Controllable synthesis of CuAlO_(2) via solid-phase method and its catalytic performance for methanol steam reforming to hydrogen

This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.

A review of in-situ high-temperature characterizations for understanding the processes in metallurgical engineering

For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.

Integrated multi-scale approach combining global homogenization and local refinement for multi-field analysis of high-temperature superconducting composite magnets

Second-generation high-temperature superconducting(HTS)conductors,specifically rare earth-barium-copper-oxide(REBCO)coated conductor(CC)tapes,are promising candidates for high-energy and high-field superconducting applications.With respect to epoxy-impregnated REBCO composite magnets that comprise multilayer components,the thermomechanical characteristics of each component differ considerably under extremely low temperatures and strong electromagnetic fields.Traditional numerical models include homogenized orthotropic models,which simplify overall field calculation but miss detailed multi-physics aspects,and full refinement(FR)ones that are thorough but computationally demanding.Herein,we propose an extended multi-scale approach for analyzing the multi-field characteristics of an epoxy-impregnated composite magnet assembled by HTS pancake coils.This approach combines a global homogenization(GH)scheme based on the homogenized electromagnetic T-A model,a method for solving Maxwell's equations for superconducting materials based on the current vector potential T and the magnetic field vector potential A,and a homogenized orthotropic thermoelastic model to assess the electromagnetic and thermoelastic properties at the macroscopic scale.We then identify“dangerous regions”at the macroscopic scale and obtain finer details using a local refinement(LR)scheme to capture the responses of each component material in the HTS composite tapes at the mesoscopic scale.The results of the present GH-LR multi-scale approach agree well with those of the FR scheme and the experimental data in the literature,indicating that the present approach is accurate and efficient.The proposed GH-LR multi-scale approach can serve as a valuable tool for evaluating the risk of failure in large-scale HTS composite magnets.

Solid-phase extraction of trace Au(Ⅲ) with SDG and determination by the catalytic spectrophotometric method

The new catalytic kinetic spectrophotometric method for Au（III） determination was developed and validated. It was based on the catalytic effect of gold on the oxidation of sudan red III by ammonium peroxodisulfate （（NH4）2S2O8） with nitrilo triacetic acid as an activator in microemulsion and H2SO4 medium. Under optimum conditions, there was the linearity of the calibration curve in the concentration range from 0 to 20 μg/L Au（Ⅲ） at 520 nm. The relative standard deviation was 3.0% with a correlation coefficient of 0.9986. The detection limit achieved was 9.75 × 10^-5 μg/mL. A new method using a column packed with sulfhydryl dextrose gel （SDG） as a solid-phase extractant has been developed for the preconcentration and separation of Au（Ⅲ） ions. The method has been applied to the determination of trace gold with satisfactory results.

High-temperature thermal stability of C/C−ZrC−SiC composites via region labeling method

To investigate the thermal stability of ceramic-matrix composites,three kinds of C/C−ZrC−SiC composites with different Zr/Si molar ratios were synthesized by reactive melt infiltration.Employing region labeling method,the high-temperature thermal stability of the composites was systematically studied by changing the temperature and holding time of thermal treatment.Results show that the mass loss rate of low Si composites has a growth trend with increasing temperature,and a crystal transformation from β-SiC toα-SiC occurs in the composites.In the calibrated area,SiC phase experiences Ostwald ripening and volume change with location migration,while ZrC phase experiences a re-sintering process with diffusion.Moreover,it is found that increasing temperature has a more obvious effect on the thermal stability than extending holding time,which is mainly attributed to the faster diffusion rate of atoms.

Analysis on high-temperature oxidation and growth stress of iron-based alloy using phase field method

High-temperature oxidation is an important property to evaluate thermal protection materials. However, since oxidation is a complex process involving microstructure evolution, its quantitative analysis has always been a challenge. In this work, a phase field method （PFM） based on the thermodynamics theory is developed to simulate the oxidation behavior and oxidation induced growth stress. It involves microstructure evolution and solves the problem of quantitatively computational analysis for the oxidation behavior and growth stress. Employing this method, the diffusion process, oxidation performance, and stress evolution axe predicted for Fe-Cr-A1-Y alloys. The numerical results agree well with the experimental data. The linear relationship between the maximum growth stress and the environment oxygen concentration is found. PFM provides a powerful tool to investigate high-temperature oxidation in complex environments.

