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All sources NASA NTRS DOE OSTI

DOE OSTI2022

In Situ Determination of Speciation and Local Structure of NaCl–SrCl 2 and LiF–ZrF 4 Molten Salts

Understanding the local environment of the metal atoms in salt melts is important for modeling the properties of melts and predicting their behavior and thus helping enable the development of technologies such as molten salt reactors and solar-thermal power systems and new approaches to recycling rare-earth metals. Toward that end, we have developed an in situ approach for measuring the coordination of metals in molten salt coupling X-ray absorption spectroscopy (XAS) and Raman spectroscopy. Our approach was demonstrated for two salt mixtures (1.9 and 5 mol % SrCl 2 in NaCl, 0.8 and 5 mol % ZrF 4 in LiF) at up to 1100 °C. Near-edge (X-ray absorption near-edge structure, XANES) and extended X-ray absorption fine structure (EXAFS) spectra were measured. The EXAFS response was modeled using ab initio FEFF calculations. Strontium’s first shell is observed to be coordinated with chlorine (Sr 2+ –Cl – ) and zirconium’s first shell is coordinated by fluorine (Zr 4+ –F – ), both having coordination numbers that decrease with increasing temperature. Multiple zirconium complexes are believed to be present in the melt, which may interfere and distort the EXAFS spectra and result in an anomalously low zirconium first shell coordination number. Finally, the use of boron nitride (BN) powder as a salt diluent for XAFS measurements was found to not interfere with measurements and thus can be used for investigations of such systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Solution-Grown Ternary Semiconductors: Nanostructuring and Stereoelectronic Lone Pair Distortions in I–V–VI 2 Materials

Alkali pnictogen dichalcogenides–I–V–VI 2 or APnCh 2 –have been identified as promising semiconducting materials for energy conversion devices. However, the controlled nanoscale synthesis and our understanding of the effects of cation ordering and stereochemically active lone pairs on the structures of these ternary compounds remain underdeveloped. Here, we use solution-phase chemistry to synthesize a family of APnCh 2 materials, including LiSbSe 2 , NaSbS 2 , NaSbSe 2 , NaBiS 2 , and NaBiSe 2 . Our approach utilizes alkali metal hydrides (AH) or carboxylates, A(O 2 CR), PnPh 3 , and elemental chalcogens as synthetic precursors and oleylamine or 1-octadecene as solvents. Synthetic manipulation via fine-tuning of reaction temperature enables control over the degree of ordering caused by the Sb 5s 2 lone pair-induced distortions in NaSbS 2 . Pair distribution function analysis demonstrates that the structure of the Sb-containing phases deviates much more from a disordered rock salt structure than that of the Bi-containing phases. This local distortion, induced by the Sb lone pair, leads to a previously unreported noncentrosymmetric NaSbS 2 crystal structure, which is additionally supported by second-harmonic generation measurements. Infrared and multinuclear solid-state NMR spectroscopies show that oleylamine or chelating carboxylates and, in some cases, unreacted precursors (LiH and PnPh 3 ) remain bound to the nanocrystalline surfaces. Further, a deeper understanding of the local atomic environment, long-range ordering, surface chemistry, and optoelectronic properties of these materials may speed up their fundamental study and application.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Atomically Dispersed Metals on Well-Defined Supports including Zeolites and Metal–Organic Frameworks: Structure, Bonding, Reactivity, and Catalysis

When metals in supported catalysts are atomically dispersed, they are usually cationic and bonded chemically to supports. Investigations of noble metals in this class are growing rapidly, leading to discoveries of catalysts with new properties. Characterization of these materials is challenging because the metal atoms reside on surfaces that are typically nonuniform in composition and structure. We posit that understanding of structures and catalytic properties of these materials is emerging most strongly from investigations of structurally uniform catalysts (metal atoms dispersed on crystalline supports) which can be characterized incisively with atomic-resolution electron microscopy, X-ray absorption spectroscopy, and infrared spectroscopy, bolstered by density functional theory. We assess the literature of such catalysts supported on zeotype materials, metal–organic frameworks, and covalent organic frameworks. Finally, assessing characterization, reactivity, and catalytic performance of catalysts for oxidation, hydrogenation, the water–gas shift reaction, and others, we consider metal–support interactions and ligand effects for various metal–support combinations, evaluating the degree of structural uniformity of exemplary catalysts and summarizing structure–reactivity and structure–catalytic property relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Structural analyses of amorphous calcium carbonate before and after removing strontium ions from an aqueous solution

