在Rh16/In_(2)O_(3)催化剂上催化二氧化碳加氢合成甲醇的机理:密度泛函理论与微动力学模型的联合研究

本研究采用密度泛函理论(DFT)和微动力学模型分析了Rh16/In_(2)O_(3)催化剂上二氧化碳(CO_(2))氢化成甲醇(CH_(3)OH)的情况;研究了Rh16/In_(2)O_(3)界面上H_(2)的自发解离和CO_(2)的有效吸附,其中,In_(2)O_(3)中的氧空位提供了有利的效果。此外,Bader电荷分析显示Rh16上带有轻微的正电荷,这对于理解催化剂的电子特性和活性非常重要。证实了RWGS+CO-Hydro途径是甲醇合成的主要途径,其特点是经过一系列中间转化:CO_(2)→COOH→CO+OH→HCO→CH_(2)O→CH_(2)OH→CH_(3)OH。在不同温度(373−873 K)和压力(10^(−2)−10^(3)bar)下进行的反应速率控制程度分析(DRC)揭示了两个关键的动力学现象,在较低温度和较高压力下,转化步骤CO+H→HCO显著影响总体反应速率;而在较高温度下,CH_(2)O+H→CH_(3)O的步骤占主导地位。

微动力学在多相催化中的应用

介绍了微动力学和催化反应综合的基本概念 ,论述了进行微动力学分析的基本方法 ,扼要分析了微动力学用于多相催化的研究实例 。

Conserved quantities from Lie symmetries for nonholonomic systems

This paper presents a new method to seek the conserved quantity from a Lie symmetry without using either Lagrangians or Hamiltonians for nonholonomic systems. The differential equations of motion of the systems are established. The definition of the Lie symmetrical transformations of the systems is given, which only depends upon the infinitesimal transformations of groups for the generalized coordinates. The conserved quantity is directly constructed in terms of the Lie symmetry of the systems. The condition under which the Lie symmetry can lead to the conserved quantity and the form of the conserved quantity are obtained. Finally, an example is given to illustrate the application of the result.

Precipitation kinetics of NZ30K-Mg alloys based on electrical resistivity measurement

The electrical resistivity of NZ30K-Mg alloy was measured at different heating rates during continuous heating to stud the precipitation kinetics.Two kinds of metastable phases,β＂ and β＇,formed during the heating.Kissinger method and differentia isoconversional method were employed to assess the precipitation kinetic parameters of NZ30K-Mg alloy,activation energy Eα an pre-exponential factor A＇α.The fraction of transformation（α） and the precipitation sequence in NZ30K-Mg alloy were determinec Continuous heating transformation（CHT） and isothermal heating transformation（IHT） diagrams were further obtained for guidin the aging of NZ30K-Mg alloy.The analysis shows that the precipitation kinetic parameters of NZ30K-Mg alloy can be obtaine accurately using isoconversional method.

Carburization of ferrochromium metals in chromium ore fines containing coal during voluminal reduction by microwave heating

Chromium ore fines containing coal (COFCC) can be rapidly heated by microwave to conduct the voluminal reduction, which lays a foundation of getting sponge ferrochromium powders with a lower content of C. Under the conditions of COFCC with n(O)-n(C) (molar ratio) as 1.00-0.84 and n(SiO2)-n(CaO) as 1.00-0.39, the samples were heated by 10 kW microwave power to reach the given temperatures and held for different times respectively. The results show that the low-C-Cr ferrochromium metal phase in the reduced materials forms before the high-C-Cr ferrochromium metal phase does. With increasing temperature the C content of ferrochromium metals is in a positive correlation with the content of Cr. The C content of ferrochromium metal in reduced materials is 0-10.07% with an average value of 4.68%. With the increase of holding time the Cr content in ferrochromium metals is in a negative correlation with the content of C, while the content of Fe changes in the contrary way. In the microwave field the kinetic conditions of carburization are closely related with the temperature of microwave heating, holding time and carbon fitting ratio.

Effect of Long-Term Straw Incorporation on SoilMicrobial Biomass and C and N Dynamics

A study was performed on the long-term effect of straw incorporation on soil microbial biomass C contents, C and N dynamics in both Rothamsted and Woburn soils. The results showed that for both soils,the microbial biomass C contents were significantly different among all the treatments, and followed the sequence in treatments of straw chopped and incorporated into 10 cm (CI10) > straw burnt and incorporated into 10 cm (BI10) > straw chopped and incorporated into 20 cm (CI20) > straw burnt and incorporated into 20 cm (BI20). Laboratory incubation of soils showed that the cumulative CO2 evolution was closely related to the soil microbial biomass C content. Carbon dioxide evolution rates (CO2-C, μg (g d) -1 ) decreased rapidly in the first two weeks’ incubation, then decreased more slowly. The initial K2SO4-extractable NH4-N and NO3-N contents were low and similar in all the treatments, and all increased gradually with the incubation time. However, net N immobilization was observed in chopped treatments for Rothamsted soils during the first 4 weeks. Nevertheless, more N mineralization occurred in neatment CI10 than any other treatment at the end of incubation for both soils. The Woburn soils could more easily suffer from the leaching of nitrate because the soils were more permeable and more N was mineralized during the incubation compared to the Rothamsted soils.

