三维多枝雪花状银粉的制备及催化性能

室温下,以聚乙烯醇为保护剂,采用抗坏血酸还原硝酸银,于水相中一步合成出三维多枝雪花状银粉。结合X射线粉末衍射(XRD)、扫描电子显微镜(SEM)等结构表征手段,对三维多枝雪花状银粉的微观结构进行详细分析,在此基础上提出其可能的形成机理。此外,三维多枝雪花状银粉在4-硝基苯酚催化加氢反应中还表现出优异的催化活性。     

多孔雪花状氧化锌分级纳米结构的制备、表征及其光催化性能研究

在H2O和乙二醇(EG)构成的二元体系中,通过Zn AC2与NH4F和H2O的水热反应制备了六角雪花状Zn OHF。Zn OHF在空气中退火,制备出了由单晶Zn O纳米片构建的多孔六角雪花状Zn O。用X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM)及其热重等多种手段对产物进行结构表征,并提出了可能的化学反应。以甲基橙和酸性大红为例,研究了其光催化性能,结果表明,多孔雪花状Zn O是一种有效的光催化剂。     

具有枝状结构二阶非线性光学高分子的研究进展

树状分子是指一类结构高度支化的大分子或高分子化合物,其独特的三维纳米球形结构、分子内空腔以及大量富集的表面基团,可产生诸多特殊且有趣的功能及光物理性质,在化学、生物和材料等领域获得了广泛的关注和研究.本文主要综述了我们课题组在具有枝状结构二阶非线性光学高分子方面的研究进展,重点介绍了如何通过合理分子设计,发展不同类型枝状拓扑结构以有效提高材料的综合性能,并展望了该领域的今后发展趋势.     

Texture and Structure Characteristics of Ore from Typical Deposits of Lead-Zinc Ore Belt in the Southwestern Margin of Tarim

通过对位于西昆仑北带奥依塔格-库尔良晚古生代（弧后）裂陷盆地塔西南缘铅锌矿带典型矿床矿石结构构造特征进行研究,总结出该矿带各个矿床（点）之间具有相同或相似的矿物共生组合（黄铁矿-方铅矿-闪锌矿-黄铜矿）以及相似的组构特征。主要结构包括草莓状结构、骸晶结构、自形晶结构、固溶体分离结构、交代结构及揉皱结构等;构造包括浸染状构造、流动构造、条带状构造、脉状构造及角砾状构造等,这些组构特征的共性表明成矿作用均具有多期多阶段的特征,并指示出热水沉积成矿兼有后期热液改造的结构构造特征。结合野外地质特征,该区铅锌矿床形成经历了同生沉积与后期改造过程。     

特殊形貌类雪花状ZSM-5分子筛的合成、表征及甲醇制烯烃催化性能(英文)

