Unusual mesomorphic behaviour of an ethynyl-substituted phthalocyanine

An ethynyl-substituted nickel(II) phthalocyanine has been synthesised and its thermotropic properties studied; optical microscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) techniques revealed an unusual mesomorphic behaviour observed for the first time in phthalocyanine systems where each disk of the hexagonal columnar mesophase is formed by two ethynyl-substituted phthalocyanine units.     

The application of synchrotron X-ray techniques to the study of rechargeable batteries

The increased use of rechargeable batteries in portable electronic devices and the continuous development of novel applications(e.g. transportation and large scale energy storage), have raised a strong demand for high performance batteries with increased energy density, cycle and calendar life, safety and lower costs. This triggers significant efforts to reveal the fundamental mechanism determining battery performance with the use of advanced analytical techniques. However, the inherently complex characteristics of battery systems make the mechanism analysis sophisticated and difficult. Synchrotron radiation is an advanced collimated light source with high intensity and tunable energies. It has particular advantages in electronic structure and geometric structure(both the short-range and long-range structure)analysis of materials on different length and time scales. In the past decades, synchrotron X-ray techniques have been widely used to understand the fundamental mechanism and guide the technological optimization of batteries. In particular, in situ and operando techniques with high spatial and temporal resolution, enable the nondestructive, real time dynamic investigation of the electrochemical reaction,and lead to significant deep insights into the battery operation mechanism.This review gives a brief introduction of the application of synchrotron X-ray techniques to the investigation of battery systems. The five widely implicated techniques, including X-ray diffraction(XRD), Pair Distribution Function(PDF), Hard and Soft X-ray absorption spectroscopy(XAS) and X-ray photoelectron spectroscopy(XPS) will be reviewed, with the emphasis on their in situ studies of battery systems during cycling.     

Microstructure Investigation of (Y,Ce)-TZP-Al_2O_3 Composite Materials

The microstructure of selected specimens in the (Y,Ce)-TZP-Al2O3 composite systems was studied. The investigation techniques used in this work included X-ray diffractometry ( XRD ) , Scanning Electroscope ( SEM ) , Transmission Electroscope (TEM), X-ray Energy Dispersion Analysis(EDAX) and High Resolution Electron Microscopy (HREM). Based on the experimental results, the relationship between microstructure and mechanical properties of the specimens was discussed.     

The application of synchrotron techniques to the study of lithium-ion batteries

This paper gives a brief review of the application of synchrotron X-ray techniques to the study of lithium-ion battery materials. The two main techniques are X-ray absorption spectroscopy (XAS) and high-resolution X-ray diffraction (XRD). Examples are given for in situ XAS and XRD studies of lithium-ion battery cathodes during cycling. This includes time-resolved methods. The paper also discusses the application of soft X-ray XAS to do ex situ studies on battery cathodes. By applying two signal detection methods, it is possible to probe the surface and the bulk of cathode materials simultaneously. Another example is the use of time-resolved XRD studies of the decomposition of reactions of charged cathodes at elevated temperatures. Measurements were done both in the dry state and in the presence of electrolyte. Brief reports are also given on two new synchrotron techniques. One is inelastic X-ray scattering, and the other is synchrotron X-ray reflectometry studies of the surface electrode interface (SEI) on highly oriented single crystal lithium battery cathode surfaces. Dedicated to the 85th birthday of John O’M. Bockris     

Cr/MSU-1催化剂中Cr含量对CO2氧化丙烷脱氢反应催化性能的影响

研究了CO2氧化丙烷脱氢制丙烯高效wCr/MSU-1 (w＝2, 4, 6, 8, 10, 质量分数, 以Cr2O3计算)催化剂中Cr含量对催化剂结构和催化活性的影响. 催化剂活性评价结果表明, 随Cr含量的增加, 催化剂的活性呈现先提高后降低的变化趋势. 在600 ℃条件下, 6.0Cr/MSU-1表现出最佳的催化反应活性, 其中丙烷、CO2转化率分别达到62.6%和22.1%. 为明确Cr含量对催化剂结构的具体影响, 对催化剂样品进行了XRD, UV-Vis和XPS表征: 催化剂样品的XRD表征发现Cr/MSU-1催化剂不仅能够保持良好的MSU-1分子筛的孔道结构, 而且活性金属Cr在载体表面具有很高的分散度, 随着Cr含量的增加催化剂表面形成明显的Cr2O3晶相; UV-Vis表征结果证实低Cr含量催化剂表面主要以Cr6＋的形式存在, 高Cr含量催化剂表面有明显的Cr3＋出现; 反应前后的催化剂XPS表征结果进一步证实催化剂表面的Cr6＋与催化反应活性具有良好对应关系. 基于上述结果, 我们认为Cr6＋是该催化剂重要的活性中心.     

