三功能策略设计制备具有优异低温抗积碳性能的Ni-CeO2@SiO2催化剂催化甲烷干重整反应

随着全球人为温室气体排放量(主要是甲烷和二氧化碳)的增加,全球变暖的趋势逐渐增加,因此,迫切需要通过各种技术来捕获和利用这些温室气体.甲烷干气重整反应(DRM)可以有效地将甲烷和二氧化碳这两种资源丰富、价格低廉的温室气体转化为高附加值化学品,减少它们向大气排放.尽管DRM工艺的应用具有许多优势,但是反应期间碳沉积和活性组分的烧结是阻碍其工业应用的两个主要原因.这些碳沉积物可能覆盖活性中心或阻塞催化剂的孔道,从而导致催化剂活性降低.镍基催化剂因其价格低廉、初始活性高和资源丰富而得到广泛的应用.但应用于DRM反应的Ni基催化剂在反应中容易烧结和积碳,导致催化剂迅速失活.为解决上述问题,本文从三功能策略角度出发,即SiO2壳层的限域作用和Ni-Ce之间的协同作用以及CeO2的消除积碳作用,采用原位一锅法设计合成了一种限域型Ni-CeO2核壳结构催化剂(Ni-CeO2@SiO2).通过X射线衍射、透射电子显微镜、能量色散X射线光谱、N2吸附/脱附、氢气程序升温还原和脱附、氧气程序升温脱附、拉曼光谱、热重分析和原位漫反射红外傅里叶变换光谱测试对催化剂进行了系统的表征,来揭示催化剂的理化性质和反应机理.催化剂应用于甲烷干气重整反应结果表明,在温度区间为550～800℃时,与传统浸渍法合成的催化剂相比,Ni-CeO2@SiO2催化剂具有更高的活性.高温800℃下的稳定性测试结果显示,传统浸渍法合成的催化剂在反应20 h后就出现了大量的积碳且活性下降明显;而Ni-CeO2@SiO2催化剂在800℃下反应100 h后未检测到积碳,并且催化剂中的Ni纳米颗粒的平均粒径从5.01 nm仅增长到5.77 nm,表现出很好的高温抗积碳和耐烧结性能.值得注意的是,Ni-CeO2@SiO2催化剂在低温600℃(形成碳沉积的最可能温度区域)下反应20h后也未检测到积碳的形成,表现出催化剂良好的低温稳定性和抗积碳性能.这可能归因于对Ni-CeO2@SiO2催化剂的三功能作用,即多孔二氧化硅壳层的限域作用、Ni与CeO2之间强的金属-金属氧化物相互作用以及具有丰富活性氧物种CeO2的消除积碳的作用.通过原位漫反射红外傅里叶变换光谱测试来探究反应机理.结果 表明,DRM反应在Ni-CeO2@SiO2催化剂上遵循L-H机理,添加CeO2可以消除碳沉积并促进CO2活化.该三功能策略为设计其他应用于DRM的高性能催化剂提供了指导,有望加快该工艺的工业化.     

飞秒激光冲击AZ31B镁合金过程的数值模拟

采用有限元分析法对飞秒激光冲击AZ31B镁合金进行数值模拟,研究了激光冲击处理对镁合金变形过程的影响,分析了单脉冲激光冲击下材料内部的位移、动能、应力和应变的分布情况,得到了材料的瞬态速度和应变率变化过程.仿真结果表明,单脉冲飞秒激光冲击镁合金产生的塑性变形,可在材料表面形成微米级凹坑,中心点处最大位移为34μm,最大变形速度390m/s;在冲击初期,材料表面的应力和应变主要分布在冲击区域中心节点和边缘附近,并且得到镁合金的最大应力和最大应变率分别为955 MPa和1.8×106 s-1.研究结果能够为深入分析飞秒激光与镁合金作用时材料变形参量的变化规律提供数值理论依据.     

Measurement of micro weld joint position based on magneto-optical imaging

In a laser butt joint welding process,it is required that the laser beam focus should be controlled to follow the weld joint path accurately.Small focus wandering off the weld joint may result in insufficient penetration or unacceptable welds.Recognition of joint position offset,which describes the deviation between the laser beam focus and the weld joint,is important for adjusting the laser beam focus and obtaining high quality welds.A new method based on the magneto-optical(MO)imaging is applied to measure the micro weld joint whose gap is less than 0.2 mm.The weldments are excited by an external magnetic field,and an MO sensor based on principle of Faraday magneto effect is used to capture the weld joint images.A sequence of MO images which are tested under different magnetic field intensities and different weld joint widths are acquired.By analyzing the MO image characteristics and extracting the weld joint features,the influence of magnetic field intensity and weld joint width on the MO images and detection of weld joint position is observed and summarized.     