Dissolution-precipitation mechanism of self-propagating high-temperature synthesis of TiC-Cu cermets

The mechanism of self-propagating high-temperature synthesis （SHS） of TiC-Cu cermets was studied using a combustion front quenching method. Microstructural evolution in the quenched sample was observed using scanning electron microscope （SEM） with energy dispersive X-ray （EDX） spectrometry, and the combustion temperature was measured. The results showed that the combustion reaction started with local formation of Ti-Cu melt and could be described with the dissolution-precipitation mechanism, namely, Ti, Cu, and C particles dissolved into the Ti-Cu solution and TiC particles precipitated in the saturated Ti-Cu-C liquid solution. The local formation of Ti-Cu melt resulted from the solid diffusion between Ti and Cu particles.

Solid-Phase Preparation and Characterization of Chitosan

Chitosan was prepared with stressing method by blending chitin and solid alkali in a single-screw extruder at given temperature and characterized by potentiometric titration, gel permeation chromatography (GPC), infrared spectrum (IR) and carbon-13 magnetic resonance sperctroscopy ( 13 C NMR) . Chitosan with a deacetylation degree (DD) of 76.1% was obtained at a mass ratio 0.2∶1∶1 for H_ 2 O/chitin/NaOH at 160 ℃ for 12 min. Compared to conventional solution method(usually 1∶10 for chitin/NaOH), the alkali assumption greatly decreased. Molecular weight of chitosan obtained by solid-phase method(S3,M_w1.54×10 5 ) was lower than that obtained by suspension method(Y2,M_w3.34×10 5 ). During deacetylation, molecular weight decreased with high reaction temperature and long reaction time but remained same at different initial ratios of NaOH/chitin. It might be concluded that degradation of chitosan was caused by breakout of the main chain of the oxidized chitosan catalyzed by alkali during the deactylation. IR and 13 C NMR showed that structures of chitosans prepared by solid-phase method were not changed.

Spatial Distribution of High-temperature Risk with a Return Period of Different Years in the Yangtze River Delta Urban Agglomeration

Against the background of global warming,research on the spatial distribution of high-temperature risk is of great significance to effectively prevent the adverse effects of high temperatures.By using air temperature data from 1951 to 2018 measured by meteorological stations located in the Yangtze River Delta urban agglomeration,the daily maximum air temperature distribution is interpolated at a resolution of 1 km based on the local thin disk smooth spline function;the high-temperature threshold for return periods of 5,10,20 and 30 yr are then calculated by using the generalized extreme value method.The yearly average high-temperature intensity and high-temperature days are finally calculated as high-temperature danger factors.Socioeconomic statistical data and remotely sensed image data in 2018 are used as the background data to calculate the spatial distribution of high-temperature vulnerability factors and prevention capacity factors,which are then used to compute the high-temperature risk index during different recurrence periods in the Yangtze River Delta urban agglomerations.The results show that the spatial distribution features of high-temperature risk in different return periods are similar.The high-temperature risk index gradually increases from northeast to southwest and from east coast to inland,which has obvious latitude variation characteristics and a relationship with the comprehensive influence of the underlying surface and urban scale.In terms of time variation,the high-temperature risk index and its spatial distribution difference gradually decreases with increasing return period.In different cities,the high-temperature risk in the central area of the city is generally higher than that in the surrounding suburban areas.Jinhua,Hangzhou of Zhejiang Province and Xuancheng of Anhui Province are the top three cities with high-temperature risk in the study area.

