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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17): Site-Selective Substitution, Electronic Structure, Chemical Bonding, and Structural Transformation

CoSn-type intermetallic compounds have emerged as a model platform for Kagome-derived flat-band physics, where subtle chemical perturbations can strongly influence electronic structure and phase stability. Here, we present a combined experimental and theoretical study of Sb-substitution in CoSn-type NiIn1–xSbx (0 ≤ x ≤ 0.17) to elucidate the interplay between site selectivity, solubility limit, chemical bonding, and electronic structure. Rietveld refinements on Neutron powder diffraction data confirmed the selective Sb-substitution at the electron-rich In2 (2d) site forming the honeycomb substructure, while the In1 (1a) site within the Kagome layer remains exclusively occupied by In. Density functional theory (DFT) calculations revealed that pristine CoSn-type NiIn hosts Ni 3d-dominated flat bands near the Fermi level (EF), originating from the Kagome-like Ni substructure. Partial replacement of In by Sb within the honeycomb layer alters these flat-band features below EF, reducing the density of states and suppressing the flat-band topology near the Fermi level. Orbital-resolved electronic structure and chemical-bonding analyses show that Sb-substitution enhances Ni-p-block (In/Sb) covalency and optimizes charge compensation, stabilizing the CoSn-type structure up to the solubility limit x ≈ 0.17. Beyond the limit, the higher-Sb compositions show satellite reflections consistent with an incommensurately modulated phase. These results establish a link between site-selective chemical substitution, bonding optimization, and flat-band electronic structure evolution, providing fundamental insights into how chemical substitution influences the electronic properties of Kagome-based intermetallic compounds.

Roy, Nilanjan [National Institute of Technology Si↗
DOE OSTI2016

Crystal Structure of AgBi 2 I 7 Thin Films

Synthesis of cubic-phase AgBi 2 I 7 iodobismuthate thin films and fabrication of air-stable Pb-free solar cells using the AgBi 2 I 7 absorber have recently been reported. Based on X-ray diffraction (XRD) analysis and nominal composition, it was suggested that the synthesized films have a cubic ThZr 2 H 7 crystal structure with AgBi 2 I 7 stoichiometry. Through careful examination of the proposed structure and computational evaluation of the phase stability and bandgap, we find that the reported “AgBi 2 I 7 ” films cannot be forming with the ThZr 2 H 7 -type structure, but rather more likely adopt an Ag-deficient AgBiI 4 type. Both the experimental X-ray diffraction pattern and band gap can be better explained by the AgBiI 4 structure. Additionally, the proposed AgBiI 4 structure, with octahedral bismuth coordination, removes unphysically short Bi–I bonding within the BiI8 hexahedra of the ThZr 2 I 7 model. Our results provide critical insights for assessing the photovoltaic properties of AgBi 2 I 7 iodobismuthate materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

New Insights on the Structure of Electrochemically Deposited Lithium Metal and Its Solid Electrolyte Interphases via Cryogenic TEM

Lithium metal has been considered as the “holy grail” anode material for rechargeable batteries though the dendritic growth and low Coulombic efficiency (CE) have crippled its practical use for decades. Its high chemical reactivity and low stability make it difficult to explore the intrinsic chemical and physical properties of the electrochemically deposited lithium (EDLi) and its accompanied solid electrolyte interphase (SEI). To prevent the dendritic growth and enhance the electrochemical reversibility, it is crucial to understand the nano- and meso- structures of EDLi. However, Li metal is very sensitive to beam damage and has low contrast for commonly used characterization techniques such as electron microscopy. Inspired by biological imaging techniques, this work demonstrates the power of cryogenic (cryo)- electron microscopy to reveal the detailed structure of EDLi and the SEI composition at the nano scale while minimizing beam damage during imaging. Surprisingly, the results show that the nucleation dominated EDLi (five minutes at 0.5 mA cm-2) is amorphous while there is some crystalline LiF present in the SEI. The EDLi grown from various electrolytes with different additives exhibits distinctive surface properties. Consequently, these results highlight the importance of the SEI and its relationship with the CE. Our findings not only illustrate the capabilities of cryogenic microscopy for beam (thermal)-sensitive materials, but it yields crucial structural information of the EDLi evolution with and without electrolyte additives.

