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DOE OSTI2025

Modulation of thermal conductivity of iron-doped ß-Ga2O3 by helium-ion irradiation

This study examines the impact of helium-ion irradiation on the thermal conductivity of ß-Ga2O3. A laser-based spatial domain thermoreflectance technique is used to investigate thermal conductivity map for both un-irradiated and irradiated ß-Ga2O3, which are then validated against simulation results derived from density functional theory-based phonon transport simulations. Since helium bubble evolution was ob- served at the nanoscale using transmission electron microscopy, the simulation study was carried out on eight distinct helium-induced sites in ß-Ga2O3. Our findings indicate a reduction in thermal conductivity for the irradiated samples. Experimental results show a significant reduction in thermal conductivity in irradiated samples, with de- creases of approximately 25% along the [100] direction and 40% along [001] directions. Phonon transport simulations closely replicate these findings, particularly when helium occupying interstitial sites, predicting reductions of ˜53% along [100] and ˜50% along [001] directions. This work underscores the role of irradiation-induced microstructural changes in the heat transport properties of ß-Ga2O3 which is crucial for its application in sensor devices in extreme environments.

36 - MATERIALS SCIENCE↗

DOE OSTI2026

Field-resolved observation of exciton coherence in a van der Waals magnet

The emergence of coherence among electronic quasiparticles underlies collective quantum phenomena from superconductivity to superradiance. In semiconductors, exciton coherence is generally thought to decay rapidly due to scattering and dephasing, limiting its persistence on ultrafast timescales. Here, in this work, we demonstrate a light-field-driven mechanism that creates and stabilizes exciton coherence in the layered antiferromagnet CrSBr. We directly record the coherent optical field emitted by excitons and track in real time how a deterministic phase, imprinted by the excitation laser, drives incoherent excitons to synchronize into a collective state. This ensemble remains phase coherent for more than 2 ps, whereas its resonance energy undergoes an ultrafast modulation mediated by spin and lattice interactions. The time-resolved field evolution indicates that the multiple peaks seen in conventional spectra originate from a single excitonic resonance subject to dynamic energy modulation. Our findings establish optical phase imprinting as a mechanism to control and sustain collective order in semiconducting magnets, bridging light-driven dynamics with excitonic and magnetic correlations in layered quantum materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Radiation damage effects in beryllium for next generation neutrino beam targetry (Final Technical Report)

Current and future high-power accelerators put severe requirements on materials used for target and beam windows and target facilities have been recognized as a critical challenge in development of future particle accelerators. In accelerators, window and target materials are exposed to extreme conditions, which include bombardment with very high energy protons (1- 100 GeV) and thermomechanical shock waves. Radiation can cause direct damage in the material, and it leads to production of transmutation products (especially helium), both phenomena having a potential adverse effect on the stability and durability of the target/window material. At high enough temperatures, He can aggregate to form gas bubbles, which in turn cause significant dimensional changes (swelling), enable easy crack propagation, and eventually cause failure by fracture. On the other hand, if the temperature is too low, radiation damage accumulates in the form of internal defects (e.g., dislocations), leading to hardening and a decreased ductility of the material. In this project, we will focus on beryllium since it is considered to be one of the candidate materials for beam windows and targets in the next-generation proton accelerators, e.g., the Long Baseline Neutrino Facility (LBNF). Radiation effects in Be have been studied in the context of nuclear fusion reactor applications. However, key differences exist between reactor and accelerator conditions, including neutron vs. proton irradiation, continuous vs. pulsed beam flux, much higher energies of bombarding particles in accelerators, and higher operating temperatures for typical reactors. For example, the impact of beam pulsing on the radiation damage and the He bubble kinetics is largely unknown. While results obtained on Be from fusion research might not be directly transferrable to understanding target materials, there is an opportunity to bring state-of-the-art tools from materials research in nuclear reactors to aid design of target and beam window materials in high-power accelerators. To this end, the overarching goal of this project are to develop an experimentally-validated computational framework capable of predicting radiation damage evolution in beryllium relevant to beam window and target conditions, focusing on He bubble formation and growth as a function of irradiation temperature. Our model will be based on the cluster dynamics formalism, where size distribution of defects and He bubbles is simulated as a function of time, temperature, and radiation dose. Parameters for the model will be taken from published experiments and from high-fidelity atomistic simulations proposed in this project. In addition, we will carry out a series of targeted ex-situ and in-situ dual-beam experiments using low-energy protons to provide critical data for validation of the model on the effects of radiation on He clustering, He bubble distribution, and dislocation loop density/size in proton irradiated Be.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Broadband Rotational Spectroscopy in Uniform Supersonic Flows: Chirped Pulse/Uniform Flow for Reaction Dynamics and Low Temperature Kinetics

