单分散核-壳结构介孔二氧化硅微球的合成

在酸性条件下, 采用非离子表面活性剂嵌段共聚物为模板剂, 季铵盐阳离子表面活性剂为共导向剂, 在预先合成的尺寸均一的单分散实心氧化硅微球表面包裹了有序介孔氧化硅层, 进一步通过高温水热处理, 获得了具有良好分散性和均匀尺寸的介孔壳层(孔径7 nm)氧化硅微球(~500 nm). 氧化硅微球外部包裹的介孔壳层具有较大的比表面积(188 m2/g)和孔容(0.23 cm3/g).     

水中痕量非离子表面活性剂的测定Ⅱ.苦味酸钡配合萃取比色法

研究了Na~+、K~+、Ca~(2+)、Ba~(2+)等苦味酸盐与聚氧乙烯醚型非离子表面活性剂形成配合物的萃取常数和表观吸光系数(380nm),发现Ba~(2+)>>K~+>Ca~(2+)>Na~+。提出了苦味酸钡配合萃取比色法测定水中痕量非离子表面活性剂,测定浓度为0.02～1.0mg/l时变异系数20.0％～4.5％,回收率95％。     

介孔氧化钨电色薄膜的制备与性能研究

采用一种新的非离子型gemini表面活性剂结构导向模板, 成功制备了介孔氧化钨薄膜. 通过SAXRD, TEM和N₂吸附-脱附等方法考察薄膜的制备和微结构特性, 发现获得的产物具有三维蠕虫介孔结构, 比表面积可达145.5 m²• g^－1. 测定了该薄膜在无水高氯酸锂/碳酸丙烯酯电解质溶液中的循环伏安和电致变色性能, 并与无模板薄膜进行了对比研究. 研究表明, 由于具有更大的电化学活性比表面, 纳米介孔氧化钨薄膜表现出增强的电色性能, 在633 nm波长处的透过率调制幅度可达60%以上, 着色效率为51.7 cm²•C^－1.     

金复合介孔SBA-15吸附血红蛋白在H2O2电催化反应中的应用

以P123嵌段共聚物表面活性剂为模板剂制备介孔氧化硅SBA-15,并用沉积-沉淀(DP)法在SBA-15介孔表面负载纳米Au颗粒制备得到金复合介孔SBA-15材料(Au-SBA-15).再以Au-SBA-15材料制备玻碳修饰电极,将血红蛋白固定于修饰电极上用循环伏安法考察其对不同浓度H2O2溶液的电催化反应.在固定了血红蛋白的Hb/Au-SBA-15/GC修饰电极上,H2O2在+0.95 V处出现了氧化峰,且随着H2O2浓度的增大峰电流不断增加,说明金复合介孔氧化硅材料具有良好的生物兼容性,有利于血红蛋白的固定,其修饰电极对H2O2溶液具有一定的电催化作用.     

阳离子表面活性剂增敏碳糊电极电化学测定维生素E胶丸中维生素E的含量

以硝酸作氧化剂,将非电活性的维生素E氧化为具有电活性的醌型化合物-生育酚红,采用循环伏安法研究了生育酚红在碳糊电极上的电化学行为,探讨了阳离子表面活性剂的增敏效果、电极反应机理和表面活性剂的增敏机制。试验结果表明:在乙醇-硝酸(69+31)电解质溶液中,在一定量的阳离子表面活性剂十八烷基三甲基氯化铵存在时,生育酚红在碳糊电极上,具有一对可逆的氧化还原峰,峰电位差为30 mV,维生素E的浓度在1.6×10~(-8)～4.0×10~(-6)mol·L~(-1)范围内与其峰电流呈线性关系,检出限(3S/N)为4.0×10~(-9)mol·L~(-1)。该阳极溶出伏安法应用于分析维生素E药品,回收率在92.9%～110.2%之间。     