Quantitative multielemental analysis of titaniferous magnetites

Two representative titaniferous magnetite samples procured from Moulabhanj, Orissa, India have been studied by PIXE, EDXRF, Mössbauer spectroscopy, and XRD techniques. Major iron-bearing phases identified in the samples by Mössbauer spectroscopy and XRD are magnetite, hematite, ferrous ilmenite and ferric ilmenite. The Fe²⁺/Fe³⁺ ratio and the relative percentages of different minerals were determined from the resonance areas of Mössbauer spectra. Quantitative multielemental analysis was carried out by energy dispersive X-ray fluorescence (EDXRF) and proton induced X-ray emission (PIXE). Nineteen minor and trace elements have been quantified by EDXRF whereas by PIXE eighteen elements have been analyzed quantitatively. Concentrations of trace elements determined by EDXRF and PIXE were used in interpreting the physico-chemical condition of the depositional basin.     

基于同步辐射光源研究水热合成纳米氧化物的生长机理

纳米氧化物的可控制备是提高其应用性能的前提条件。水热反应目前被广泛用于制备纳米氧化物材料,然而由于水热反应是在密闭环境中进行,很难研究前驱体的溶解过程,溶解后在溶液中的配位情况、晶体成核、生长过程以及形成的中间相,因此,难以实现材料的目标制备。同步辐射具有高强度、高亮度、高准直、宽频谱等诸多优点,通过设计和构建特殊的反应装置,可以应用同步辐射光源原位研究纳米氧化物在水热条件下的生长过程。本文结合本课题组及国际的研究工作介绍了原位反应装置的设计原则,以及基于同步辐射光源的原位X射线衍射(XRD)、X射线吸收精细结构谱(XAFS)和小角X射线散射(SAXS)研究纳米氧化物水热生长机理的最新进展,并展望了其发展趋势。     

Determination of nanocrystal sizes: a comparison of TEM, SAXS, and XRD studies of highly monodisperse CoPt3 particles

One of the most fundamental tasks in nanoscience is the accurate determination of particle sizes. Various methods have been developed to elucidate the mean particle diameter and the standard deviation for an ensemble of nanocrystals. However, good agreement between the results from different methods is not always encountered in the literature. In this study, we investigate colloidally prepared, highly monodisperse CoPt3 nanoparticles by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and powder X-ray diffraction (XRD). The results are compared in order to examine to which extent agreement is obtained by the different techniques when applied to small nanocrystals in the size range below 10 nm. In particular, the applicability of the simple Scherrer formula for size determination from the broadening of XRD reflections is checked. When the different techniques are correctly applied, the results from all methods are in good agreement.     

两相热法处理Cyanex 301-Ag+/Cu2+萃取体系制备Ag2S纳米和CuS微米材料

以Cyanex 301萃取剂为硫源,分别萃取Ag+和Cu2+,两相热法制备了Ag2S纳米颗粒和CuS微结构,采用X射线粉末衍射、紫外可见光谱、红外光谱以及电子显微镜对产物进行了表征。 表明制得的Ag2S和CuS分别为单斜相和六方相。 产物粒径随着反应温度的升高而增大,因而可通过加热温度调控产物尺寸,另外还考虑了其它反应条件对产物的影响。     

Characterization of Japanese color sticks by energy dispersive X-ray fluorescence,X-ray diffraction and Fourier transform infrared analysis