ConspectusThe study of gas-phase chemical reactions at very low temperatures first became possible with the development and implementation of the CRESU (French acronym for Reaction Kinetics in Uniform Supersonic Flows) technique. CRESU relies on a uniform supersonic flow produced by expansion of a gas through a Laval (convergent-divergent) nozzle to produce a wall-less reactor at temperatures from 10 to 200 K and densities of 1016-1018 cm-3 for the study of low temperature kinetics, with particular application to astrochemistry. In recent years, we have combined uniform flows with revolutionary advances in broadband rotational spectroscopy to yield an instrument that affords near-universal detection for novel applications in photodissociation, reaction dynamics, and kinetics. This combination of uniform supersonic flows with chirped-pulse Fourier-transform microwave spectroscopy (Chirped-Pulse/Uniform Flow, CPUF) permits detection of any species with a modest dipole moment, thermalized to the uniform temperature of the gas flow, with isomer, conformer, and vibrational state specificity. In addition, the use of broadband, high-resolution, and time-dependent (microsecond time scale) micro- and mm-wave spectroscopy makes it an ideal tool for characterizing both transient and stable molecules, as well as studying their spectroscopy and dynamics.In this Account, we review recent advances made using the CPUF technique, including studies of photodissociation, radical-radical reaction dynamics, and low temperature kinetics. These studies highlight both the strength of universal and multiplexed detection and the challenges of coupling it to a high-density collisional environment. Product branching and product evolution as a function of time have been measured for astrochemically relevant systems, relying on the detailed characterization of these flow conditions via experiments and fluid dynamics simulations. In the photodissociation of isoxazole, an unusual heterocyclic molecule with a very low-energy conical intersection, we have identified 7 products in 5 reaction channels and determined the product branching, pointing to both direct and indirect pathways. We have also approached the same system from separated NO and C3H3 reactants to explore a broader range of the potential energy surface, demonstrating the power of multichannel branching measurements for complex radical-radical reactions. We determined the product branching in the C3H2 isomers in the photodissociation of the propargyl radical and identified the importance of a hydrogen atom catalyzed isomerization to the lowest energy cyclic form. This then motivated a study of direct D-H exchange reaction in radicals, in which we demonstrate that it is an important and overlooked pathway for deuterium fractionation in astrochemical environments. Recently, we have shown the measurement of low temperature kinetics inside an extended Laval nozzle, after which a shock-free secondary expansion to low temperature and density affords an ideal environment for detection by rotational spectroscopy. These results highlight the power and potential of the CPUF approach, and future prospects will also be discussed in light of these developments.

Dias, Nureshan↗

DOE OSTI2024

Electronic reconstruction in confined SrRuO 3 monolayers

Here, we report the observation of an electronic reconstruction in dimensionally controlled ruthenate heterostructures synthesized by pulsed laser deposition. High structural and electronic quality of superlattices comprised of a single SrRuO 3 layer inter-spaced with varying thicknesses of insulating SrTiO 3 layers was verified by reflection high energy electron diffraction, atomic force microscopy, x-ray diffraction, reciprocal space mapping, and x-ray absorption spectroscopy. X-ray absorption spectroscopy evidences a confinement-driven evolution of the Ru electronic configuration from the 𝑑 5 $\underline{L}$ to the 𝑑 4 state. Significant increases of the spin-orbit coupling are observed in connection with the configuration changes supporting recent works identifying large enhancement of the magnetic anisotropy. The growth of high quality two-dimensional confined ruthenate layers under precisely controlled environments highlights the potential to directly manipulate interlayer coupling and selectively perturb the electronic state in ruthenates in analogy to superconducting Sr 2 ⁢RuO 4 .