美国Mobil公司于1972年首先开发的ZSM-5分子筛是一种高硅三维交叉孔道的沸石分子筛,其孔道结构具有良好的择形作用,因此被广泛应用于芳构化、异构化、烷基化和催化裂化等工业催化过程.ZSM-5分子筛的催化性能与其晶粒尺寸、酸性及形貌等密切相关.改变合成方法和制备参数可以合成出不同形貌的ZSM-5分子筛,但目前关于ZSM-5分子筛形貌对其物理化学性质和催化性能的影响报道较少.本文通过改变模板剂类型,采用水热合成法,制备出了类雪花状、椭圆柱状和夹心糖状三种不同形貌的ZSM-5分子筛.通过X射线荧光光谱(XRF)、N_2物理吸脱附(BET)、扫描电镜(SEM)、X射线衍射(XRD)、固体核磁共振(MAS NMR)、NH_3程序升温脱附(NH_3-TPD)及吸附吡啶的红外光谱(Py-IR)等手段对不同形貌分子筛的物理化学性质、形貌、晶体骨架结构和酸性进行了表征.采用浸渍法制备了Ca/HZSM-5催化剂,以甲醇制烯烃(MTO)为探针反应、着重研究了ZSM-5分子筛形貌和晶体结构特性对其酸性和催化性能的影响.合成的三种不同形貌的ZSM-5分子筛具有相近的SiO_2/Al_2O_3比和比表面积.XRD结果表明,通过改变模板剂类型,可制得结晶度较好的ZSM-5分子筛,其中类雪花状分子筛的(101)晶面比例明显多于其它两种分子筛,而椭圆柱状分子筛则暴露更多的(020)晶面.~(27)Al MAS NMR结果表明,绝大部分Al都以四配位形式存在于三种分子筛骨架中,而类雪花状分子筛的峰强度较低,这是由于Al的配位环境不同(偶极作用弱),说明在类雪花状分子筛的交叉晶面中存在大量扭曲、错位和不对称结构;与其它两种分子筛相比,类雪花状分子筛的~(29)Si MAS NMR谱峰宽化、进一步证明该分子筛骨架结构中存在扭曲、错位和不对称性.NH_3-TPD结果表明,类雪花状HZSM-5分子筛的酸量明显高于其它两种分子筛,在SiO_2/Al_2O_3比相近的情况下、类雪花状HZSM-5分子筛晶体骨架结构的错位、扭曲和不对称性造成了该分子筛中酸量增加;但Py-IR结果表明,类雪花状HZSM-5分子筛的酸量低于其它两种分子筛,这与NH_3-TPD结果有差异,主要是由于类雪花状分子筛几何空间结构和晶界处的扭曲、错位对孔道结构的影响,不利于比NH_3分子大的吡啶分子的扩散,进而影响了吡啶分子在酸性位上的吸附.三种不同形貌的ZSM-5分子筛经Ca改性后比表面积和微孔比表面积均明显下降,其中类雪花状和椭圆柱状催化剂的微孔比表面积下降幅度较大,外比表面积下降幅度较小.这是因为各分子筛的晶体结构和晶面的取向差异,导致Ca离子在分子筛上的扩散行为不同.同时,经Ca改性后,三个催化剂的总酸量均有下降,尤其是类雪花状分子筛酸量下降较为明显,表明其中Ca离子更容易扩散到分子筛孔道内,与更多的酸性位作用,而夹心糖状分子筛表面具有更多的Z字形孔道,不利于Ca离子扩散到分子筛孔道内,因而酸量下降较少.Py-IR结果表明,Ca改性后催化剂的总酸量下降,尤其是B酸明显降低,L酸略有增加,其中类雪花状ZSM-5分子筛催化剂的B酸量最低.甲醇制烯烃反应评价结果表明,随着反应温度升高,三个催化剂的总烯选择性和丙烯选择性均呈先升高后降低的趋势.类雪花状ZSM-5分子筛催化剂在甲醇转化率相近时具有最高的烯烃选择性,在反应温度为460℃时,总烯烃选择性为72%,丙烯选择性达39%.     

氨基酸辅助合成多种形貌纳米材料的研究进展

氨基酸等生物大分子作为一种特殊的表面活性剂,在合成特殊形貌纳米材料方面具有很大的应用潜力.本文综述了使用多种氨基酸辅助合成的不同形貌的纳米材料,包括一维纳米材料、雪花状纳米结构、三维纳米球等,并对生物科学和化学学科间的交叉发展进行了展望.     

枝状分子表面组装结构的形成与结构转变

本文是对近期有关枝状分子在石墨表面吸附组装研究的综述.利用扫描隧道显微技术,系统研究了5-甲氧基间苯二酸类枝状分子在石墨表面组装结构的形成及结构转变,发现虽然该类枝状分子大都可以在石墨表面自发有序组装,但是最终形成的组装结构不仅与分子本身结构例如烷基链的数目有关,与分子浓度有关,还与所用溶剂有关.分子浓度和溶剂的变化,影响组装体系内的相互作用力如分子与基底间的作用力、分子间氢键的作用力等,影响分子迁移和结构转变的动力学过程,从而影响枝状分子组装的最终结构.研究揭示了特定体系中枝状分子组装结构与分子浓度、所用溶剂的定量和定性关系.研究结果有助于认识和掌握枝状分子组装规律,进而可以通过改变相关技术参数,调控得到不同的枝状分子表面组装体,为实现可控构筑分子表面组装结构提供了新的思路.     

基于三维纳米银修饰电极的硝酸根微型传感芯片研究

研制一种基于金叉指微电极阵列(IDA)的电流型硝酸根离子(NO-3)微传感电极芯片.基于微机电系统(Micro-Electro-Mechanical Systems,MEMS)工艺制备金IDA微电极,通过电化学沉积技术在IDA微电极表面修饰三维枝状结构纳米银敏感膜,利用敏感膜对硝酸根离子良好的电催化还原性能,采用脉冲方波伏安(SWV)电化学测量方法,实现对硝酸根离子在25～1000μmol/L浓度范围内的快速检测,灵敏度达9.5 nA/(μmol/L),线性度为99.98%,检测下限为10μmol/L.考察水体中常见的NO-2,F-,3PO 4-,SO 42-,2CO3-,NH+4,Na+和K+等离子对该传感芯片的干扰性能,传感芯片表现出较好的抗干扰性能.制备的三维枝状结构纳米银修饰IDA微电极可实现水环境(pH 5.0～9.0)中NO-3的电化学检测,对应用于自然水环境中硝酸根离子的现场检测具有积极意义.     

