In situ synthesis of mixed-valent manganese oxide nanocrystals: an in situ synchrotron X-ray diffraction study

Phase transformations of materials can be studied by in situ synchrotron X-ray diffraction. However, most reported in situ synchrotron XRD studies focus on solid state/gel systems by measuring phase/structure changes during application of pressure or heat. Phase transformations during material synthesis and their applications, especially in wet chemistry processes with different media, have not drawn much attention. Here, using manganese oxides as examples, we report the successful characterization of phase transformations in in situ hydrothermal synthesis conditions by the in situ synchrotron XRD method using a quartz/sapphire capillary tube as the synthesis reactor. The results were used for better design of materials with controlled structures and properties. This method can be generally used for synthesis of manganese oxides as well as for in situ characterization of other material syntheses using hydrothermal, sol-gel, and other methods. In addition, catalytic processes in liquid-solid, gas-solid, and solid-solid systems can also be studied in such an in situ way so that catalytic mechanisms can be better understood and catalyst synthesis and catalytic processes can be optimized.     

In situ X-ray diffraction study of cesium exchange in synthetic umbite

The exchange of Cs(+) into H(1.22)K(0.84)ZrSi(3)O(9)·2.16H(2)O (umbite-(HK)) was followed in situ using time-resolved X-ray diffraction at the National Synchrotron Light Source. The umbite framework (space group P2(1)/c with cell dimensions of a = 7.2814(3) ?, b = 10.4201(4) ?, c = 13.4529(7) ?, and β = 90.53(1)°) consists of wollastonite-like silicate chains linked by isolated zirconia octahedra. Within umbite-(HK) there are two unique ion exchange sites in the tunnels running parallel to the a-axis. Exchange Site 1 is marked by 8 member-ring (MR) windows in the bc-plane and contains K(+) cations. Exchange Site 2 is marked by a larger 8-MR channel parallel to [100], and contains H(2)O molecules. The occupancy of the Cs(+) cations through these channels was modeled by Rietveld structure refinements of the diffraction data and demonstrated that there is a two-step exchange process. The incoming Cs(+) ions populated the larger 8-MR channel (Exchange Site 2) first and then migrated into the smaller 8-MR channel. During the exchange process a structural change occurs, transforming the exchanger from monoclinic P2(1)/c to orthorhombic P2(1)2(1)2(1). This structural change occurs when Cs(+) occupancy in the small cavity becomes greater than 0.50. The final in situ ion exchange diffraction pattern was refined to yield umbite-(CsK) with the molecular formula H(0.18)K(0.45)Cs(1.37)ZrSi(3)O(9)·0.98H(2)O and possessing an orthorhombic unit cell with dimensions a = 10.6668(8) ?, b = 13.5821(11) ?, c = 7.3946(6) ?. Solid state (133)Cs MAS NMR showed there is only a slight difference between the two cavities electronically. Valence bond sums for the completely occupied Exchange Site 1 demonstrate that Cs-O bonds of up to 3.8 ? contribute to the coordination of the Cs(+) cation.     

First seconds in a building's life-in situ synchrotron X-ray diffraction study of cement hydration on the millisecond timescale

Setting cement: highly dynamic hydration processes that occur during the first seconds of cement hydration were studied by time-resolved synchrotron X-ray diffraction. Polycarboxylate ether additives were found to influence the formation of the initial crystalline hydration products on a molecular level.     

A new in situ synchrotron X-ray diffraction technique to study the chemical delithiation of LiFePO4

We report a new synchrotron based in situ X-ray diffraction (XRD) technique to study the chemical delithiation of LiFePO(4). This technique provides a new powerful tool to study chemical reactions with excellent time-resolving power for dynamic studies.     

In situ X-ray diffraction studies of structural transformations in V-P-O catalysts

Structural transformations of V-P-O catalysts have been studied in situ in oxidative, inert and reducing atmosphere by the high-temperature X-ray diffraction method. Formation of vanadyl phosphates is shown to depend on the P/V ratio in the initial sample. It has been established that transformations in the phase composition of catalysts is independent of the reaction media at P/V=2. The effect of catalyst composition on catalytic properties is discussed.

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V-P-O , . , P/V . P/V=2. V-P-O .