36 MATERIALS SCIENCE↗

DOE OSTI2024

Effects of processing temperature, pressure, and fiber volume fraction on mechanical and morphological behaviors of fully-recyclable uni-directional thermoplastic polymer-fiber-reinforced polymers

This work explores a type of composite called thermoplastic polymer-fiber-reinforced polymers (PFRPs), often referred to as self-reinforced composites (SRCs). A representative PFRP was exemplified using unidirectional (UD) ultra-high-molecular-weight polyethylene (UHMWPE) fibers embedded in a high-density polyethylene (HDPE) matrix. The effects of compression molding temperature and pressure on the mechanical and morphological behaviors of the filament-wound PFRPs with various fiber volume fractions (V f ) were experimentally investigated. The results elucidate the evolution of morphologies and tensile properties of the PFRPs due to thermal melting, fiber misalignment from pressure, and (V f )-induced structural variance, which has not been comprehensively reported yet. The highest specific tensile strength and modulus of the PFRP laminae reach 600 MPa/(g/cm 3 ) and 31 GPa/(g/cm 3 ), respectively. These properties are comparable to glass-/aramid-fiber-reinforced polymers (GFRPs, GFRTPs, AFRPs, and AFRTPs), with PFRPs exhibiting better ductility (specific strain at peak load ≈ 4%/(g/cm 3 )) than other common polymer composites. The motivation for this work was the high recyclability of PFRPs, which can be recycled by melting both the fibers and the matrix, and then reshaped them for re-manufacturing composites to maximize the efficiency in material reuse. This process simplifies the implementation of closed-loop recycling, re-manufacturing, and reuse to support sustainability in composites. This work aims to contribute to advancing thermoplastic PFRPs for their potential applications in various industries.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Dust-void evolution driven by turbulent dust flux can induce runaway migration of Earth-mass planets

Torques from asymmetric dust structures (so-called dust-void and filamentary structures) formed around low-mass planets embedded in a nonturbulent dust-gas disk can exceed the torques produced by the gas disk component and then go on to dominate the planet’s orbital dynamics. Here, we investigate how these structures (hence the dust torque) change when the effect of turbulent dust diffusion and dust feedback are included, along with the direct implications on the migration of Earth-like planets. Using the FARGO3D code, we performed 2D and 3D multifluid hydrodynamic simulations, focusing on a non-migrating planet with a mass of M p = 1.5 M ⊕ in 2D and on migrating planets with M p ∈ [1.5, 12] M ⊕ in 3D. We varied the δ-dimensionless diffusivity parameter in the range [0, 3 × 10 −3 ] and considered three different Stokes numbers, St = {0.04, 0.26, 0.55}, which are representative of the gas-dominated, the transitional, and the gravity-dominated regimes, respectively. In our 2D models, we find that turbulent diffusion of dust prevents the formation of the dust-void and filamentary structures when δ > 3 × 10 −4 . Otherwise, dust structures survive turbulent diffusion flow. However, dust and total torques become positive only in transitional and gravity-dominated regimes. In our 3D models, we find that the dust-void is drastically modified and the high-density ring-shaped barrier delineating the dust-void disappears if δ ≳ 10 −4 , due to the effect of dust turbulent diffusion along with the back-reaction of the dust. For all values of δ, the filament in front of the planet is replaced by a low-density trench. Remarkably, as we have allowed the planets to migrate, the evolving dust-void can drive either runaway migration or outward (inward) oscillatory-torque migration. Our study thus suggests that low-mass Earth-like planets can undergo runaway migration in dusty disks.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2025

Uncovering heterogeneous intercommunity disease transmission from neutral allele frequency time series

The COVID-19 pandemic has underscored the need for accurate epidemic forecasting to predict pathogen spread, evolution, and evaluate intervention strategies. Forecast reliability hinges on detailed knowledge of disease transmission across population segments, which may be inferred from contact surveys or mobility data. However, these indirect approaches make it difficult to estimate rare transmissions between socially or geographically distant communities. We show that the steep ramp-up of genome sequencing surveillance during the pandemic can be leveraged to directly identify transmission patterns between geographically defined communities. Our approach uses a hidden Markov model to infer the fraction of infections a community imports from others based on how rapidly allele frequencies in the focal community converge to those in the donor communities. Applying this method to SARS-CoV-2 sequencing data from England and the United States, we uncover networks of intercommunity transmission that reflect geographical relationships while exposing significant long-range interactions. The scaling of importation rate with distance is consistent across both countries, yet weaker than expected based on mobility data, highlighting limitations of indirect inference. We show that transmission patterns can change between waves of variants of concern and analyze how the inferred heterogeneity in intercommunity transmission impacts evolutionary forecasts. While applied here to geographically defined communities, our approach could be applied to those defined by other traits (e.g., age, socioeconomic status), provided time-series data can be stratified accordingly. Overall, our study highlights population genomic time series data as a crucial record of epidemiological interactions, which can be deciphered using tree-free inference methods.