Effect of ageing temperature on precipitation of A1-Cu-Li-Mn-Zr alloy

The precipitation behaviors of an A1-Cu-Li-Mn-Zr alloy at different ageing temperatures （120, 160 and 200 ~C） were investigated using Vickers hardness measurements and transmission electron microscopy （TEM） characterization. Age hardening curves show an increase in precipitation kinetics with increasing ageing temperature. The results of TEM show that for the samples peak aged at 120 ~C, the amount of g＇ （A13Li）, GP zones/0＇ （A12Cu） and Z （A15Cu6Li2） phases is obviously higher than that of T1 （A12CuLi） precipitates; while the samples peak aged at 160 and 200 ~C are usually dominated by T1 phase with a minor fraction of GP zones/0＇ and g＇, and the Z phase almost does not form. In addition, quantitative analysis on the T1 platelets demonstrates that the samples peak aged at 200 ~C have larger plate diameter and smaller area fraction of T1, as compared to the samples peak aged at 160 ~C. Correspondingly, the possible reasons for such phenomena are discussed.

Effect of small tensile deformation on damping capacities of Mg-1%Al alloy

Tensile tests with small deformation amounts of 0.5%,1%,3%and 5%were performed at room temperature on as cast Mg-1%Al alloy.Microstructures of the Mg-1%Al alloys before and after deformation were observed by optical microscopy(OM) and transmission electron microscopy(TEM).The strain amplitude dependent and temperature dependent damping capacities of the as-cast and deformed Mg-1%Al alloys were investigated by dynamic mechanical analysis(DMA).The mechanism of deformation on damping capacity of Mg-1%Al alloy was discussed.The results show that the as-cast Mg-1%Al alloy has high damping value at high strain.When the tensile elongation is higher than 3%,the damping values of this alloy in high strain region are significantly decreased at room temperature.But the large amount of dislocations produced by tensile deformation are activated by heat,and then increase the damping value at high temperature.

Effect of precipitation on internal friction of AZ91 magnesium alloy

The effect of precipitation on the internal friction(IF)of AZ91 magnesium alloy was investigated by using X-ray diffraction(XRD)analysis,scanning electron microscope(SEM)observation,and dynamic mechanical analysis(DMA).Six different states of alloy were prepared by applying different heat treatment processes:as-cast,in-complete solid solution,complete solid solution,micro-precipitation,continuous precipitation and continuous-discontinuous precipitation.It was found that the internal friction of in-completely solid-solutionized,completely solid-solutionized and micro-precipitated specimens showed a similar characteristic,and the grain boundary relaxation is completed depressed due to the Al atoms supersaturated in theα-Mg solution.However,a thermal relaxation internal friction peak was observed for continuously precipitated and continuously-discontinuously precipitated specimens at around 438 K and frequency of about 1 Hz,which was attributed to the grain boundaries relaxation.Furthermore,it was found that the relaxation of theβ-Mg17Al12/α-Mg phase interfaces should give its contribution to the background internal friction in the as-cast,continuously precipitated and continuously-discontinuously precipitated specimens.

Design of CuCs-doped Ag-based Catalyst for Ethylene Epoxidation

Our recent theoretical studies have screened out CuCs-doped Ag-based promising catalysts for ethylene epoxidation[ACS Catal.11,3371(2021)].The theoretical results were based on surface modeling,while in the actual reaction process Ag catalysts are particle shaped.In this work,we combine density functional theory(DFT),Wulff construction theory,and micro kinetic analysis to study the catalytic performance of Ag catalysts at the particle model.It demonstrates that the CuCs-doped Ag catalysts are superior to pure Ag catalysts in terms of selectivity and activity,which is further proved by experimental validation.The characterization analysis finds that both Cu and Cs dopant promote particle growth as well as particle dispersion,resulting in a grain boundary-rich Ag particle.Besides,CuCs also facilitate electrophilic atomic oxygen formation on catalyst surface,which is benefitial for ethylene oxide formation and desorption.Our work provides a case study for catalyst design by combining theory and experiment.

