萘酞菁类配合物的气敏特性

在阐述了萘酞菁配合物的结构特点和气敏机理的基础上,讨论了影响萘酞菁配合物气敏性的主要因素,介绍了近年来萘酞菁配合物气敏物特性研究的最新进展,并对萘酞菁配合物作为气敏材料的发展趋势进行了展望。     

酞菁配合物的结构与气敏性

综述了酞菁配合物的气敏机理及其结构与气敏性之间的关系。阐述了酞菁环的电子结构是其具有气敏性的基础,讨论了配合物中的中心原子和取代基团对配合物气敏性的影响。     

油溶非对称取代酞菁铜的合成、表征及LB膜

本文以邻苯二甲酰亚胺为原料,合成了两种新的非对称取代酞菁铜配合物:4-(对羧基苯氧基)-三-4-(2,4-二特戊基苯氧基)酞菁铜(Ⅳ)和4-(邻氨基苯氧基)-三-4-(2,4-二特戊基苯氧基)酞菁铜(Ⅴ)。并经元素分析、红外光谱、核磁共振谱、质谱、顺磁共振谱及紫外光谱,对其结构进行了表征。两种配合物都易溶于二氯甲烷、氯仿和甲苯等有机溶剂,不溶于水。配合物的氯仿溶液能在水面上展开形成单分子膜。π-A曲线测定表明,配合物在亚相液面(水)上,随着表面压力的增大,膜面积连续不停地减少,有明显的“气”“固”变化过程,表明配合物能形成较好的LB膜。分子在膜中主要以倾斜的方式排列。以Z型累积方式沉积于金制梳状电极上的LB膜能导电,属于半导体材料,碘掺杂可改善膜的电导。膜电极的气敏特性研究发现,配合物对氨气有专一的气敏特性,氨气浓度为33ppm时即有响应,且灵敏度高。     

酞菁配合物掺杂对芘/硅树脂材料光学-氧猝灭特性的影响

基于氧对荧光的猝灭作用, 含荧光探针的高分子复合物已成为定量测定氧浓度或氧分压的新型功能材料. 本工作将酞菁及酞菁的氯铝、镁、硅和铜配位化合物掺杂在芘/聚二甲基硅氧烷光学-氧压传感材料中, 观察了它们的氧猝灭光物理作用. 结果表明, 酞菁配合物掺杂对氧猝灭显示良好的线性响应; 酞菁的硅和铜配合物可有效地增加氧猝灭灵敏度; 而酞菁氯铝降低了氧猝灭的温度系数. 这与发射谱上芘的I₃/I₁值, 芘的微环境极性相对应, 并可归因为芘与酞菁配合物的电子转移性质对荧光猝灭的影响, 以及共轭结构的稳定化和均质化作用.     

酞菁铜衍生物LB膜的结构研究

酞菁铜衍生物作为LB膜材料具有良好的热稳定性,与衬底的附着力强,有丰富的光电特性,并对NH_3有较高的气敏特性,本文应用透射电子显微镜研究了2种新型酞菁铜衍生物LB膜成膜过程的结构变化。     

可溶性亚酞菁的合成,光谱及聚集性质的研究

酞菁类化合物作为一类有机功能材料,如导体或半导体、气敏元件、电化学催化剂、电致变色及光致变色材料、光动力疗法的药物以及非线性光学材料等^[1],已经受到化学家和材料学家们的关注.近几十年来,化学家们已经成功地合成出了带各种不同取代基和含有不同中心金属原子的酞菁或萘酞菁类化合物,并对它们的物化性质进行了广泛而深入的研究.     

四-4-(烷氧基-羰基)酞菁铜(Ⅱ)的合成、结构及其成膜性

本文合成了两种新型取代酞菁铜(Ⅱ)配合物:四-4-(戊氧基-羰基)酞菁铜(Ⅱ)(A)和四-4-(癸氧基-羰基)酞菁铜(Ⅱ)(B),并通过元素分析、ESR、~1H-NMR和FT-IR进行了表征.用可见光谱研究了它们在氯仿溶液中的聚集形式;用X-ray粉末衍射方法研究了配合物的固相堆积排列结构.两种配合物的氯仿溶液在亚相(水)上的π-A曲线表明,它们均有明显的“气”“液”“固”变化过程;并能在不同的表面压力区间形成较好的单分子层和多分子层膜.     