Okada, Takashi [Department of Physics; University ↗

DOE OSTI2024

Evolution of magnetism in the magnetic topological semimetal NdSb x Te 2–x+δ

Magnetic topological semimetals LnSbTe (Ln = Lanthanide) have attracted intensive attention because of the presence of interplay between magnetism, topological, and electron correlations depending on the choices of magnetic Ln elements. Recently, varying Sb-Te composition has been found to effectively control the electronic and magnetic states in LnSb x Te 2-x . Here, with this motivation, we report the evolution of magnetic properties with Sb-Te substitution in NdSb x Te 2-x+δ , (0 ≤ x ≤ 1). Our work reveals the interesting non-monotonic change in magnetic ordering temperature with varying composition stoichiometry. In addition, reducing the Sb content x drives the reorientation of moments from in-plane (ab-plane) to out-of-plane (c-axis) direction that results in the distinct magnetic structures for two end compounds NdTe 2 (x = 0) and NdSbTe (x = 1). Furthermore, the moment orientation in NdSb x Te 2-x+δ is also found to be strongly tunable upon application of weak magnetic field, leading to rich magnetic phases depending on the composition stoichiometry, temperature, and magnetic field. Such strong tuning of magnetism in this material establishes it as a promising platform for investigating tunable topological states and correlated topological physics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Commodity Thermoplastic Elastomer-Enabled Templated Synthesis of Large-Pore Ordered Mesoporous Materials

Fabrication of ordered mesoporous materials (OMMs) has predominantly relied on templating-based methods. However, these methods are constrained by several limitations, especially the limited pore sizes attainable with commercially available surfactants used as structure-directing agents. To unlock the full potential of the OMMs, it is essential to develop synthetic strategies that facilitate the production of large-pore OMMs using scalable processes and cost-effective precursors. This work demonstrates the use of thermoplastic elastomer (TPE)-derived carbon replicas for synthesizing ordered mesoporous silica (OMS) and metal oxides (OMMOs) via precursor infiltration and template removal. The nanostructural evolution of the resulting inorganic materials was systematically investigated. Specifically, using tetraethyl orthosilicate (TEOS) as a silica precursor, this method can produce an OMS with relatively large pores. To establish the generalizability of this process, the fabrication approach was extended to other commercially available TPEs with varied chemical compositions and molecular weights while consistently resulting in ordered structures. Additionally, this synthetic strategy can be successfully applied to the production of OMMOs, including tin and titanium oxide matrix chemistries, yielding pore sizes of 16.0 and 19.2 nm, respectively. By developing a general method and using low-cost precursors, this work presents a scalable approach for fabricating large-pore OMMs with tunable pore textures and matrix chemistries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Future Anthropogenic Land Use Change Impacts on Carbonaceous Aerosol and Implications for Climate and Air Quality

Future anthropogenic land use change (LUC) may alter atmospheric carbonaceous aerosol (black carbon and organic aerosol) burden by perturbing biogenic and fire emissions. However, there has been little investigation of this effect. We examine the global evolution of future carbonaceous aerosol under the Shared Socioeconomic Pathways projected reforestation and deforestation scenarios using the CESM2 model from present‐day to 2100. Compared to present‐day, the change in future biogenic volatile organic compounds emission follows changes in forest coverage, while fire emissions decrease in both projections, driven by trends in deforestation fires. The associated carbonaceous aerosol burden change produces moderate aerosol direct radiative forcing (−0.021 to +0.034 W/m 2 ) and modest mean reduction in PM 2.5 exposure (−0.11 μg/m 3 to −0.23 μg/m 3 ) in both scenarios. We find that future anthropogenic LUC may be more important in determining atmospheric carbonaceous aerosol burden than direct anthropogenic emissions, highlighting the importance of further constraining the impact of LUC.>

anthropogenic land use change↗

DOE OSTI2026

Error quantification and comparison of binary neutron star gravitational waveforms from numerical relativity codes