This work comprises the use of energy dispersive X-ray fluorescence (EDXRF), X-ray diffraction (XRD) and Fourier transformed infrared (FTIR) techniques for the study of the composition of twentieth century traditional Japanese color sticks. By using the combination of analytical techniques it was possible to obtain information on inorganic and organic pigments, binders and fillers present in the sticks. The colorant materials identified in the sticks were zinc and titanium white, chrome yellow, yellow and red ochre, vermillion, alizarin, indigo, Prussian and synthetic ultramarine blue. The results also showed that calcite and barite were used as inorganic mineral fillers while Arabic gum was the medium used. EDXRF offered great potential for such investigations since it allowed the identification of the elements present in the sample preserving its integrity. However, this information alone was not enough to clearly identify some of the materials in study and therefore it was necessary to use XRD and FTIR techniques.     

Intercalation compounds between a Spanish bentonite (Gador montmorillonite) and ethyl 2-oxocyclopentanecarboxylate (EOCPC)

The process of retention of ethyl 2-oxocyclopentanecarboxylate (EOCPC) by samples of natural bentonite containing Gador montmorillonite has been studied. Firstly, the adsorbent and the adsorbate were studied by different techniques. Intercalation compounds between them were prepared by two different methods: imbibition at room temperature and reflux heating at 60°C. The compounds obtained by both treatments were characterized structurally by X-ray diffraction (XRD), infrared spectroscopy (FT-IR), differential thermal analysis (DTA) and thermogravimetric analysis (TGA).     

磺化聚苯乙炔/多壁碳纳米管复合材料导电特性和机理的研究

将磺化聚苯乙炔(SPPA)与多壁碳纳米管(MWCNTs)超声共混制备得到SPPA/MWCNTs复合材料. 用X光电子能谱仪、固体紫外-可见分光光度计、X射线衍射仪、四探针、场发射扫描电镜等对复合材料导电特性及机理进行研究. 结果表明: SPPA/MWCNTs 复合材料中SPPA与MWCNTs发生电荷转移而被掺杂, 并且由于SPPA与MWCNTs间的电荷转移, 彼此间存在一定的相互作用力; 复合材料电阻呈负温度系数效应; SPPA/MWCNTs复合材料电导率发生两次突跃. 可能的导电机理为, 复合材料中SPPA不仅被MWCNTs物理填充, 同时还被MWCNTs掺杂, 复合材料中存在两种导电通路, 一是SPPA与MWCNTs的碳原子发生电荷转移而被掺杂, 彼此之间存在一定的相互作用力, 导致SPPA包裹MWCNTs形成独立导体单元, 这种独立单元相互接触形成导电通路; 二是MWCNTs彼此之间相互接触形成导电通路, 并建立了该导电机理的理论模型.     

大孔炭载Pd催化剂对甲酸氧化的电催化性能

用X射线能量色散谱(EDS)、X射线衍射(XRD)谱、拉曼光谱和电化学技术研究和比较了直接甲酸燃料电池(DFAFC)中Vulcan XC-72炭黑载Pd (Pd/XC)和大孔炭载Pd (Pd/MC)催化剂对甲酸氧化的电催化性能. 循环伏安曲线测量表明甲酸在Pd/XC和Pd/MC催化剂电极上主要氧化峰的峰电位基本相同, 在0.15 V左右, 但在Pd/MC催化剂电极上的峰电流密度比在Pd/XC催化剂上的大30%左右. 计时电流曲线测量表明, 在6000 s时, 在Pd/MC催化剂电极上的峰电流密度比在Pd/XC催化剂上的大38%左右, 这些结果说明Pd/MC催化剂对甲酸氧化的电催化活性和稳定性要好于Pd/XC催化剂. 由于Pd/MC和Pd/XC催化剂的Pd粒子平均粒径和相对结晶度相似, 因此, Pd/MC催化剂电催化性能好的原因只能归结于MC大的孔径和高的石墨化程度引起的高电导率.     

Growth and characterization of NLO based l-arginine maleate dihydrate single crystal

Single crystals of l-arginine maleate dihydrate (LAMD) were successfully grown from aqueous solution by solvent evaporation technique. As-grown crystals were analyzed by different instrumentation techniques such as X-ray powder diffraction (XRD), Fourier transform infrared (FTIR) spectra and UV–vis near infrared (NIR) transmittance spectra. Thermal behavior has been studied with TGA/DTA analyses. The optical second harmonic generation (SHG) conversion efficiency of LAMD was determined using Kurtz powder technique and found to be 1.5 times that of KDP.     