     

Strain-induced disorder, phase transformations, and transformation-induced plasticity in hexagonal boron nitride under compression and shear in a rotational diamond anvil cell: in situ x-ray diffraction study and modeling

Plastic shear significantly reduces the phase transformation (PT) pressure when compared to hydrostatic conditions. Here, a paradoxical result was obtained: PT of graphitelike hexagonal boron nitride (hBN) to superhard wurtzitic boron nitride under pressure and shear started at about the same pressure ( approximately 10 GPa) as under hydrostatic conditions. In situ x-ray diffraction measurement and modeling of the turbostratic stacking fault concentration (degree of disorder) and PT in hBN were performed. Under hydrostatic pressure, changes in the disorder were negligible. Under a complex compression and shear loading program, a strain-induced disorder was observed and quantitatively characterized. It is found that the strain-induced disorder suppresses PT which compensates the promotion effect of plastic shear. The existence of transformation-induced plasticity (TRIP) was also proved during strain-induced PT. The degree of disorder is proposed to be used as a physical measure of plastic straining. This allows us to quantitatively separate the conventional plasticity and transformation-induced plasticity. Surprisingly, it is found that TRIP exceeds the conventional plasticity by a factor of 20. The cascade structural changes were revealed, defined as the reoccurrence of interacting processes including PTs, disordering, conventional plasticity, and TRIP. In comparison with hydrostatic loading, for the same degree of disorder, plastic shear indeed reduces the PT pressure (by a factor of 3-4) while causing a complete irreversible PT. The analytical results based on coupled strain-controlled kinetic equations for disorder and PT confirm our conclusions.     

Mechanochemical synthesis of glycine oligomers in a virtual rotational diamond anvil cell

Mechanochemistry of glycine under compression and shear at room temperature is predicted using quantum-based molecular dynamics (QMD) and a simulation design based on rotational diamond anvil cell (RDAC) experiments. Ensembles of high throughput semiempirical density functional tight binding (DFTB) simulations are used to identify chemical trends and bounds for glycine chemistry during rapid shear under compressive loads of up to 15.6 GPa. Significant chemistry is found to occur during compressive shear above 10 GPa. Recovered products consist of small molecules such as water, structural analogs to glycine, heterocyclic molecules, large oligomers, and polypeptides including the simplest polypeptide glycylglycine at up to 4% mass fraction. The population and size of oligomers generally increases with pressure. A number of oligomeric polypeptide precursors and intermediates are also identified that consist of two or three glycine monomers linked together through C–C, C–N, and/or C–O bridges. Even larger oligomers also form that contain peptide C–N bonds and exhibit branched structures. Many of the product molecules exhibit one or more chiral centers. Our simulations demonstrate that athermal mechanical compressive shearing of glycine is a plausible prebiotic route to forming polypeptides.

Compressive shearing forces can induce mechanochemical oligomerization reactions in glycine.     

In situ high-pressure x-ray diffraction study of H2O ice VII

Ice VII was examined over the entire range of its pressure stability by a suite of x-ray diffraction techniques in order to understand a number of unexplained characteristics of its high-pressure behavior. Axial and radial polycrystalline (diamond anvil cell) x-ray diffraction measurements reveal a splitting of diffraction lines accompanied by changes in sample texture and elastic anisotropy. In situ laser heating of polycrystalline samples resulted in the sharpening of diffraction peaks due to release of nonhydrostatic stresses but did not remove the splitting. Radial diffraction measurements indicate changes in strength of the material at this pressure. Taken together, these observations provide evidence for a transition in ice VII near 14 GPa involving changes in the character of the proton order/disorder. The results are consistent with previous reports of changes in phase boundaries and equation of state at this pressure. The transition can be interpreted as ferroelastic with the appearance of spontaneous strain that vanishes at the hydrogen bond symmetrization transition near 60 GPa.     

