物理化学学报 >> 2004, Vol. 20 >> Issue (08): 843-848.doi: 10.3866/PKU.WHXB20040812

研究论文 上一篇    下一篇

混配型配合物Ni(mnt)(bipyO2)的合成与气敏性能

傅铁祥;陶钧;李丹   

  1. 长沙理工大学化学系,长沙 410077
  • 收稿日期:2004-02-16 修回日期:2004-04-05 发布日期:2004-08-15
  • 通讯作者: 傅铁祥

Synthesis and Gas Sensitive Properties of Mixed-Ligand Complex Ni(mnt)(bipyO2) with Big Conjugate System

Fu Tie-Xiang;Tao Jun;Li Dan   

  1. Department of Chemistry, Changsha University of Science & Technology, Changsha 410077
  • Received:2004-02-16 Revised:2004-04-05 Published:2004-08-15
  • Contact: Fu Tie-Xiang

摘要: 以cis-1,2-二氰基乙烯-1,2-二硫醇钠(Na2(mnt))、2,2′-联吡啶-1,1′-二氧化物(bipyO2)和NiCl2为原料,合成了一种具有大共轭体系的混配型配合物.用元素分析、差热热重分析、摩尔电导、红外和紫外光谱对配合物进行表征.该配合物化学式为Ni(mnt)(bipyO2),平面正方形结构,属电中性物质,热分解温度高于335 ℃.不溶于水和常规有机溶剂,可溶于DMSO.该配合物是一种氨敏材料,用它制作的传感器对氨气具有良好的敏感性和选择性;当工作电压为10 V时,在氨气浓度小于2.6 mmol•L-1的范围,传感器的输出信号对氨气呈线性响应.传感器的平均回收率为100.2%,响应时间为20 s,恢复时间为45 s.可用于微量氨的定量分析.

关键词: 镍, 传感器, 配合物, cis-1,2-二氰基乙烯-1,2-二硫醇钠(Na2(mnt)), 2,2′-联吡啶-1,1′-二氧化物(bipyO2)

Abstract: A mixed-ligand complex Ni(mnt)(bipyO2) with large conjugate system was synthesized by reaction of bipyO2(2,2′-bipyridine-1,1′-dioxide),mnt2-(maleonitriledithiolate) and NiCl2. The determinations of elemental analysis, IR, UV, molar conductivity and TG-DTA showed the complex to have electroneutrality and a square planar structure. It is a thermostable brown solid under temperature 335 ℃. The ultraviolet absorption spectra of the complex in DMSO solution exhibited intensive absorption bands at 255~290 nm(π-π* in bipyO2 and mnt), 310~340 nm(n-π*, metel cation to ligands), 370~420 nm(π-π* in mnt) and 440~520 nm, and the latter was assigned as a large conjugate system interlocking metal ion and ligands π to π* transition. The study of sensitive properties showed the complex to be a good sensitive material of ammonia. The sensor manufactured using the complex has a good sensitivity and selectivity to ammonia. When working voltage is 10 V and NH3 concentration is less than 2.6 mmol•L-1. The output voltage of the sensor varied linearly in response to the change of NH3 concentration (Fig.3). The average recovery rate of the sensor is 100.2%(Table 4). The responsive time is about 20 s, and the return time is about 45 s. The sensor could be used in quantitative analysis of trace ammonia.

Key words: Nickel, Sensor, Complex, Maleonitriledithiolate(mnt), 2,2′-bipyridine-1,1′-dioxide(bipyO2)