Correlated-Electron Systems and High-Temperature Superconductivity

We present recent theoretical results on superconductivity in correlated-electron systems, especially in the two-dimensional Hubbard model and the three-band d-p model. The mechanism of superconductivity in high-temperature superconductors has been extensively studied on the basis of various electronic models and also electron-phonon models. In this study, we investigate the properties of superconductivity in correlated-electron systems by using numerical methods such as the variational Monte Carlo method and the quantum Monte Carlomethod. The Hubbard model is one of basic models for strongly correlated electron systems, and is regarded as the model of cuprate high temperature superconductors. The d-p model is more realistic model for cuprates. The superconducting condensation energy obtained by adopting the Gutzwiller ansatz is in reasonable agreement with the condensation energy estimated for YBa2Cu3O7. We show the phase diagram of the ground state using this method. We have further investigated the stability of striped and checkerboard states in the under-doped region. Holes doped in a half-filled square lattice lead to an incommensurate spin and charge density wave. The relationship of the hole density x and incommensurability δ, δ~x, is satisfied in the lower doping region, as indicated by the variationalMonte Carlocalculations for the two-dimensional Hubbard model. A checkerboard-like charge-density modulation with a roughly period has also been observed by scanning tunneling microscopy experiments in Bi2212 and Na-CCOC compounds. We have performed a variational Monte Carlo simulation on a two-dimensional t-t′-t″- U Hubbard model with a Bi-2212 type band structure and found that the period checkerboard spin modulation, that is characterized by multi Q vectors, is indeed stabilized. We have further performed an investigation by using a quantumMonte Carlomethod, which is a numerical method that can be used to simulate the behavior of correlated electron systems. We present a new algorithm of the quantum Monte Carlo diagonalization that is a method for the evaluation of expectation value without the negative sign problem. We compute pair correlation functions and show that pair correlation is indeed enhanced with hole doping.

Effect of Dopant Concentration on Luminescence Properties of KCaPO4:Sm

KCaPO4 doped with different concentrations of Sm was synthesised by a high-temperature solid-state method, and the crystal structure, morphology, TL and OSL properties of Sm-doped KCaPO4 were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermoluminescence (TL), and optically stimulated luminescence (OSL) techniques. The results show that 0.3 mol% Sm-doped KCaPO4 annealed at 1073 K for 1 h has the highest TL intensity, and thus is expected to be a candidate material for thermoluminescence dosimetry applications.

Preparation and characterization of continuous high-temperature resistant Si-Al-C fibers by one-step method

Using polymer-derived technology, continuous high-temperature resistant Si-Al-C fibers were prepared by one step method, which included melt-spinning of polyaluminocarbosilane (PACS), curing of continuous PACS fibers, and sintering of the cured products. The results show that the average diameter and tensile strength of continuous Si-Al-C fibers are 11 to 12 μm and 1.8 to 2.0 GPa, respectively. The chemical formula of Si-Al-C fibers is SiC1.01O0.0400Al0.024, which is nearly stoichometric. The fibers are mainly composed of β-SiC crystalline, small amount of α-SiC, and amorphous SiC. Continuous Si-Al-C fibers exhibit excellent thermal stability. When the fibers were exposed in argon for 1 h, the tensile strength did not decrease until 1500°C. After heat treatment at 1800°C in argon for 1 h, the fibers maintained about 80% of the initial strength. It was higher than that of Nicalon and Hi-Nicalon fibers.

Thermal Performances of High-Temperature Thermal Energy Storage System with Tin Embedded in Copper Matrix by Theoretical Methods

There is a critical need to develop advanced high-temperature thermal storage systems to improve efficiencies and reduce the costs of solar thermal storage system.In this work,two typical systems composed with Cu as matrix and Sn as the phase change material(PCM)are explored,namely,the 3-deimentional(3D)structure system by embedding Sn particles into Cu matrix and the 2-deimentional(2D)structure system by embedding Sn wires into Cu matrix.Given the thermophysical properties of a nanomaterial could be importantly different from that of a bulk one,we thus firstly derive the thermophysical properties of PCM and matrix theoretically,like the thermal conductivity by kinetic method and the specific heat capacity based on Lindemann’s criterion.And then,these properties are utilized to estimate the energy storage ability in both 3D and 2D structure system,and the influence of structure on heat transfer efficiency is theoretically investigated in both 3D and 2D structure system.Results turn out that 3D structure system is a better choice than a 2D structure system,because of larger specific surface area,a larger sensitive heat capacity and a larger thermal conductivity.When the feature size of the PCM decreases to be less than a critical value which is about 500 nm for Sn,the thermal conductivity of the system decreases exponentially while the heat storage capacity increases lineally.Moreover,when the feature size of Sn geometry is less than a critical value,which is 15 nm for 3D structure system and 25 nm for 2D structure,the Cu matrix can’t play a role in improving the effective thermal conductivity of the whole system.

