Guang Mo

A SMALL-ANGLE X-RAY SCATTERING STATION AT BEIJING SYNCHROTRON RADIATION FACILITY

This article presents the development and current state of a small-angle X-ray scattering station at beamline 1W2A of the Beijing Synchrotron Radiation Facility, China. The source of the beamline is introduced from a 14-pole wiggler. A triangular bending Si(111) crystal is used to horizontally focus the beam and provide a monochromatic X-ray beam (8.052 keV). A bending cylindrical mirror coated with rhodium downstream from the monochromator is used to vertically focus the beam. The X-ray beam is focused on the detector which is fixed at 30 m from the source. The focused beam size (full width at half maximum) is 1.4 × 0.2 mm2 (horizontal × vertical) with a flux of 5.5 × 1011 phs/s at 2.5 GeV and 250 mA. Besides the routine mode of small-angle X-ray scattering, the combination of small- and wide-angle X-ray scattering, grazing incidence small-angle X-ray scattering, and time-resolved small-angle X-ray scattering in sub-second level are also available for the users. Dependent on the measurement requirements, several detectors can be chosen for the collection of scattering signals. Furthermore, multiple sample environments, including temperature, stress-strain, and liquid sampling are available for in situ measurements. In a typical camera length of 1.5 m, the small-angle X-ray scattering resolution is about 115 nm. The steady operation of the small-angle X-ray scattering station at Beijing Synchrotron Radiation Facility not only provides the small-angle X-ray scattering beam time for users, but also promotes the development and application of these techniques in China.

One-step synthesis of highly efficient nanocatalysts on the supports with hierarchical pores using porous ionic liquid-water gel.

Stable porous ionic liquid-water gel induced by inorganic salts was created for the first time. The porous gel was used to develop a one-step method to synthesize supported metal nanocatalysts. Au/SiO2, Ru/SiO2, Pd/Cu(2-pymo)2 metal-organic framework (Cu-MOF), and Au/polyacrylamide (PAM) were synthesized, in which the supports had hierarchical meso- and macropores, the size of the metal nanocatalysts could be very small (<1 nm), and the size distribution was very narrow even when the metal loading amount was as high as 8 wt %. The catalysts were extremely active, selective, and stable for oxidative esterification of benzyl alcohol to methyl benzoate, benzene hydrogenation to cyclohexane, and oxidation of benzyl alcohol to benzaldehyde because they combined the advantages of the nanocatalysts of small size and hierarchical porosity of the supports. In addition, this method is very simple.

Shape and Size Controlled Synthesis of MOF Nanocrystals with the Assistance of Ionic Liquid Mircoemulsions

In this work, the La-metal-organic frameworks (La-MOFs) were synthesized using lanthanum(III) nitrate and 1,3,5-benzenetricarboxylic acid (BTC) in H2O-in-1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF6), bmimPF6-in-water, and the bicontinuous microemulsions stabilized by surfactant TX-100. The MOFs prepared were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and FT-IR methods, and the microstructures of the microemulsions in the H2O/bmimPF6/TX-100 system were studied by small-angle X-ray scattering (SXAS) technique. It was shown that the dispersed droplets in the water-in-bmimPF6, bicontinuous and bmimPF6-in-water microemulsions were spherical, lamellar, and cylindrical, respectively. The shapes of the La-MOFs synthesized were similar to that of the droplets in the corresponding microemulsions. This indicated that the morphology of MOFs could be controlled by the microstructures of the microemulsions. On the basis of the systematic experimental results, the mechanism for controlling the morphology of the MOFs was proposed.

Effect of high hydrostatic pressure on the supramolecular structure of corn starch with different amylose contents

Corn starches with amylose contents ranging from 0 to 80% were suspended in 60 wt% water or ethanol and subjected to high hydrostatic pressure (HHP) up to 600 MPa. The impact of HHP treatment on the granule morphology, lamellae structures, and crystalline characteristics were examined with a combination of SAXS, WAXS and optical microscopy. All starch dispersed in water showed a decrease in area of the lamellar peak in the SAXS data at q∼0.6 nm(-1). The lamellae thickness (d) increased for pressurized waxy, normal, and Gelose80 corn starches, suggesting water is forced into starch lamellae during HHP. However, for Gelose50 corn starch, the d remained constant over the whole pressure range and light microscopy showed no obvious granule swelling. WAXS studies demonstrated that HHP partially converted A-type starches (waxy and normal corn) to starches with a faint B-type pattern while starches with a B+V-type pattern (Gelose50 and Gelose80), were not affected by HHP. All corn starches suspended in ethanol showed no detectable changes in either granule morphology, or the fractal, the lamellae, and the crystalline structures.

Ionic liquid accelerates the crystallization of Zr-based metal–organic frameworks

The Zr-based metal–organic frameworks are generally prepared by solvothermal procedure. To overcome the slow kinetics of nucleation and crystallization of Zr-based metal–organic frameworks is of great interest and challenging. Here, we find that an ionic liquid as solvent can significantly accelerate the formation of Zr-based metal–organic frameworks at room temperature. For example, the reaction time is shortened to 0.5 h in 1-hexyl-3-methylimidazolium chloride for Zr-based metal–organic framework formation, while that in the conventional solvent N,N-dimethylformamide needs at least 120 h. The reaction mechanism was investigated in situ by 1H nuclear magnetic resonance, spectroscopy synchrotron small angle X-ray scattering and X-ray absorption fine structure. This rapid, low-energy, and facile route produces Zr-based metal–organic framework nanoparticles with small particle size, missing-linker defects and large surface area, which can be used as heterogeneous catalysts for Meerwein–Ponndorf–Verley reaction.Crystallization kinetics of metal-organic frameworks in conventional organic solvents are usually very slow. Here, the authors show that an ionic liquid medium accelerates considerably the formation of Zr-based metal-organic frameworks that are active catalysts in the Meerwein-Ponndorf-Verley reaction.

