Direct hydrothermal synthesis of novel functional mesoporous materials

A direct synthesis method of preparing alkaline earth or transition metal oxides supporting mesoporous materials is reported. Distinguishing from those traditionaltechniques characterized by “synthesis at first and then modification”, this new method adds the precursor salts that have no perturbation in the strong acid synthetic system but easily form oxides after calcinations, into the initial syntheticmixture, performing the “synthesis” and “modification” in one-pot procedure.     

介孔碳基材料的制备及电化学性能

有序介孔碳因具有均一的孔径、大的比表面积和特殊的孔道结构而具有独特的物理化学性质,使其在电化学领域得以广泛应用。作为双电层电容器电极材料,有序介孔碳材料尽管表现出来良好的充放电性能,但比电容有限,因此对有序介孔碳材料进行改性一直是热门的研究课题之一。非金属杂原子(N、S、P、B等)掺杂是提高有序介孔碳电化学水平简单且有效的方法。杂原子的介入,通过共价键相连引入新的官能团改变碳材料的理化性质,经过法拉第氧化还原反应提高材料的赝电容。     

离子液体中合成介孔材料的研究进展

离子液体作为一种新型的绿色环保溶剂,在介孔材料合成中的应用引起越来越多研究者的关注.目前,已经利用离子液体为模板合成出介孔SiO2、TiO2和Al2O3等多种介孔材料.与传统的表面活性剂相比,离子液体在合成过程中体现出很多优势,为介孔材料的合成开辟了一条新的途径.综述了离子液体在介孔材料合成中的研究进展.     

硫酸盐在水泥基材料中的扩散和渗透特征

采用偏光显微镜和扫描电镜分析了含镁质类膨胀剂的水泥砂浆在硫酸盐溶液中浸泡1 a后的微观结构,提出了硫酸盐溶液在水泥基材料中的3种迁移方式;通过SEM-EDS分析得出了该水泥基材料被侵蚀后所形成的产物主要是石膏和钙矾石的结果,没有发现硫酸镁和碳硫硅钙石膨胀物形成;在水泥基材料中添加适当种类和掺量的镁质类膨胀剂,水化的与未水化的膨胀剂填充到集料与浆体的间隙内,增大了水泥基材料的密实度,改善了界面结构,提高了水泥基材料抗硫酸盐侵蚀能力.     

介孔ZSM-5分子筛材料的制备及催化应用研究进展

介孔沸石分子筛具有沸石优良的水热稳定性、酸性和择形性,并兼具介孔的传质优势,使反应物更易接触到催化剂内表面活性中心,从而提高材料的催化活性,所以,介孔沸石分子筛近年来得到大量研究.综述了介孔ZSM-5沸石分子筛的制备方法,主要评述了模板法和后处理改性法;介绍了该催化材料在裂化、芳构化、异构化及烷基化过程中的应用;指出了介孔ZSM-5分子筛的发展方向.     

Exploration of molecular dynamics during transient sorption of fluids in mesoporous materials

In recent years, considerable progress has been made in the development of novel porous materials with controlled architectures and pore sizes in the mesoporous range. An important feature of these materials is the phenomenon of adsorption hysteresis: for certain ranges of applied pressure, the amount of a molecular species adsorbed by the mesoporous host is higher on desorption than on adsorption, indicating a failure of the system to equilibrate. Although this phenomenon has been known for over a century, the underlying internal dynamics responsible for the hysteresis remain poorly understood. Here we present a combined experimental and theoretical study in which microscopic and macroscopic aspects of the relaxation dynamics associated with hysteresis are quantified by direct measurement and computer simulations of molecular models. Using nuclear magnetic resonance techniques and Vycor porous glass as a model mesoporous system, we have explored the relationship between molecular self-diffusion and global uptake dynamics. For states outside the hysteresis region, the relaxation process is found to be essentially diffusive in character; within the hysteresis region, the dynamics slow down dramatically and, at long times, are dominated by activated rearrangement of the adsorbate density within the host material.     

Direct imaging of the pores and cages of three-dimensional mesoporous materials

Mesostructured composite materials, with features ranging from 20 to 500 A in size, are obtained by the kinetically controlled competitive assembly of organic and inorganic species into nanostructured domains. Short-range order is limited, and long-range order is determined by weak forces such as van der Waals or hydrogen-bonding. Three-dimensional mesoporous materials obtained by removing the organic phase are of particular interest for applications such as catalysis and chemical sensing or separation, for which structural features such as cavity shape, connectivity and ordered bimodal porosity are critical. But atomic-scale structural characterization by the usual diffraction techniques is challenging for these partially ordered materials because of the difficulty in obtaining large (> 10 microm) single crystals, and because large repeat spacings cause diffraction intensities to fall off rapidly with scattering angle so that only limited small-angle data are available. Here we present a general approach for the direct determination of three-dimensional mesoporous structures by electron microscopy. The structure solutions are obtained uniquely without pre-assumed models or parametrization. We report high-resolution details of cage and pore structures of periodically ordered mesoporous materials, which reveal a highly ordered dual micro- and mesoscale pore structure.     

