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A new non-stoichiometric calcium ruthenate [Ca4−xRuO6−x with x = 1.17(1)] was synthesized by the flux growth method and characterized by the X-ray powder diffraction. The crystal structure is isostructural to the K4CdCl6 type with space group R$\bar 3$c. Unit-cell parameters are a = 9.2881(1), c = 11.1634(2) Å, V = 834.03(3) Å3, and Z = 6.
Hydrophobic functionalized SBA-15 has been developed via postsynthesis modification with trimethylchlorosilane (TMCS) and used for volatile organic compounds (VOCs) removal. The adsorption and desorption performance of different SBA-15-TMCS under static and dynamic conditions were investigated. Experimental results indicated that all samples showed a highly ordered two dimensional hexagonal mesostructure, and the organic groups were chemically incorporated into the pore surface of SBA-15 substrate. Comparing with commercial silica gel and activated carbon, SBA-15-TMCS shows higher static adsorption capacities of n-hexane and 93# gasoline, good recyclability, lower water vapor adsorption capacity, higher dynamic adsorption capacity, and longer breakthrough time. The high adsorption efficiency and stability of SBA-15-TMCS are associated with their hydrophobic surface, uniform and large pore size, high surface area and pore volume. The designed SBA-15-TMCS with high VOC adsorption capacity and recyclability shows great potential for VOC removal.
Novel plate-stratiform nanostructured Bi12O17Cl2 was studied with its visible-light photocatalytic performance. The Bi12O17Cl2 photocatalyst synthesized by a solid-state reaction was constructed of dozens of primary nanosheets, which were stacked by a parallel array of ultrathin secondary nanosheets. The microstructure and crystal structure of Bi12O17Cl2 primary and secondary nanosheets were discovered by high-resolution transmission electron microscopy and selected-area electron diffraction analyses. Its absorption edge was determined as about 590 nm and the band gap energy was 2.1 eV. The Bi12O17Cl2 nanomaterial exhibited superior visible-light-responsive photocatalytic activity and confirmed successful photodegradation of methyl orange (MO) under visible-light irradiation. The degradation efficiency was up to 97% in 90 min. Furthermore, the Bi12O17Cl2 photocatalyst exhibited excellent photostability and high mineralization capacity for MO photodegradation reaction. The MO photodegradation process was dominated by the direct photocatalytic mechanism. The contribution from its morphology and microstructure to superior photocatalytic activity was discussed.
We have used conventional X-ray powder diffraction to study one of the largest volume inorganic mixed oxide unit-supercell structures done so far. This necessitated some small-angle X-ray scattering-like observations at low angles from <2° 2θ to concord with electron diffraction, which had indicated an 8 × 8 × 8 huge volume supercell of a fluorite-type basic sub-cell. Emphasis is on the detection of, possibly very weak, fingerprint, low-angle/long lines/peaks which will indicate the (often unsuspected) presence of complex polytypic arrangements of simple very strong basic sub-cells and so facilitate future synthetic studies.
The dibromo-dioxo-(1,10-phenanthroline-N,N′)-molybdenum(VI) complex (C12H8N2MoBr2O2) was prepared from molybdic acid and 1,10-phenanthroline using hydrobromic acid as solvent. The molybdenum complex solid was separated by filtration and washed with ethyl ether. The X-ray powder diffraction pattern for the title compound was analyzed and found to crystallizes in monoclinic system, space group P21/c (No14) with refined unit-cell parameters a = 12.036 (1), b = 9.819 (1), c = 12.671 (2) Å, and β = 110.44° (1). The volume of the unit cell is V = 1403.2 (3) Å3.
N- and p-type filled-skutterudite materials prepared for thermoelectric power generation modules were analyzed by neutron diffraction at the POWGEN beam line of the Spallation Neutron Source (SNS) and X-ray diffraction (XRD). The skutterudite powders were processed by melt spinning, followed by ball milling and annealing. The n-type material consists of Ba–Yb–Co–Sb and the p-type material consists of Di–Fe–Ni–Sb or Di–Fe–Co–Sb (Di = didymium, an alloy of Pr and Nd). Powders for prototype module fabrication from General Motors and Marlow Industries were analyzed in this study. XRD and neutron diffraction studies confirm that both the n- and p-type materials have cubic symmetry. Structural Rietveld refinements determined the lattice parameters and atomic parameters of the framework and filler atoms. The cage filling fraction was found to depend linearly on the lattice parameter, which in turn depends on the average framework atom size. This knowledge may allow the filling fraction of these skutterudite materials to be purposefully adjusted, thereby tuning the thermoelectric properties.