A rapid and sensitive liquid chromatography-tandem mass spectrometric assay for duloxetine in human plasma:Its pharmacokinetic application

This paper describes a simple, rapid and sensitive liquid chromatography tandem mass spectrometry assay for the determination of duloxetine in human plasma. A duloxetine stable labeled isotope （duloxetine ds） was used as an internal standard. Analyte and the internal standard were extracted from 100 btL of human plasma via solid phase extraction technique using Oasis HLB cartridges. The chromatographic separation was achieved on a Cl8 column by using a mixture of acetonitrile 5 mM ammonium acetate buffer （83：17, v/v） as the mobile phase at a flow rate of 0.9 mL/min. The calibration curve obtained was linear （r2≥0.99） over the concentration range of 0.05 101 ng/mL. Multiple-reaction monitoring mode （MRM） was used for quantification of ion transitions at rn/z 298.3/154.1 and 303.3/159.1 for the drug and the internal standard, respectively. Method validation was performed as per FDA guidelines and the results met the acceptance criteria. A run time of 2.5 min for each sample made it possible to analyze more than 300 plasma samples per day. The proposed method was found to be applicable to clinical studies.

Solid-phase synthesis of huwentoxin-I and its structure and bioactivity analysis

Huwentoxin-I, a neurotoxic peptide from the spider Selenocosmia huwena, was synthesized by sol-id-phase method with Fluorenylmethoxycarbonyl amino acid pentafluorophenyl esters (Fmoc-AA-OPfp). The carboxyl and the hydroxy groups were protected by tBu; the side chains of Lys and His were protected by Roc; the guanidine group of Arg was protected by Mtr and the mercaptan group of Cys was protected by Trt. The solid-phase carrier was ethylene diamine-polyethylene-polystyrene (DEA-PEG-PS) resin. The synthetic peptide was cleaved from the resin and deprotected by a 90% TFA solution containing 5% thioanisole, 3% ethanedithiol and 2% anisole. The product was reduced with DTT and then incubated with GSSG and GSH to form the correct disulfide bond linkages. The syn-thetic peptide was purified by HPLC and then characterized by amino acid composition and sequence analysis, peptide mapping and NMR. The biological activity of the synthetic product was tested by electrophysiological method using the isolated mouse phrenic nerve diaphragm preparation. The results indicated that the synthetic huwentoxin-I has the same chemical and conformational structure and biological activity as those of the native huwentoxin-I from the spider.

GC-MS, GC-O and OAV analyses of key aroma compounds in Jiaozi Steamed Bread

Jiaozi Steamed Bread(JSB)has a unique aroma as a traditional staple food in China.The volatile compounds in JSBwere extracted by simultaneous distillation and extraction(SDE)and headspace solid-phasemicroextraction(HS-SPME).These volatile substances were analyzed by gas chromatography-mass spectrometry(GC-MS)and gas chromatographyolfactometry-mass spectrometry(GC-O-MS).The results demonstrated that 61 volatile compounds were identified totally in samples,of which 15 were confirmed as potent aroma compounds with odor active values(OAVs)>1.The 15 potent aroma compounds were ethanol,1-butanol,1-pentanol,1-hexanol,heptanol,1-octen-3-ol,3-methyl-1-butanol,hexanal,heptanal,nonanal,(E)-2-heptenal,benzaldehyde,(E,E)-2,4-decadienal,2-pentylfuran and naphthalene.The SDEmethod had better linearity with coefficients of determination(R2)equal to or higher than 0.9991.Furthermore,the SDE method also achieved lower sensitivity and better repeatability and recovery than HS-SPME.This work provides reference method and parameters for future research on the flavor of JSB for commercial products.