辅助模板剂对EISA法制备硅基介孔材料的影响

采用EISA法,以PEG为主模板剂,根据辅助模板剂添加情况的不同,分别制备出S-N-A-T,S-NH3,S-TMAOH3种不同的硅基介孔材料.用X线衍射、氮气吸附脱附以及红外光谱等手段对3种材料进行了表征,在此基础上,通过吸附实验对比材料的吸附性能.表征结果显示,添加辅助模板剂后扩孔作用显著,大大改善产物的介孔结构,因此EISA法中添加辅助模板剂非常必要.其中以TMAOH为辅助模板剂合成的样品S-TMAOH介孔短程有序,各参数最佳.吸附研究表明,S-TMAOH对铅离子的吸附性能明显高于S-N-A-T和S-NH3,其吸附量受溶液pH值影响,在pH值为6.0时吸附容量最大.以TMAOH为辅助模板剂,制备的S-TMAOH材料对铅离子具有良好的吸附性和再生性.     

预测氯离子在水泥基复合材料中有效扩散系数

基于水泥基复合材料界面区水泥颗粒的分布特征,给出了界面区孔隙率分布函数和界面区的有效扩散系数;将水泥基复合材料视为骨料、基体、界面区以及其均匀化后的等效介质相四相复合球模型,采用n层球夹杂理论,逐尺度地预测了氯离子在水泥基复合材料中的有效扩散系数.结果表明:预测的氯离子扩散系数与实测结果基本吻合;n层球夹杂理论适合于预...     

制备体系酸度对AlMSU介孔材料结构性能的影响

利用β沸石纳米簇和曲拉通TX-100分别作为骨架构筑前驱物和孔道导向剂,在酸性介质中通过(N^oH⁺)Cl^-S⁺组装机制合成了蠕虫状孔道排列的AlMSU介孔材料,并借助测试手段对其进行了系统表征。结果表明：制备体系盐酸浓度对AlMSU的结构性能、骨架组成及收率有着显著影响。介质酸浓度较低（<0.5mol/L）时所得AlMSU的物化性质较差,而且产物收率低（基于样品粉末质量）;而体系酸浓度大于2.5mol/L时将造成部分铝原子从骨架中析出,导致最终产物中铝元素含量显著降低。基于结构性能、骨架组成和样品收率等综合因素,体系酸浓度介于1.5~2.0mol/L时是合成AlMSU介孔材料的合适区间     

硫化镉/介孔碳复合材料的原位制备与表征

以有序介孔硅材料SBA—15为模板,苯胺为碳源,氯化镉为镉的前驱体,过硫酸铵既做聚合引发剂又提供硫源,通过液相浸渍的方法原位制备出硫化镉/介孔碳复合材料,并考察了氯化镉的加入量对所得复合材料结构的影响.结果表明:该复合物为SBA—15的反相复制品,具有类似CMK—3结构;另外,随着氯化镉加入量的增加,该复合物的结构和孔径分布没有明显变化,但其比表面积和孔体积呈下降趋势.     

扩散焊接多层材料淬火过程的有限元分析

采用有限元方法模拟了TC4/V/Cu/Ni/GCr15焊后多层材料淬火过程中的温度及应力场,模拟中考虑了轴承钢中马氏体相变的影响. 模拟结果表明:淬火过程中,中间层是应力最为集中的区域,钢中发生的马氏体相变起到了降低应力的作用;中间Cu层是剪切应力最为集中的区域;最大剪切应力出现在马氏体相变前铜层外表面处,是引起工件失效的主要原因;轴承钢层厚度的减小可以明显降低工件中最大剪切应力,但不能从根本上消除引起工件失效的危险因素.     

Kondo resonance in a single-molecule transistor

When an individual molecule, nanocrystal, nanotube or lithographically defined quantum dot is attached to metallic electrodes via tunnel barriers, electron transport is dominated by single-electron charging and energy-level quantization. As the coupling to the electrodes increases, higher-order tunnelling and correlated electron motion give rise to new phenomena, including the Kondo resonance. To date, all of the studies of Kondo phenomena in quantum dots have been performed on systems where precise control over the spin degrees of freedom is difficult. Molecules incorporating transition-metal atoms provide powerful new systems in this regard, because the spin and orbital degrees of freedom can be controlled through well-defined chemistry. Here we report the observation of the Kondo effect in single-molecule transistors, where an individual divanadium molecule serves as a spin impurity. We find that the Kondo resonance can be tuned reversibly using the gate voltage to alter the charge and spin state of the molecule. The resonance persists at temperatures up to 30 K and when the energy separation between the molecular state and the Fermi level of the metal exceeds 100 meV.     

