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

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At least 1,153 records · Page 64
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Heterogeneous microstructural evolution during hydrodynamic penetration of a high-velocity copper microparticle impacting copper

Microparticle hydrodynamic penetration (HDP) may be associated with the erosion regime in cold spray processing and other high-velocity impact events. Here, in an experimental approach where we can individually launch particles and study the impact sites, we explore copper microparticles impacted on copper substrates at velocities above 900 m/s where HDP begins. We lift cross-sectional lamellae from the impact sites with a focused-ion beam for further microstructural characterization using electron backscatter diffraction and scanning transmission electron microscopy. Due to the gradients of strain, strain rate, and temperature associated with HDP, heterogeneous microstructures result. The structural evolution processes observed include deformation twinning and multiple dislocation-mediated grain recrystallization mechanisms—geometric dynamic recrystallization (gDRX), discontinuous DRX (dDRX), and meta DRX (mDRX). The higher strains at the interface lead to the most significant structural changes and complex mechanisms. In contrast, there is a gradient to more conventional dislocation plasticity away from the interface (on either the particle or substrate side). Here, these microstructural observations are consistent with the deformation map for copper and extend the observations of impact-induced recrystallization across new regimes of behavior.

Cold spray process↗
DOE OSTI2017

Role of Modulators in Controlling the Colloidal Stability and Polydispersity of the UiO-66 Metal–Organic Framework

We report nanoscale UiO-66 Zr 6 (OH) 4 O 4 (C 8 O 4 H 4 ) 6 has been synthesized with a series of carboxylic acid modulators, R-COOH (where R = H, CH 3 , CF 3 , and CHCl 2 ). The phase purity and size of each MOF was confirmed by powder X-ray diffraction, BET surface area analysis, and scanning transmission electron microscopy (STEM). Size control of UiO-66 crystals from 20 nm to over 1 μm was achieved, and confirmed by STEM. The colloidal stability of each MOF was evaluated by dynamic light scattering and was found to be highly dependent on the modulator conditions utilized in the synthesis, with both lower pKa and higher acid concentration resulting in more stable structures. Furthermore, STEM was carried out on both colloidally stable samples and those that exhibited a large degree of aggregation, which allowed for visualization of the different degrees of dispersion of the samples. The use of modulators at higher concentrations and with lower pKas leads to the formation of more defects, as a consequence of terephthalic acid ligands being replaced by modulator molecules, thereby enhancing the colloidal stability of the UiO-66 nanoparticles. These findings could have a significant impact on nanoscale MOF material syntheses and applications, especially in the areas of catalysis and drug delivery.

36 MATERIALS SCIENCE↗
DOE OSTI2018

In situ coherent diffractive imaging

Coherent diffractive imaging (CDI) has been widely applied in the physical and biological sciences using synchrotron radiation, X-ray free-electron laser, high harmonic generation, electrons, and optical lasers. One of CDI’s important applications is to probe dynamic phenomena with high spatiotemporal resolution. Here, we report the development of a general in situ CDI method for real-time imaging of dynamic processes in solution. By introducing a time-invariant overlapping region as real-space constraint, we simultaneously reconstructed a time series of complex exit wave of dynamic processes with robust and fast convergence. We validated this method using optical laser experiments and numerical simulations with coherent X-rays. Our numerical simulations further indicated that in situ CDI can potentially reduce radiation dose by more than an order of magnitude relative to conventional CDI. With further development, we envision in situ CDI could be applied to probe a range of dynamic phenomena in the future.

47 OTHER INSTRUMENTATION↗
DOE OSTI2020

In situ characterization of foreign object damage (FOD) in environmental-barrier-coated silicon carbide (SiC) ceramic