Amorphous calcium carbonate (ACC) is a precursor of crystalline calcium carbonate; hence, its structural information at the atomic level is very important for controlling the morphology of crystalline calcium carbonate. In this study, we attempted to elucidate the process of Sr extraction from aqueous solution by using ACC for the purpose of removal of radioactive Sr from the contaminated water leaked after the Fukushima Daiichi nuclear accident. Here, the pair distribution functions, g(r) obtained by X-ray and neutron diffraction (ND) measurements show that ACC has a structure partially similar to that of monohydrocalcite, suggesting that ACC is transferred to the crystalline calcium carbonate starting from its crystal nucleus. Rietveld analysis of the ND data showed that the ACC that removed Sr was crystallized to calcite. However, the Sr–O coordination analyzed using extended X-ray absorption fine structure (EXAFS) implies that the local environment of O around Sr is similar to that in crystalline calcium carbonate aragonite.

36 MATERIALS SCIENCE↗

NASA NTRS2011

An Icy Kuiper-Belt Around the Young Solar-Type Star HD 181327

HD 181327 is a young Main Sequence F5/F6 V star belonging to the Beta Pictoris moving group (age approx 12 Myr). It harbors an optically thin belt of circumstellar material at approx90 AU, presumed to result from collisions in a populat.ion of unseen planetesimals. Aims. We aim to study the dust properties in the belt in great details, and to constrain the gas-to-dust ratio. Methods. We obtained far-IR photometric observations of HD 181327 with the PACS instrument onboard the Herschel Space Observatory, complemented by new 3.2 nun observations carried with the ATCA array. The geometry of the belt is constrained with newly reduced HST /NICMOS scattered light images that break the degeneracy between the disk geometry and the dust properties. We then use the radiative transfer code GRaTer to compute a large grid of dust models, and we apply a Bayesian inference method to identify the grain models that best reproduce the SED. We attempt to detect the oxygen and ionized carbon fine-structure lines with Herschel/PACS spectroscopy, providing observables to our photochemical code ProDiMo. Results. The HST observations confirm that the dust is confined in a narrow belt. The continuum is detected with Herschel/PACS completing nicely the SED in the far-infrared. The disk is marginally resolved with both PACS and ATCA. A medium integration of the gas spectral lines only provides upper limits on the [OI] and [CII] line fluxes. We show that the HD 181327 dust disk consists of micron-sized grains of porous amorphous silicates and carbonaceous material surrounded by an import.ant layer of ice for a total dust mass of approx 0.05 stellar Mass. We discuss evidences that the grains consists of fluffy aggregates. The upper limits on the gas atomic lines do not provide unambiguous constraints: only if the PAH abundance is high, the gas mass must be lower than approx 17 Stellar Mass Conclusions. Despite the weak constraints on the gas disk, the age of HD 181327 and the properties of the dust disk suggest that it has passed the stage of gaseous planets formation. The dust reveals a population of icy planetesimals, similar to the primitive Edgeworth-Kuiper Belt, that may be a source for the future delivery of water and volatiles onto forming terrestrial planets.

Lebreton, J.↗

DOE OSTI2022

High-Platinum-Content Catalysts on Atomically Dispersed and Nitrogen Coordinated Single Manganese Site Carbons for Heavy-Duty Fuel Cells

Fuel cells for heavy-duty vehicles (HDVs) have attracted considerable attention because of their unique scalability, better fuel economy, the less demand for hydrogen refilling infrastructure. However, the potential application requires more stringent fuel cell durability up to 25,000 h. Membrane electrode assemblies (MEAs) made from platinum group metal (PGM) catalyst with relatively high loading 0.3 mgPt cm –2 play a crucial role in ensuring high-power and long-term durability. Integrating fine PGM nanoparticles and robust carbon support with strengthened interactions is critical for improving MEA performance and durability. Herein, a unique atomically dispersed and nitrogen coordinated single Mn site-rich carbon (M–N–C) support was developed for high content (40 wt%) platinum catalysts for the oxygen reduction reaction (ORR) cathode with reduced thickness. Compared with two controls studied in this work (e.g., a porous graphitic carbon-supported Pt and a commercial TKK Pt/C catalysts), the Pt (40 wt%)/Mn–N–C catalyst exhibited much enhanced catalytic activity and stability for the ORR in both aqueous acidic electrolyte and polymer electrolyte-based MEA. Here, we carefully elucidated the—role of the Mn–N–C support in promoting Pt catalyst concerning its high surface area, partially graphitic structure, and nitrogen dopants, providing better Pt nanoparticle dispersion, and strengthened interactions between Pt and carbon. Consequently, the MEA from the Pt (40 wt%)/Mn–N–C catalyst generated a 1.61 A cm –2 at 0.7 V based on HDV conditions (0.2 mgPt cm –2 and 250 kPa air). More importantly, the MEA is highly durable and can retain 1.31 A cm –2 at 0.7 V after 30,000 voltage cycles (~19% loss), surpassing the commercial Pt/C catalyst (loss of ~56%). Therefore, the Mn–N–C carbon-supported Pt catalyst holds a great promise to meet the challenging DOE target (1.07 A cm –2 at 0.7 V after 150,000 cycles) for HDVs.