枝状体系中分子内光诱导能量转移

枝状分子因具有独特的化学结构,其光化学与光物理研究引起人们的关注。本文重点介绍了近二十年来报道的具有光诱导分子内能量转移的枝状分子的化学结构特点,分析了不同因素对光诱导枝状分子内能量转移效率的影响;阐述了可以根据能量给体与受体的性质,对枝状体的分子内光诱导能量转移进行调控;概括了具有光诱导分子内能量转移性质的枝状分子的目前应用领域;总结了枝状体分子内能量转移面临的关键科学问题,并展望了具有光诱导分子内能量转移的枝状分子的发展方向。     

高度有序ZnO-SnO_2异质外延枝状纳米结构的制备及其光催化性质研究

采用一种简单的热蒸发法制备了高度有序的ZnO-SnO2异质外延枝状纳米结构。制备过程分两步进行:首先,在氧化铝片基底上制备SnO2纳米线;然后,以此SnO2纳米线为模板在其上生长ZnO纳米线。用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)等手段对产物的形貌、结构进行了表征。XRD表征结果证实第一步和第二步生长的产物分别为SnO2和ZnO。SEM观察结果表明,第一步热蒸发得到直径约100nm、长度达几十微米的SnO2纳米线,第二步热蒸发后得到以第一步SnO2纳米线为主干、沿四个方向有序排列的枝状ZnO纳米结构。TEM观察结果表明,ZnO枝状纳米线沿[001]方向由SnO2纳米线(-101)晶面外延生长。所制备的枝状纳米结构由于具有巨大的比表面积,且外延异质结可以促进电荷的分离和快速转移,因此非常适合于光催化应用。该ZnO-SnO2异质外延枝状纳米结构用于光催化降解甲基橙,表现出优异的性能。     

Role of anions for the reduction behavior of silver ions in polymer/silver salt complex membranes

The reduction of silver ions to silver nanoparticles is an essential issue in polymer/silver salt complex membranes for facilitated olefin transport, because it has a critical influence on the long-term stability of membrane performance. In this study, the role of anions for the formation of silver nanoparticles in polymer/silver salt complexes was investigated. This role was assessed for the complexes of poly(N-vinyl pyrrolidone) (PVP) with three silver salts including AgBF₄, AgCF₃SO₃, and AgNO₃. Especially, UV irradiation to the membranes was used to clearly investigate the reduction behavior of silver ions. Separation performance test, UV–vis spectroscopy and transmission electron microscopy (TEM) clearly show that the reduction rate of silver ions strongly depends on the counteranions of salt, and has the following order: AgBF₄ > AgCF₃SO₃ > AgNO₃. This behavior of the formation of silver nanoparticles in polymer/silver salt complex membranes is explained in terms of the interaction strength of silver ions with the carbonyl oxygens of polymer, and that of silver ions with counteranions. It is concluded that when the former interaction is strong and the latter one is weak, the reduction rate of silver ions to silver nanoparticles is fast, and vice versa. These interactions were characterized using FT-IR, FT-Raman spectroscopy, and theoretical ab initio calculation.     

Preparation of polyimide/BaTiO3/Ag nanocomposite films via in situ technique and study of their dielectric behavior

Triphase polyimide nanocomposite films were fabricated using barium titanate （BaTiO3） with high dielectric constant and silver （Ag） with high conductivity as fillers. In situ method was utilized to obtain the homogeneous dispersion of nanoparticles. The in situ polymerization of polyimide precursor-poly（amic acid） was performed in the presence of BaTiO3 particles. Silver compound 1,1,1-trifluoro-2,4-pentadionato silver（I） was added into the BaTiO3 containing poly（amic acid） solution to achieve silver nanoparticles via in situ self metallization technique. The thermally induced reduction converted silver （I） to metallic silver with concomitant imidization of poly（amic acid） to polyimide. Both BaTiO3 and silver nanoparticles were uniformly dispersed in the polyimide substrate. The dependence of dielectric behavior on the BaTiO3 and Ag contents was studied. The incorporation of small amount of silver nanoparticles greatly increased dielectric constant of composite films.     

