过渡金属酞菁衍生物薄膜的制备及其气敏性质研究

【作者】 王萍；

【导师】 贺春英；

【作者基本信息】 黑龙江大学 ， 无机化学， 2009， 硕士

【摘要】 环境保护是人类面临的共同问题,运用气敏传感器制作而成的气体检测与监控警报系统为环境保护提供了一种有效的监控手段。在气敏传感器中,气敏材料是研制气敏传感器的关键。由于酞菁衍生物具有较大的π电子共轭体系的结构和优异的气敏特性,成为气敏材料领域研究的热点。本文采用旋涂膜技术制备了四种金属酞菁旋涂膜,即2,9,16,24-四(三乙氧基)-酞菁铅(PbPc(OR)4-4),2,9,16,24-四(三乙氧基)-酞菁锌(ZnPc(OR)4-4),2,9,16,24-四(三乙氧基)-酞菁镍(NiPc(OR)4-4)和2,9,16,24-四(三乙氧基)-酞菁铜(CuPc(OR)4-4),通过原子力显微电镜(AFM)、紫外-可见吸收光谱(UV)、红外光谱(IR)对所制备出的不同中心金属的酞菁旋涂膜进行了表征,测试了薄膜对氨气、一氧化氮和二氧化氮的气敏特性,研究了薄膜结构与性能之间的关系。研究结果表明,在适当的旋涂条件下,可溶性酞菁配合物能够制得较为理想的旋涂膜,与溶液相比,旋涂膜电子吸收光谱的Q-band吸收峰发生红移并明显变宽。这说明在薄膜中酞菁分子的聚集程度加大。对薄膜的气敏特性研究表明,室温下酞菁旋涂膜对二氧化氮有较高的敏感性和较好的响应恢复特性,对一氧化氮次之,对氨气的灵敏度很低(S<2)；而且不同中心金属酞菁对氮氧化物(NO2、NO)的敏感性不同,灵敏度顺序为PbPc(OR)4-4> ZnPc(OR)4-4> NiPc(OR)4-4＞CuPc(OR)4-4;另外,旋涂速度、非探测气体等条件都会对气敏性有较大的影响。更多还原

【Abstract】 Environmental protection is a common problem for humanity. Gas detection and monitoring alarm system made of gas sensors provides an effective monitoring tool for environmental protection. Gas-sensing materials is the key to development of gas sensors. Phthalocyanine derivatives are the active part in gas sensing materials field because they haveπelectronic conjugated system and behave excellent gas-sensing properties. In the paper, four kinds of metallophthalocyanine derivative films containing 2,9,16,24-4(triethoxysilyl)-metallophthalocyanine (MPc(OR)4-4, M=Pb, Zn, Ni, Cu) was made by spin-coating technology. The films were characterized by atomic force microscopy (AFM), UV-visible absorption spectra (UV), infrared spectroscopy (IR). The gas-sensing properties of the films to ammonia, nitric oxide and nitrogen dioxide, and the relationships between the film structure and gas-sensing properties were investigated.The films containing 2,9,16,24-4(triethoxysilyl)-metallophthalocyanine were prepared by spin-coating technique under the appropriate the experimental conditions. The Q-band of electronic absorption spectra of the spin-coating film red-shifted and broaden compared to that of the corresponding phthalocyanine solutions. We can conclude that the phthalocyanine molecules aggregated in the film. The four kinds of phthalocyanine film showed high sensitivity to nitrogen dioxide at room temperature, and the response and recovery time is short. The selective properties of the films to the nitrogen dioxide (NO2), nitric oxide (NO) and ammonia (NH3) were also investigated. The four kinds of thin films show the same sequences for above three kinds of gases, and the order is NO2>NO>NH3. Simultaneously, the gas-sensing properties of the film to NO2 varies with the nature of the central metal of the phthalocyanine complexes, and the order is PbPc(OR)4-4> ZnPc(OR)4-4> NiPc(OR)4-4> CuPc(OR)4-4. In addition, the experimental conditions, such as spin-coating speed and undetectable gas had a greater impact to the gas sensitivity.更多还原