不同表面活性剂对多巴胺电化学行为的影响

利用循环伏安法(CV)制备了银掺杂聚L-半胱氨酸修饰电极,以神经递质药物多巴胺(DA)为探针,研究了DA分别在阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)、阴离子表面活性剂十二烷基硫酸钠(SDS)和非离子表面活性剂TritonX-100存在下,在修饰电极上的电化学行为。结果表明,在阳离子表面活性剂和阴离子表面活性剂及非离子表面活性剂中,DA的氧化还原电位变化不大,峰电流有所降低,且对峰电流的影响CTMAB最大、SDS最小。     

氯醇盐溶胶-凝胶法纳米结构氧化钨薄膜的光谱学特性

由非离子型Gemini表面活性剂TMDD(HO(EO)xC14(EO)yOH)为结构导向模板, 改进EISA(挥发诱导自组装)镀膜工艺经300 ℃焙烧制得具有连续、均一和光学透明特点的蠕虫介孔纳米晶孔壁氧化钨薄膜. 采用SEM、TEM和Raman光谱对此种薄膜的介孔纳米结构进行了表征, 通过光谱电化学、XPS和椭偏谱等方法, 研究了该薄膜在电解质溶液中的电致变色行为. 结果表明, 所制备的纳米结构氧化钨薄膜在633 nm波长处的循环可逆透过率调制幅度可达75%以上, 并且其电致变色机理具有显著的双注入吸收调制特性.     

脉冲激光沉积纳米TiO2薄膜电极的现场光电化学

在O3 /O2 气氛中采用 35 5nm激光烧蚀金属钛靶的反应性沉积薄膜方法 ,成功地在镀ITO膜的玻璃基片上制备了纳米锐钛矿相TiO2 薄膜电极 .用循环伏安法研究了在Li/TiO2 电池中TiO2 薄膜电极的电化学嵌入Li离子的行为 .由现场快速紫外可见吸收光谱实时监测TiO2 薄膜电极的显色特性 ,在波长 42 0和 6 5 0nm附近出现 2个明显的吸收峰 ,并发现TiO2 薄膜电极的吸收谱的涨落过程与Li离子的嵌入和脱嵌过程具有相关性与可逆性 ,表明该纳米TiO2 薄膜电极具有高质量的光电化学性能 .     

金复合介孔SBA-15吸附血红蛋白在H2O2电催化反应中的应用

以P123嵌段共聚物表面活性剂为模板剂制备介孔氧化硅SBA-15,并用沉积-沉淀(DP)法在SBA-15介孔表面负载纳米Au颗粒制备得到金复合介孔SBA-15材料(Au-SBA-15).再以Au-SBA-15材料制备玻碳修饰电极,将血红蛋白固定于修饰电极上用循环伏安法考察其对不同浓度H₂O₂溶液的电催化反应.在固定了血红蛋白的Hb/Au-SBA-15/GC修饰电极上,H₂O₂在+0.95 V处出现了氧化峰,且随着H₂O₂浓度的增大峰电流不断增加,说明金复合介孔氧化硅材料具有良好的生物兼容性,有利于血红蛋白的固定,其修饰电极对H₂O₂溶液具有一定的电催化作用.     

表面高巯基功能化介孔材料的制备及对Hg~(2+)的吸附性能

在酸性条件下,以三嵌段非离子表面活性剂P123为模板剂,四氧基硅烷(TEOS)预水解后与3-巯基丙基三乙基硅(MPTES)共聚,合成了具有不同巯基官能团比例x[n(MPTES)/n(TEOS+MPTES)]的功能化介孔材料(SBA-SH-x),其结构和性能经FT-IR,元素分析,SEM,TEM,小角X-ray和N2吸附-脱附表征。结果表明:x10%,SBA-SH-x为六方p6mm介观结构;10%x15%,SBA-SH-x为立方Ia3d介孔结构;x20%,SBA-SH-x为无序结构。SBA-SH-x在水溶液中吸附Hg2+的研究结果表明:SBA-SH-10和SBA-SH-15对Hg~(2+)吸附性能较好。     

循环伏安法的电扫描方式对苯胺聚合产物形貌影响的观察

在含有0.2 mol.L-1苯胺的0.5 mol.L-1H2SO4溶液中,以扫描速度50 mV.s-1,扫描电位为-0.1~0.9 V,采用循环伏安法(CV),在金属Ti基体上,通过控制扫描方式分别得到了颗粒状、纤维状及管-片状的苯胺聚合产物,分析了形成不同形貌聚苯胺的原因,并通过扫描电子显微镜(SEM)、循环伏安法和电化学阻抗谱(EIS)对不同形貌聚苯胺的结构和性能进行了表征.结果表明,不同形貌聚苯胺的形成是由于聚苯胺的成核及生长模式不同,而无论何种形貌的聚苯胺膜都具有很大的比表面积和良好的导电性能,其中,管-片状聚苯胺的膜层阻抗最小,导电性能最好.     

