Competition between acidic sites and hydrogenation sites in Cu/ZrO_(2) catalysts with different crystal phases for conversion of biomass-derived organics

Oxides with different crystal phases can have important effects on the configuration of surface atoms,which can further affect the distribution of hydrogenation sites and acidic sites as well as the competitions of these varied types of catalytic sites.This could be potentially used to tailor the distribution of the products.In this study,zirconium oxides with different crystal phases supported copper catalysts were prepared for the hydrogenation of the biomass-derived furfural,vanillin,etc.The results showed that both calcination temperature and Cu species affected the shift of zirconia from tetragonal phase to the monoclinic phase.Monoclinic zirconia supported copper catalyst can effectively catalyze the hydrogenation of furfural to furfuryl alcohol via hydrogenation route due to its low amount of Brønsted acidic sites,although the surface area and the exposed metallic Cu surface area were much lower than the tetragonal zirconia supported copper catalyst.Zirconia with tetragonal or tetragonal/monoclinic phases supported copper catalysts contain abundant acidic sites and especially the Br?nsted acidic sites,which catalyzed mainly the conversion of furfural via the acid-catalyzed routes such as the acetalization,rather than the hydrogenation.The acidic sites over the Cu/ZrO_(2)catalyst played more predominant roles than the hydrogenation sites in determining the conversion of the organics like furfural and vanillin.

Crystal Phases and Chemical Stabilities of YSi2 Powders Fabricated from Low and High Purity Si and Y Powders

Y-Si compounds with the composition of Y:Si = 1:2 were fabricated using Yttrium and Silicon raw powders with low and high purity in various atmospheres and temperatures. Although the latest Y-Si phase diagram shows that the α- and β-YSi2 phases are the stable phases for the stoichiometric composition of Y:Si = 1:2, the current experimental results suggest that the high temperature phase with the hexagonal structure, β-Y3Si5, would be the stable phase for this composition, and that the high temperature phase with the orthorhombic structure, β-YSi2, would be the meta-stable phase with high oxygen impurity content. It was demonstrated that YSi2 powders possess much superior chemical stability than Yttrium metal. It was found that the best dispersing solvent was 2-propanol for YSi2 powder.

Effect of Plasma Spheroidization Process on the Microstructure and Crystallographic Phases of Silica, Alumina and Nickel Particles

During the plasma spheroidization process powders undergo different changes in their microstructures and crystal phases. In this paper, simple calculation of heat transfer between the plasma and a suspended particle was performed based on three hypotheses for the purpose of guiding experiments. Experimental investigation of the crystal phases and microstructural changes during the plasma processing was made using silica, alumina and nickel powders as starting materials. It has been revealed from the experimental results that these materials undergo different changes in crystal phases and microstructures, and these changes are essentially determined by the structures, properties and aggregate states of the starting materials.

Regulating crystal phase of TiO_(2) to enhance catalytic activity of Ni/TiO_(2) for solar-driven dry reforming of methane

Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.

Effects of Additive AlCl_3 on Crystal Phase, Particle Size and Microstructural Parameters of Nanocrystalline TiO_2 Prepared by HF-PCVD

Nanocrystalline TiO2 was prepared by high frequency plasma chemical vapor deposition (HF-PCVD). The effects of additive AlCl3 on crystal phase, particle size and microstructurai parameters of TiO2 nanocrystallites were investigated by X-ray diffraction(XRD) and transmission electron microscopy (TEM). The nanocrystallites obtained experimentally are mixture of anatase and rutile, the uniform diameters of particles are about 30 nm. The phase transformation from anatase to rutile was accelerated by AlCl3, and rutile content is increased from 26.7 wt pct to 53.6 wt pct with increasing of addition of AlCl3 from 0.0 wt pct to 5.0 wt pct. The particle size is reduced and the size distribution becomes very narrow. The crystal lattice constants have the trend to decrease, and celi volumes appear as shrinkable.