25 ENERGY STORAGE↗

DOE OSTI2024

Water-induced surface ordering facilitating the microcutting of ductile metals

Metal cutting is a crucial process in modern manufacturing. Enhancing the machinability of metals can significantly improve their production efficiency and surface integrity. Coating surface-active media (SAM) on the free surface of the metals before cutting is an easy method to improve machinability, which usually pertains to the category of the renowned Rehbinder effect. However, the existing SAM is usually hazardous and complex materials. Besides, the effect of SAM on the local structure of the metal surface remains unclear. In this study, water is employed as a simple yet often overlooked SAM in the microcutting of copper. Using water as SAM also allows the employment of X-ray absorption fine structure spectroscopy (XAFS) to study the local structure of copper with and without water coating. Results show that water coating on the free surface of copper can significantly reduce the cutting force and chip thickness, and improve the surface finish. Interestingly, removing the water coating enables the recovery of the cutting force, demonstrating a reversible effect. Based on the XAFS results and molecular dynamics simulation, a water-induced surface ordering mechanism is proposed to explain the findings from the microcutting experiments. This mechanism suggests that water molecules can induce surface ordering in copper, resulting in reduced surface energy and fracture toughness of copper, thus enhancing machinability. In conclusion, this work provides valuable insights into the comprehension of the Rehbinder effect and shows that picometer-scale modifications of the surface atom arrangement can considerably alter the deformation mode of metals, paving the way for the development of new manufacturing processes.

36 MATERIALS SCIENCE↗

DOE OSTI2024

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

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

Chemistry↗

NASA NTRS2012

An Icy Kuiper Belt Around the Young Solar-type Star HD 181327

Context. HD 181327 is a young main sequence F5/F6 V star belonging to the Beta Pictoris moving group (age approx.. 12 Myr). It harbors an optically thin belt of circumstellar material at radius approx.. 90 AU, presumed to result from collisions in a population of unseen planetesimals. Aims. We aim to study the dust properties in the belt in details, and to constrain the gas-to-dust ratio. Methods. We obtained far-infrared photometric observations of HD 181327 with the PACS instrument onboard the Herschel Space Observatory, complemented by new 3.2 mm observations carried with the ATCA array. The geometry of the belt is constrained with newly reduced HST/NICMOS scattered light images that allow the degeneracy between the disk geometry and the dust properties to be broken. We then use the radiative transfer code GRaTeR to compute a large grid of models, and we identify the grain models that best reproduce the spectral energy distribution (SED) through a Bayesian analysis. We attempt to detect the oxygen and ionized carbon fine-structure lines with Herschel/PACS spectroscopy, providing observables to our photochemical code ProDiMo. Results. The HST observations confirm that the dust is confined in a narrow belt. The continuum is detected with Herschel/PACS completing nicely the SED in the far-infrared. The disk is marginally resolved with both PACS and ATCA. A medium integration of the gas spectral lines only provides upper limits on the [OI] and [CII] line fluxes.We show that the HD 181327 dust disk consists of micron-sized grains of porous amorphous silicates and carbonaceous material surrounded by an important layer of ice, for a total dust mass of approx.. 0.05 Solar Mass (in grains up to 1 mm). We discuss evidences that the grains consists of fluffy aggregates. The upper limits on the gas atomic lines do not provide unambiguous constraints: only if the PAH abundance is high, the gas mass must be lower than approx. 17 Solar Mass. Conclusions. Despite the weak constraints on the gas disk, the age of HD 181327 and the properties of the dust disk suggest that it has passed the stage of gaseous planets formation. The dust reveals a population of icy planetesimals, similar to the primitive Edgeworth-Kuiper belt, that may be a source for the future delivery of water and volatiles onto forming terrestrial planets.

