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聚苯胺/四-β-羧基酞菁钴(Ⅱ)复合材料的制备及其氨敏性能研究

Preparation and NH₃-sensing properties of polyaniline/tetra-β-carboxyphthalocyanine cobalt（Ⅱ） hybrid

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【Author】 Hao Wu;Zhimin Chen;Jialin Zhang;Feng Wu;Fei Xiao;Bin Wang;Chunying He;Yiqun Wu;Key Laboratory of Functional Inorganic Material Chemistry (Ministry of Education of China), School of Chemistry and Materials Science, Heilongjiang University;

【机构】黑龙江大学化学化工与材料学院功能无机材料化学教育部重点实验室；

【摘要】在环境安全和工农业过程控制等领域,对空气中的氨气浓度数据进行实时采集、监控和预警是至关重要的。本文以四-β-羧基酞菁钴（Ⅱ）（TcPcCo）为掺杂剂,采用过二硫酸铵为氧化剂,通过软模板法,成功制备了聚苯胺/四-β-羧基酞菁钴（Ⅱ）复合材料（PANI-TcPcCo）。利用UV-Vis,FT-IR,XPS,Raman,SEM和TEM对复合材料进行了表征,进一步研究了复合材料薄膜的NH₃敏感性能。研究发现,所制备的PANI-TcPcCo呈现一种由纳米管（线）织成的三维网状结构,具有较大的比表面积和良好的导电性。室温下,以该材料构筑的气体传感器对NH₃展示出优异的气敏特性,包括高的灵敏度（检测10 ppm NH₃时,灵敏度为203.6%）和低的检测限（10ppb）、宽的线性范围（50 ppb-250 ppm）以及优异的选择性和稳定性。产生这种优异的NH₃传感性能的原因可归于:（a）掺杂TcPcCo,获得了由纳米管（线）组成的三维网状结构,这种结构一方面可以增加PANI的电导率,使载流子在PANI中的传输变得更加顺畅,另一方面增大了材料的比表面积,使PANI暴露出更多的活性位点;（b）TcPcCo的中心金属会与NH₃发生强烈的作用,它的掺入会大量增加材料的活性位点,提高气敏性能。更多还原

【Abstract】 One area of critical importance is the detection of ammonia in the environment for security and industrial, agricultural process monitoring. Here, polyaniline/tetra-b-carboxyphthalocyanine cobalt（Ⅱ） hybrid（PANI-TcPcCo） with 3D nanotubes（nanofibers） network structure was prepared by a "soft-template" method based on chemical oxidative polymerization. The resultant sensing device shows outstanding NH₃-sensing performance at room temperature, such as high gas response（10 ppm, 203.6 %）, low detection limit（10 ppb）, wide linear range（50 ppb-250 ppm）, and excellent stability and selectivity. The significant enhancement of NH₃-sensing performance is likely attributed to the 3D nanotubes（nanofibers） network morphology which offers a large accessible surface for gas diffusion, and provides unimpeded pathways for the carrier transport. Further performance boost might be made by the strong interactions between NH₃ and central metal Co in TcPcCo resulting in much increased active sites.更多还原