Environmental barrier coatings (EBCs) protect advanced ceramics and ceramic matrix composites (CMCs) from oxidation and corrosion in gas turbine engine environments. Foreign object damage (FOD), where debris impact the protective coatings, is a critical hazard which limits the turbine durability. Despite previous efforts to understand FOD in EBCs, a detailed understanding of the fundamental transient damage mechanisms is still lacking. In the current work, the real-time FOD behavior of a Mullite / Silicon EBC was visualized via a dynamic synchrotron X-ray source in phase contrast imaging (PCI) configuration. Prior to the in situ FOD experiments, the microstructure and composition of the coating were respectively characterized using a scanning electron microscope (SEM) and X-ray diffraction (XRD). The variation in the properties of the debris was modeled by ~ 1.5 mm diameter Partially Stabilized Zirconia (PSZ) and Silicon Nitride (Si 3 N 4 ) spheres. A modified light-gas gun setup, synchronized with the X-ray beam, was used to propel the projectiles at velocities ranging between 300 and 355 m·s -1 . Coated samples were impacted under a fully backed support configuration and at normal incidence. Coating penetration and delamination, as well as projectile deformation at the bond coat resulted for FOD by PSZ spheres. Comparatively, projectile fracture, with subsequent rebound of fragments, as well as complete coating penetration and delamination at the substrate interface occurred for FOD by Si 3 N 4 spheres. It should be noted that only cone cracking was observed for FOD by PSZ spheres while back surface cracking was present for both projectile types. Qualitative understanding of the driving forces for the observed damage mechanisms were provided.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Remote monitoring of environmental particulate pollution - A problem in inversion of first-kind integral equations

The determination of the microstructure, chemical nature, and dynamical evolution of scattering particulates in the atmosphere is considered. A description is given of indirect sampling techniques which can circumvent most of the difficulties associated with direct sampling techniques, taking into account methods based on scattering, extinction, and diffraction of an incident light beam. Approaches for reconstructing the particulate size distribution from the direct and the scattered radiation are discussed. A new method is proposed for determining the chemical composition of the particulates and attention is given to the relevance of methods of solution involving first kind Fredholm integral equations.

Fymat, A. L.↗
DOE OSTI2021

Molecular dynamics simulations of a dicationic ionic liquid for CO 2 capture

A dicationic ionic liquid ([DBU-PEG][Tf 2 N] 2 ) was studied using classical molecular dynamics simulations to examine its structural and gas separation properties. The dication was designed in an attempt to improve CO 2 solubility by means of tuning the cation-anion interactions of the ionic liquid (IL). The computational model was compared to experimentally obtained density, viscosity, and powder X-ray diffraction spectra. The structure of the IL was further investigated with radial distribution functions and free volume analysis through cavity distributions. It was found that the shape and charge distribution of the dication enhances CO 2 interaction: the CO 2 molecule is hugged by the dication along the PEG linker and close to one of the cationic ends. Here, the geminal design of the dication allows for strong interaction with CO 2 , showing promise as a means of carbon capture.

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

Current Status of Single Particle Imaging with X-ray Lasers

The advent of ultrafast X-ray free-electron lasers (XFELs) opens the tantalizing possibility of the atomic-resolution imaging of reproducible objects such as viruses, nanoparticles, single molecules, clusters, and perhaps biological cells, achieving a resolution for single particle imaging better than a few tens of nanometers. Improving upon this is a significant challenge which has been the focus of a global single particle imaging (SPI) initiative launched in December 2014 at the Linac Coherent Light Source (LCLS), SLAC National Accelerator Laboratory, USA. A roadmap was outlined, and significant multi-disciplinary effort has since been devoted to work on the technical challenges of SPI such as radiation damage, beam characterization, beamline instrumentation and optics, sample preparation and delivery and algorithm development at multiple institutions involved in the SPI initiative. Currently, the SPI initiative has achieved 3D imaging of rice dwarf virus (RDV) and coliphage PR772 viruses at ~10 nm resolution by using soft X-ray FEL pulses at the Atomic Molecular and Optical (AMO) instrument of LCLS. Meanwhile, diffraction patterns with signal above noise up to the corner of the detector with a resolution of ~6 Ångström (Å) were also recorded with hard X-rays at the Coherent X-ray Imaging (CXI) instrument, also at LCLS. Achieving atomic resolution is truly a grand challenge and there is still a long way to go in light of recent developments in electron microscopy. However, the potential for studying dynamics at physiological conditions and capturing ultrafast biological, chemical and physical processes represents a tremendous potential application, attracting continued interest in pursuing further method development. In this paper, we give a brief introduction of SPI developments and look ahead to further method development.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Thermal disorder and phonon softening in the ferroelectric phase transition of lead titanate