X-ray powder diffraction data, unit-cell parameters, and space group for thiamphenicol, C12H15Cl2NO5S, are reported [a = 17.346(3), b = 15.341(0), c = 5.790 (2) Å, α = β = γ = 90°, unit-cell volume V = 1540.8(3) Å3, Z = 4, and space group P212121]. All measured lines were indexed and are consistent with the P212121 space group. No detectable impurities were observed.
Van der Waals (vdW) heterojunctions consisting of vertically-stacked individual or multiple layers of two-dimensional layered semiconductors, especially the transition metal dichalcogenides (TMDs), show novel optoelectronic functionalities due to the sensitivity of their electronic and optical properties to strong quantum confinement and interfacial interactions. Here, monolayers of n-type MoSe2 and p-type Mo1−xWxSe2 are grown by vapor transport methods, then transferred and stamped to form artificial vdW heterostructures with strong interlayer coupling as proven in photoluminescence and low-frequency Raman spectroscopy measurements. Remarkably, the heterojunctions exhibit an unprecedented photoconductivity effect that persists at room temperature for several days. This persistent photoconductivity is shown to be tunable by applying a gate bias that equilibrates the charge distribution. These measurements indicate that such ultrathin vdW heterojunctions can function as rewritable optoelectronic switches or memory elements under time-dependent photo-illumination, an effect which appears promising for new monolayer TMDs-based optoelectronic devices applications.
Magnetotactic bacteria mineralize nanometer-size crystals of magnetite (Fe3O4) through a series of protein-mediated reactions that occur inside of organelles called magnetosomes. Mms6 is a transmembrane protein thought to play a key role in magnetite mineralization. We used both electron and fluorescent microscopy to examine the subcellular location of Mms6 protein within single cells of Magnetospirillum magneticum AMB-1 using Mms6-specific antibodies. We also purified magnetosomes from M. magneticum to determine if Mms6 was physically attached to magnetite crystals. Our results show that Mms6 proteins are present during crystal growth, and Mms6 is found in direct contact with the magnetite crystals or within the lipid/protein membrane surrounding the magnetite crystals. Mms6 was not detected at other subcellular locations within the bacteria or isolated fractions. Because Mms6 was found to completely surround the magnetosomes rather than being localized to one specific area of the magnetosome, it appears that this protein could act on the entire magnetite crystal during the biomineralization process. This supports a model in which Mms6 functions to regulate Fe3O4 crystal morphology. This knowledge is important for future in vitro experiments utilizing Mms6 to synthesize tailored nanomagnets with specific physical or magnetic properties.
The effect of applied pressure on reactive hot pressing (RHP) of zirconium (Zr):graphite (C) in molar ratios of 1:0.5, 1:0.67, 1:0.8, and 1:1 was studied at 1200 °C for 60 min. The relative density achievable increased with increasing pressure and ranged from 99% at 4 MPa for ZrC0.5 to 93% for stoichiometric ZrC at 100 MPa. The diminishing influence of pressure on the final density with increasing stoichiometry is attributed to two causes: the decreasing initial volume fraction of the plastically deforming Zr metal which leads to the earlier formation of a contiguous, stress shielding carbide skeleton and the larger molar volume shrinkage during reaction which leads to pore formation in the final stages. A numerical model of the creep densification of a dynamically evolving microstructure predicts densities that are consistent with observations and confirm that the availability of a soft metal is primarily responsible for the achievement of such elevated densification during RHP. The ability to densify nonstoichiometric compositions like ZrC0.5 at pressures as low as 4 MPa offers an alternate route to fabricating dense nonstoichiometric carbides.
In this study, hematite nanoparticles (α-Fe2O3 NPs) were synthesized by hydrothermal method, with morphologies (e.g., nanorhombohedra, nanobars, and nanospheres) facilely tuned by changing the concentrations of glycol in the hydrothermal solution. Then a low-cost and scalable electrophoretic deposition method was used to fabricate nanostructured α-Fe2O3 films as photoanodes for solar hydrogen generation. It was found that the film of α-Fe2O3 nanobars showed the highest photoelectrochemical (PEC) performance compared to those films of α-Fe2O3 nanorhombohedra and nanospheres, with photocurrent density reaching 0.7 mA/cm2 at 0.6 V versus Ag/AgCl. This PEC improvement may be related to the smaller diameters of nanobars shortening the carrier migration distance, reducing the recombination rate of photo-generated carriers. Moreover, all the α-Fe2O3 films showed much higher PEC performances with surface modified by Sn4+, mainly due to the reduced surface charge recombination, as the Sn4+ doped overlayer passivated surface defects. For the film of α-Fe2O3 nanobars, the photocurrent density was increased by 100%, reaching 1.4 mA/cm2 at 0.6 V versus Ag/AgCl.