In situ approaches to establish colloidal growth kinetics

A technique based on the back scattering phenomenon of dynamic light scattering has been employed to monitor the kinetics of gold and platinum metal nanoparticle growth and silver nanoparticle oxidation as well as in the determination of particle sizes ranging from 1 to 200 nm in diameter. The systems were chosen to examine the applicability of dynamic light scattering to nanoresearch over a broad range of sizes as well as both metallic and nonmetallic systems. The advantages of this instrumentation over traditional instruments such as X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) have been highlighted.     

Composites based on modified clay assembled Rh(III)–heteropolymolybdates as catalysts in the liquid-phase hydrogenation of cinnamaldehyde

New composites based on the [RhMo₆O₂₄H₆]³⁻ (RhMo₆) heteropolyanion supported on pillared (PILC), heterostructured (PCH) and functionalized(PILC-F) and (PCH-F) systems based on clays were prepared, characterized and tested as catalysts in the liquid-phase hydrogenation of cinnamaldehyde. The original phases and supported systems were characterized using several techniques such as powder X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM–EDS), Raman microprobe studies, X-ray photoelectron spectroscopy (XPS), thermogravimetry and differential thermal analyses (TG-DSC), temperature programmed reduction (TPR), and textural analysis (BET method), which confirmed their functionalization, physicochemical modification and the nature of Mo adsorbed species. Active acidic, basic and redox sites were determined by temperature programmed surface reaction (TPSR). Mo loading reached 7 wt% for the system RhMo₆/PCH-F and 3 wt% for the system RhMo₆/PILC-F, while unfunctionalized clay systems showed a value of 1 wt% of Mo. The catalytic performance showed that PCH-based composites were the most active and reached up to 56% conversion at 360 min of reaction when tested in liquid-phase cinnamaldehyde hydrogenation. The selectivity for all the systems was mainly toward hydrocinnamic aldehyde (HCAL) and reached 77% for the RhMo₆/PCH-F catalyst at 25% conversion.     

镧助剂对铜硅催化剂结构及其甘油氢解性能影响研究

在沉淀凝胶法制备的Cu/SiO2催化剂中采用浸渍法添加La助剂,制备了一系列不同La含量的Cu-La2O3/SiO2催化剂,利用BET、XRD、TPR、XPS和TEM对催化剂进行了系统表征,并在高压反应釜中对其进行了甘油氢解制备1,2-丙二醇活性评价,研究了La含量对催化剂高温热稳定性及甘油氢解活性的影响.结果表明:适量La的引入能明显抑制催化剂的高温烧结,维持催化剂的大比表面及活性组分的高分散,提高催化剂的结构稳定性;同时对减少反应过程中活性组分的流失也有很好的效果.铜镧之间存在着协同作用,经高温焙烧后得到加强,对Cu/SiO2催化剂的甘油氢解活性有很好的促进作用.     

Properties of oligopyrrole doped dodecylbenzene–sulfonic acid prepared with different oxidants in reversed microemulsion

The calcium silicate systems were prepared by sol–gel methods—varying the synthesis conditions (precursor solutions, chemical compositions, catalysts, temperature and time of aging and heat treatment). The precursors of sol–gel procedures were calcium nitrate and tetraetoxysilane. Acetic acid, water, ammonia and nitric acid were applied as catalysts. The atomic and supramolecular structures of calcium silicate products have been varied from amorphous to crystalline phases depending strongly on the preparation conditions. The structures were investigated in atomic range with Fourier transform infrared (FTIR), X-ray diffraction (XRD) and in supramolecular ranges with small angle X-ray scattering (SAXS), ultra small angel X-ray scattering (USAXS) measurements. The mechanical properties could be most efficiently improved by heat treatments (min. 600 °C) and a post-treatment with tetraetoxysilane (TEOS). The mechanical strength of bulk biomaterials has been controlled by Brinell hardness test.