HD 181327↗

DOE OSTI2021

Interface creation on a mixed-terminated perovskite surface

In the field of complex oxide heterostructures, understanding of the initial substrate surface can be critical to fundamental studies regarding the development of emergent properties at the film–substrate interface. For this reason, a considerable amount of effort has gone into the development of techniques to achieve surfaces with single termination for a variety of perovskite single crystals. However, a decisive understanding of how an interface is created when epitaxial growth occurs on a mixed terminated surface remains lacking. Employing in situ synchrotron X-ray scattering during thin film growth by molecular beam epitaxy, we investigate the initial stages of growth on (LaAlO 3 )(Sr 2 AlTaO 6 ) (001) substrates with mixed termination. Using LaNiO 3 as a model system, we find that the surface layers of the substrate restructure during deposition such that while a NiO 2 monolayer is weakly bound, a LaO monolayer bonds strongly, effectively incorporating with (Al, Ta)O 2 from the surface and forming a La(Al, Ta)O 3 ultrathin film.  With regard to the synthesis of high-quality complex oxide heterostructures, it is important that the substrate meet an array of criteria related to the crystal structure, lattice parameter, thermodynamic properties, electrical and optical properties, and so on. In particular, the surface of the substrate should be atomically smooth and exhibit the step-terrace structure ideal for epitaxial thin film growth. Perovskite oxides with the formula ABO 3 have two possible (001) surfaces: AO (A-site termination) and BO 2 (B-site termination). The ability to consistently achieve one of these surface terminations on SrTiO 3 , i.e., TiO 2 , has helped SrTiO 3 become the predominant oxide in the field.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Actinides and Correlated Electron Materials

The Actinides and Correlated Electron Materials area of leadership spans Los Alamos National Laboratory competency in actinide materials research dating to the Manhattan Project as articulated in the Integrated Plutonium Science and Research Strategy and competency in strongly correlated electron systems dating back to at least the early 1980s. This area of leadership focuses on the goals of discovering, understanding, and controlling emergent electronic states and predictive performance of actinide materials. They are quintessentially linked by the fact that the physics of actinides—and plutonium in particular—are governed by strong electronic correlations. Not only is the electronic structure of actinides dictated by fine details of electron correlations, but chemical bonding and physical structure are as well. Hence, by addressing the first goal of this leadership area we can significantly accelerate progress on the second goal. To understand such matter requires probing the intertwined spin, charge, orbital, and lattice degrees of freedom with greater precision and developing models that accurately predict the consequences of these coupled degrees of freedom, on multiple length and time scales and including acute reactivity and effects of self-irradiation phenomena in these materials.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Evolution of Charge-Lattice Dynamics across the Kuramoto Synchronization Phase Diagram of Quantum Tunneling Polarons in Cuprate Superconductors

Because of its sensitivity to the instantaneous structure factor, S(Q,t = 0), Extended X-ray Absorption Fine Structure (EXAFS) is a powerful tool for probing the dynamic structure of condensed matter systems in which the charge and lattice dynamics are coupled. When applied to hole-doped cuprate superconductors, EXAFS has revealed the presence of internal quantum tunneling polarons (IQTPs). An IQTP arises in EXAFS as a two-site distribution for certain Cu–O pairs, which is also duplicated in inelastic scattering but not observed in standard diffraction measurements. The Cu–Sr pair distribution has been found to be highly anharmonic and strongly correlated to both the IQTPs and to superconductivity, as, for example, in YSr 2 Cu 2.75 Mo 0.25 O 7.54 (T c =84 K). In order to describe such nontrivial, anharmonic charge-lattice dynamics, we have proposed a model Hamiltonian for a prototype six-atom cluster, in which two Cu-apical-O IQTPs are charge-transfer bridged through Cu atoms by an O atom in the CuO 2 plane and are anharmonically coupled via a Sr atom. By applying an exact diagonalization procedure to this cluster, we have verified that our model indeed produces an intricate interplay between charge and lattice dynamics. Then, by using the Kuramoto model for the synchronization of coupled quantum oscillators, we have found a first-order phase transition for the IQTPs into a synchronized, phase-locked phase. Most importantly, we have shown that this transition results specifically from the anharmonicity. Finally, we have provided a phase diagram showing the onset of the phase-locking of IQTPs as a function of the charge-lattice and anharmonic couplings in our model. We have found that the charge, initially confined to the apical oxygens, is partially pumped into the CuO 2 plane in the synchronized phase, which suggests a possible connection between the synchronized dynamic structure and high-temperature superconductivity (HTSC) in doped cuprates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2025

