热处理对[NiFe/Cu/Co/Cu]_n多层纳米线磁性能的影响

采用双槽控电位法在阳极氧化铝(AAO)模板中制备了有序均一的[NiFe/Cu/Co/Cu]n多层纳米线阵列,并在不同温度下进行了热处理.利用X射线衍射(XRD)对热处理前后多层线的晶体结构进行了测试.考察了不同退火温度对多层线矫顽力、剩磁比、巨磁电阻(GMR)效应、磁灵敏度的影响.随热处理温度升高,多层纳米线中磁性微晶晶型取向越来越明显,晶体结构更均匀;多层纳米线的矫顽力和剩磁比先增大后减小.300°C下多层纳米线矫顽力达到最大值,GMR最大值可达59%,对应的磁电阻灵敏度(SV)为0.233%Oe-1.     

Co/Cu多层纳米线阵列的制备与磁性能

利用双槽直流电沉积技术在阳极氧化铝(AAO)模板的纳米孔中获得调制波长为50 和200 nm 的Co/Cu多层纳米线, 多层纳米线的调制波长由电沉积时间控制. 运用扫描电子显微镜(SEM)和透射电子显微镜(TEM)表征纳米线的形貌, Co/Cu多层纳米线的长度约20 μm, 直径约80 nm; 用X射线衍射(XRD)研究多层线的结构; 用振动样品磁强计(VSM)测试纳米线阵列的磁性能; 利用可变磁场结合高灵敏度恒流装置研究巨磁电阻(GMR)特性. 结果表明, Co/Cu多层纳米线具有磁各向异性. 当磁场与纳米线平行和垂直时, 调制波长为50 nm的多层线的矫顽力分别为87500 和34200 A·m-1, 而调制波长为200 nm的多层线阵列的矫顽力分别为28600 和8000 A·m-1. 调制波长为50 nm的多层纳米线的磁电阻变化率高达-%, 而调制波长为200 nm的多层线未产生明显的GMR效应.     

纳米金属多层膜与多层纳米线的电化学制备及其表征

分别采用单槽法和双槽法电沉积Cu/Co多层膜.研究了两种电沉积方法制备多层膜的工艺条件,利用电化学方法、XRD和SEM对多层膜进行表征,并对Cu/Co多层膜的巨磁阻性能进行了测试. 采用电沉积多层膜的方法，以多孔铝阳极氧化膜（AAO）为模板,在纳米孔内沉积Cu/Co多层线,采用TEM对多层纳米线进行了表征.     

对叔丁基杯[8]芳烃/钼磷杂多酸纳米杂化LB膜的制备与表征

以含有共轭大π键的对叔丁基杯[8]芳烃(Cal8)和十八(烷)铵(ODA)与Keggin结构和Dawson结构钼磷杂多酸(HPA)做成膜材料, 用LB技术制备了2种新型无机-有机杂化LB膜. 用π-A曲线、UV-Vis吸收光谱、荧光光谱和原子力显微镜(AFM)对标题LB膜的成膜性质、结构及发光性质进行了表征. 结果表明在空气/水界面Cal8/ODA/HPA杂化可形成稳定的单层与多层膜. 标题杂化LB膜的崩溃压为39.0 mN/m, 其粒子具有纳米尺寸, 在激发波长为280 nm时, 可观察到322～387 nm处由Cal8分子π-π*跃迁引起的荧光发射峰及510 nm处 杂多阴离子的配体到金属的荷移跃迁(LMCT)三重发射谱带.     

pH对一锅法合成葫芦[n]脲修饰金纳米颗粒形貌影响

采用一锅法制备葫芦[n]脲(n=6,7)修饰的金纳米颗粒(Au-NPs@CB[n]),并研究了pH、温度对其尺寸的影响.通过紫外-可见-近红外(UV-Vis-NIR)光谱和透射电子显微镜(TEM)表征,证明合成了形貌规整、尺寸均一的Au-NPs@CB[n].具体表现为CB[7]修饰的Au-NPs尺寸为7?14 nm,C...     

电结晶铜/钴纳米多层膜结构与磁性能研究

以n型Si(111)为基底, 在硼酸镀液体系中采用双槽法电结晶制备Cu/Co纳米多层膜, 确定了工艺条件. 用扫描电镜(SEM)和X射线衍射(XRD)对纳米多层膜的结构和形貌进行了表征, 显示多层膜具有良好周期性和超晶格结构. 并用物性测量系统PPMS测试了不同结构 Cu/Co纳米多层膜的磁性能. 磁滞回线表明: 不同周期数的纳米多层膜其矫顽力均较小. 巨磁阻(GMR)性能与纳米多层膜结构有关. GMR值随Co磁性层厚度增长先增大后减小, 有一极值; 随着Cu非磁性层厚度的增加GMR值发生周期性的振荡; 随周期数N的增大, GMR值先增大, 在N为60时达到了90%, 随着N的继续增加而减小, 当达到80周期时, GMR值趋于稳定.     

