纳米Fe/C复合材料的原位合成

在石油渣油中加入二茂铁，通过热缩聚反的位合成纳米级铁粒子均匀分散于炭基体中的新型复合材料，研究了在420℃热缩聚时停时间和二茂铁添加量对Fe/C形成的影响，并用TEM和XRD观测和分析了Fe/C的形态和结构，结果表明，在基体中铁粒子的粒径为25－50nm，在一定条件下，二茂铁添加量的增加和停留时间的延长均使Fe/C产率提高，停留时间对热缩聚反应的影响遵循一级反应动力学，二茂铁的添加能显著提高反应速率常数k值。     

Effect of functional group of ferrocene redox substance on the transport properties of newly designed ion exchange membrane prepared from polymer gel

A different newly designed cationic exchange polymer membrane and anionic exchange polymer membrane were introduced, and also the transport properties of these polymeric membranes were investigated in this study. The transport properties of these polymer membranes in contact with ferrocene redox derivatives were estimated by using electrochemical techniques such as cyclicvoltammetry, chronopotentiometry, and chronoamperometry techniques, respectively. The used ferrocene redox substances, which have different functional groups, were (Ferrocenylmethyl) trimethylamonium iodide, FcMA, Ferrocenedimethanol, FcDM, and Ferrocene carboxylic acid, FcCA. It indicated that the performance of a membrane depended on the content of polymer gel, anionic exchange polymer site (20 wt % and 50 wt %) or cationic polymer exchange site (20 wt % and 50 wt %), and the efficiency of the functional groups of cationic and anionic exchange polymer site as well. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ionic liquids as electrolytes

Salts having a low melting point are liquid at room temperature, or even below, and form a new class of liquids usually called room temperature ionic liquids (RTIL). Information about RTILs can be found in the literature with such key words as: room temperature molten salt, low-temperature molten salt, ambient-temperature molten salt, liquid organic salt or simply ionic liquid. Their physicochemical properties are the same as high temperature ionic liquids, but the practical aspects of their maintenance or handling are different enough to merit a distinction. The class of ionic liquids, based on tetraalkylammonium cation and chloroaluminate anion, has been extensively studied since late 1970s of the XX century, following the works of Osteryoung. Systematic research on the application of chloroaluminate ionic liquids as solvents was performed in 1980s. However, ionic liquids based on aluminium halides are moisture sensitive. During the last decade an increasing number of new ionic liquids have been prepared and used as solvents. The general aim of this paper was to review the physical and chemical properties of RTILs from the point of view of their possible application as electrolytes in electrochemical processes and devices. The following points are discussed: melting and freezing, conductivity, viscosity, temperature dependence of conductivity, transport and transference numbers, electrochemical stability, possible application in aluminium electroplating, lithium batteries and in electrochemical capacitors.     

Synthesis and characterization of liquid crystalline polymers containing aromatic ester mesogen and a nonmesogenic ferrocene unit in the spacer

A new series of liquid crystalline polymers containing aromatic triad ester mesogen and 1,1′‐disubstituted ferrocene as a nonmesogenic unit along with polymethylene spacer was synthesized. The polymer was synthesized by a room temperature polycondensation reaction between bis(4‐chloroformyl phenyloxy alkyl ferrocene dicarboxylate) and quinol. The alkyl groups have been varied by an even number of methylene groups with a range from two to ten groups. All the polymers were found to possess liquid crystalline properties. The identification of the mesophase is more transparent with an increase in the spacer. The thermal characteristics were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results reveal that the thermal stability of the polymers was decreased with increasing spacer length. The T_g, T_m, and T_i of the polymers decreased with increasing methylene groups. The incorporation of the ferrocene moiety also has a considerable effect on the glass transition temperature. The char yield of the polymer decreases with an increasing methylene chain length. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3494–3501, 2002     

Fabrication of Fe3O4 Dots Embedded in 3D Honeycomb‐Like Carbon Based on Metallo–Organic Molecule with Superior Lithium Storage Performance

