采用X射线吸收光谱表征单原子催化剂:至关重要与持久挑战

X射线吸收光谱(XAS)可为负载型单中心(单原子或单核金属络合物)催化剂的结构和电子特性提供重要信息.虽然XAS技术可表征真实反应条件下、无需长程有序结构的催化剂,并且可提供对于负载型单中心催化剂非常重要的金属-载体界面信息;但是它给出的信息是包括与催化有关或无关的所有负载型金属物种的平均信息.负载型催化剂的准确表征具有长期挑战性,也限制了我们准确地理解催化剂的构效关系.为了更好地利用XAS表征技术,深入研究催化剂的构效关系,并最终用其指导设计开发出高效的催化剂,制备具有均一结构活性位的负载型单中心催化剂,并采用XAS及相关技术对其表征至关重要.本文列举了一些实例以说明XAS在表征具有均一结构活性位的负载型单中心催化剂方面的能力,以及XAS如何与其他技术(如扫描透射电子显微镜和红外光谱)互补,为以分子筛和金属-有机骨架材料为载体而制得的具有均一结构活性位的负载型单中心催化剂提供原子尺度的信息.     

Fischer-Tropsch synthesis by nano-structured iron catalyst

Effects of nanoscale iron oxide particles on textural structure, reduction, carburization and catalytic behavior of precipitated iron catalyst in Fischer-Tropsch synthesis (FTS) are investigated. Nanostructured iron catalysts were prepared by microemulsion method in two series. Firstly, Fe2O3, CuO and La2O3 nanoparticles were prepared separately and were mixed to attain Fe/Cu/La nanostructured catalyst (sep-nano catalyst); Secondly nanostructured catalyst was prepared by co-precipitation in a water-in-oil microemulsion method (mix-nano catalyst). Also, conventional iron catalyst was prepared with common co-precipitation method. Structural characterizations of the catalysts were performed by TEM, XRD, H2 and CO-TPR tests. Particle size of iron oxides for sep-nano and mix-nano catalysts, which were determined by XRD pattern (Scherrer equation) and TEM images was about 20 and 21.6 nm, respectively. Catalyst evaluation was conducted in a fixed-bed stainless steel reactor and compared with conventional iron catalyst. The results revealed that FTS reaction increased while WGS reaction and olefin/paraffin ratio decreased in nanostructured iron catalysts.     

Microfluidic System for Synthesis of Trigonal Selenium Nanowires

<正>A microfluidic system was developed for the synthesis of trigonal selenium(t-Se) nanowires,which was composed of a glass microchip coupled with a poly(methyl methacrylate)(PMMA) microchip.In the glass microchip, amorphous selenium(a-Se) colloid was prepared by reducing selenious acid with an excess amount of hydrazine at a temperature of 100℃.In the coupled PMMA microchip,a-Se was transformed into more stable t-Se seeds via sonication at room temperature.The residence time of the reactants in both microchips was optimized by varying the dimension and length of the microchannel each.The t-Se nanowires were formed by anisotropic growth of selenium crystallite during sonication and aging under the assistance ofβ-cyclodextrin(β-CD).Various stages of the nanowires' growth were investigated.The as-synthesized products were characterized by powder X-Ray diffraction(XRD),Raman spectroscopy,scanning electron microscopy(SEM),transmission electron microscopy(TEM) and selected-area electron diffraction(SAED).     

鲨鱼肝铁蛋白亚基解离与组装机理的研究

小批量制备质谱纯鲨鱼肝铁蛋白(Liver Ferritin of Sphyrna zygaena,SZLF)。在弱酸介质(pH1.0)中,天然电泳结果显示,SZLF蛋白质亚基20 min后开始解离。选用透射电子显微镜跟踪SZLF亚基解离与重组装全过程和蛋白壳与铁核尺寸变化,发现SZLF在亚基酸解离过程中,随着pH值的降低,铁核和蛋白壳的尺寸呈现相同的变化趋势,这种变化趋势可能与铁核内层铁的释放和蛋白壳的解离与去折叠有关。SZLF蛋白壳的重组装过程则是一个快速过程,并且是由松散熔球态向紧密态转变的过程。SZLF由单类型亚基组成,而马脾铁蛋白(Horse Spleen Ferritin,HSF)由H和L两种亚基类型组成。在基质pH3.0条件和激光辅助下,混合HSF和SZLF仍然可释放各自的亚基且形成准亚基离子,供基质辅助激光解析电离飞行时间质谱分析,说明此时SZLF的亚基间相互作用强度减弱但并没有去折叠。TEM技术在铁蛋白解离和重组装过程中的应用,为进一步研究铁蛋白纳米包装的过程和机理提供新颖的、可行的和更加直观的研究手段。     

Controlled Synthesis of Sea-urchin-like ZnO Nanomaterials with the Aid of Ethylene Glycol Using a Solvothermal Method

Sea-urchin-like ZnO nanomaterials were successfully synthesized by decomposition of zinc acetate precursor in the presence of sodium hydroxide and ethylene glycol(EG) in an ethanol solution using a solvothermal method at 180 ℃ for 12 h.The crystalline phase and morphology of the resultant nanomaterials were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),selected-area electronic diffraction(SAED) and high-resolution electron microscopy(HRTEM).Interestingly,the sizes and prod length of the samples can be easily tuned by changing the amount of directing agent EG and keeping other reaction conditions unchangeable.On the basis of our experimental outcomes,EG-controlled-nucleation-growth formation mechanism was proposed to correspond for the sea-urchin-like ZnO growth processes.And the photoluminescence(PL) spectra of the as-selected samples were measured at room temperature,presenting two emission peaks centered at～388 and 480 nm.     