硼酸系电结晶制[Co/Pt]_n(n≥40)金属多层膜的研究

于钝铜片及玻碳上采用双电解池恒电位结晶制取了［Ｃｏ（０．５ｎｍ～２．２ｎｍ）／Ｐｔ（２．０ｎｍ）］ｎ（ｎ≥４０）金属多层膜．低角度Ｘ射线衍射表明多层膜有良好的周期性调制结构,其Ｂｒａｇｇ峰的半幅值随着钴层电结晶电位的负移和铂层电结晶电位正移而减小．中角度Ｘ射线衍射表明界面上存在ＣｏＰｔ３金属化合物．多层膜的磁滞回线表明该多层膜的易磁化轴平行于膜面,表现出平面磁各向异性．以低过电位镀Ｃｏ（厚度约０．５ｎｍ）的多层膜的垂直方向磁滞回线形状较好,有望表现出垂直磁各向异性．     

电化学方法制备铜钴纳米多层膜

采用旋转圆盘电极、双脉冲电位法从单一的含有铜离子和钴离子的镀液中电沉积Ｃｕ－Ｃｏ纳米多层膜、并用ＴＥＭ．ＡＥＳ和Ｘ－射线衍射研究镀层的形貌和组成。结果表明：多层膜结构为纯铜和含有少量铜的铜钴合金层交替组成,铜在钴层中的含量,随镀液中的铜含量的增大和转速的提高而提高。     

多酸导向的间苯二酚杯[4]芳烃[Co8]配位笼的组装及电化学性质

基于多金属氧酸盐（POM）的超分子配位笼的设计和组装引起了广泛的研究兴趣,但在合成过程中仍然存在挑战。本文中,我们报道了一例基于POM-杯芳烃的大型[Co₈]配位笼[Co₈（MTR4A）₆Cl₈]（α-SiW₁₂O₄₀）₂·30DMF·74EtOH （cage-1）,该配位笼由6个碗状间苯二酚杯[4]芳烃（MTR4A）分子、8个Co(Ⅱ)阳离子、2个α-SiW₁₂O₄₀^4-抗衡阴离子和8个Cl^-阴离子组装而成。值得注意的是,α-SiW₁₂O₄₀^4-阴离子通过氢键夹在层与层之间,形成一个三维超分子结构。此外,作为锂离子电池的负极材料,cage-1表现出良好的锂离子存储能力。cage-1也能够实现对亚硝酸盐（NO₂^-）的还原和抗坏血酸（AA）的氧化,是一种具有高活性的双功能催化剂。     

多酸导向的间苯二酚杯[4]芳烃[Co8]配位笼的组装及电化学性质

基于多金属氧酸盐(POM)的超分子配位笼的设计和组装引起了广泛的研究兴趣,但在合成过程中仍然存在挑战。本文中,我们报道了一例基于POM-杯芳烃的大型[Co₈]配位笼[Co₈(MTR4A)₆Cl₈](α-SiW₁₂O₄₀)₂·30DMF·74EtOH (cage-1),该配位笼由6个碗状间苯二酚杯[4]芳烃(MTR4A)分子、8个Co(Ⅱ)阳离子、2个α-SiW₁₂O₄₀^4-抗衡阴离子和8个Cl^-阴离子组装而成。值得注意的是,α-SiW₁₂O₄₀^4-阴离子通过氢键夹在层与层之间,形成一个三维超分子结构。此外,作为锂离子电池的负极材料,cage-1表现出良好的锂离子存储能力。cage-1也能够实现对亚硝酸盐(NO₂^-)的还原和抗坏血酸(AA)的氧化,是一种具有高活性的双功能催化剂。     

Electrochemical Studies of Calixarene-[60]Fullerene Inclusion Processes

[60]Fullerene (C₆₀)-calix[n]areneinteractions were studied in toluene:MeCN = 10:1 (v/v)using an electrochemical method. In the presence ofhomooxacalix[3]arenes and calix[5]arenes, bothE_pc and _pa shifted to the negativepotential, whereas they were scarcely affected by theaddition of calix[4]arenes. The₂values electrochemically determined forthe association with C₆₀ ^- are generallysmaller than the ₁ valuesspectroscopically determined for the association withC₆₀. The tendency indicates that thecharge-transfer-type interaction is one of thedriving forces for C₆₀ inclusion.thanks|Author for correspondence     

双槽法电沉积Cu/Ni多层纳米线有序阵列

以多孔阳极氧化铝（AAO）为模板，采用双槽法电沉积工艺制得高度有序的Cu/Ni多层纳米线阵列。利用扫描电镜（SEM）和透射电镜（TEM）对Cu/Ni多层纳米线进行了表征，观察到纳米线表面平滑，多层结构清晰，各子层厚度均匀，直径约为 100 nm，与AAO模板孔径基本一致。由选区电子衍射（SAED）照片可知，多层纳米线中Cu层和Ni层均为单晶结构。振动样品磁强计（VSM）测试结果表明，Cu/Ni多层纳米线阵列具有明显的垂直磁各向异性，外加磁场垂直和平行于AAO模板表面时，磁滞回线的矩形比分别为 0.701 和 0.101 ，矫顽力分别为 589 Oe和 202 Oe。通过控制铝阳极氧化工艺及电沉积时间，可获得不同直径、不同子层厚度的Cu/Ni多层纳米线阵列。     