Modeling phase transformations in Mn-rich disordered rocksalt cathodes with machine-learning interatomic potentials

Mn-rich disordered rocksalt (DRX) cathode materials exhibit a phase transformation from a disordered to a partially disordered spinel-like structure (δ-phase) during electrochemical cycling. Here, in this computational study, we use charge-informed molecular dynamics with a fine-tuned CHGNet foundation potential to investigate the phase transformation in LixMn 0.8 Ti 0.1 O 1.9 F 0.1 . Our results indicate that transition metal migration occurs and reorders to form the spinel-like ordering in an FCC anion framework. The transformed structure contains a higher concentration of nontransition metal (0-TM) face-sharing channels, which are known to improve Li transport kinetics. Analysis of the Mn valence distribution suggests that the appearance of tetrahedral Mn 2+ is a consequence of spinel-like ordering, rather than the trigger for cation migration as previously suggested. Calculated equilibrium intercalation voltage profiles demonstrate that the δ-phase, unlike the ordered spinel, exhibits solid-solution signatures at low voltage. A higher Li capacity is obtained than in the DRX phase. This study provides atomic insights into solid-state phase transformation and its relation to experimental electrochemistry, highlighting the potential of machine-learning interatomic potentials for understanding complex oxide materials.

Zhong, Peichen [University of California, Berkeley↗

DOE OSTI2021

BISON microstructure-based pulverization criterion in high burnup structure

To improve the economics of commercial nuclear power production, utilities are seeking to increase the allowable burnup limit of UO$_2$ fuel. One of the main factors that contributes to the current burnup limit of 62 GWd/MTU in commercial light water reactors (LWRs) is the risk of fine fragmentation or pulverization during a loss of coolant accident (LOCA). Pulverization primarily occurs at high burnups, especially when the high burnup structure (HBS) has formed. To allow the industry to pursue increased burnup and develop mitigation strategies, it is essential to have improved capability to predict the onset of pulverization. However, the mechanism of pulverization is not well understood, and the existing predictive capabilities implemented in the BISON fuel performance code are empirical in nature. In this report, mesoscale simulations are used to improve understanding of the formation mechanism of the HBS and how it responds during a LOCA transient, and inform development of a BISON pulverization criterion. A phase-field model was used to simulate the evolution of bubble pressure as a result of HBS formation. The simulations showed that gas atoms diffuse from grain interiors to the new grain boundaries created during HBS formation, and diffuse rapidly along these grain boundaries to reach existing bubbles. This causes an increase in bubble pressure in existing bubbles, leading to bubble growth during steady-state operation. To simulate the response of HBS bubbles to a LOCA transient, a newly developed phase-field model was used; in agreement with preliminary results from FY20, bubble size did not change significantly during the duration of the transient. A phase-field fracture model was used to study fragmentation patterns in the HBS, including using input from the phase-field model as initial conditions. Phase-field fracture simulations were used to determine a pulverization criterion for BISON. A function for the critical pressure for pulverization to occur was fit to data from the phase-field fracture simulations, and this function was implemented as a material property in BISON. For comparison, an analytical criterion for pulverization was developed and implemented within the same material property.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

The 1.66 μm spectrum of the ethynyl radical, CCH

Frequency-modulated diode laser transient absorption spectra of the ethynyl radical have been recorded at wavelengths close to 1.66 μm. The observed spectrum includes strong, regular, line patterns. The two main bands observed originate in the ground $\tilde{χ}$ 2 Σ + state and its first excited bending vibrational level of 2 $Π$ symmetry. The upper states, of 2 Σ + symmetry at 6055.6 cm -1 and 2 $Π$ symmetry at 6413.5 cm -1 , respectively, had not previously been observed and the data were analyzed in terms of an effective Hamiltonian representing their rotational and fine structure levels to derive parameters which can be used to calculate rotational levels up to J = 37/2 for the 2 $Π$ level and J = 29/2 for the 2 Σ one. Additionally, a weaker series of lines have been assigned to absorption from the second excited bending, (0 2 0), level of 2 Σ symmetry, to a previously observed state of 2 $Π$ symmetry near 6819 cm -1 . These strong absorption bands at convenient near-IR laser wavelengths will be useful for monitoring CCH radicals in chemical systems.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2025

Fluorinated polythiophenes with ester side chains for boosting the V OC and efficiency in non-fullerene polymer solar cells