We report a molecular dynamics study of ab initio quality of the ferroelectric phase transition in crystalline PbTi⁢O3. We model anharmonicity accurately in terms of potential energy and polarization surfaces trained on density functional theory data with modern machine learning techniques. Our simulations demonstrate that the transition has a strong order-disorder character, in agreement with diffraction experiments, and provide fresh insight into the approach to equilibrium across the phase transition. We find that the emergence and disappearance of the macroscopic polarization is driven by dipolar switching at the nanometer scale. We also computed the infrared optical absorption spectra in both the ferroelectric and the paraelectric phases, finding good agreement with the experimental Raman frequencies. Often, the almost ideal displacive character of the soft mode detected by Raman scattering in the paraelectric phase has been contrasted with the order-disorder character of the transition suggested by diffraction experiments. We settle this issue by showing that the soft mode coexists with a strong Debye relaxation associated with thermal disordering of the dipoles. The Debye relaxation feature is centered at zero frequency and appears near the transition temperature in both the ferroelectric and the paraelectric phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Peculiarities of the phase transformation dynamics in bulk FeRh based alloys from magnetic and structural measurements

We analyze coexistence of antiferromagnetic and ferromagnetic phases in bulk iron-rhodium and its alloys with palladium, Fe 50,4 Rh 49,6 , Fe 49,7 Rh 47,4 Pd 2,9 and Fe 48,3 Rh 46,8 Pd 4,9 , using neutron diffraction, magnetization and scanning Hall probe imaging. Temperature dependencies of the lattice parameters, AFM and FM phase weight fractions, and Fe magnetic moment values were obtained on cooling and heating across the AFM-FM transition. Substantial thermomagnetic hysteresis for the phases’ weight fractions and a relatively narrow one for the unit cell volume has been observed on cooling-heating. Furthermore, a clear dependence of hysteretic behavior on Pd concentration has been traced. Additional direct magnetic measurements of the spatial distribution of the phase transition are acquired using scanning Hall probe microscopy, which reveals the length scale of the phase coexistence and the spatial progression of the transition in the presence of external magnetic field. Also, the magnetic phase diagram has been constructed for a series of Pd-doped FeRh alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Site-Selective Modification of Lanthanum Oxychloride to Modulate Halide-Ion Conduction

Design principles for solid-state halide-ion conduction remain poorly defined despite the increasing importance of halide ions as charge carriers in a variety of energy storage and electrochemical computing technologies. Here, we employ a siteselective modification strategy in which aliovalent cations are preferentially introduced at the La 3+ crystallographic site of LaOCl in the 2c Wyckoff position, enabling controlled generation of chloride vacancies and modification of lattice dynamics to enhance chloride-ion conductivity. Aliovalent substitution of La 3+ with Mg 2+ , Ca 2+ , and Sr 2+ generates charge-compensating Cl vacancies while preserving the matlockite crystal structure. X-ray excited optical luminescence measurements with Dy 3+ as a reporter chromophore evidence vacancy-derived midgap electronic states and an extended energy range of radiation-less Auger electron emission corresponding to substantial modification of electronic structure and local electrostatic potentials. Ca alloying at 8−10 at. % increases the chloride-ion conductivity by three- to 4 orders of magnitude as compared to unalloyed LaOCl, whereas comparable amounts of Sr- and Mg-alloying in LaOCl imbue less pronounced conductivity enhancements. Temperature-dependent Raman spectroscopy measurements reveal that Ca- and Sr-alloying substantially soften the La−Cl sublattice and yield a more compliant crystal lattice that can deform to accommodate Cl-ion migration. Structure solutions derived from Rietveld refinements to powder Xray diffraction reveal larger O−La−Cl bond-angle deviations and enhanced out-of-plane cation displacements for Ca- and Sr-alloyed compositions as compared to Mg-alloyed LaOCl. Such local distortions enhance chloride-ion mobility by reshaping and flattening vacancy migration energy landscapes and by modulating lattice dynamics governing anion conduction. We further illustrate that coalloying of Ca with Mg and Sr induces a nonmonotonic conductivity−defect stoichiometry relationship that can be rationalized based on cooperative interactions. Together, these results establish site-selective aliovalent alloying of LaOCl as an effective route to halide-ion solid electrolytes and provide broadly generalizable design principles for site-selective modification to induce vacancy formation and lattice softening to engender facile anion transport