Microanalysis and preliminary pharmacokinetic studies of a sulfated polysaccharide from Laminariajaponica

A rapid, sensitive and reproducible high performance liquid chromatography （HPLC） method with post-column fluorescence derivatization has been developed to determine the amount of low-molecular- weight sulfated polysaccharide （GFS） in vivo. The metabolism of GFS has been shown to fit a two component model following its administration by intravenous injection, and its pharmacokinetic parameters were determined to be as follows： half-time of distribution phase （t1/2α）=11.2±2.93 min, half-time of elimination phase （tl/2α）=98.20±25.78 min, maximum concentration （Cmax）=110.53 gg/mL and peak time （Tmax）=5 min. The pharmacokinetic behavior of GFS was also investigated following intragastric administration. However, the concentration of GFS found in serum was too low for detection, and GFS could only be detected for up to 2 h after intragastric administration （200 mg/kg body weight）. Thus, the bioavailability of GFS was low following intragastric administration because of the metabolism of GFS. In conclusion, HPLC with post-column derivatization could be used for quantitative microanalysis and pharmacokinetic studies to determine the presence of polysaccharides in the serum following intravenous injection.

Microstructure-Fatigue Crack Propagation Kinetics Relationships of Rail Steels

Microstructural analysis and fatigue crack propagation behavior of three types of rail steels, was performed. These are premium pearlitic, austenitic manganese （AM） and bainitic rail steels. Rectangular un-notched and notched test specimens were machined from railheads of each material using electrical discharge machining （EDM） and used for the mechanical properties and fatigue evaluation respectively. Bainitic steel has the highest yield strength, ultimate strength, and strain to failure as compared to both pearlitic and austenitic manganese steels. Fatigue studies showed that the crack speed for the bainitic steel is lower than that for the pearlitie and the AM steels over the entire range of the energy release rate. The bainitic steel exhibits a higher rate of crack deceleration in the second stage, as indicated by the lower slope of the fatigue crack propagation kinetics curve in comparison with the pearlitic and manganese rail steels. This attests to the superior fatigue damage tolerance of the bainitic rail steel in comparison to pearlitic and austenitic manganese rail steels. Microstructural analysis of the three rail steels revealed that bainitic steel has a more intricate structure than AM and pearlitic steels. AM steel shows very few signs of being work hardened or toughened, which usually increases the mechanical properties of the material. As the number of alloying elements increase, the microstructure of the steel becomes more complex, resulting in the increase of mechanical properties and fatigue fracture resistance of bainitic rail steel.

Aurora A orchestrates entosis by regulating a dynamic MCAK-TIP150 interaction

Entosis, a ceU-in-ceU process, has been implicated in the formation of aneuploidy associated with an aberrant cell division control. Microtubule plus-end-tracking protein TI P150 facilitates the loading of MCAK onto the microtubule plus ends and orchestrates micro- tubule plus-end dynamics during cell division. Here we show that TIP150 cooperates with MCAK to govern entosis via a regulatory cir- cuitry that involves Aurora A-mediated phosphorylation of MCAK. Our biochemical analyses show that MCAK forms an intra-molecular association, which is essential for TIP150 binding. Interestingly, Aurora A-mediated phosphorylation of MCAK modulates its intra-mo- lecular association, which perturbs the MCAK-TI P150 interaction in vitro and inhibits entosis in vivo. To probe if MCAK-TIP150 inter- action regulates microtubule plasticity to affect the mechanical properties of ceUs during entosis, we used an optical trap to measure the mechanical rigidity of live MCF7 ceils. We find that the MCAK cooperates with TIP150 to promote microtubule dynamics and modulate the mechanical rigidity of the cells during entosis. Our results show that a dynamic interaction of MCAK-TI P150 orchestrated by Aurora A-mediated phosphorylation governs entosis via regulating microtubule plus-end dynamics and cell rigidity. These data reveal a previously unknown mechanism of Aurora A regulation in the control of microtubule plasticity during ceU-in-ceU pro- cesses.

Biosolid Application to Agricultural Land a Contribution to Global Phosphorus Recycle： A Review

Phosphorus(P) is an essential nutrient required for plant development.Continuous population growth and rising global demand for food are expected to increase the demand for phosphate fertilizers.However,high-quality phosphate rock reserves are progressively becoming scarce.Part of the increased pressure on P resources could be alleviated by recycling P present in biosolids.Therefore,it is crucial to understand the dynamics of P in biosolid-amended soils,the effects of residual biosolid-borne P in soils,the way in which microorganisms may control P dynamics in biosolid-amended soils and the environmental implications of the use of biosolids as a source of P.Further research is needed to maximize biosolid-borne P uptake by crops and minimize its loss from biosolid-amended soils.The analysis of the microbiological control of P dynamics in biosolid-amended soils indicates interactions of biosolid P with other nutrients such as carbon(C) and nitrogen(N),suggesting that harmonization of the current regulation on the use of biosolids in agriculture,mainly based on total N and pollutant contents,is needed to better recycle P in agriculture.