Effect of substrate temperature on microstructure and optical properties of single-phased Ag20 film deposited by using radio-frequency reactive magnetron sputtering method

Using a radio-frequency reactive magnetron sputtering technique, a series of the single-phased Ag20 films are deposited in a mixture of oxygen and argon gas with a flow ratio of 2：3 by changing substrate temperature （Ts）. Effects of the Ts on the microstructure and optical properties of the films are investigated by using X-ray diffractometry, scanning electron microscopy and spectrophotometry. The single-phased Ag20 films deposited at values of Ts below 200℃ are （111） preferentially oriented, which may be due to the smallest free energy of the （111） crystalline face. The film crystallization becomes poor as the value of Ts increases from 100℃ to 225℃. In particular, the Ag20 film deposited at Ts=225℃ loses the （111） preferential orientation. Correspondingly, the film surface morphology obviously evolves from a uniform and compact surface structure to a loose and gullied surface structure. With the increase of Ts value, the transmissivity and the reflectivity of the films in the transparent region are gradually reduced, while the absorptivity gradually increases, which may be attributed to an evolution of the crystalline structure and the surface morphology of the films.     

Effect of Metallic Film in Diamond Growth from an Fe—Ni—C System at High Temperature and High Pressure

The metallic film surrounding a diamond single crystal,which plays an important role the diamond growth from and Fe-Ni-C system,has been successfully investigated by using transmission-electron microscopy(TEM),Raman layer(near diamond)of the film by TEM and Raman spectroscopy,but a parallel relationship exists between the(111) plane of γ-(Fe,Ni) and the (100) plane of (Fe2Ni)3C in this region.Compared with that of the film has an increase of 0.9V.According to the microstructures on the film obtained by the TEM.Raman spectra,and XPS,the catalytic mechanism of the film may be assumed as follows.In the surface layer of the film,iron and nickel atoms in the γ-(Fe,Ni) lattice can absorb carbon atoms in the (Fe,Ni)3C lattice and make them transform to an sp^3-like state.Then carbon atoms with the sp^3-like structure are separated from the (Fe,Ni)3C and stack on the growing diamond crystal.This study provides a direct evidence for the diamond growth from a metallic catlayst-graphite system under high temperature and high pressure.     

飞秒激光脉冲与金属光阴极相互作用

本文从理论上分析了飞秒激光与光阴极相互作用过程，采用双温模型分析了飞秒激光脉冲辐照下金属薄膜的温度效应。通过建立一个简单的光电效应模型，获得了最佳的金属光阴极厚度，通过该模型可以发现，产生的光电流对在飞秒激光脉冲辐照下的电子温度和晶格温度有着很大的依赖关系。     

Effect of void formation during MEVVA tungsten ion implantation on the microstructure and surface properties of H13 die steel

H13 die steel was implanted with tungsten using a metal vapour vacuum arc (MEVVA) ion source. When the pulsed beam current density of tungsten ions increased to 6mA?cm^-2, some voids appeared in the high voltage electron microscope (HVEM) micrograph, which would disappear at an annealing temperature of 600℃. HVEM and x-ray diffraction were used for observing the phase structure of the annealed and un-annealed H13 steel after the steel was implanted. Results of wear and hardness tests indicated that whether the voids appear significantly influences the hardness and wear of H13 steel. Reasons for the formation of voids and the relation between the surface mechanical property and voids are discussed in terms of collision theory.     

MOCVD生长InP/GaInAsP DBR结构及相关材料特性

采用金属有机化学气相沉积(MOCVD)法InP衬底上成功地制备了GaxIn1-xAsyP1-y/InP交替生长的分布布喇格反射镜(DBR)结构以及与之相关的四元合金GaxIn1-xAsyP1-y和InP外延层。利用X射线衍射、扫描电子显微镜(SEM)、低温光致发光(PL)光谱等测量手段对材料的物理特性进行了表征。结果表明,在InP衬底上生长的InP外延层和四元合金GaxIn1-xAsyP1-y外延层77K光致发光(PL)谱线半峰全宽(FWHM)分别为9.3meV和32meV,说明形成DBRs结构的交替层均具有良好的光学质量。X射线衍射测量结果表明,四元合金GaxIn1-xAsyP1-y外延层与InP衬底之间的相对晶格失配仅为1×10-3。GaxIn1-xAsyP1-y/InP交替生长的DBR结构每层膜的光学厚度约为λ/4n(λ=1.55/μm)。根据多层膜增反原理计算得出当膜的周期数为23时,反射率可达90％。