β-萘磺酸掺杂聚苯胺纳米粒子的固相反应法制备及其表征

利用固相反应法制备了 β 萘磺酸掺杂的聚苯胺纳米粒子 ,并以红外光谱 (FTIR) ,扫描电子显微镜(SEM) ,透射电镜 (TEM) ,X 射线衍射 (XRD)以及粉末微电极等测试方法对其进行了表征 .结果表明 ,固相反应法合成的 β 萘磺酸掺杂聚苯胺粒子直径为 30～ 5 0nm ,聚苯胺分子链排列有序 ,晶化率较好 .粉末微电极的循环伏安测试表明 ,β 萘磺酸掺杂聚苯胺有较好的电化学活性 .     

Evaporation induced self-assembly of templated silica and organosilica thin films on various electrode surfaces

A new one-step method is reported for the deposition of hybrid mesoporous thin films on various electrode surfaces (gold, platinum, glassy carbon). Deposition was achieved by spin-coating sol–gel mixtures in the presence of a surfactant template to get mesostructured thin layers on the various conducting substrates. Film formation occurred by evaporation induced self-assembly (EISA) involving the hydrolysis and (co)condensation of silane and/or organosilane precursors on the electrode surface. Extraction of the surfactant from the ordered mesoporous films led to a large increase of mass transport rates into the materials and imparted high accessibility to the organic moieties in case of functionalized mesoporous overlayers. The electrochemical properties of the film-modified electrodes have been studied by cyclic voltammetry (CV), and also via the chemical accumulation of mercury ions prior to their stripping analysis by differential pulse voltammetry (i.e. for thiol-functionalized thin films). Some evidences to support the formation of self-assembled monolayers (SAMs) on electrodes, have been also discussed. The formation of well-adhering mesoporous thin films on solid electrode surfaces is expected to have a high impact on the development of new electrochemical sensors.     

Electrochromic properties of sputtered TiO2 thin films

TiO₂ thin films were deposited on ITO/Glass substrates by the rf magnetron sputtering in this study. The electrochromic properties of TiO₂ films were investigated using cyclic voltammograms (CV), which were carried out on TiO₂ films immersed in an electrolyte of 1 M LiClO₄ in propylene carbonate (PC). As- deposited TiO₂ thin film was amorphous, while the films post-annealed at 300~600°C contained crystallized anatase and rutile. With the increase of the annealing temperature, the surface roughness of film increased from 1.232 nm to 1.950 nm. Experimental results reveal that the processing parameters of TiO₂ thin films will influence the electrochromic properties such as transmittance, ion-storage capacity, inserted charge, optical density change, coloration efficiency and insertion coefficient.     

高功率超级电容器用介孔炭电极材料

以纳米CaCO3为模板、蔗糖为前躯体制备超级电容器用介孔炭电极材料.材料的结构由氮吸附、TEM表征,借助恒流充放电、循环伏安和交流阻抗评价了其在6 mol.L-1KOH电解液中的电化学电容性能.结果表明,蔗糖基介孔炭的比表面积606 m2/g,富含10~30 nm的介孔.恒流放电法测得介孔炭在电流密度50 mA/g下的比电容为125 F/g,大电流倍率性能特别突出.电流密度增大到20 000 mA/g,比电容还保持有88F/g,远高于进口电容炭,该介孔炭是一种很有前景的高功率超级电容器炭电极材料.     