Future gravitational wave detections of merging binary neutron star systems have the possibility to tightly constrain the equation of state of dense nuclear matter. In order to extract such constraints, gravitational waveform models need to be calibrated to accurate numerical relativity simulations of the late inspiral and merger. In this work, we take an essential step toward classifying the error and potential systematics in current generation numerical relativity simulations of merging binary neutron stars. To this end, we perform a direct comparison of two codes (fil, spec), which differ in many aspects, including the numerical methods and discretizations used and equations solved. We find that despite these different approaches, the codes are—within current numerical resolution bounds—fully consistent, and broadly comparable in cost for a given accuracy level. Our results indicate that the error in the waveforms is primarily dominated by the hydrodynamic evolution, consistent with earlier findings in the literature. Finally, we also discuss current limitations and cost estimates for numerical relativity simulations to reach the accuracies required in the era of next-generation gravitational detectors.

gravitational waves↗

DOE OSTI2025

Oxygen vacancies in niobium pentoxide as a source of two-level system losses in superconducting niobium

Two-level systems (TLS) have long been a catch-all explanation for RF loss and quantum decoherence in superconducting devices. In our study, the first to directly link TLS losses to a specific physical mechanism, we demonstrate that oxygen vacancies in the naturally formed Nb₂O₅ on oxidized niobium are a major driver of such dissipation. We performed sequential in situ vacuum-baking treatments on niobium superconducting radio-frequency (SRF) cavities and used time-of-flight secondary ion mass spectrometry (TOF-SIMS) to reveal a nonmonotonic evolution in cavity quality factor (Q₀). This behavior correlates with the interplay of Nb₂O₅ vacancy generation and oxide-thickness dissolution. We localize this effect to the oxide itself and present the insignificant role of diffused interstitial oxygen in the underlying Nb by regrowing the oxide via wet oxidation, revealing a mitigation of aggravated TLS losses. We hypothesize that such vacancies in the pentoxide serve as magnetic impurities and are a source of TLS-driven rf loss. Although our measurements center on 3-D SRF cavities, the insights gained here have significant implications for mitigating decoherence in 2-D superconducting qubits.

Bafia, Daniel P. [Fermilab]↗

DOE OSTI2026

Single-shot ultrafast dynamics of nanosecond pulsed plasmas: Transition from ps–ns nonequilibrium to near-full ionization

The ultrafast multi-stage evolution of state-defining properties in atmospheric-pressure nanosecond pulsed plasmas is quantified using single-discharge, jitter-free, continuous streak-sweep spectroscopy of N 2 (C → B) molecular and N + /O + ionic species with a single-shot time resolution as short as ∼160 ps. An early period of extreme nonequilibrium is observed with vibrational temperatures [T V (C)] dropping from ∼8000 K at <200 ps after plasma breakdown to <4000 K within ∼1 ns, with near-ambient rotational temperatures [T R (C)] ∼ 300 K due to limited collisional energy transfer. This early-time T V (C) trend is representative of a direct and unquenched look into the high-energy tail of the electron energy distribution function; thus, it tracks real-time changes in the mean electron energy via the N2(C) emission signatures. This is followed by the rapid onset of N + /O + ionic emission after a distinct time delay of ∼14.9 ns due to multistep chemical kinetics. The ionic emission enables determination of electron densities (n e ) >2 × 10 19 cm −3 and electron temperatures (T e ) >36 000 K, indicating the transition to a nearly fully ionized regime. The ps–ns temporal dynamics are also compared between air and N 2 plasmas to assess the influence of collisional partners, as well as across the anode, cathode, and central gap regions to identify spatial variations in plasma behavior. Finally, this work demonstrates versatile continuously probing approach capable of spectro-temporal and spatially resolved single-shot measurements of key state variables in the ps–ns evolution of atmospheric-pressure nanosecond pulsed plasmas.

