厚度效应对La0.67Ca0.33MnO3单晶薄膜电输运特性的影响

研究了外延La0.67Ca0.33MnO3（LcMO）／SrTiO3（100）和LCMO／NdGaO3（110）（NGO）薄膜的电输运特性随薄膜厚度的变化。尽管LCMO／STO和LCMO／NGO表现出不同的晶格畸变，但是，研究发现，在结构与输运特性之间没有直接的依赖关系，表现晶格应变效应对薄膜的电输运特性没有影响，如电阻率、金属-半导体转变、极化子激发能。     

电子导电金属有机框架薄膜的研究进展

电子导电金属有机框架是一类兼具导电性和多孔性的新型固体导电材料, 目前在燃料电池、电催化、超级电容器、热电、传感等电学领域得到广泛研究. 由于导电金属有机框架材料不易加工成膜, 阻碍了其在电子器件领域的进一步发展, 因此近年来导电金属有机框架薄膜及其电学性能的研究备受关注. 从电子导电金属有机框架薄膜的制备方法及其在电学领域中的应用出发, 总结了该类电学材料最新的研究进展, 并对其今后发展所面临的机遇和挑战进行了简单展望.     

金属-多孔有机分子笼纳米复合物的研究进展

多孔有机分子笼(POC)是一类具有固定腔隙的离散分子,因其稳定的孔隙结构、较高的比表面积和良好的可溶性,正成为一类可用于容纳特定大小的分子或离子的新兴功能性材料.除此之外,该类材料中稳定存在的开放孔隙结构,使其在气体分离与储存、传感器件、药物运输等领域具有广泛的应用,已逐渐成为国内外研究的热点.目前,多孔有机分子笼存在能与金属结合的位点,并具有空间限域效应,能有效防止金属纳米颗粒的团聚,故常被用于特定尺寸金属纳米颗粒的制备,从而形成金属-多孔有机分子笼纳米复合材料.多孔有机分子笼不仅可调控金属纳米粒子的大小,还可通过多孔笼体结构的保护,在不影响其原子表面可及率的条件下,稳定其微纳结构.相比于传统金属纳米催化剂,金属-多孔有机分子笼纳米复合物不仅具有更优越的稳定性,还可提供更多的催化活性位点.总结了近年来金属-多孔有机分子笼复合领域的研究成果,以及其应用领域的重要进展,为金属-多孔有机分子笼纳米复合物在催化、传感、医学等方面的后续研究提供启示.     

基于亚组分自组装的金属有机超分子研究进展

亚组分自组装是构建金属有机超分子结构最为简便有效的手段,利用简单的亚组分单元与金属离子快速组装构建复杂的金属有机超分子结构体系,已经成为构筑超分子结构的一个重要研究方法.重点介绍了几种亚组分自组装的金属有机超分子体系,包括螺旋结构、四面体结构、六面体结构、八面体结构等,并介绍了利用这些超分子结构的内部空腔所提供了独特的化学微环境,进行客体的识别、保护、催化、萃取等功能化研究.此外,还对基于亚组分自组装的金属有机超分子的发展前景加以展望.     

拓扑结构不同金属有机聚合物的电化学聚合行为和光谱电化学性质北大核心CSCD

金属有机聚合物的拓扑结构是影响其光电性质的重要原因之一。通过吡啶配体不同位点引入的电化学活性基团乙烯基或乙炔基,在电极表面电化学聚合制备了拓扑结构不同的钌金属有机聚合物薄膜,并利用循环伏安、紫外-可见吸收光谱、红外反射光谱、扫描电子显微镜等手段对其电化学特性、光电性质、表面形貌等性质进行了表征。结果表明,电活性配合物反应活性位点的空间位阻效应影响了电化学聚合的效率,其不同拓扑结构的聚合产物具有明显的光谱电化学性质差异。     

双层铜金属薄膜纳米压痕机械性能的分子动力学模拟

多层金属薄膜的机械性质在纳米组件的设计上是非常重要的.目前,纳米尺度材料的机械性质测量的最主要方法为纳米压痕检测技术.本文应用分子动力学理论对双层铜金属薄膜界面的结构形态与特性进行分析探讨.选用FCC结构单晶铜的(100)面,(110)面和双层铜金属薄膜作为探讨界面性质的材料,进而探讨了单晶铜及双层铜金属薄膜的纳米压痕变形性质.     

