field extending ~2 μm into the underlying p-type Si absorber due to Al in-diffusion as designed. Such high spatial resolution methods for photovoltaic performance mapping are especially promising for directly visualizing the effects of processing parameters, as well as identifying signatures of degradation for silicon and other solar cell technologies.

14 SOLAR ENERGY↗
DOE OSTI2021

Corrosion integrity of oil cement modified by environment responsive microspheres for CO2 geologic sequestration wells

In order to ensure the safe and effectiveness of CO{sub 2} geological storage, an environmental responsive polymer microspheres (ERPM) was prepared to improve the corrosion resistance of cement stone. The structure and environmental response characteristics of ERPM were characterized, and then the anti-corrosion performance and anti-corrosion mechanism for ERPM were discussed. The results shown that ERPM had good environmental response characteristics and temperature resistance. ERPM could effectively suppressed the corrosion rate and the damage degree of mechanical properties of cement stone. The corrosion integrity of cement stone was improved due to the acidic response characteristic and form polymer films of ERPM, which effectively shield the direct contact between corrosion medium and hydration products.

36 MATERIALS SCIENCE↗
DOE OSTI2024

An unstructured body-of-revolution electromagnetic particle-in-cell algorithm with radial perfectly matched layers and dual polarizations

A novel electromagnetic particle-in-cell algorithm has been developed for fully kinetic plasma simulations on unstructured (irregular) meshes in complex body-of-revolution geometries. The algorithm, implemented in the BORPIC++ code, utilizes a set of field scalings and a coordinate mapping, reducing the Maxwell field problem in a cylindrical system to a Cartesian finite element Maxwell solver in the meridian plane. The latter obviates the cylindrical coordinate singularity in the symmetry axis. The choice of an unstructured finite element discretization enhances the geometrical flexibility of the BORPIC++ solver compared to the more traditional finite difference solvers. Symmetries in Maxwell’s equations are explored to decompose the problem into two dual polarization states with isomorphic representations that enable code reuse. The particle-in-cell scatter and gather steps preserve charge conservation at the discrete level. Our previous algorithm (BORPIC+) discretized the E and B field components of TE Φ and TM Φ polarizations on the finite element (primal) mesh. Here, we employ a new field-update scheme. Using the same finite element (primal) mesh, this scheme advances two sets of field components independently: (1) E and B of TE Φ polarized fields, (E z , E ρ , B Φ ) and (2) D and H of TM Φ polarized fields, (D Φ , H z , H ρ ). Since these field updates are not explicitly coupled, the new field solver obviates the coordinate singularity, which otherwise arises at the cylindrical symmetric axis, ρ = 0 when defining the discrete Hodge matrices (generalized finite element mass matrices). Here, a cylindrical perfectly matched layer is implemented as a boundary condition in the radial direction to simulate open space problems, with periodic boundary conditions in the axial direction. We investigate effects of charged particles moving next to the cylindrical perfectly matched layer. We model azimuthal currents arising from rotational motion of charged rings, which produce TMΦ polarized fields. Several numerical examples are provided to illustrate the first application of the algorithm.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Interactions among soil texture, pore structure, and labile carbon influence soil carbon gains

Perennial vegetation with high plant diversity, e.g., restored prairie, is known for stimulation of soil carbon (C) gains, due in part to enhanced formation of pore structure beneficial for long-term C storage. However, the prevalence of this phenomenon across soils of different types remains poorly understood. The aim of the study was to assess the associations between pore structure, soil C, and their differences in monoculture switchgrass and polyculture restored prairie vegetation across a wide range of soils dominating the Upper Midwest of the USA. Six experimental sites were sampled, representing three soil types with texture ranging from sandy to silt loams. The two vegetation systems studied at each site were (i) monoculture switchgrass (Panicum virgatum L.), and (ii) polyculture restored prairie, also containing switchgrass as one of its species. X-ray computed micro-tomography (µCT) was employed to analyze soil pore structure. Structural equation modeling and multiple path analyses were used to assess direct and indirect effects of soil texture and pore characteristics on microbial biomass C (MBC), particulate organic matter (POM), dissolved organic C (DOC), short-term respiration (CO 2 ), and, ultimately, soil organic C (SOC). Across studied sites, prairie increased fractions of medium (50–150 µm Ø) pores by 11–45 %, SOC by 3–69 %, and MBC by 18–59 % (except for one site). The greater were the prairie-induced increases in the medium pore volumes, the greater were the prairie-induced SOC gains. Greater C losses via CO 2 and DOC contributed to slower C accumulation in the prairie soil. We surmise that the interactive feedback loop relating medium pores and soil C acts across a wide range of soil textures and is an important mechanism through which perennial vegetation with high plant diversity, such as restored prairie, promotes rapid SOC gains.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Electronic structure and magnetism of pristine, defected, and strained $\mathrm{Ti_2N}$ $\mathrm{MX}$ene