In situ Magnesiothermal Synthesis of Mesoporous MgO/OMC Composite for Sensitive Detection of Lead Ions

Mesoporous materials have exceptional properties for application owing to their ability to absorb and interact with guest species. A novel MgO/OMC composite with mesoporous structure was successfully synthesized via in situ magnesiothermic reduction. The structure was confirmed by N₂ sorption isotherms, X‐ray diffraction pattern (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). By using nafion and bismuth films as co‐modifiers, the MgO/OMC composite material shows high sensitivity of 0.113 μA ? L μg^?1 and lower background current for electrochemical determination of lead ion (Pb²⁺) by using anodic stripping voltammetry. The high specific surface area and good mass transfer on the proposed mesoporous material, as well as the outstanding adsorption abilities of MgO to metal ions and the excellent conductivity of the carbon skeleton contribute to the enhanced electrochemical response of Pb²⁺. As the stripping response of Bi/MgO/OMC‐Nafion/PGE is highly linear (R²=0.998) over a Pb²⁺ concentration range of 2 to 300 μg/L, it was successfully used to analyse Pb²⁺ in real tap‐water samples with good recoveries.     

Dependence of electrochemical properties of vanadium oxide films on their nano- and microstructures

Platelet- and fibrillar-structured V2O5 films have been prepared by solution methods, and their electrochemical Li+ intercalation properties have been studied. Platelet film consists of 20-30 nm sized V2O5 particles with random orientation, whereas fibrillar film is comprised of randomly oriented fibers though most of them protrude from the substrate surface. These platelet- and fibrillar-structured films exhibit relatively larger surface area and shorter diffusion path for Li+ intercalation than plain thin film structure. The processing methods, the discharge capacity, and cyclic performance of these films are compared with those of the conventional plain structured film.     

Lithium intercalation on amorphous V2O5 thin film,obtained by r.f. deposition,using in situ sample transfer for XPS analysis

Spectroscopic and electrochemical properties of amorphous V₂O₅ films, prepared by r.f. sputter deposition, were compared before and after electrochemical lithium intercalation. The films gave a cyclic voltammogram typical of vanadium pentoxide with two/three steps of reversible electrochromism (yellow–green–blue). The expected effect of lithiation on chemical state and surface composition was monitored using XPS. A careful curve‐fitting procedure of the detailed spectra was adopted and the in‐depth profile analysis of the intercalated films clearly showed their surface reorganization as a function of time and ultrahigh vacuum conditions. The first objective of this work was to establish the influence of lithium intercalation while minimising degradation effects due to its high reactivity with the atmosphere, taking advantage of the in situ sample transfer facility. Copyright © 2003 John Wiley & Sons, Ltd.     

乳液分散法制备高分散纳米锡/介孔碳复合材料及其电化学性能

以间苯二酚和糠醛聚合而成的可溶性树脂为碳源,SnCl2为锡源,表面活性剂F127为模板剂,通过乳液分散法将锡源原位复合嵌入于介孔碳材料中,制备了纳米锡基材料高度分散于介孔碳中的复合材料。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N2吸脱附(BET)、循环伏安(CV)等对材料的微观结构和电化学性能进行了表征。结果显示锡基材料在介孔碳中较为密集,分布均匀,粒径小于5 nm。介孔碳丰富的孔道结构有效限制和缓解了锡基材料的生长、团聚和体积膨胀,同时高比表面积增加了电解液与锡基活性材料的接触,提供了更多的反应活性点,从而获得了更高的电化学活性。充放电测试结果显示,700℃热处理后,锡/介孔碳纳米复合材料经过50次循环后实际放电比容量达203.4 mAh.g-1,表现出良好的电化学性能。     

Electrochemical behaviour of electrodeposited nanostructured palladium+platinum films in 2 M H2SO4

Nanostructured palladium+platinum films were electrodeposited from an aqueous binary mixture that contained a non-ionic surfactant to produce a liquid crystalline phase. This phase acts as a template for the formation of mesoporous nanostructured films. The films produced were characterised by X-ray diffraction and transmission electron microscopy in order to assess the existence of a regular nanostructure. Furthermore, cyclic voltammetry in 2 M H₂SO₄ was used to obtain information about the electrochemical properties of the films. Here we report the existence of two unexpected very sharp peaks in the hydrogen region that were observed by cyclic voltammetry.