Insights into effects of ZrO_(2) crystal phase on syngas‐to‐olefin conversion over ZnO/ZrO_(2) and SAPO‐34 composite catalysts

The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous.Herein,typical metal oxides(ZnO/ZrO_(2))with different crystal phases(monoclinic(m‐ZrO_(2))and tetragonal(t‐ZrO_(2)))were employed for syngas conversion.The(ZnO/m‐ZrO_(2)+SAPO‐34)composite catalyst exhibited 80.5%selectivity for C_(2)–C_(4) olefins at a CO conversion of 27.9%,where the results are superior to those(CO conversion of 16.4%and C_(2)–C_(4) olefin selectivity of 76.1%)obtained over(ZnO/t‐ZrO_(2)+SAPO‐34).The distinct differences are ascribed to the larger number of hydroxyl groups,Lewis acid sites,and oxygen defects in ZnO/m‐ZrO_(2) compared to ZnO/t‐ZrO_(2).These features result in the formation of more formate and methoxy intermediate species on the ZnO/m‐ZrO_(2) oxides during syngas conversion,followed by the formation of more light olefins over SAPO‐34.The present findings provide useful information for the design of highly efficient ZrO_(2)‐based catalysts for syngas conversion.

Morphological evolution and growth kinetics of Kirkendall voids in binary alloy system during deformation process-Phase field crystal simulation study

The formation and growth of Kirkendall voids in a binary alloy system during deformation process were investigated byphase field crystal model.The simulation results show that Kirkendall voids nucleate preferentially at the interface,and the averagesize of the voids increases with both the time and strain rate.There is an obvious coalescence of the voids at a large strain rate whenthe deformation is applied along the interface under both constant and cyclic strain rate conditions.For the cyclic strain rate appliedalong the interface,the growth exponent of Kirkendall voids increases with increasing the strain rate when the strain rate is largerthan1.0×10-6,while it increases initially and then decreases when the strain rate is smaller than9.0×10?7.The growth exponent ofKirkendall voids increases initially and then decreases gradually with increasing the length of cyclic period under a square-waveform constant strain rate.

Bichromatic coherent random lasing from dye-doped polymer stabilized blue phase liquid crystals controlled by pump light polarization

In this paper,we investigate the bichromatic coherent random lasing actions from the dye-doped polymer stabilized blue phase liquid crystals.Two groups of lasing peaks,of which the full widith at half maximum is about 0.3 nm,are clearly observed.The shorter-and longer-wavelength modes are associated with the excitation of the single laser dye（DCM） monomers and dimers respectively.The experimental results show that the competition between the two groups of the lasing peaks can be controlled by varying the polarization of the pump light.When the polarization of the pump light is rotated from 0？to 90？,the intensity of the shorter-wavelength lasing peak group reduces while the intensity of the longer-wavelength lasing peak group increases.In addition,a red shift of the longer-wavelength modes is also observed and the physical mechanisms behind the red-shift phenomenon are discussed.

Optical simulation of in-plane-switching blue phase liquid crystal display using the finite-difference time-domain method

The finite-difference time-domain method is used to simulate the optical characteristics of an in-plane switching blue phase liquid crystal display.Compared with the matrix optic methods and the refractive method,the finite-difference timedomain method,which is used to directly solve Maxwell＇s equations,can consider the lateral variation of the refractive index and obtain an accurate convergence effect.The simulation results show that e-rays and o-rays bend in different directions when the in-plane switching blue phase liquid crystal display is driven by the operating voltage.The finitedifference time-domain method should be used when the distribution of the liquid crystal in the liquid crystal display has a large lateral change.

Ordering of the α-Fe(Si) Crystallization Phase in Annealed Fe_(73.5)Cu_1Mo_3Si_(13.5)B_9 Alloy

The ordering of the α-Fe(Si) crystallization phase in annealed Fe73.5Cu1Mo3Si13.5B9 alloy has been studied using XRD method. The α-Fe(Si) phase in Fe73.5Cu1Mo3Si13.5B9 alloy annealed at 460℃ for 1 h consists of the DO3-type ordered region with spherical shape and disordered region. The size of DO3 ordered region increases with the annealing temperature. When the annealing temperature is 560℃, the size of the ordered region in the α-Fe(Si) grain is 14.0nm,which is nearly as large as that of the α-Fe(Si) grain (14.2 nm) and the degree of order of the α-Fe(Si) phase is about 0.78. When Fe73.5Cu1 Mo3Si13.5B9 amorphous alloy is annealed at 520℃， with the increment of the annealing time, the shape of the DO3 ordered region in the α-Fe(Si) phase is spheroidal at the beginning of the annealing and becomes spherical and has asize of 12.8 nm when the annealing time is 60 min. In addition, the DO3 superlattice lines of the α-Fe(Si) phase will vanish if Fe73.5Cu1Mo3Si13.5 B9 amorphous alloy is annealed for 1 h at 750℃.