Dissimilar materials of S235JR steel and AZ31B Mg alloy were welded by metal inert-gas arc welding. Interface characteristics and mechanical behavior of intermetallic compound layer at the Mg/steel interface in the welded joint were investigated. The intermetallic compound layer was mainly made up of FeAl phase, which exhibited unequal thickness at different positions in the interface. The growth coefficient of FeAl intermetallic compound layer could be expressed as K = K0 exp(−Q/RT) with Q of 195 kJ/mol. The kinetics of growth of the intermetallic compound layer indicated that its formation and growth were mainly driven by elements diffusion, and hence the thickness of the layer was dependent on peak temperature and reaction time which were determined by welding parameters. The FeAl intermetallic compound layer with high hardness was the weak zone where cracks inclined to derive and propagate during tensile testing. The fracture surfaces displayed both brittle and ductile features.
Two kinds of Ag/ZnO electrical contact materials were fabricated by powder metallurgy method. The electrical life testing was done to investigate the arc erosion behavior of the prepared contact materials. Their properties and morphologies were characterized and discussed in detail. Results showed that Ag/ZnO(c) with coprecipitated ZnO as the second phase had better mechanical and electrical properties compared with Ag/ZnO(a) with ZnO purchased from Aladdin Industrial, Inc. Besides, some typical morphologies, such as holes, Ag or ZnO enrichment zone, Ag skeletons and bubbling area, occurred on the surface of the contacts. Especially for Ag/ZnO(c), vertically aligned ZnO nanorod arrays were detected after the life testing without any other supporting equipment. The existence of a solid solution Zn1−xAgxO and different energy generated during arcing process were possible reasons resulting in this phenomenon. A solid–vapor–solid mechanism was put forward to analyze the phenomenon mentioned above. These evidences could also offer some valuable information desired for reducing the splashing of Ag droplet under arcing.
The evolution behavior of Ni2(Cr, Mo) phase with Pt2Mo-type structure in the Ni–Cr–Mo alloy with a low atomic Mo/Cr ratio subjected to a long-term thermal exposure of 100–340 h at 600 °C was investigated using transmission electron microscopy and microhardness. Results demonstrate that there is a linear relationship between major axis cube (L3) of ordered domain and thermal exposure time (t) followed by a coarsening regime described by the Lifshitz–Slyozov–Wagner model, as well as between the aspect ratio (D) of ordered domain and thermal exposure time. The volume fraction of ordered domain increases with increasing thermal exposure time, whereas the hardening of samples decreases due to growth-coarsening of ordered domain. Prolonged thermal exposure time led to the coarsening of ordered domain by rate of (3.39 ± 0.02) × 10−30 m3/s without changing their crystallography and ordering characteristics during thermal exposure. Plastic deformation before thermal exposure do not lead to decomposition of initial Ni2(Cr, Mo) phase, but both plastic deformation and thermal exposure affect their morphology and distribution.
To investigate the effects of cold rolling on the microstructure, the precipitation behavior and the morphology of δ-phase, Inconel 718 alloy samples with different cold rolling reductions were aged for different periods at temperatures range from 850 °C to 1000 °C. Detailed microstructural observations and quantitative measurements were conducted to characterize the evolution of the δ-phase during aging. The results show that the microstructure consists of large deformed grains as a result of a slow static recovery at the low aging temperatures (850 and 900 °C); whereas the austenite matrix is fully recrystallized at the high aging temperatures (950 and 1000 °C). It is also found that the amount of δ-phase and the number density of spherical δ-phase particles increase with the increase in the degree of cold rolling both at low and high aging temperatures. With respect to different microstructural changes for the cold-rolled samples at the low or the high aging temperatures, two distinct mechanisms have been, respectively, introduced to interpret the changes in the precipitation behavior and the appearance of δ-phase.
Electroreduction of solid V2O3 pellets (∼0.7 g) to V in molten CaCl2 at 900 °C has been studied by cyclic voltammetry and potentiostatic electrolysis, together with scanning electron microscopy, energy dispersive x-ray, and elemental analyses. The intermediate products of the potentiostatic electrolysis are various, forming some lower valence state compounds (VO, V16O3, V7O3, VO0.2) and higher valence state which are likely VO2, CaVO3, or CaV2O5. At potentials more negative than −0.6 V versus Ag/AgCl, fine vanadium powder (aggregates of nodular ∼500 nm particles) can be prepared by electrolysis of porous solid of the V2O3 pellets. The current efficiency and energy consumption were satisfactory, about 53.4% and 2.5 kW h/(kg V) at −0.6 V versus Ag/AgCl, respectively. Moreover, V–20Ti alloys were electrochemically synthesized by constant voltage electrolysis at the indicated potentials, the control of composition as well as the reduction optimization of the mixtures were demonstrated. This electrochemical route is efficient and offers a product with controlled stoichiometry, with particular advantage of manufacturing of low cost alloys and intermetallics directly from mixed oxide precursors, and has potential to produce functional vanadium alloys.