单氨基取代3∶1不对称酞菁锌的合成及其在有机溶剂中聚集状态的研究

酞菁(Phthalocyanine,Pc)金属配合物是一类性能优异、应用广泛的功能材料。由于酞菁类配合物有18共轭π电子,使其具有许多独特的物理化学性质,已经成为一种性能良好的多功能材料,在催化化学、光化学、电化学、非线性光学、信息存储学、医学等学科的前沿领域及相关的高新技术领域都有着广泛而重要的应用潜力和发展前景[1,2]。因而,近年来引起人们越来越浓厚的研究兴趣。至今为止,酞菁配合物的合成和应用研究大多仍以对称性酞菁配合物为主[3],有关不对称酞菁配合物的报道和研究较少,这主要是由于不对称酞菁在合成和分离方面都比较困难的缘故…     

单冠醚取代不对称酞菁LB膜的制备和表征

酞菁化合物有序聚集体已成为材料化学中的研究热点［１,２］,在酞菁分子中引入冠醚会大大改善酞菁化合物的气敏性,在提高响应速度和重复性的同时,其响应温度可降到室温［３,４］．研究冠醚酞菁气敏性质的通常方法是将其制成浇铸膜［４］,这种膜是无序的．膜中分子的...     

酞菁LB膜气敏性的研究进展

综述了酞菁类化合物ＬＢ膜的导电性、气敏性、气敏的检测，以及气敏机理和动力学机制。     

Nanofibrous polyaniline thin film prepared by plasma‐induced polymerization technique for detection of NO2 gas

A nanofibrous polyaniline (PANI) thin film was fabricated using plasma‐induced polymerization method and explored its application in the fabrication of NO₂ gas sensor. The effects of substrate position, pressure, and the number of plasma pulses on the PANI film growth rate were monitored and an optimum condition for the PANI thin film preparation was established. The resulting PANI film was characterized with UV–visible spectrophotometer, FTIR, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The PANI thin film possessed nanofibers with a diameter ranging from 15 to 20 nm. The NO₂ gas sensing behavior was studied by measuring the change in electrical conductivity of PANI film with respect to NO₂ gas concentration and exposure time. The optimized sensor exhibited a sensitivity factor of 206 with a response time of 23 sec. The NO₂ gas sensor using nanofibrous PANI thin film as sensing probe showed a linear current response to the NO₂ gas concentration in the range of 10–100 ppm. Copyright © 2009 John Wiley & Sons, Ltd.     

光波导二氧化氮气敏传感元件的研究

本文用离子交换法制备K+交换玻璃光波导元件,并在其表面固定纳米级敏感层酞菁铜(CuPc)薄膜,利用光波导气体检测系统对NO2气体进行测试.结果表明,该传感元件常温下对NO2等气体有快速、可逆的响应,并具有重现性好,灵敏度高等特点.     

Gold nanoparticles to boost the gas sensing performance of porous sol–gel thin films

In this paper we review our research work of the last few years on the synthesis and the gas sensing properties of nanocomposite thin films of sensitive materials with a large specific surface area, which consist of porous matrices containing functional nanocrystals of metal oxides and gold. The film porosity provides a path for the gas molecules to reach the active reaction sites on the nanoparticles surface undergoing chemical reactions which nature depends on the nature of the active material. The introduction of Au nanoparticles affects the reactions mechanism improving the sensing process, moreover the Au Surface Plasmon Resonance peak can be used for the realization of selective optical gas sensor. Two different synthetic approaches will be described, each of them characterized by a peculiar control of the final materials morphology, structure and micro-structure.     