Electric discharges↗

DOE OSTI2026

Measurement of transverse polarization of Λ and hyperons inside jets in unpolarized proton-proton collisions at $\sqrt{s}$ = 200 GeV

A surprisingly large transverse polarization of Λ hyperons in unpolarized hadron-nucleon/nucleus collisions has been observed for 50 years, and the origin of this polarization remains an important open question. Recently, theoretical frameworks have advanced in describing this puzzle with the polarizing fragmentation function (PFF). We report the first measurement of Λ and $\overline{Λ}$ transverse polarization inside jets in unpolarized proton-proton collisions, which is directly attributed to the PFF. The polarization is measured as a function of the jet transverse momentum, the fraction of the jet momentum carried by Λ ($\overline{Λ}$) hyperons, and the transverse momentum of Λ ($\overline{Λ}$) hyperons relative to the jet axis. Covering a wide jet-energy range, these data provide the first constraints on the gluon PFF and allow tests of TMD evolution and its universality.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2026

Microstructural evolution, defect mitigation, and precipitation behavior in AA6061 via laser powder bed fusion with high-temperature substrate heating

Defects, particularly solidification cracking, remain persistent challenges in the laser powder bed fusion (LPBF) processing of AA6061 aluminum alloy. This study systematically investigates defect mitigation, microstructural evolution, and mechanical properties associated with high-temperature substrate preheating at 500 °C. Comprehensive microstructural analyses, including characterization of defects, grain structures, and precipitation behavior, were performed on samples in both as-built and T6 heat-treated states. Elevated preheating substantially reduced solidification cracking across a wide processing window, while demonstrating decreased crack sensitivity to laser parameters. Columnar cracks along the build direction were observed despite substrate preheating. Lack-of-fusion and keyhole porosity were effectively eliminated, though gas-induced microporosity persisted at higher powers. In-depth characterization of two distinct laser power and speed conditions confirmed the formation of micron-sized, non-coherent Mg 2 Si precipitates under heated substrate conditions, alongside α-AlFeCrMnSi intermetallic phases indicative of in-situ thermal effects during fabrication. Subsequent T6 heat treatment revealed the formation of fine, coherent needle-shaped β″ strengthening precipitates. Despite substantial differences in processing parameters, comparable mechanical properties were measured in the as-built samples (∼52 MPa yield strength, ∼130 MPa tensile strength), primarily due to reduced strain hardening effects and consistent precipitation characteristics. Meanwhile, the T6 heat treatment led to significant improvement in properties, enhancing yield strength by over 400%, aligning closely with the performance of conventional wrought AA6061-T6. These findings underscore that high-temperature substrate preheating offers an effective means to suppress cracks, control precipitation, and enhance mechanical performance in LPBF-processed AA6061.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Electronic Structure Progression across the ACu 2 Q 2 (MQ 2 ) n Semiconductor Series

Moving beyond the engineering of known materials and elemental substitution within common structure types is critical for designing unique properties. Here, we present a new homologous series, ACu 2 Q 2 (MQ 2 ) n (A = Sr, Ba, 2Na; MQ 2 = ZrS2, HfSe 2 ), establishing 11 new members. In β-BaCu 2 Q 2 and Na 2 Cu 2 Se 2 (n = 0), the [Cu 2 Q 2 ] 2– motifs extend in two dimensions, whereas those in α-BaCu 2 Q 2 extend in three dimensions. Hence, there are two structural evolutions within the ACu 2 Q 2 (MQ 2 )n family driven by the polymorphism of the host structures. MQ 2 (n → ∞) displays 2D layers of edge-sharing [MQ 6 ] 8– octahedra that are 1-octahedron-thick and connected via van der Waals bonding. Each insertion of MQ 2 into ACu 2 Q 2 incorporates [MQ 6 ] 8– octahedra extending infinitely in one direction, confined to being 1-octahedron-thick in the second direction, with n controlling the number of [MQ 6 ] 8– octahedra in the third direction. Therefore, increasing n predictively expands the [Cu 2 MnQ 2n+2 ] 2– network in the direction controlled by n and relative to the A + /A 2+ ions. We demonstrate that for a given set of elements, one can enforce a “Host(Insertion)n” formula to systematically evolve both crystal and electronic structures from the host (n = 0) to the insertion (n → ∞) materials through intermediate values of n. Specifically, the energetic misalignment of the electronic band extrema of the parents predictively determines the band extrema and the resulting band gaps of all intermediate n members.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Reactive capture and electrochemical conversion of CO 2 with ionic liquids and deep eutectic solvents

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO 2 due to their wide electrochemical stability window, low volatility, and high CO 2 solubility. There is environmental and economic interest in the direct utilization of the captured CO 2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO 2 , eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO 2 with aqueous electrolytes presents limited CO 2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO 2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO 2 , often diluting them with aqueous or non-aqueous solvents. The resulting electrode–electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO 2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation.

36 MATERIALS SCIENCE↗