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Decoupling Lattice and Magnetic Instabilities in Frustrated CuMnO2

The AMnO 2 delafossites (A = Na, Cu) are model frustrated antiferromagnets, with triangular layers of Mn 3+ spins. At low temperatures (T N = 65 K), a C2/m → P$\bar1$ transition is found in CuMnO 2 , which breaks frustration and establishes magnetic order. In contrast to this clean transition, A = Na only shows short-range distortions at T N . Here, we report a systematic crystallographic, spectroscopic, and theoretical investigation of CuMnO 2 . We show that, even in stoichiometric samples, nonzero anisotropic Cu displacements coexist with magnetic order. Using X-ray/neutron diffraction and Raman scattering, we show that high pressures act to decouple these degrees of freedom. This manifests as an isostuctural phase transition at ~10 GPa, with a reversible collapse of the c-axis. This is shown to be the high-pressure analogue of the c-axis negative thermal expansion seen at ambient pressure. Density functional theory (DFT) simulations confirm that dynamical instabilities of the Cu + cations and edge-shared MnO 6 layers are intertwined at ambient pressure. However, high pressure selectively activates the former, before an eventual predicted reemergence of magnetism at the highest pressures. Our results show that the lattice dynamics and local structure of CuMnO 2 are quantitatively different from nonmagnetic Cu delafossites and raise questions about the role of intrinsic inhomogeneity in frustrated antiferromagnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Porosity and Variations in Microgravity Aerogel Nano-Structures: New Laser Speckle Characterization Methods - 2

The transition from sol to gel is a process that is critical to the properties of engineered nanomaterials, but one with few available techniques for observing the dynamic processes occurring during the evolution of the gel network. Specifically, the observation of various cluster aggregation models, such as diffusion-limited and reaction-limited cluster growth can be quite difficult. This can be rather important as the actual aggregation model can dramatically influence the mechanical properties of gels, and is significantly affected by the presence of convective flows, or their absence in microgravity. We have developed two new non-intrusive optical methods for observing the aggregation processes within gels in real time. These make use of the dynamic behavior of laser speckle patterns produced when an intense laser source is passed through a gelling sol. The first method is a simplified time-correlation measurement, where the speckle pattern is observed using a CCD camera and information on the movement of the scattering objects is readily apparent. This approach is extremely sensitive to minute variations in the flow field as the observed speckle pattern is a diffraction-based image, and is therefore sensitive to motions within the sol on the order of the wavelength of the probing light. Additionally, this method has proven useful in determining a precise time for the gel-point, an event often difficult to measure. Monitoring the evolution of contrast within the speckle field is another method that has proven useful for studying aeration. In this case, speckle contrast is dependent upon the size (correlation length) and number of scattering centers, increasing with increasing size, and decreasing with increasing numbers. The dynamic behavior of cluster growth in gels causes both of these to change simultaneously with time, the exact rate of which is determined by the specific aggregation model involved. Actual growth processes can now be observed, and the effects of varying gravity fields on the growth processes qualitatively described. Results on preliminary ground-based measurements have been obtained.

Hunt, A. J.↗
DOE OSTI2016

Microstructural evolution and mechanical properties on an ARB processed IF steel studied by X-ray diffraction and EBSD