无机金属聚合物合成及性能研究

本文报道了三类新型的无机金属聚合物—原子簇聚合物、金属配聚物和金属有机／金属配聚物的结构和性能。     

二维层状水合酸式硫酸铈H3O[Ce(SO4)2·(H2O)3]·H2O的水热合成与结构表征

镧系金属硫酸盐由于在稀土分离等方面具有重要的应用而受到广泛关注。但是，因其适于结构测定的单晶相对难以得到，迄今，关于稀土硫酸盐的结构报道仍然较少，且主要局限于水合硫酸盐和三元硫酸盐．近几年中，基于硫酸根与磷酸根在结构上的相似性，借鉴在水热／溶剂热体系中采用有机胺作模板剂大量合成具有空旷骨架结构的微孔磷酸盐的成功经验，以有机胺为模板剂合成具有空旷骨架结构的镧系金属硫酸盐的工作也已见诸报道．在这些化合物中，由于硫酸根配位方式的多样性和稀土元素配位数和配位构型的可调变性，展现出了一些有趣的结构特征．     

茂金属聚乙烯薄膜中晶点的组成与结构

茂金属聚乙烯薄膜中晶点的组成与结构;茂金属聚乙烯;晶点;薄膜;组成;结构     

多金属氧酸盐-三（2，2’-联吡啶）钌层接层自组装纳米复合膜的制备及光致发光性质

层接层自组装技术作为制备均匀、超薄多层薄膜的有效方法已引起人们极大的关注．利用这种方法可以将无机、有机组分有序地组合在薄膜中，在固体基底上构建功能性分子的超分子结构，并且可以在分子水平上调控每层膜的结构和厚度，从而实现薄膜的光、电、磁、非线性光学等功能化．多金属氧酸盐具有独特、优异的物理化学性能，在药物化学、电化学、催化化学及材料化学等方面具有     

Ag/TCNQ薄膜中的传质行为研究

采用真空蒸发的方法在玻璃基板上交替蒸发Ag和TCNQ(四氰基对醌二甲烷), 形成不同厚度的双层膜, 经Ag的固体化学扩散与TCNQ反应, 形成金属有机络合物. 利用透射光谱作为表征, 研究了Ag的传质规律, 给出了60~110 ℃温度下的恒温传质系数k和对应的激活能, 并对传质机制进行了探讨.     

Ag(TCNQ)准一维微米结构的制备及表征

利用溶液化学反应法制备了准一维结构的金属有机配合物Ag(TCNQ). X射线衍射(XRD)表明，所制备的Ag(TCNQ)为晶态结构;扫描电子显微镜(SEM)的观察证明，Ag(TCNQ)为准一维的微米管或线；Raman 测试结果表明，单根的Ag(TCNQ)形成时,Ag原子与TCNQ分子之间发生了电荷转移.对样品的制备工艺,即 Ag膜厚度和浸入溶液的反应时间对生成Ag(TCNQ)晶体形貌的影响进行了研究.结果表明，Ag膜越薄，生长出的晶体越稀疏;Ag膜与TCNQ乙腈溶液的反应时间影响其形貌的变化.反应历经三个阶段,晶体形成和长大阶段、反应完全阶段及溶解阶段.     

湿度对Cu/TCNQ金属有机双层膜化学传质的影响研究

采用真空蒸发方法制备了Cu/TCNQ金属机双层膜. 系统研究了湿度对CuTCNQ络合物形成过程的影响规律, 结果表明湿度对膜的化学反应传质过程有明显加速作用. 过程机制在干燥条件与湿度作用条件下有本质不同: 前者为固体化学扩散机制, 而后者为水溶液电化学反应机制. 进一步深入分析传质时间与湿度的关系后发现, 湿度条件下薄膜对水分子的吸附是反应传质速度的控制步骤.     

