Sanjit Ghose

Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal-Organic Framework

The cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal-organic frameworks (MOFs) containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid-state adsorbents, but no experimental insights into the nature of the Xe-network interaction are available to date. Here we report a new microporous MOF (designated SBMOF-2) that is selective toward Xe over Kr under ambient conditions, with a Xe/Kr selectivity of about 10 and a Xe capacity of 27.07 wt % at 298 K. Single-crystal diffraction results show that the Xe selectivity may be attributed to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both of which serve as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBMOF-2 was investigated with experimental and computational breakthrough methods. These experiments showed that Kr broke through the column first, followed by Xe, which confirmed that SBMOF-2 has a real practical potential for separating Xe from Kr. Calculations showed that the capacity and adsorption selectivity of SBMOF-2 are comparable to those of the best-performing unmodified MOFs such as NiMOF-74 or Co formate.

Understanding the Adsorption Mechanism of Xe and Kr in a Metal-Organic Framework from X-ray Structural Analysis and First-Principles Calculations.

Enhancement of adsorption capacity and separation of radioactive Xe/Kr at room temperature and above is a challenging problem. Here, we report a detailed structural refinement and analysis of the synchrotron X-ray powder diffraction data of Ni-DODBC metal organic framework with in situ Xe and Kr adsorption at room temperature and above. Our results reveal that Xe and Kr adsorb at the open metal sites, with adsorption geometries well reproduced by DFT calculations. The measured temperature-dependent adsorption capacity of Xe is substantially larger than that for Kr, indicating the selectivity of Xe over Kr and is consistent with the more negative adsorption energy (dominated by van der Waals dispersion interactions) predicted from DFT. Our results reveal critical structural and energetic information about host-guest interactions that dictate the selective adsorption mechanism of these two inert gases, providing guidance for the design and synthesis of new MOF materials for the separation of environmentally hazardous gases from nuclear reprocessing applications.

Evidence of tetragonal nanodomains in the high-pressure polymorph of BaTiO3

The pressure induced P4mm {yields} Pm{bar 3}m phase transition in BaTiO{sub 3} perovskite was investigated by x-ray total scattering. The evolution of the structure was analyzed by fitting pair distribution functions over a pressure range from ambient pressure up to 6.85(7) GPa. Evidence for the existence of tetragonal ferroelectric nanodomains at high pressure was found. The average size of the nanodomains in the high-pressure phase decreases with increasing pressure. Extrapolation of the domain size to pressures higher than studied experimentally suggests a disappearance of the ferroelectric domains at about 9.3(5) GPa and a cubic symmetry of BaTiO{sub 3} high-pressure phase.

Performance calculations of the X-ray powder diffraction beamline at NSLS-II.

The X-ray Powder Diffraction (XPD) beamline at the National Synchrotron Light Source II is a multi-purpose high-energy X-ray diffraction beamline with high throughput and high resolution. The beamline uses a sagittally bent double-Laue crystal monochromator to provide X-rays over a large energy range (30-70 keV). In this paper the optical design and the calculated performance of the XPD beamline are presented. The damping wiggler source is simulated by the SRW code and a filter system is designed to optimize the photon flux as well as to reduce the heat load on the first optics. The final beamline performance under two operation modes is simulated using the SHADOW program. For the first time a multi-lamellar model is introduced and implemented in the ray tracing of the bent Laue crystal monochromator. The optimization and the optical properties of the vertical focusing mirror are also discussed. Finally, the instrumental resolution function of the XPD beamline is described in an analytical method.

High-energy X-ray focusing and applications to pair distribution function investigation of Pt and Au nanoparticles at high pressures.

We report development of micro-focusing optics for high-energy x-rays by combining a sagittally bent Laue crystal monchromator with Kirkpatrick-Baez (K–B) X-ray focusing mirrors. The optical system is able to provide a clean, high-flux X-ray beam suitable for pair distribution function (PDF) measurements at high pressure using a diamond anvil cell (DAC). A focused beam of moderate size (10–15 μm) has been achieved at energies of 66 and 81 keV. PDF data for nanocrystalline platinum (n-Pt) were collected at 12.5 GPa with a single 5 s X-ray exposure, showing that the in-situ compression, decompression, and relaxation behavior of samples in the DAC can be investigated with this technique. PDFs of n-Pt and nano Au (n-Au) under quasi-hydrostatic loading to as high as 71 GPa indicate the existence of substantial reduction of grain or domain size for Pt and Au nanoparticles at pressures below 10 GPa. The coupling of sagittally bent Laue crystals with K–B mirrors provides a useful means to focus high-energy synchrotron X-rays from a bending magnet or wiggler source.