A Novel Thin‐Film Copper Array Based on an Organic/Inorganic Sensor Hybrid: Microfabrication,Potentiometric Characterization,and Flow‐Injection Analysis Application

A first step towards the microfabrication of a thin‐film array based on an organic/inorganic sensor hybrid has been realized. The inorganic microsensor part incorporates a sensor membrane based on a chalcogenide glass material (Cu‐Ag‐As‐Se) prepared by pulsed laser deposition technique (PLD) combined with an PVC organic membrane‐based organic microsensor part that includes an o‐xylyene bis(N,N‐diisobutyl‐dithiocarbamate) ionophore. Both types of materials have been electrochemically evaluated as sensing materials for copper(II) ions. The integrated hybrid sensor array based on these sensing materials provides a linear Nernstian response covering the range 1×10^?6–1×10^?1 mol L^?1 of copper(II) ion concentration with a fast, reliable and reproducible response. The merit offered by the new type of thin‐film hybrid array includes the high selectivity feature of the organic membrane‐based thin‐film microsensor part in addition to the high stability of the inorganic thin‐film microsensor part. Moreover, the thin‐film sensor hybrid has been successfully applied in flow‐injection analysis (FIA) for the determination of copper(II) ions using a miniaturized home‐made flow‐through cell. Realization of the organic/inorganic thin‐film sensor hybrid array facilitates the development of a promising sophisticated electronic tongue for recognition and classification of various liquid media.     

Structurally integrated organic light emitting device-based sensors for gas phase and dissolved oxygen

A compact photoluminescence (PL)-based O2 sensor utilizing an organic light emitting device (OLED) as the light source is described. The sensor device is structurally integrated. That is, the sensing element and the light source, both typically thin films that are fabricated on separate glass substrates, are attached back-to-back. The sensing elements are based on the oxygen-sensitive dyes Pt- or Pd-octaethylporphyrin (PtOEP or PdOEP, respectively), which are embedded in a polystyrene (PS) matrix, or dissolved in solution. Their performance is compared to that of a sensing element based on tris(4,7-diphenyl-l,10-phenanthroline) Ru II (Ru(dpp)) embedded in a sol-gel film. A green OLED light source, based on tris(8-hydroxy quinoline Al (Alq3), was used to excite the porphyrin dyes; a blue OLED, based on 4,4'-bis(2,2'-diphenylviny1)-1,1'-biphenyl, was used to excite the Ru(dpp)-based sensing element. The O2 level was monitored in the gas phase and in water, ethanol, and toluene solutions by measuring changes in the PL lifetime tau of the O2-sensitive dyes. The sensor performance was evaluated in terms of the detection sensitivity, dynamic range, gas flow rate, and temperature effect, including the temperature dependence of tau in pure Ar and O2 atmospheres. The dependence of the sensitivity on the preparation procedure of the sensing film and on the PS and dye concentrations in the sensing element, whether a solid matrix or solution, were also evaluated. Typical values of the detection sensitivity in the gas phase, S(g) identical with tau(0% O2)/tau(100% O2), at 23 degrees C, were approximately 35 to approximately 50 for the [Alq3 OLED[/[PtOEP dye] pair; S(g) exceeded 200 for the Alq3/PdOEP sensor. For dissolved oxygen (DO) in water and ethanol, S(DO) (defined as the ratio of tau in de-oxygenated and oxygen-saturated solutions) was approximately 9.5 and approximately 11, respectively, using the PtOEP-based film sensor. The oxygen level in toluene was measured with PtOEP dissolved directly in the solution. That sensor exhibited a high sensitivity, but a limited dynamic range. Effects of aggregation of dye molecules, sensing film porosity, and the use of the OLED-based sensor arrays for O2 and multianalyte detection are also discussed.     

PVA薄膜光波导气敏元件及其应用研究

将纯聚乙烯醇(PVA)和掺有维生素C的PVA作为敏感试剂,通过旋转甩涂法分别研制出了PVA薄膜/锡掺杂玻璃光波导元件和VC-PVA薄膜/锡掺杂玻璃光波导元件并检测其气敏特性.实验结果表明,PVA薄膜/锡掺杂玻璃光波导元件对二甲苯气体有良好的选择性响应,其响应浓度范围为10-4～10-7(体积比);加入VC后,使此敏感元...     