Facile synthesis of high-concentration, stable aqueous dispersions of uniform silver nanoparticles using aniline as a reductant

A facile method was developed for preparing uniform silver nanoparticles with small particle sizes of less than 10 nm at high concentrations, in which aniline was used to reduce silver nitrate (AgNO(3)) to silver nanoparticles in the presence of dodecylbenzenesulfonic acid (DBSA) as a stabilizer. Upon the addition of excess NaOH to the DBSA-aniline-AgNO(3) (DAA) system, the formation of silver nanoparticles was almost complete in just 2 min at 90 °C (in 94% yield). The average size of those resultant silver nanoparticles was 8.9 ± 1.1 nm, and the colloids were stable for more than 1 year at ambient temperature. A possible mechanism for the formation of silver nanoparticles was proposed to be related to two factors: one was the mesoscopic structures of the DAA system in which silver ions were restricted in the dispersed phases composed of DBSA and aniline; the other was Ag(2)O nanocrystallites generated in situ that could be readily reduced by aniline to small silver nanoparticles at high concentrations.     

Ag(PHZ)NO_3对PTG材料热显影性能的影响

为了考察酞嗪在PTG材料热显影过程中的作用,制备了硝酸银与酞嗪(Phthalazine,PHZ)的配合物Ag(PHZ)NO3,SEM照片显示该配合物为棱柱状晶体.研究了Ag(PHZ)NO3对PTG材料热显影性能的影响.结果表明,与酞嗪相比,同等显影条件下使用Ag(PHZ)NO3能降低胶片的影像密度及灰雾,但显影银的形貌结构和尺寸大小并未发生明显变化.文中讨论了Ag(PHZ)NO3对热显影性能产生影响的原因.     

Electrochemical deposition of silver in room-temperature ionic liquids and its surface-enhanced Raman scattering effect

The use of room-temperature ionic liquids (RTILs) as media for electrochemical application is very attractive. In this work, the electrochemical deposition of silver was investigated at a glassy carbon electrode in hydrophobic 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6) and hydrophilic 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) RTILs and in KNO3 aqueous solution by cyclic voltammetric and potentiostatic transient techniques. The voltammograms showed the presence of reduction and oxidation peaks associated with the deposition and dissolution of silver from AgBF4 in both BMIMPF6 and BMIMBF(4), resembling the redox behavior of AgNO3 in KNO3 aqueous solution. A crossover loop was observed in all the cyclic voltammograms of these electrochemical systems, indicating a nucleation process. From the analysis of the experimental current transients, it was shown that the electrochemical deposition process of silver in these media was characteristic of 3D nucleation with diffusion-controlled hemispherical growth, and the silver nucleation closely followed the response predicted for progressive nucleation in BMIMPF6 and instantaneous nucleation in KNO3 aqueous solution, respectively. Compared with these two cases, the electrochemical deposition of silver in BMIMBF4 deviated from both the instantaneous and progressive nucleation models, which could be controlled by mixed kinetics and diffusion. On the basis of the experimental results, it was shown that parameters such as viscosity and water miscibility of RTILs would affect the electrodeposition behavior of silver. Atom force microscopy was employed to probe the surface morphology of the silver deposit, and it showed that the shining electrodeposit of silver was fairly dense and separate nanoclusters of <100 nm were in evidence, corresponding to an island growth model. The strongly enhanced Raman scattering from the monolayer film of 4-mercaptobenzoic acid demonstrated that as-prepared silver nanoparticular film was surface-enhanced Raman scattering (SERS) active. The enhancement factor was calculated to be up to 9.0 x 10(5) and 1.0 x 10(6) for the silver film obtained in BMIMPF6 and BMIMBF4 RTILs, respectively.     

Enhancement of the Surface Activity for Some Monomeric and Polymeric Thiol Surfactants Using Silver Nanoparticles

In the present work, the self-assembling of some synthesized thiol surfactants namely (6-(3-amino phenoxy) hexane-1-thiol, 8-(3-amino phenoxy) octane-1-thiol, 10-(3-amino phenoxy) decane-1-thiol, 12-(3-amino phenoxy) dodecane-1-thiol, and their polymers on silver nanoparticles was investigated. The self-assembling of these surfactants on silver nanoparticles was characterized using different techniques such as ultraviolet (UV) spectroscopy, powder x-ray diffraction (XRD), electrone diffraction (ED), and transmission electron microscopy (TEM). The effect of the self-assembling of these surfactants on the stabilization of the silver nanoparticles (AgNPs) was studied using TEM images. The growth of the silver nanoparticles was investigated with respect to the increase of alkyl chain in the synthesized thiol surfactants. The effect of silver nanoparticles on the surface, interfacial tension, and the emulsion stability of these surfactants with paraffin oil was studied. The results show that the silver nanoparticles have the ability to effect on the behavior of these surfactants in solution and improve their surface activity.     