electrochemical deposition↗
DOE OSTI2012

Structure of a Specialized Acyl Carrier Protein Essential for Lipid A Biosynthesis with Very Long-chain Fatty Acids in Open and Closed Conformations

The solution nuclear magnetic resonance (NMR) structures and backbone (15)N dynamics of the specialized acyl carrier protein (ACP), RpAcpXL, from Rhodopseudomonas palustris, in both the apo form and holo form modified by covalent attachment of 4'-phosphopantetheine at S37, are virtually identical, monomeric, and correspond to the closed conformation. The structures have an extra α-helix compared to the archetypical ACP from Escherichia coli, which has four helices, resulting in a larger opening to the hydrophobic cavity. Chemical shift differences between apo- and holo-RpAcpXL indicated some differences in the hinge region between α2 and α3 and in the hydrophobic cavity environment, but corresponding changes in nuclear Overhauser effect cross-peak patterns were not detected. In contrast to the NMR structures, apo-RpAcpXL was observed in an open conformation in crystals that diffracted to 2.0 Å resolution, which resulted from movement of α3. On the basis of the crystal structure, the predicted biological assembly is a homodimer. Although the possible biological significance of dimerization is unknown, there is potential that the resulting large shared hydrophobic cavity could accommodate the very long-chain fatty acid (28-30 carbons) that this specialized ACP is known to synthesize and transfer to lipid A. These structures are the first representatives of the AcpXL family and the first to indicate that dimerization may be important for the function of these specialized ACPs.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal-Organic Frameworks

Three new metal-organic frameworks [MOF-525, Zr 6 O 4 (OH) 4 (TCPP-H 2 ) 3 ; MOF-535, Zr 6 O 4 (OH) 4 (XF) 3 ; MOF-545, Zr 6 O 8 (H 2 O) 8 (TCPP-H 2 ) 2 , where porphyrin H 4 -TCPP-H 2 = (C 48 H 24 O 8 N 4 ) and cruciform H 4 -XF = (C 42 O 8 H 22 )] based on two new topologies, ftw and csq, have been synthesized and structurally characterized. MOF-525 and -535 are composed of Zr 6 O 4 (OH) 4 cuboctahedral units linked by either porphyrin (MOF-525) or cruciform (MOF-535). Another zirconium-containing unit, Zr 6 O 8 (H 2 O) 8 , is linked by porphyrin to give the MOF-545 structure. The structure of MOF-525 was obtained by analysis of powder X-ray diffraction data. The structures of MOF-535 and -545 were resolved from synchrotron single-crystal data. MOF-525, -535, and -545 have Brunauer-Emmett-Teller surface areas of 2620, 1120, and 2260 m 2 /g, respectively. In addition to their large surface areas, both porphyrin-containing MOFs are exceptionally chemically stable, maintaining their structures under aqueous and organic conditions. MOF-525 and -545 were metalated with iron(III) and copper(II) to yield the metalated analogues without losing their high surface area and chemical stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Crystal structure of rhodopsin bound to arrestin by femtosecond X-ray laser

G-protein-coupled receptors (GPCRs) signal primarily through G proteins or arrestins. Arrestin binding to GPCRs blocks G protein interaction and redirects signalling to numerous G-protein-independent pathways. Here we report the crystal structure of a constitutively active form of human rhodopsin bound to a pre-activated form of the mouse visual arrestin, determined by serial femtosecond X-ray laser crystallography. Together with extensive biochemical and mutagenesis data, the structure reveals an overall architecture of the rhodopsin-arrestin assembly in which rhodopsin uses distinct structural elements, including transmembrane helix 7 and helix 8, to recruit arrestin. Correspondingly, arrestin adopts the pre-activated conformation, with a ~20° rotation between the amino and carboxy domains, which opens up a cleft in arrestin to accommodate a short helix formed by the second intracellular loop of rhodopsin. In conclusion, this structure provides a basis for understanding GPCR-mediated arrestin-biased signalling and demonstrates the power of X-ray lasers for advancing the frontiers of structural biology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Topologically guided tuning of Zr-MOF pore structures for highly selective separation of C6 alkane isomers