Here, from first principles electronic structure calculations, we unravel the evolution of structural, electronic, and magnetic properties of pristine, defected, and strained titanium nitride MXene with different functional groups (-F, -O, -H, and -OH). The formation and cohesive energies reveal their chemical stability. The dynamical stability of Ti 2 N mono-layer is also confirmed by phonon calculations. The MAX phase and defect free functionalized MXenes are metallic except for oxygen terminated (Ti 2 NO 2 ) one which is 100% spin polarized half-metallic ferromagnet. The spin–orbit coupling significantly influences the bare MXene (Ti 2 N) to exhibit Dirac topology and band inversion near the high symmetry directions. The strain effect sways the Fermi level thereby shifting it towards lower energy state under compression and towards higher energy state under tensile strain in Ti 2 NH 2 . The Ti 2 NO 2 exhibits exotic electronic structure not only in pristine but also in strained and defected structures. Its half-metallic nature changes to semi-metallic under 1% compression and it is completely destroyed under 2% compression. In single vacancy defect, its band structure remarkably transforms from half-metallic to semi-conducting with large band gap in 12.5% Ti, weakly semi-conducting in 5.5% Ti, and semi-metallic in 12.5% O. The 25% N defect changes its half-metallic characteristic to metallic. Further, the 12.5% Co substitution preserves its half-metallic character, whereas Mn substitution allows it to convert half-metallic characteristic into weak semi-metallic characteristic preserving ferromagnetism. However, Cr substitution converts half-metallic ferromagnetic state to half-metallic anti-ferromagnetic state. The understanding made here on collective structural stability, and electronic band structure, and magnetic phenomena in novel 2D Ti 2 N derived MXenes open up their possibility in designing them for synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Heteroepitaxial control of thickness, strain, and domain architecture in few-layer ferroelectric tin monochalcogenides

Thin-film epitaxy and epitaxial strain have been widely exploited to tune domain configurations, switching behavior, and ferroic properties in conventional three-dimensional ferroelectric thin films; however, its application to controlling the properties of two-dimensional (2D) ferroelectrics has remained largely unexplored. Here, using SnX (X = Se, S) as a model system, we demonstrate heteroepitaxial control of thickness, strain state, and domain architecture in few-layer ferroelectric SnX via growth on monolayer MoS2 van der Waals (vdW) templates. Compared with conventional growth, MoS2-templated heteroepitaxy promotes epitaxial alignment, yielding ultrathin SnSe films with improved crystalline quality, full areal coverage, and enlarged lateral dimensions. Strong interfacial epitaxial coupling induces pronounced in-plane strain and stabilizes a hierarchical ferroelastic domain architecture, in which long-range 90° stripe domains are further subdivided into nanoscale rotational variants, as revealed by scanning transmission electron microscopy and synchrotron X-ray microscopy. Piezoresponse force microscopy and second-harmonic polarimetry confirm robust in-plane polarization, while ferroelectricity in SnSe is established through polarization-electric field hysteresis and nonvolatile ferroelectric resistive switching with on/off ratios approaching 1000. A nonvolatile, switchable ferroelectric diode effect further evidences direct coupling between polarization and charge transport. Notably, ferroelectric switchability exhibits a strong thickness dependence and is preserved only below ∼10 layers. This vdW heteroepitaxial strategy is further extended to ferroelectric SnS. The seamless heteroepitaxial integration of 2D ferroelectrics with CMOS-compatible, wafer-scale MoS2 templates provides a general and scalable route for strain-enabled structural and ferroelectric engineering in emerging memory and low-power optoelectronic applications.

Wang, Yueyin↗
DOE OSTI2024

Reduction of CO to Methanol with Recyclable Organic Hydrides

We report the reaction steps for the selective conversion of a transition metal carbonyl complex to a hydroxymethyl complex that releases methanol upon irradiation with visible light have been successfully quantified in acetonitrile solution with dihydrobenzimidazole organic hydride reductants. Dihydrobenzimidazole reductants have been shown to be inactive toward H 2 generation in the presence of a wide range of proton sources and have been regenerated electrochemically or photochemically. Specifically, the reaction of cis-[Ru(bpy) 2 (CO) 2 ] 2+ (bpy = 2,2'-bipyridine) with one equivalent of a dihydrobenzimidazole quantitatively yields a formyl complex, cis-[Ru(bpy) 2 (CO)(CHO)] + , and the corresponding benzimidazolium on a seconds time scale. Kinetic experiments revealed a first-order dependence on the benzimidazole hydride concentration and an unusually large kinetic isotope effect, inconsistent with direct hydride transfer and more likely to occur by an electron transfer-proton-coupled electron transfer (EΤ-PCET) or related mechanism. Further reduction/protonation of cis-[Ru(bpy) 2 (CO)(CHO)] + with two equivalents of the organic hydride yields the hydroxymethyl complex cis-[Ru(bpy) 2 (CO)(CH 2 OH)] + . Visible light excitation of cis-[Ru(bpy) 2 (CO)(CH 2 OH)] + in the presence of excess organic hydride was shown to yield free methanol. Identification and quantification of methanol as the sole CO reduction product was confirmed by 1 H NMR spectroscopy and gas chromatography. The high selectivity and mild reaction conditions suggest a viable approach for methanol production from CO, and from CO 2 through cascade catalysis, with renewable organic hydrides that bear similarities to Nature's NADPH/NADP + .

14 SOLAR ENERGY↗