As the power conversion efficiency (PCE) of organic photovoltaics (OPVs) approximates the 19 % threshold, wide bandgap (WBG) polythiophenes (PTs) have gained increasing attention due to their simple chemical structures and ease of synthesis, making them promising candidates for large-scale production. However, the benchmark polymer poly(3-hexylthiophene) (P3HT) is limited by its high-lying HOMO energy level, which restricts the open-circuit voltage (V OC ) in solar cells. Here, in this study, we introduce a novel series of PT derivatives (PDC8-T, PDC8-3T, PDC16-3T, and PDC16-3T-2F) featuring ester side chains designed to fine-tune electronic properties through a streamlined three-step synthesis. Additionally, we incorporated a π-spacer to reduce steric hindrance and elongated alkyl side chains to improve solubility and processability. Compared to P3HT, these PT derivatives demonstrate a significant reduction in HOMO energy levels, lowering by approximately 0.3–0.4 eV. Among them, PDC16-3T-2F—with fluorine atom substitution—achieves the lowest HOMO energy level, induces a coplanar molecular conformation, and enhances polymer aggregation behavior. We evaluated these PT derivatives in inverted non-fullerene bulk-heterojunction (NFA BHJ) OPVs. The PDC8-3T device showed a relatively low PCE of 0.69 %, with a V OC of 0.76 V, a short-circuit current density (J SC ) of 3.32 mA/cm 2 , and a fill factor (FF) of 27.3 %. In contrast, the PDC16-3T-2F device achieved an impressive PCE of 7.21 %, with a V OC of 0.85 V, a J SC of 14.60 mA/cm 2 , and an FF of 58.4 %. This remarkable improvement is attributed to the fluorine substitution, which not only enhances molecular orientation but also downshifts the HOMO energy level and further boosts the V OC . Hence, these molecular design strategies have led to a fibrillar bicontinuous interpenetrating network with optimal nanoscale phase separation within the active layer.

14 SOLAR ENERGY↗

DOE OSTI2025

Materials Graph Library (MatGL), an open-source graph deep learning library for materials science and chemistry

Graph deep learning models, which incorporate a natural inductive bias for atomic structures, are of immense interest in materials science and chemistry. Here, we introduce the Materials Graph Library (MatGL), an open-source graph deep learning library for materials science and chemistry. Built on top of the popular Deep Graph Library (DGL) and Python Materials Genomics (Pymatgen) packages, MatGL is designed to be an extensible “batteries-included” library for developing advanced model architectures for materials property predictions and interatomic potentials. At present, MatGL has efficient implementations for both invariant and equivariant graph deep learning models, including the Materials 3-body Graph Network (M3GNet), MatErials Graph Network (MEGNet), Crystal Hamiltonian Graph Network (CHGNet), TensorNet and SO3Net architectures. MatGL also provides several pre-trained foundation potentials (FPs) with coverage of the entire periodic table, and property prediction models for out-of-box usage, benchmarking and fine-tuning. Finally, MatGL integrates with PyTorch Lightning to enable efficient model training.

chemistry↗

DOE OSTI2020

EXAFS investigations of temperature-dependent structure in cobalt-59 molecular NMR thermometers

Cobalt-59 nuclei are known for extremely thermally sensitive chemical shifts (δ), which in the long term could yield novel magnetic resonance thermometers for bioimaging applications. In this manuscript, we apply extended X-ray absorption fine structure (EXAFS) spectroscopy for the first time to probe the exact variations in physical structure that produce the exceptional thermal sensitivity of the 59 Co NMR chemical shift. We apply this spectroscopic technique to five Co(III) complexes: [Co(NH3)6]Cl3 (1), [Co(en) 3 ]Cl 3 (2) (en = ethylenediamine), [Co(tn) 3 ]Cl 3 (3) (tn = trimethylenediamine), [Co(tame) 2 ]Cl 3 (4) (tame = 1,1,1-tris(aminomethyl)ethane), and [Co(diNOsar)]Cl 3 (5) (diNOsar = dinitrosarcophagine). The solution-phase EXAFS data reveal increasing Co–N bond distances for these aqueous complexes over a ~50 °C temperature window, expanding by Δr (Co–N) = 0.0256(6) Å, 0.0020(5) Å, 0.0084(5) Å, 0.0006(5) Å, and 0.0075(6) Å for 1–5, respectively. Computational analyses of the structural changes reveal that increased connectivity between the donor atoms encourages complex structural variations. Finally, these results imply that rich temperature-dependent structural variations define 59 Co NMR thermometry in macrocyclic complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