Composite PET Membrane with Nanostructured Ag/AgTCNQ Schottky Junctions: Electrochemical Nanofabrication and Charge‐Transfer Properties

Large‐area nanostructured Ag/Ag‐tetracyanoquinodimethane (TCNQ) Schottky junctions are fabricated electrochemically on a mesoporous polyethylene terephthalate (PET) membrane‐supported water/1, 2‐dichloroethane (DCE) interface. When the interface is polarized, Ag⁺ ions transfer across the PET membrane from the aqueous phase and are reduced to form metallic Ag on the PET membrane, which reacts further with tetracyanoquinodimethane (TCNQ) in the DCE phase to form nanostructured Ag/AgTCNQ Schottky junctions. Once the mesoporous membrane is blocked by metallic Ag, a bipolar mechanism is proposed to explain the successive growth of AgTCNQ nanorods and Ag film on each side of the PET membrane. Due to the well‐formed nanostructure of Ag/AgTCNQ Schottky junctions, the direct electrochemical behavior is observed, which is essential to explain the physicochemical mechanism of its electric performance. Moreover, the composite PET membrane with nanostructured Ag/AgTCNQ Schottky junctions is tailorable and can be assembled directly into electric devices without any pretreatment.     

Tuning the electrocrystallization parameters of semiconducting Co[TCNQ]2-based materials to yield either single nanowires or crystalline thin films

Electrocrystallization of single nanowires and/or crystalline thin films of the semiconducting and magnetic Co[TCNQ]2(H2O)2 (TCNQ=tetracyanoquinodimethane) charge-transfer complex onto glassy carbon, indium tin oxide, or metallic electrodes occurs when TCNQ is reduced in acetonitrile (0.1 M [NBu4][ClO4]) in the presence of hydrated cobalt(II) salts. The morphology of the deposited solid is potential dependent. Other factors influencing the electrocrystallization process include deposition time, concentration, and identity of the Co2+(MeCN) counteranion. Mechanistic details have been elucidated by use of cyclic voltammetry, chronoamperometry, electrochemical quartz crystal microbalance, and galvanostatic methods together with spectroscopic and microscopic techniques. The results provide direct evidence that electrocrystallization takes place through two distinctly different, potential-dependent mechanisms, with progressive nucleation and 3-D growth being controlled by the generation of [TCNQ]*- at the electrode and the diffusion of Co2+(MeCN) from the bulk solution. Images obtained by scanning electron microscopy reveal that electrocrystallization of Co[TCNQ]2(H2O)2 at potentials in the range of 0.1-0 V vs Ag/AgCl, corresponding to the [TCNQ]0/*- diffusion-controlled regime, gives rise to arrays of well-separated, needle-shaped nanowires via the overall reaction 2[TCNQ]*-(MeCN)+Co2+(MeCN)+2H2O right harpoon over left harpoon {Co[TCNQ]2(H2O)2}(s). In this potential region, nucleation and growth occur at randomly separated defect sites on the electrode surface. In contrast, at more negative potentials, a compact film of densely packed, uniformly oriented, hexagonal-shaped nanorods is formed. This is achieved at a substantially increased number of nucleation sites created by direct reduction of a thin film of what is proposed to be cobalt-stabilized {(Co2+)([TCNQ2]*-)2} dimeric anion. Despite the potential-dependent morphology of the electrocrystallized Co[TCNQ]2(H2O)2 and the markedly different nucleation-growth mechanisms, IR, Raman, elemental, and thermogravimetric analyses, together with X-ray diffraction, all confirmed the formation of a highly pure and crystalline phase of Co[TCNQ]2(H2O)2 on the electrode surface. Thus, differences in the electrodeposited material are confined to morphology and not to phase or composition differences. This study highlights the importance of the electrocrystallization approach in constructing and precisely controlling the morphology and stoichiometry of Co[TCNQ]2-based materials.     