Surface curvatures and diffraction profiles of sagittally bent Laue crystals

The performance of a bent Laue crystal monochromator crucially depends on the sagittal and meridional bending curvatures of the crystal. To optimize the design of monochromator crystals, the surface curvatures and diffraction profiles of a set of sagittally bent Laue crystals with different aspect ratios have been studied experimentally by optical metrology and X-ray measurements. The results were confirmed with finite-element analysis using large-deformation theory. The nonlinear relationship between the curvatures necessitates an experimentally determined parameter in the theoretical modeling of the diffraction profiles. By taking into account the local stress and the aspect ratio of the sagittally bent Laue crystal, the modified analytical approach successfully predicts the rocking-curve width and the integrated reflecting power. The effect of extreme sagittal bending on the rocking curve is also discussed. To retain high reflectivity, the bending curvature should not exceed its critical value for the specified crystal geometry. Furthermore, the uniformity of the bending curvatures across the crystal surface has been examined, which suggests that the minimum crystal dimension should be approximately twice the size of the beam footprint.

Structural changes related to the magnetic transitions in hexagonal InMn O 3

Two magnetic ordering transitions are found in InMnO3, the paramagnetic to antiferromagnetic transition near ~118 K and a lower possible spin rotation transition near ~42 K. Multiple length scale structural measurements reveal enhanced local distortion found to be connected with tilting of the MnO5 polyhedra as temperature is reduced. Strong coupling is observed between the lattice and the spin manifested as changes in the structure near both of the magnetic ordering temperatures (at ~42 K and ~ 118 K). External parameters such as pressure are expected to modify the coupling.

Large Thermal Motion in Halide Perovskites

Solar cells based on hybrid perovskites have shown high efficiency while possessing simple processing methods. To gain a fundamental understanding of their properties on an atomic level, we investigate single crystals of CH3NH3PbI3 with a narrow transition (~5 K) near 327 K. Temperature dependent structural measurements reveal a persistent tetragonal structure with smooth changes in the atomic displacement parameters (ADPs) on crossing T*. We show that the ADPs for I ions yield extended flat regions in the potential wells consistent with the measured large thermal expansion parameter. Molecular dynamics simulations reveal that this material exhibits significant asymmetries in the Pb-I pair distribution functions. We also show that the intrinsically enhanced freedom of motion of the iodine atoms enables large deformations. This flexibility (softness) of the atomic structure results in highly localized atomic relaxation about defects and hence accounts for both the high carrier mobility as well as the structural instability.

Combined computational and experimental investigation of the La2CuO4–xSx (0 ≤ x ≤ 4) quaternary system

Significance Discovery of new materials enabling new technologies, from novel electronics to better magnets, has so far relied on serendipity. Computational advances show promise that new materials can be designed in a computer and not in the lab, a proposal called “Materials by Design.” We present here a detailed comparison between theory and experiment, carrying out the synthesis of a high-temperature superconductor in an X-ray beam to elucidate the sequence of chemical reactions as the compound forms. Parallel computations of the stabilities of possible compounds that could form from the selected elements accurately predict the observed reactions. Paired with our chemical intuition, this methodology provides understanding and potentially control of the essential chemical principles responsible for stabilizing virtually any compound. The lack of a mechanistic framework for chemical reactions forming inorganic extended solids presents a challenge to accelerated materials discovery. We demonstrate here a combined computational and experimental methodology to tackle this problem, in which in situ X-ray diffraction measurements monitor solid-state reactions and deduce reaction pathways, while theoretical computations rationalize reaction energetics. The method has been applied to the La2CuO4−xSx (0 ≤ x ≤ 4) quaternary system, following an earlier prediction that enhanced superconductivity could be found in these new lanthanum copper(II) oxysulfide compounds. In situ diffraction measurements show that reactants containing Cu(II) and S(2−) ions undergo redox reactions, leaving their ions in oxidation states that are incompatible with forming the desired new compounds. Computations of the reaction energies confirm that the observed synthetic pathways are indeed favored over those that would hypothetically form the suggested compounds. The consistency between computation and experiment in the La2CuO4−xSx system suggests a role for predictive theory: to identify and to explicate new synthetic routes for forming predicted compounds.

Robust Nanostructure from High Throughput Powder Diffraction Data

Modern materials under study for next generation technologies in energy conversion and storage, environmental remediation, and health are highly complex, often heterogeneous and nano-structured. Here we refer to these as real materials. A full understanding of the structure requires us to go beyond crystallography and to study the local structure, which is a major experimental and theoretical challenge [1].