Selectivity in vibrationally mediated single-molecule chemistry

The selective excitation of molecular vibrations provides a means to directly influence the speed and outcome of chemical reactions. Such mode-selective chemistry has traditionally used laser pulses to prepare reactants in specific vibrational states to enhance reactivity or modify the distribution of product species. Inelastic tunnelling electrons may also excite molecular vibrations and have been used to that effect on adsorbed molecules, to cleave individual chemical bonds and induce molecular motion or dissociation. Here we demonstrate that inelastic tunnelling electrons can be tuned to induce selectively either the translation or desorption of individual ammonia molecules on a Cu(100) surface. We are able to select a particular reaction pathway by adjusting the electronic tunnelling current and energy during the reaction induction such that we activate either the stretching vibration of ammonia or the inversion of its pyramidal structure. Our results illustrate the ability of the scanning tunnelling microscope to probe single-molecule events in the limit of very low yield and very low power irradiation, which should allow the investigation of reaction pathways not readily amenable to study by more conventional approaches.     

无机介孔材料在第三代电化学生物传感器中的应用研究

无机介孔材料是一种孔直径在2,50nm的多孔材料。这种材料具有结构规则,机械性能高、化学和热能稳定性好等特点。近年来,随着材料合成技术的提高,不断有新型高负载能力和生物相容性好的介孔材料被开发出来。同时,实验表明,无机介孔材料是固载生物大分子的良好载体。利用无机介孔材料固载氧化还原蛋白质并结合其的直接电子转移,为我们提供了一种新的构建第三代生物传感器的方法。基于无机介孔材料的特点及氧化还原蛋白质的直接电子转移,所构建的第三代电化学生物传感器有望具有较传统电化学传感器更好的性能。将介孔材料分为二氧化硅基和非二氧化硅基2大类,描述了无机介孔材料在第三代电化学生物传感器中的应用。     

红外光谱法与X射线衍射法分析介孔复合材料组分变化机理

分析了介孔复合材料的原材料、中间产品及最终产品的傅里叶变换红外光谱图和X射线衍射图,得出材料制备过程中有机及无机组分定性及定量变化.结合透射电镜观测结果提出了介孔复合材料制备过程中组分变化机理,从作用力和热力学角度分析了有机离子载入反应的驱动力种类及作用机制.     

新型介孔材料M41S的合成机理及影响产物结构的因素

综述了新型介孔材料M41S合成机理的研究进，硅酸盐物种以液晶或胶束作模板剂形成介孔结构，可用液晶模板机理解释；硅酸盐物种与表面活性剂离子在较低浓度下形成六方堆积的介孔结构，可用协同模板机理解释。水热反应混合物组成、表面活性剂与硅酸盐摩尔比和酸碱性等对介孔产物的结构有很大影响。另外，讨论了影响孔径和稳定性的因素。     

孔道结构对有序介孔炭电化学性能的影响

以三嵌段共聚物（F127）为模板剂,间苯二酚（R）和甲醛（F）为碳前驱体,在外加的酸性条件下通过自组装的方法制得了F127/RF复合材料,然后经碳化处理得到具有高度有序孔道结构的介孔炭材料（OMCs）,通过XRD、TEM、N₂吸/脱附手段(77K低温下)对其进行结构表征。测试结果表明有序介孔炭材料的BET比表面积和总孔体积分别为770m²/g和0.65cm³/g。以有序介孔炭材料为电极制备超级电容器,对其进行直流恒流充放电测试、循环伏安测试和交流阻抗测试,结果显示在电流密度为0.02A/g时OMC-3比容量为130F/g,100次充放电循环后电容量保持率在99%以上。     

生物模板剂合成介孔氧化铈及其催化性能

以无污染简单易得的天然材料壳聚糖为模板剂合成介孔氧化铈材料,并研究了材料的结构和催化性能.介孔Ce02的孔道结构由直径为5-8 nm的颗粒堆积形成,孔道孔径分布较为均匀,集中在5-10 nm,材料的比表面积约为102 m^2·g^-1.与氧化铈参比样相比,介孔氧化铈具有更好的氧化能力和催化活性,因为材料高比表面积导致了更多活性位点的暴露和表面活性氧的增多.介孔氧化铈的%T50转化率为50％时的温度点）约为300℃,远低于亚微米参比样的430℃.     

Computational diffusion kinetics and its applications in study and design of rare metallic materials

Computational diffusion kinetics(CDK),with a spirit of and being coupled with the computational thermodynamics(CT,or called as the CALPHAD technique),plays increasingly important role in the alloy design/optimization and microstructure control during the processing of advanced metallic materials.This paper is to highlight recent progress of CDK in research with great focus on novel Ti and Zr alloys,which was largely performed in the authors’group.It ends with one representative example of the applications of CDK,coupled with CT,quantitative phase field,and three-dimensional(3D)statistical calculation,in designing the heattreatment schedule for the dual phase(αβ)Ti–6Al–4V alloys.