Accumulative Roll Bonding (ARB) is one of the so-called severe plastic deformation (SPD) processes, allowing the production of metals and alloys with ultrafine (micro-nano) structures. Materials with ultrafine grains present attractive properties like the simultaneous increase in strength and ductility. Our interest in these materials is focused on their microstructural evolution during ARB processing, eventually responsible for the enhancement of those mechanical properties. In the current work we follow the evolution of the microstructure in an interstitial-free (IF) steel deformed by ARB after consecutive processing cycles, by means of Electron BackScatter Diffraction (EBSD) and X-ray diffraction (XRD). Particularly, we present results related to texture, grain (GS) and domain sizes, grain boundary character, density of Geometrically Necessary Dislocations (GND), Grain Orientation Spread (GOS), lattice parameters, microstrain, dislocation density and their spatial arrangement. After 5 ARB cycles the system shows a microstructure constituted mainly by submicrometric grains with high angle boundaries and low presence of dislocations inside the grains. - Highlights: •The evolution of microstructure is followed simultaneously by using GAM, GOS and GND (EBSD) and XRD. •LAGBs and subgrains disappear after few cycles SSDs and HAGBs persist at the end. •Dynamic recrystallization counterbalances dislocation arrays and diminishes hardening rate. •Grain size stabilization is revealed as a mechanism for increasing ductility after few ARB cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Static and dynamic properties of the frustrated spin-$\frac{1}{2}$ depleted-kagome antiferromagnet Cu 7 (TeO 3 ) 2 (SO 4 ) 2 (OH) 6

The structural and magnetic properties of the two-dimensional spin-$\frac{1}{2}$ depleted-kagome compound Cu 7 (TeO 3 ) 2 (SO 4 ) 2 (OH) 6 are investigated using x-ray diffraction, magnetization, heat capacity, and 1 H Nuclear Magnetic Resonance (NMR) measurements. From the analysis of magnetic susceptibility, we found a large Curie-Weiss temperature [𝜃 CW = −50⁢(2)⁢K] and the coexistence of antiferromagnetic and ferromagnetic interactions. The value of 𝜃 CW gives an estimate of the average nearest-neighbor antiferromagnetic interaction of 𝐽/𝑘 B ≃ 66K. The NMR relaxation rates (1/𝑇 1 and 1/𝑇 2 ) exhibit a peak, providing evidence for a magnetic long-range order at 𝑇* ≃ 4K which appears to be canted antiferromagnetic type. Heat capacity also features a broad maximum at 𝑇* that moves towards higher temperatures with increasing magnetic field, reflecting defect induced Schottky anomaly. The frustration parameter 𝑓 𝑟 = |𝜃 CW |/𝑇* ≃ 12.5 renders the compound a highly frustrated low-dimensional magnet.

Akshay, K. U. [Indian Institute of Science Educati↗
DOE OSTI2023

Investigating microstructural evolution in SolidStir™ extruded oxide dispersion strengthened 14YWT alloy fuel cladding tube

Structural components for extreme environments require advanced materials and manufacturing processes. One such advanced material is oxide dispersion strengthened (ODS) Fe–14 wt.%Cr–3W–0.4Ti–0.3Y 2 O 3 (14YWT), which is developed for components to be used in Gen IV and fusion nuclear reactors. However, the conventional manufacturing processes to produce components, such as fuel cladding tubes, either do not retain the desired microstructural attributes or are costly and less efficient. As a result, a more attractive option is a novel manufacturing process developed on the principle of friction stir welding or processing (FSW/P) and commercially referred to as SolidStir™ Extrusion (SSE). Here this study used the SSE technique to study the manufacturing and microstructural evolution of a fuel cladding tube made of ODS 14YWT alloy. The cladding extrusion by the SSE technique involved the use of ball-milled 14YWT powders with Y, Ti, and O in the solid solution and the use of a specially designed W-25Re-Hf tool for consolidation and extrusion of the powders. A scanning electron microscope (SEM), electron backscattered diffraction (EBSD), and transmission electron microscope (TEM) were utilized for microstructural characterization. A Keyence microscope captured macrostructural photographs of the extruded tube. EBSD examination of the extruded tube on both transverse and longitudinal cross-sections showed the presence of dynamically recrystallized grains and revealed that the average grain size of the transverse cross-section was smaller than that of the longitudinal cross-section. The texture was weak and consisted of some amount of shear texture. The presence of nano-oxide clusters or precipitates of Y, Ti, and O (pyrochlores) in the extruded tube was determined by TEM. Aging heat treatment caused the average precipitate size to decrease and the density to increase compared to the as-processed condition. The results indicated that SSE is a viable tool for manufacturing fuel cladding tubes with the desired microstructural attributes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Multimodal and multiscale strengthening mechanisms in Al-Ni-Zr-Ti-Mn alloy processed by laser powder bed fusion additive manufacturing