Phase field crystal study of the crystallization modes within the two-phase region

Using the phase field crystal approach, the crystallization process within the liquid-solid coexistence region is inves- tigated for a square lattice on an atomic scale. Two competing growth modes, i.e., the diffusion-controlled growth through long-range atomic migration in liquid and the diffusionless growth through local atom rearrangement, which give rise to two completely different crystallization behaviors, are compared. In the diffusion-controlled regime, the interface migrates in a layerwise manner, leading to a gradual change of crystal morphology from truncated square to four-fold symmetric dendrite with the increase of driving force. For the diffusionless growth mode, a single crystal with no significant density change occupies the whole system at a faster rate while exhibiting a small growth anisotropy. The competition between these two modes is also discussed from the key input of the phase field crystal model： the correlation function.

Crystal Growth and Nucleation in Glasses in the Lithium Silicate System

The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi2O·(100 ﹣ x)SiO2 (where x = 23.4, 26.0, 29.1, and 33.5 mol% Li2O) has been studied. The glasses of these compositions have been homogenized using the previously established special temperature-time conditions, which make it possible to provide a maximum dehydration and removal of bubbles from the glass melt. The parameters of nucleation and growth of phase separated in homogeneities and homogeneous crystal nucleation have been determined. The absolute values of the stationary nucleation rates Ist of lithium disilicate crystals in the 23.4Li2O·76.6SiO2, 26Li2O·74SiO2 and 29.1Li2O·70.9SiO2 glasses with the compositions lying in the metastable phase separation region have been compared with the corresponding rates Ist for the glass of the stoichiometric lithium disilicate composition 33.51Li2O·66.5SiO2. It has been found that the crystal growth rate has a tendency toward a monotonic increase with an increase in the temperature, whereas the dependences of the crystal growth rate on the time of low temperature heat treatment exhibit an oscillatory behavior with a monotonic decrease in the absolute value of oscillations. The character of crystallization in glasses with the compositions lying in the phase separation region of the Li2O-SiO2 system is compared with that in the glass of the stoichiometric lithium disilicate composition. The conclusion has been made that the phase separation weakly affects the nucleation parameters of the lithium disilicate and has a strong effect on the crystal growth.

Faceting transitions in crystal growth and heteroepitaxial growth in the anisotropic phase-field crystal model

We modify the anisotropic phase-field crystal model （APFC）, and present a semi-implicit spectral method to numerically solve the dynamic equation of the APFC model. The process results in the acceleration of computations by orders of magnitude relative to the conventional explicit finite-difference scheme, thereby, allowing us to work on a large system and for a long time. The faceting transitions introduced by the increasing anisotropy in crystal growth are then discussed. In particular, we investigate the morphological evolution in heteroepitaxial growth of our model. A new formation mechanism of misfit dislocations caused by vacancy trapping is found. The regular array of misfit dislocations produces a small-angle grain boundary under the right conditions, and it could significantly change the growth orientation of epitaxial layers.

Preparation of High-Quality Poly-Si Films by a Solid Phase Crystallizing Method

A solid phase crystallizing method has been developed to grow a Si crystal at tem-peratures as low as 550 ℃. Using this method, a high-quality thin-film polycrystalline silicon (Poly-Si) was obtained. The largest grain size, examined with X-ray diffraction spectroscopy and scanning electron microscopy images of recrystallized samples, is approximately 1 /μm for substrate temperature at 300 ℃ and annealed at 550℃ for 3 hours.

PHASE SEPARATION AND CRYSTALLIZATION OF CHALCOGENIDE GLASSES

In this paper the experimental results associated until the phase separation and nucleation and crystallization of chalcogenidc glasses are described. Experi-ments demonstrate that the phas separation may be affected by small amount of additives. It has been found that some chalcogenide glasses could be converted into glass-ceramics without phase separation. The different mechanisms of nucleated crystallization of chalcogenide glasses are discussed and propossed.