A novel metallo–organic molecule, ferrocene, is selected as building block to construct Fe₃O₄ dots embedded in 3D honeycomb‐like carbon (Fe₃O₄ dots/3DHC) by using SiO₂ nanospheres as template. Unlike previously used inorganic Fe₃O₄ sources, ferrocene simultaneously contains organic cyclopentadienyl groups and inorganic Fe atoms, which can be converted to carbon and Fe₃O₄, respectively. Atomic‐scale Fe distribution in started building block leads to the formation of ultrasmall Fe₃O₄ dots (≈3 nm). In addition, by well controlling the feed amount of ferrocene, Fe₃O₄ dots/3DHC with well‐defined honeycomb‐like meso/macropore structure and ultrathin carbon wall can be obtained. Owing to unique structural features, Fe₃O₄ dots/3DHC presents impressive lithium storage performance. The initial discharge and reversible capacities can reach 2047 and 1280 mAh g^?1 at 0.05 A g^?1. With increasing the current density to 1 and 3 A g^?1, remarkable capacities of 963 and 731 mAh g^?1 remain. Moreover, Fe₃O₄ dots/3DHC also has superior cycling stability, after a long‐term charge/discharge for 200 times, a high capacity of 1082 mAh g^?1 can be maintained (80% against the capacity of the 2nd cycle).     

二茂铁功能化石墨烯复合材料的制备及其电催化多巴胺性质研究

利用氧化石墨烯片边缘的羧基和表面的环氧基团共价修饰的方法制备了二茂铁功能化石墨烯的复合材料,通过FT-IR、TEM等测试方法对复合材料的结构和形貌进行了表征,二茂铁共价修饰石墨烯复合材料呈现出了良好的稳定性。我们进一步利用二茂铁功能化石墨烯修饰电极对多巴胺电化学催化性质进行研究,该修饰电极对多巴胺显示出良好的催化活性,并推测出可能的催化反应机理,当信噪比为3时,检测限达到0.01μM。     

Redox-flexible NADH oxidase biosensor: A platform for various dehydrogenase bioassays and biosensors

A generic amperometric bioassay based on the enzymatic oxidation catalysed by the stable NADH oxidase (NAox) from Thermus thermophilus has been developed for NADH measurements. The NAox uses O₂ as its natural electron acceptor and produces H₂O₂ in a two-electron process. Electrochemical and spectrophotometric experiments showed that the NAox used in this work, presents a very good activity towards its substrate and, in contrary to previously mentioned NADH oxidases, does not require the addition of any exogenous flavin cofactor neither to promote nor to maintain its activity. In addition, the NAox used also works with artificial electron acceptors like ferrocene derivatives. O₂ was successfully replaced by redox mediators such as hydroxymethyl ferrocene (FcCH₂OH) for the regeneration of the active enzyme. Combining the NAox with the mediator and the horseradish peroxidase we developed an original, high sensitive “redox-flexible” NADH amperometric bioassay working in a large window of applied potentials in both oxidation and reduction modes. The biosensor has a continuous and complementary linearity range permitting to measure NADH concentrations starting from 5 × 10⁻⁶ M in reduction until 2 × 10³ M in oxidation. This redox-flexibility allows choosing the applied potential in order to avoid electrochemical interferences. The association of the “redox-flexible” concept with NADH dependent enzymes opens a novel strategy for dehydrogenases based bioassays and biosensors. The great number of dehydrogenases available makes the concept applicable for numerous substrates to analyse. Moreover it allows the development of a wide range of biosensors on the basis of a generic platform. This gives several advantages over the previous manufacturing techniques and offers a general and flexible scheme for the fabrication of biosensors presenting high sensitivities, wide calibration ranges and less affected by electrochemical interferences.     

纳米金与二茂铁在葡萄糖传感器中的相互作用

针对纳米金颗粒修饰的葡萄糖生物传感器对葡萄糖的响应电流随着工作电压的下降快速下降的问题,进一步利用电子媒介体二茂铁对其进行修饰,并选用丝网印刷电极研究了纳米金颗粒和二茂铁之间的相互作用。实验结果表明:二茂铁有效地降低了纳米金颗粒修饰的葡萄糖生物传感器响应电流的下降值,纳米金颗粒降低了电子媒介体二茂铁的氧化还原反应电位,并且,纳米金颗粒与电子媒介体二茂铁在葡萄糖生物传感器中表现协同增效效应。