Condensed lamellar phase in ternary DNA-DLPC-cationic gemini surfactant system: a small-angle synchrotron X-ray diffraction study

We report on a small-angle synchrotron X-ray diffraction study of dilauroylphosphatidylcholine (DLPC) liposomes aggregated with high molecular DNA in the presence of 1,4-butanediammonium-N,N'-dilauryl-N,N,N',N'-tetramethyl gemini surfactant cations (C12GS). The aggregates prepared at the DLPC/C12GS/DNA phosphate group=2:1:1.6 molar ratio in 0.0015 mol x l(-1) NaCl aqueous solution exhibit Bragg reflections due to lamellar lipid bilayer stacking and the Bragg reflection typical of one-dimensional DNA lattice with parallel strands intercalated between lipid bilayers. In this condensed fluid lamellar L(alpha)(c) phase, the interactions between DNA and charged bilayers damp the thermally induced bilayer undulations. The diffraction data obtained with the mixture of DLPC liposomes and DNA (at DNA phosphate group/DLPC=0.8:1 molar ratio) indicate a DNA-lipid interaction in the absence of C12GS.     

Propene adsorption sites in zeolite ITQ-12: a combined synchrotron X-ray and neutron diffraction study

The adsorption site of propene in the small-pore, pure silica zeolite [Si24O48]-ITW-ITQ-12 has been characterized via Rietveld refinement of the crystal structure of propene-loaded ITQ-12 on the basis of synchrotron X-ray and neutron diffraction data taken at 298 K. The structure can be described with a monoclinic unit cell having Cm symmetry and unit cell parameters a = 10.436 angstroms, b = 15.018 angstroms, c = 8.855 angstroms, beta = 105.74 degrees, and volume = 1335.9 angstroms3. Four-fold disordered adsorption sites that are nearly equivalent relative to the cage's 2/m pseudosymmetry are located near the center of each ellipsoidally shaped [4(4)5(4)6(4)8(4)] cage. At this site, the adsorbed propene molecule lies on a plane close and approximately parallel to the equatorial plane of the cage and is aligned with its methylene group pointing toward the pore's eight-ring window. The refined propene concentration, 1.8 per unit cell content, is close to one propene molecule per [4(4)5(4)6(4)8(4)] cage and the amount observed in adsorption experiments at 298 K and 1 atm propene partial pressure.     

Characterisation of salt films on dissolving metal surfaces in artificial corrosion pits via in situ synchrotron X-ray diffraction

The salt films formed on metal surfaces dissolving inside artificial corrosion pits formed in 1 M HCl have been probed with synchrotron X-ray diffraction. NiCl₂ · 6H₂O is the main phase in the salt film on nickel, whereas salt films on both iron and 316 L stainless steel are predominantly FeCl₂ · 4H₂O. However, the salt film on iron has a very fine homogeneous crystallite size whereas that on stainless steel is much coarser. The potential-dependence of the film formed on iron has been determined.     

Synthesis of double core chromophore-functionalized nanothreads by compressing azobenzene in a diamond anvil cell

Carbon nanothreads are likely the most attracting new materials produced under high pressure conditions. Their synthesis is achieved by compressing crystals of different small aromatic molecules, while also exploiting the applied anisotropic stress to favor nontopochemical paths. The threads are nanometric hollow structures of saturated carbon atoms, reminiscent of the starting aromatic molecule, gathered in micron sized bundles. The examples collected so far suggest that their formation can be a general phenomenon, thus enabling the design of functionalities and properties by suitably choosing the starting monomer on the basis of its chemical properties and crystal arrangement. The presence of heteroatoms or unsaturation within the thread is appealing for improving the processability and tuning the electronic properties. Suitable simple chromophores can fulfill these requirements and their controlled insertion along the thread would represent a considerable step forward in tailoring the optical and electronic properties of these mechanically extraordinary materials. Here, we report the synthesis and extensive characterization of double core nanothreads linked by azo groups. This is achieved by compressing azobenzene in a diamond anvil cell, the archetype of a wide class of dyes, and represents a fundamental step in the realization of nanothreads with tailored photochemical and photophysical properties.

One-step high-pressure synthesis of 2D crystalline double nanothreads linked by azo groups.     