镍铁氢化酶活性中心的结构、催化机理及化学模拟

镍铁氢化酶具有催化分裂重组氢分子的功能，由于其独特的活性中心结构和催化性能及方便、廉价利用氢能源的前景，引起生物学家和化学家的关注，他们对镍铁氢化酶活性中心结构、催化机理及化学模拟做了深入细致研究，本文对此做系统概述和总结。     

ZnO纳米线的电化学制备研究

High-quality ZnO nanowires have been synthesized at relatively low temperature via one-step electrochemical anodization technique. In this method, Zn sheet acted as the anode and Pb sheet served as the counter electrode, and the complex solution of HF-C₂H₅OH-H₂O was used as electrolyte. ZnO nanowires were characterized by Field Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED) and X-ray Diffraction (XRD). The results show that the nanowires were wurtzite crystalline ZnO, and the ZnO nanowires with the diameters of 70 nm and 30～40 nm were obtained by adjusting preparation conditions, respectively.     

基于新型NiFe氢化酶催化中心模拟物的光诱导产氢研究

本文成功利用金属中心为NiRu的NiFe氢化酶模拟物,在乙腈和水的混合溶剂中实现了人工光合成制氢。最优条件下,体系基于NiRu催化剂的产氢TON值高达1893,前10 min的TOF为2.6 s^-1,并且通过电化学测试对催化循环过程中所生成的金属氢化物中间体进行了表征。     

Combined computational and crystallographic study of the oxidised states of [NiFe] hydrogenase

[NiFe] hydrogenases catalyse the reaction H₂↔2H⁺+2e⁻. Several states of the enzyme have been observed by spectroscopic methods. Among these, the two most oxidized states, called the unready Ni–A and Ni–SU states, have been especially intriguing, because they take a much longer time to activate than the corresponding ready Ni–B and Ni–SI states. It has recently been suggested that the unready states actually contain a (hydro)peroxide bridge between the Ni and Fe ions, in contrast to the hydroxide bridge in the ready states. In this paper, we use quantum refinement (crystallographic refinement, in which the molecular mechanics [MM] calculations, normally employed to supplement the crystallographic data, are replace by more accurate quantum mechanics [QM] calculations), combined QM/MM calculations, and accurate energy estimates to study the nature of a recent oxidised crystal structure of [NiFe] hydrogenase from Desulfovibrio fructosovorans. We show that the structure contains a mixture of several states in the active site. The experimental data is best explained by structures with a hydroxide bridge but with two of the cysteine ligands (one bridging and one terminal) partly oxidised. When the terminal Cys-543 ligand is oxidised, the sulphur occupies an alternative position, observed in several crystal structures. The Glu-25 residue, that forms a hydrogen bond to this sulphur, also changes position. A peroxide ligand may exist as a minor component in the crystal and the suggested structure is supported by the calculations. We suggest that oxidised states are slow-equilibrium mixtures of structures with a peroxide bound and structures with oxidised Cys residues, and that the former can be activated by replacement of the protonated peroxide with a H₂ or CO ligand, as has been observed in electrochemical experiments.     

Electrochemical Properties of Multilayered Coatings Implementing Thiacalix[4]arenes with Oligolactic Fragments and DNA

Layer‐by‐layer assembling of polyelectrolyte complexes on glassy carbon electrode utilizing derivatives of p‐tert‐butylthiacalix[4]arene modified with oligolactic acid in cone, partial cone and 1,3‐alternate configurations has been performed and characterized by atomic force microscopy, electrochemical impedance spectroscopy and cyclic voltammetry. Structure, surface morphology and permeability of the coatings depended on the number and nature of individual layers. Configuration of macrocyclic core influenced the charge distribution and flexibility of polyelectrolytes and the electrochemical properties of the coatings. Partial substitution of oligolactic derivatives with the DNA molecules allowed distinguishing native, thermally and oxidatively damaged DNA by ferricyanide ion signals. The relationships between the coating structure and the content can be further used for development of electrochemical sensors devoted to the detection of specific DNA interactions.     

半导体硅上电沉积Cu/Co层状薄膜

由磁性层和非磁性层组成的人工调制层状结构多层膜,其物性和磁性都表现出与其它结构的多层膜显著不同的特点,如巨磁阻效应［’,‘l、易磁性方向的改变等”］．其性能的研究不但在磁性理论上具有重大意义,而且有望应用于高性能的磁阻敏感设备及提高磁记录密度等．因而近年来有关这方面的研究越来越引起人们的重视．目前,磁性多层膜的制备主要采用气相沉积、磁控溅射、分子束外延等真空技术．由于电沉积技术具有设备简单、操作方便等特点而成为制备多层膜的颇具活力的工艺．CO／Cll多层膜在C。层厚度较薄时具有较高室温巨磁阻（GMR）…