Silver(I) complexes of a sterically demanding fluorinated triazapentadienyl ligand [N((C3F7)C(Dipp)N)2]- (Dipp = 2,6-diisopropylphenyl)

Sterically demanding triazapentadiene [N((C3F7)C(Dipp)N)2]H affords the isolation of thermally stable, two- and three-coordinate silver complexes. The free ligand [N((C3F7)C(Dipp)N)2]H has a W-shaped ligand backbone in the solid state.[N((C3F7)C(Dipp)N)2]H reacts with silver(I) oxide in acetonitrile leading to CH(3)CNAg [N((C3F7)C(Dipp)N)2]HIt features a two-coordinate silver center and a kappa(1)-coordinated triazapentadienyl ligand. This silver acetonitrile complex serves as an excellent precursor to obtain thermally stable, silver isocyanide t-BuNCAg [N((C3F7)C(Dipp)N)2]Hand silver phosphine [[N((C3F7)C(Dipp)N)2]HAgPPh(3) adducts. IR spectroscopic data for the silver(I) isocyanide t-BuNCAg [N((C3F7)C(Dipp)N)2]Hshows nu(CN) at 2219 cm(-)(1). The silver ion coordinates to the triazapentadienyl ligand via the central nitrogen atom. The silver PPh(3) adduct,[N((C3F7)C(Dipp)N)2]HAgPPh(3), was synthesized by treating CH3CNAg [N((C3F7)C(Dipp)N)2]Hwith PPh(3). It displays relatively large Ag-P coupling in the (31)P NMR spectrum. The triazapentadienyl ligand in[N((C3F7)C(Dipp)N)2]HAgPPh(3) acts as a chelating kappa(2)-donor. The Ag-P bond is relatively short (2.3487(10) A).     

Well-defined N-heterocyclic carbene silver halides of 1-cyclohexyl-3-arylmethylimidazolylidenes: synthesis, structure and catalysis in A3-reaction of aldehydes, amines and alkynes

Structurally well-defined N-heterocyclic carbene silver chlorides and bromides supported by 1-cyclohexyl-3-benzylimidazolylidene (CyBn-NHC) or 1-cyclohexyl-3-naphthalen-2-ylmethylimidazolylidene (CyNaph-NHC) were synthesized by reaction of the corresponding imidazolium halides with silver(I) oxide while cationic bis(CyBn-NHC) silver nitrate was isolated under similar conditions using imidazolium iodide in the presence of sodium nitrate. Single-crystal X-ray diffraction revealed a dimeric structure through a nonpolar weak-hydrogen-bond supported Ag-Ag bond for 1-cyclohexyl-3-benzylimidazolylidene silver halides [(CyBn-NHC)AgX](2) (X = Cl, 1; Br, 2) but a monomeric structure for N-heterocyclic carbene silver halides with the more sterically demanding 1-cyclohexyl-3-naphthalen-2-ylmethylimidazolylidene ligand (CyNaph-NHC)AgX (X = Cl, 4; Br, 5). Cationic biscarbene silver nitrate [(CyBn-NHC)(2)Ag](+)NO(3)(-)3 assumed a cis orientation with respect to the two carbene ligands. The monomeric complexes (CyNaph-NHC)AgX 4 and 5 showed higher catalytic activity than the dimeric [(CyBn-NHC)AgX](2)1 and 2 as well as the cationic biscarbene silver nitrate 3 in the model three component reaction of 3-phenylpropionaldehyde, phenylacetylene and piperidine with chloride 4 performing best and giving product in almost quantitative yield within 2 h at 100 °C. An explanation for the structure-activity relationship in N-heterocyclic carbene silver halide catalyzed three component reaction is given based on a slightly modified mechanism from the one in literature.     

N-heterocyclic carbene-silver complexes: Potential conductive materials for silver pastes in electronic applications

New organosilver complexes, silver(I) tetraalkylbis(benzimidazolidene) halide [1a-3a] and silver(I) dimethyl-N,N′-hexyl(imidazolyl) bromide [4a], were synthesized and incorporated into electroconductive silver pastes. Complex 3a had a 15-fold higher conductivity than conventional silver salt pastes, specifically silver(I) hexanoate, and exhibited a smooth, homogeneous surface after reductive heat-treatment of the silver paste. While the conductivity of silver(I) hexanoate can be increased by up to 33% by the addition of a supporting silver source, such as Ag₂O, the conductivity of 3a was markedly decreased by Ag₂O treatment. Thus, 3a can be used in silver pastes with moderate conductivity and can reduce the amount of conventional silver supporting materials without loss of electroconductivity.