Effective separation of alkane isomers is a critical step in the petroleum refining process to produce gasoline with high octane rating. Current technology relies on energy intensive distillation method. Adsorptive separation using porous solids offers an alternative route that is more cost effective, lower energy and higher efficiency. Guided by topology-directed design and synthesis, we have developed a series of zirconium-based metal-organic frameworks with optimized pore structure for efficient separation of C6 alkane isomers, Zr-bptc adsorbs a large amount of n-hexane while excluding branched isomers. The n-hexane uptake is ~70% higher than that of a benchmark adsorbent, zeolite-5A. A derivative structure, Zr-abtc, is capable of discriminating all three C6 isomers with a high separation factor for 3-methylpentane over 2,3-dimethylbutane. This property is important for producing gasoline with further improved quality.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite

Abstract Birnessite is a low-cost and environmentally friendly layered material for aqueous electrochemical energy storage; however, its storage capacity is poor due to its narrow potential window in aqueous electrolyte and low redox activity. Herein we report a sodium rich disordered birnessite (Na 0.27 MnO 2 ) for aqueous sodium-ion electrochemical storage with a much-enhanced capacity and cycling life (83 mAh g −1 after 5000 cycles in full-cell). Neutron total scattering and in situ X-ray diffraction measurements show that both structural water and the Na-rich disordered structure contribute to the improved electrochemical performance of current cathode material. Particularly, the co-deintercalation of the hydrated water and sodium-ion during the high potential charging process results in the shrinkage of interlayer distance and thus stabilizes the layered structure. Our results provide a genuine insight into how structural disordering and structural water improve sodium-ion storage in a layered electrode and open up an exciting direction for improving aqueous batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Extended experimental inferential structure determination method in determining the structural ensembles of disordered protein states

Proteins with intrinsic or unfolded state disorder comprise a new frontier in structural biology, requiring the characterization of diverse and dynamic structural ensembles. Here we introduce a comprehensive Bayesian framework, the Extended Experimental Inferential Structure Determination (X-EISD) method, which calculates the maximum log-likelihood of a disordered protein ensemble. X-EISD accounts for the uncertainties of a range of experimental data and back-calculation models from structures, including NMR chemical shifts, J-couplings, Nuclear Overhauser Effects (NOEs), paramagnetic relaxation enhancements (PREs), residual dipolar couplings (RDCs), hydrodynamic radii (R h ), single molecule fluorescence Förster resonance energy transfer (smFRET) and small angle X-ray scattering (SAXS). We apply X-EISD to the joint optimization against experimental data for the unfolded drkN SH3 domain and find that combining a local data type, such as chemical shifts or J-couplings, paired with long-ranged restraints such as NOEs, PREs or smFRET, yields structural ensembles in good agreement with all other data types if combined with representative IDP conformers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

High-pressure X-ray diffraction, Raman, and computational studies of MgCl 2 up to 1 Mbar: Extensive pressure stability of the β-MgCl 2 layered structure

We studied magnesium chloride (MgCl 2 ) with the rhombohedral layered CdCl 2 -type structure (α-MgCl 2 ), experimentally, using synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy using a diamond-anvil cell up to 100 GPa at room temperature and theoretically using first-principles density functional calculations. Our results reveal a pressure-induced second-order structural phase transition to a hexagonal layered CdI 2 -type structure (β-MgCl 2 ) at 0.7 GPa: the stacking sequence of the Cl anions are altered resulting in a reduction of the c-axis length. Theoretical calculations confirm this phase transition sequence and the calculated transition pressure is in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phase. According to our experimental results MgCl 2 remains in a 2D layered phase up to 100 GPa and further, the 6-fold coordination of Mg cations is retained. Theoretical calculations of relative enthalpy suggest that this extensive pressure stability is due to a low enthalpy of the layered structure ruling out kinetic barrier effects. Our observation is unusual, as it contradicts with the general structural behavior of highly compressed AB 2 compounds.

36 MATERIALS SCIENCE↗