Transport of ions through the oil phase of W(1)/O/W(2) double emulsions

Using a capillary video microscopy technique, the ion transport at liquid-liquid interfaces and through a surfactant-containing emulsion liquid membrane was visually studied by preparing a double emulsion globule within the confined space of a thin-walled, transparent, cylindrical microtube. NaCl and AgNO(3) were selected as the model reactants and were prepared to form a NaCl/AgNO(3) pair across the oil film. By observing and measuring the formed AgCl deposition, it was found that both Cl(-) and Ag(+) could transport through a thick oil film and Ag(+) was transported faster than Cl(-). Interestingly, the ion transport was significantly retarded when the oil film became extremely thin (<1 microm). The results suggested that the transport of ions mainly depends on the "reverse micelle transport" mechanism, in which reverse micelles with entrapped ions and water molecules can be formed in a thick oil film and their construction will get impeded if the oil film becomes extremely thin, leading to different ion transport rates in these two cases. The direction of ion transport depends on the direction of the osmotic pressure gradient across the oil film and the ion transport is independent of the oil film thickness in the investigated thick range. Ions with smaller Pauling radii are more easily entrapped into the formed reverse micelles and therefore will be transported faster through the oil film than bigger ions. Oil-soluble surfactants facilitate ion transport; however, too much surfactant in the oil film will slow down the ion migration. In addition, this study showed no support for the "molecular diffusion" mechanism of ion transport through oils.     

Met.(Cu,Ag)-TCNQ有机薄膜的EB CL像

自从1979年Potember等人首先发现了CuTCNQ有机薄膜具有受电流控制的电开关特性以来[1]，有关CuTCNQ及AgTCNQ这些阴离子基过渡金属盐（以下简称为Met．（CU、Ag）-TCNQ）有机薄膜的光存储特性、光电开关特性，以及某些气教特性的研究结果便不断报导出来[2-4]，引起人们极大的兴趣．作为很有前途的有机光电功能材料，至今对其电导及光电特性的机理研究仍显得十分薄弱，极大影响了它们进一步向实用器件方向的发展．由于CuTCNQ的晶体参数至今未见报导，我们依据CuTCNQ粉末X射线小角衍射谱对比AgTCNQ相应的粉末X射线衍射数据，…     

两种表征金属有机双层膜络合和金属薄膜氧化反应动力学的方法

建立了两种新的薄膜反应动力学表征方法, 即透射光谱法和方块电阻法, 以克服传统动力学表征手段在薄膜体系氧化与络合反应过程中应用的局限性. 以透射光谱为表征手段, 得到了Ag/TCNQ(四氰基对醌二甲烷)金属有机双层薄膜的络合反应动力学曲线; 以方块电阻为表征手段, 得到了Cu薄膜的氧化反应动力学过程.     

Poly(3-octylthiophene) as solid contact for ion-selective electrodes: contradictions and possibilities

The hydrophobic conductive polymer, poly(3-octylthiophene) (POT), is considered as uniquely suited to be used as an ion-to-electron transducer in solid contact (SC) ion-selective electrodes (ISEs). However, the reports on the performance characteristics of POT-based SC ISEs are quite conflicting. In this study, the potential sources of the contradicting results on the ambiguous drift and poor potential reproducibility of POT-based ISEs are compiled, and different approaches to minimize the drift and the differences in the standard potentials of POT-based SC ISEs are shown. To set the potential of the POT film, it has been loaded with a 7,7,8,8-tetracyanoquinodimethane (TCNQ/TCNQ^·?) redox couple. An approximately 1:1 TCNQ/TCNQ^·?ratio in the POT film has been achieved through potentiostatic control of the potential of the redox couple-loaded conductive polymer. It is hypothesized that once the POT film has a stable, highly reproducible redox potential, it will provide similarly stable and reproducible interfacial potentials between the POT film and the electron-conducting substrate and result in SC ISEs with excellent reproducibility and potential stability. Towards this goal, the potentials of Au, GC, and Pt electrodes with drop-cast POT film coatings were recorded in KCl solutions as a function of time. Some of the POT films were loaded with TCNQ and coated with a K⁺-selective membrane. The improvement in the potential stabilities and sensor-to-sensor reproducibility as a consequence of the incorporation of TCNQ in the POT film and the potentiostatic control of the TCNQ/TCNQ^·?ratio is reported.     

Cu-TCNQ Semiconducting Film Direct Formation in Molten State,Characterization and Electical Properties

Metallic copper foil directly reacted with molten TCNQ (7, 7, 8, 8-tetracyano-quin-odimethane), resulting in Cu-TCNQ semiconduting tinf film with electrical switching and memory properties.The material was diaracterized by FT-IR spectral analysis. The degree of diarge transfer from copper ro the electron acx-optor TCNQ and the electrical switching properties were discussed as well.