In situ single-crystal X-ray diffraction studies of desorption and sorption in a flexible nanoporous molecular framework material

The subtle flexibility of the framework material Co(bpy)1.5(NO3)2.(guest) (bpy = 4,4'-bipyridine) (1.(guest)) is demonstrated quantitatively through in situ single-crystal X-ray diffraction measurements of guest desorption and sorption processes. Variable temperature unit cell determinations were employed to monitor the uptake and release of guest species, and full structural determinations have been carried out for the as-grown ethanol-loaded framework (1.(EtOH)), for the empty host framework, and for each of the five introduced guests (methanol: 1.(MeOH), acetone: 1.(ACN), acetonitrile: 1.(MeCN), tetrahydrofuran:1.(THF), dichloromethane: 1.(DCM)). The framework consists of interdigitated two-dimensional bilayers of cobalt(II) centers bridged by bpy ligands, with one-dimensional pores that account for approximately 20% of the total volume. The sorption of guest species of varying size and shape has revealed the framework's ability to adapt to different guests through a range of different framework flexibilities.     

The role played by salts in the formation of SBA-15, an in situ small-angle X-ray scattering/diffraction study

The influence of salts (NaCl, NaBr, and NaI) on the formation of mesoporous silica SBA-15 was studied in situ by small-angle X-ray scattering and diffraction. Pluronic P104 was used as structure director. The micellar properties and the dynamics of formation were clearly dependent on the presence of salt. It was also shown that the kinetics of mesophase formation, the initial value of the cell parameters, and the extent of long-range order were all influenced by salt additions. The observations are explained to primarily originate from the influence of the anions on the ethylene oxide part of the polymer, i.e., the corona region of the Pluronic micelles. Two effects are identified: a general ion effect causing dehydration of the ethylene oxide part and consequently inducing micellar growth, and a specific ion effect that counterbalances this. The study provides the basis for understanding the means by which addition of simple Na-salts influence the formation of mesoscopically ordered silicas synthesized using nonionic surfactants as structure directors, hence advancing the knowledge base toward a more rational design of mesoporous materials.     

Composition and temperature dependent phase transitions in Co-W double perovskites, a synchrotron X-ray and neutron powder diffraction study

High-resolution synchrotron and neutron powder diffraction techniques were used to determine precise structures for the series of perovskite oxides A_2−xSr_xCoWO₆ (ACa, or Ba, 0?x?2). The studies demonstrated that the symmetry decreases as the average size of the A-site cation decreases with a sequential introduction of in-phase and out-of-phase tilting of the BO₆ octahedra. A cubic structure in Fm3¯m with rock-salt like ordering of the Co and W cations was formed for Ba_2−xSr_xCoWO₆ with x∼<1.4. As the Sr content was increased, the materials became tetragonal in I4/m and ultimately monoclinic in P2₁/n. A mixture of monoclinic and tetragonal phases occurs in Sr₂CoWO₆ at room temperature but this was purely monoclinic at 20 K.     

In situ X-ray diffraction and solid-state NMR study of the fluorination of gamma-Al(2)O(3) with HCF(2)Cl.

In situ X-ray diffraction (XRD) and NMR methods were used to follow the structural changes that occur during the dismutation reaction of hydrochlorofluorocarbon-22 (CHClF(2)) over gamma-alumina. Use of a flow cell allowed diffraction patterns to be recorded, while the reaction products were simultaneously monitored downstream of the catalyst bed, by gas chromatography. No visible structural changes of gamma-Al(2)O(3) were observed at 300 degrees C, the temperature at which this material becomes active for catalysis. A new phase began to form at 360 degrees C, which by 500 degrees C completely dominated the XRD powder pattern. (19)F/(27)Al cross-polarization (CP) experiments of gamma-Al(2)O(3) activated at 300 degrees C showed that AlF(3) had already begun to form at this temperature. By 400 degrees C, resonances from a phase that resembles alpha-AlF(3) dominate both the (19)F and (27)Al NMR spectra of the used catalyst. In situ XRD experiments of the catalytically inactive alpha-AlF(3) phase were performed to investigate the structural changes of this material, associated with the extent of tilting of the AlF(6) octahedra in this ReO(3)-related structure, as a function of temperature. Structural refinements of this sample, and the catalytically active phase that grows over gamma-Al(2)O(3), demonstrate that the catalyst is structurally similar to the rhombohedral form of alpha-AlF(3). Differences between the two phases are ascribed to defects in the catalyst, which limit the flexibility of the structure; these may also be responsible for the differences in the catalytic behavior of the two materials.