Microstructural change of degummed Bombyx mori silk: an in situ stretching wide-angle X-ray-scattering study.

The microstructural change of degummed Bombyx mori silk was examined by in situ wide-angle X-ray-scattering (WAXS) with applied stretching force. WAXS patterns confirmed that the crystalline and amorphous regions coexist in the silk fibers. The crystallites with β-sheet structure have an orthorhombic unit cell with lattice parameters: a=9.10 Å, b=9.71 Å and c=6.80 Å. The crystallite size, crystallite orientation and crystallinity were also estimated based on the WAXS patterns. The results demonstrate that the crystallite size is almost unchanged with the stretching strain. The crystallinity is approximately linearly increasing with the applied stretching force. However, the change of the unit-cell orientation degree with c-axis along the fiber axis behaves as a fast stage and an approximately unchanged stage during the in situ stretching process. All these experimental phenomena confirm that the microstructure of the degummed silk fibers can be well explained by the model of oriented β-sheet structure with a banded feature.

Thermal expansion behavior study of Co nanowire array with in situ x-ray diffraction and x-ray absorption fine structure techniques

In situ x-ray diffraction and x-ray absorption fine structure techniques were used to study the structural change of ordered Co nanowire array with temperature. The results show that the Co nanowires are polycrystalline with hexagonal close packed structure without phase change up until 700 °C. A nonlinear thermal expansion behavior has been found and can be well described by a quadratic equation with the first-order thermal expansion coefficient of 4.3×10−6/°C and the second-order thermal expansion coefficient of 5.9×10−9/°C. The mechanism of this nonlinear thermal expansion behavior is discussed.

Structural Change of Human Hair Induced by Mercury Exposure

Mercury is one of the most hazardous pollutants in the environment. In this paper, the structural change of human hair induced by mercury exposure was studied. Human hair samples were, respectively, collected from the normal Beijing area and the Hg-contaminated Wanshan area of the Guizhou Province, China. Inductively coupled plasma mass spectroscopy was used to detect the element contents. A small angle X-ray scattering technique was used to probe the structural change. Three reflections with 8.8, 6.7, and 4.5 nm spacing were compared between the normal and the Hg-contaminated hair samples. The results confirm that the 4.5 nm reflection is from the ordered fibrillar structure of glycosaminoglycan (GAG) in proteoglycan (PG) that composes the matrix around the intermediate filaments. The increase of Ca content makes the regular oriented fibrillar structure of GAG transform to a random oriented one, broadening the angular extent of the reflection with 4.5 nm spacing. However, overdose Hg makes the core proteins where the ordered fibrils of GAG are attached become coiled, which destroys the ordered arrangements of fibrillar GAG in PG, resulting in the disappearance of the reflections with 4.5 nm spacing. The disappearance of the 4.5 nm reflection can be used as a bioindicator of overdose Hg contamination to the human body. A supercoiled-coil model of hair nanoscale structure and a possible mechanism of mercury effect in human hair are proposed in this paper.

Small-angle X-ray scattering study on nanostructural changes with water content in red pine, American pine, and white ash

Wood is a highly sophisticated and multihierarchical material. The nanoscale structures in natural cell walls of red pine, American pine, and white ash specimens were investigated using the small-angle X-ray scattering (SAXS) technique. A tangent-by-tangent method was used to analyze the SAXS data. The results demonstrate that the multihierarchical scatterers in the three specimens can be divided into two dominant components, i.e., a sharp component and a wide component. The sharp component mainly corresponds to the contribution of cellulose microfibrils, and its size is almost unaffected by the water content. However, the wide component includes voids or microcracks and cellulose microfibril aggregates; its size changes, reflecting swelling and water accumulation in the voids or microcracks. Because of the different morphological features of the cell walls, softwood (red pine and American pine) displays different tendencies from hardwood (white ash) in terms of changes in the wide component with water content: the average scatterer size of the wide component has an incremental tendency with the water content in softwood, but it has a descending tendency in hardwood. Fractal analysis further revealed that in white ash the surface of scatterers is coarser and the scatterers form more compact nanostructures than in the two pine woods. All this nanostructural information can be used to explain well the difference of swelling behaviors between the two pines and the white ash.

A furnace to 1200 K for in situ heating x-ray diffraction, small angle x-ray scattering, and x-ray absorption fine structure experiments

A furnace with a water-cooled outside shell has been assembled to do in situ x-ray diffraction (XRD), small angle x-ray scattering (SAXS), and x-ray absorption fine structure (XAFS) experiments. The details of the furnace are described in this paper. The in situ XRD, SAXS, and XAFS experiments during the heating process demonstrate that the available temperature range of this furnace is from room temperature to 1200 K with a temperature accuracy of +/-0.1 K. By using this furnace, in situ XRD, SAXS, and XAFS experimental techniques with temperature change can be easily combined together.