Kerr effect and Kerr constant enhancement in vertically aligned deformed helix ferroelectric liquid crystals

In this article,we review recently achieved Kerr effect progress in novel liquid crystal（LC） material：vertically aligned deformed helix ferroelectric liquid crystal（VADHFLC）.With an increasing applied electric field,the induced inplane birefringence of LCs shows quadratic nonlinearity.The theoretical calculations and experimental details are illustrated.With an enhanced Kerr constant to 130 nm/V2,this VADHFLC cell can achieve a 2π modulation by a small efficient electric field with a fast response around 100 μs and thus can be employed in both display and photonics devices.

Behavior of lysozyme adsorbed onto biological liquid crystal lipid monolayer at the air/water interface

The interaction between proteins and lipids is one of the basic problems of modern biochemistry and biophysics.The purpose of this study is to compare the penetration degree of lysozyme into 1,2-diapalmitoyl-sn-glycero-3-phosphocholine（DPPC） and 1,2-dipalmitoyl-sn-glycero-3-phosphoethano-lamine（DPPE） by analyzing the data of surface pressure–area（π–A） isotherms and surface pressure–time（π–T） curves.Lysozyme can penetrate into both DPPC and DPPE monolayers because of the increase of surface pressure at an initial pressure of 15 m N/m.However,the changes of DPPE are larger than DPPC,indicating stronger interaction of lysozyme with DPPE than DPPC.The reason may be due to the different head groups and phase state of DPPC and DPPE monolayers at the surface pressure of 15 m N/m.Atomic force microscopy reveals that lysozyme was absorbed by DPPC and DPPE monolayers,which leads to self-aggregation and self-assembly,forming irregular multimers and conical multimeric.Through analysis,we think that the process of polymer formation is similar to the aggregation mechanism of amyloid fibers.

Asymmetric dynamic phase holographic grating in nematic liquid crystal

A new scheme for recording a dynamic phase grating with an asymmetric profile in C60-doped homeotropically aligned nematic liquid crystal（NLC） was presented.An oblique incidence beam was used to record the thin asymmetric dynamic phase holographic grating.The diffraction efficiency we achieved is more than 40%,exceeding the theoretical limit for symmetric profile gratings.Both facts can be explained by assuming that a grating with an asymmetric saw-tooth profile is formed in the NLC.Finally,physical mechanism and mathematical model for characterizing the asymmetric phase holographic grating were presented,based on the photo-refractive-like（PR-like） effect.

Studies on the Phase Behavior of Lyotropic Liquid Crystal in DAD/C_4OH/n-C_8H_(18)/D_2O System

The lytropic liquid crystals in dodecanic acid diethanolamine (DAD) /n-butanol (C4OH) /octane (n-C8H18) /deuteron (D2O) system were studied to determine the phase regions and were investigated by 2H-NMR spectroscopy,optical polarizing microscope and small-angle X-ray diffraction (SAXD) methods.The results indicate that the lamellar,hexagonal and cubic liquid crystals all exist in the above system.Keeping the weight ratio of DAD and C4OH constant,the microphase Structure,2H quadruple splitting and the interlayer spacing are all changed with the addition of deuteron.

Crystallization Process of Superlattice-Like Sb/SiO_2 Thin Films for Phase Change Memory Application

After compositing with SiO_2 layers, it is shown that superlattice-like Sb/SiO_2 thin films have higher crystallization temperature（~240°C）, larger crystallization activation energy（6.22 e V）, and better data retention ability（189°C for 10 y）. The crystallization of Sb in superlattice-like Sb/SiO_2 thin films is restrained by the multilayer interfaces. The reversible resistance transition can be achieved by an electric pulse as short as 8 ns for the Sb（3 nm）/SiO_2（7 nm）-based phase change memory cell. A lower operation power consumption of 0.09 m W and a good endurance of 3.0 × 10~6 cycles are achieved. In addition, the superlattice-like Sb（3 nm）/SiO_2（7 nm） thin film shows a low thermal conductivity of 0.13 W/（m·K）.