Novel fabrication process using nanoporous anodic aluminum oxidation and MEMS technologies for gas detection

A class of nanoporous TiO₂ gas sensors processed by novel anodic aluminum oxidation (AAO) of Al thin films and microelectromechnical systems (MEMS) techniques are presented. To enhance the sensitivity and reduce the sensing dimensions of a gas sensor, a nanoporous surface of the gas-sensitive material on the sensor is required. These sensors can be implemented on silicon or silicon dioxide substrate featuring a thin membrane of micro-hotplate structure featuring micro-heaters, thermometers and electrodes, and thus operate as chemoresistive devices. Combining the AAO method with dry-etch process, a homogeneous and nanoporous SiO₂ surface of the sensor can be effectively configured by modulating various hole diameters and depth, hence replacing conventional photolithography and electrochemical etch. The process integration including AAO, reactive ion etch (RIE) and microfabrication is mainly developed and a feasibility study of PVD TiO₂ thin film deposition upon the porous device is also provided. TiO₂ thin films deposited on the nanoporous surface are investigated and compared with non-porous TiO₂ films. It is encouraging that our fabrication process is able to provide relatively high surface area to enhance sensitivity of the sensor without additional doping steps. Our promising experimental results have revealed these miniature and cost-effective devices are not only compatible, but applicable to smart bio-chemical sensors of next generation.     

光波导传感元件在检测酸性气体中的应用

采用旋转甩涂法将甲基紫传感薄膜固定在特制的锡(Sn2+,Sn4+)掺杂玻璃光波导(Sn doped glass slide)表面,研究了该传感薄膜与HCl、H2S、以及SO2作用前后的可见吸收光谱的变化,并在此基础上研制了玻璃光波导酸性气体(HCl、H2S、SO2)传感元件。传感薄膜与酸性气体作用时,薄膜的颜色发生变化,从而降低薄膜对倏逝波的吸收,使传感器的输出光强度(信号)增强。本文采用流动注射法对酸性气体进行了检测。实验结果表明,在室温下,该传感元件对硫化氢气体具有明显的响应,而对相同浓度的其他酸性气体的响应相对较小,对浓度在6×10-4～2.5×10-5(V/V)的硫化氢气体具有良好的线性响应(R=0.9979,n=4),相对标准偏差(RSD)为±3.5%,具有响应快、可逆性和重复性好、容易制备、可以在室温下工作等特点。     

An integrated low-power thin-film CO gas sensor on silicon

An approach to an integrated semiconductor gas sensor is presented. The major reasons considered for developing a semiconductor oxide gas sensor on silicon are the accurate local temperature control of the sensing area and the low level of the heating power required, together with an appropriate integrated structure. Thermal loss measurements show that the integrated gas sensor can operate up to 400 °C with less than 200 mW heating power. Depending on the deposition conditions, catalyst addition or surface conditioning, the SnO_x thin films are known to have an optimal sensitivity to CO between 250 °C and 400 °C. The sensitivity for CO gas and the response time of the device are presented for sputtered thin films of SnO_x, deposited on top of an isolated resistive heater, separated from silicon by a thin thermally-isolating membrane.     

A novel triazine‒bearing calix[4]arene: Design,synthesis and gas sensing affinity for volatile organic compounds

A novel triazine-calix[4]arene conjugate was designed and synthesized with the aim to study gas sensing against volatile organic compounds (VOCs) such as dichloromethane, chloroform and carbon tetrachloride. This novel compound was fully characterized by spectroscopic techniques such as FTIR, ¹H and ¹³C NMR along with HRMS and BET analysis. The triazine based calix[4]arene organic materials were fabricated onto quartz glasses and quartz crystal substrates to form a thin film chemical sensor element by using Langmuir-Blodgett (LB) technique. Quartz Crystal Microbalance, UV–Visible Spectroscopy, Atomic Force Microscopy and Scanning Electron Microscopy techniques were employed to characterize all these LB thin film layers. Fick's Equations were used for analyzing the swelling process of LB thin film sensor and diffusion coefficient values of organic vapours for swelling were obtained. The initial experiments have revealed that new triazine appended calix[4]arene derivative exhibited an effective chemical gas sensor characteristic with a large response to dichloromethane vapour.