A New Cells‐Compatible Microfluidic Device for Single Channel Recordings

We report the fabrication of a microfluidic apparatus and the realization of a sensors based on PEDOT : PSS, a biocompatible semiconductor polymer used in substitution of standard electrodes for electrophysiological studies and for detection of nanopores in membrane. This gives the possibility to study the mechanisms of ions balance and molecular transport though cell membranes. In particular the apparatus is based on two chambers connected through an aperture in a PTFE sheet where lipid bilayer are formed using Montal‐Mueller method, and the pore‐forming proteins activity is detected by polymeric electrodes. This methodology could be applied to examine different membrane proteins for the purpose of biosensing, drug screening and nanopore technologies.     

Structure,Antibacterial Activity and Theoretical Study of the Forming Mechanism of Compound [(5-Methyl-3-oxo-2-phenyl-1H-pyrazol-4-yl)-thiophen-2-yl-methylene] Thiosemicarbazide

A new thiosemicarbazone compound derived from 1-phenyl-3-methyl-4-(2-thenoyl) pyrazolone-5(HPMTP) and thiosemicarbazide has been synthesized and characterized by IR, HNMR, MS, elemental analysis, UV and single-crystal X-ray diffraction. The compound crystallizes in monoclinic system, Cc space group with a = 7.5925(8), b = 20.263(2), c = 11.4669(13) ,  = 107.825(8)°, V = 1679.5(3) 3, Z = 4, R = 0.0316 and wR = 0.0687. The results of antibacterial activity test against Escherichia coli and Bacillus subtilis indicate that the compound possesses the same antibacterial activity as the contrast(Norfloxacin). Theoretical study of the forming mechanism to the title compound at the RHF/6-31G(d) level shows that there are two steps. The distal amino group of thiosemicarbazide is added to the 4-carbonyl group of HPMTP which forms TM. Then a dehydration reaction occurs in TM and generates a stable product PC.     

Phospholipid Polymer Hydrogel Matrices with Dually Immobilized Cytokines for Accelerating Secretion of the Extracellular Matrix by Encapsulated Cells

Construction of 3D tissues by various types of cells with specific characteristics is an important and fundamental technology in tissue reconstruction medicine and animal‐free diagnosis system. To do so, an excellent extracellular matrix (ECM) is needed for encapsulation of cells and maintaining cell activity. Spontaneously forming hydrogel matrix is used by complexation between two water‐soluble polymers, 2‐methacryloyloxyethyl phosphorylcholine polymer bearing phenylboronic acid groups and poly(vinyl alcohol). Two cytokines for cell proliferation are immobilized in the hydrogel matrix to control the activities of the encapsulated cells. The cytokine‐immobilized hydrogel matrix can encapsulate both L929 fibroblasts and normal human dermal fibroblasts under mild condition. The physical properties of the hydrogel matrix can follow the proliferation process of the encapsulated cells. The encapsulated cells secrete ECM in the polymer hydrogel networks upon 3D culturing for 7 days. Consequently, the tissue‐mimicking ECM hybrid hydrogels are fabricated successfully.     

小断面收缩率轴类零件楔横轧成形的可行性分析

利用ANSYS/LS-DYNA软件,对楔横轧小断面收缩率轴类零件的成形过程进行了有限元数值模拟,通过与常规断面收缩率轧件对比,分析了小断面收缩率轧件的表面和心部质量情况.结果表明:相同工艺参数条件下,小断面收缩率轧件横截面的椭圆度大于常规断面收缩率轧件;由于小断面收缩率轧件中心点处的平均应力和最大主应力均较大,因而更容易发生心部缺陷.提出了改善轧件表面和心部质量的措施.经轧制实验验证,楔横轧成形小断面收缩率轴类零件是可行的.     

Influence of B,Al and Nb addition on the glass forming ability and stability of mechanically alloyed Zr-Ni amorphous alloys

We investigated the influence of minor additions of B,Al and Nb that have representative atomic sizes on the glass forming ability (GFA) and stability of Zr-Ni amorphous alloys during mechanical alloying. The results show that the minor addition of B,Al or Nb does not shorten the initial time of the full amorphization reaction or improve the glass forming ability of the Zr-Ni alloys at a low rotation speed. However,B addition can effectively improve the mechanical stability of the amorphous phase against me...     

峨眉地幔热柱活动与贵州西部二叠系煤的形成环境研究

晚二叠世乐平期,最为强烈、规模最大的一次峨眉地幔热柱强烈活动在贵州西部形成西北高、东南低的古地理格局.沉积相带由早二叠世的近东西向变为晚二叠世北东向排布.沉积相带由西向东,由陆相渐变为海陆交替相,最后变为海相环境.在贵州西北部的威宁一带形成陆相沉积环境.遵义至安顺一线以西的黔西和黔西南地区,属于海陆交替的陆地边缘相区,...     

T10A钢成型模具的失效分析及热处理工艺的改进

结合T10A钢胶木成型模具的具体工作条件、性能要求和失效形式,采用性能(硬度)测试和金相显微分析等研究手段,分析了T10A钢胶木成型模具失效的主要原因,在失效分析和试验研究的基础上,有针对性的改进了T10A钢胶木成型模具的热处理工艺.研究结果表明,通过优化和改进模具的热处理工艺及其参数,有效地改善了胶木成型模具的使用性能,提高了模具的使用寿命.