The unique thermokinetics of laser-powder bed fusion additive manufacturing (L-PBFAM) has been exploited for development of a novel high-strength Al-Ni-Ti-Zr-Mn alloy. The addition of 0.5 wt% Mn leads to extraordinary improvement in ultimate tensile strength (502 MPa) and work hardening due to the activation of two Mn-induced strengthening mechanisms. First, by a bimodal particle strengthening effect due to Al 31 Mn 6 Ni 12 nano-quasi-crystal particles rejected in inter-dendritic spaces and fibrous Al 3 Ni eutectic dendritic channels, which predominately contributes to the strength improvement, and second by solid solution strengthening from remaining Mn entrapped in Al. These mechanisms supplement the particle strengthening effect imparted by coherent and incoherent Al 3 (Ti,Zr) co-precipitates present at melt pool boundaries, dislocation strengthening due to solidification induced strain, and Hall-Petch and backstress strengthening effect due to heterogenous grain size distribution occurring at various length scales. In conclusion, the solidification dynamics and hierarchical heat distribution that are associated with L-PBFAM resulted in complex spatial variations in these strengthening phenomena and were investigated via a high-throughput multiscale structure–property correlation that involved thermokinetic simulation, X-ray diffraction, high-resolution nanoindentation mapping, and site-specific transmission electron microscopy of the alloy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Structure–Composition Relationships for Mg–Ni and Mg–Fe Olivine

Olivine is a dynamic and important mineral in the crust and mantle with relevance to processes important to climate change technology, such as geologic carbon storage and critical mineral recovery. In this work, we critically evaluated and compiled a new database of olivine diffraction data, lattice parameters, and composition to enable rapid Ni-Mg-Fe olivine composition determination. A compilation of olivine X-ray diffraction data and chemical compositions from both the literature and the International Centre for Diffraction Data (ICDD) powder database was assembled to plot both the forsterite-fayalite and forsterite-liebenbergite solid solution lines. Here we present an expanded dataset to delineate equations and relationships used for quantifying the correlations between olivine lattice parameters and chemical compositions in Mg 2 SiO 4 -Fe 2 SiO 4 (forsterite-fayalite) and Mg 2 SiO 4 -Ni 2 SiO 4 (forsterite-liebenbergite) olivine solid solution series.

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

Direct Observation of Ammonia Storage in UiO-66 Incorporating Cu(II) Binding Sites

The presence of active sites in metal–organic framework (MOF) materials can control and affect their performance significantly in adsorption and catalysis. However, revealing the interactions between the substrate and active sites in MOFs at atomic precision remains a challenging task. Here, we report the direct observation of binding of NH 3 in a series of UiO-66 materials containing atomically dispersed defects and open Cu(I) and Cu(II) sites. While all MOFs in this series exhibit similar surface areas (1111–1135 m 2 g –1 ), decoration of the -OH site in UiO-66-defect with Cu(II) results in a 43% enhancement of the isothermal uptake of NH 3 at 273 K and 1.0 bar from 11.8 in UiO-66-defect to 16.9 mmol g –1 in UiO-66-Cu II . A 100% enhancement of dynamic adsorption of NH 3 at a concentration level of 630 ppm from 2.07 mmol g –1 in UiO-66-defect to 4.15 mmol g –1 in UiO-66-Cu II at 298 K is observed. In situ neutron powder diffraction, inelastic neutron scattering, and electron paramagnetic resonance, solid-state nuclear magnetic resonance, and infrared spectroscopies, coupled with modeling reveal that the enhanced NH 3 uptake in UiO-66-Cu II originates from a {Cu(II)···NH 3 } interaction, with a reversible change in geometry at Cu(II) from near-linear to trigonal coordination. This work represents the first example of structural elucidation of NH 3 binding in MOFs containing open metal sites and will inform the design of new efficient MOF sorbents by targeted control of active sites for NH 3 capture and storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