Hydrogen production from steam reforming of ethanol over Ni/MgO-CeO_2 catalyst at low temperature

MgO,CeO2 and MgO-CeO2 with different mole ratio of Mg:Ce were prepared by solid-phase burning method.Catalysts Ni/MgO,Ni/CeO2 and Ni/MgO-CeO2 were prepared by impregnation method.The catalytic properties were evaluated in ethanol steam reforming(ESR) reaction.Specific surface areas of the supports were measured by nitrogen adsorption-desorption at 77 K,and the catalysts were characterized with X-ray diffraction(XRD),temperature programmed reduction(TPR) and thermogravimetric(TG).The results showed that well...

Evaluation of thermophoretic effects on graphite dust coagulation in high-temperature gas-cooled reactors

In high-temperature gas-cooled reactors,graphite dust particles within the reactor core and the heat transfer equipment experience large temperature gradients.Under such conditions,thermophoresis may play an important role in determining aerosol evolution.This study presents a theoretical and numerical analysis of the thermophoretic effects on aerosol coagulation within these reactors.The coagulation rates for Brownian versus thermophoretic coagulation are calculated and compared for various temperature gradients.Our results show that thermophoretic coagulation dominates over Brownian coagulation for large temperature gradients.We defined an enhancement factor to evaluate the role of thermophoretic coagulation under various reactor conditions.The enhancement factor increased dramatically with increasing temperature gradient,decreasing pressure and increasing particle diameter,but was not very sensitive to temperature change.The time evolution of the particle size distribution related to combined Brownian and thermophoretic coagulation was simulated using a log-skew-normal method of moments.The simulation results indicate that aerosol evolution can be strongly accelerated by thermophoretic coagulation under large temperature gradients.

Highly sensitive assay for the determination of therapeutic peptide desmopressin in human plasma by UPLC–MS/MS

An analytical method based on ultra-performance liquid chromatography with positive ion electrospray ionization(ESI) coupled with tandem mass spectrometry(UPLC–MS/MS) was developed and validated for the determination of therapeutic peptide desmopressin in human plasma. A desmopressin stable labeled isotope(desmopressin d_8) was used as an internal standard. Analyte and the internal standard were extracted from200 μL of human plasma via solid-phase extraction technique using Oasis WCX cartridges. The chromatographic separation was achieved on an Aquity UPLC HSS T3 column by using a gradient mixture of methanol and 1 m M ammonium formate buffer as the mobile phase. The calibration curve obtained was linear(r^2≥0.99)over the concentration range of 1.01–200 pg/m L. Method validation was performed as per FDA guidelines and the results met the acceptance criteria. The results of the intra-and inter-day precision and accuracy studies were well within the acceptable limits. The proposed method was successfully applied to pharmacokinetic studies in humans.

Preparation of (Ti, Sn)O_2 Nano-Composite Photocatalyst by Supercritical Fluid Dry Combination Technology

A series of TiO2-SnO2 nano-sized composite photo-catalysts containing Sn (9.3%-30.1%) were prepared from TiCI4 and SnCl4·5H2O by using sol-gel, supercritical fluid dry and solid-phase reaction (SCFD) combination technology. Characterizations with X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed that, in addition to anatase type TiO2, a new active phase (Ti, Sn)O2 (with particle size of 2.0-4.3 nm) formed, and there were no SnO2 crystals observed in the range of the doping concentration studied. Photo-catalytic reaction of phenol was used as a model reaction to evaluate the catalytic activities of the obtained catalysts. Compared with pure TiO2 or Ti-Sn catalyst prepared with general sol-gel method, Ti-Sn nano-composite photo-catalyst thus obtained showed significant improvement in catalytic activity. The photo-catalytic degradation rate of phenol could reach as high as 93.5% after 7 h. The preparation conditions of the new phase (Ti, Sn)O2 were investigated and its catalytic mechanism was proposed. The photo-catalytic particles prepared using SCFD combination technology exhibited small particle size, large surface area and high activity.