基于卟啉扩展共轭结构的三明治型卟啉酞菁铕配合物的自组装薄膜的氨气传感性质研究  

NH3 Sensors Properties of(Porphyrinato)(Phthalocyaninato)Europium Complex with Extended Conjugated Porphyrin Ring

作　　者：王鸿远 魏闯宇 高鑫宇 于金石 陈艳丽 姜建壮[2] Wang Hongyuan;Wei Chuangyu;Gao Xinyu;Yu Jinshi;Chen Yanli;Jiang Jianzhuang(School of Materials Science and Engineering,School of Chemistry and Chemical Engineering,China University of Petroleum(East China),Qingdao 266580,China;Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials,Department of Chemistry,University of Science and Technology Beijing,Beijing 100083,China)

机构地区：[1]中国石油大学(华东)材料科学与工程学院,化学化工学院,山东青岛266580 [2]北京科技大学化学系,功能分子与晶态材料科学与应用北京市重点实验室,北京100083

出　　处：《中国稀土学报》2023年第1期168-177,共10页Journal of the Chinese Society of Rare Earths

基　　金：国家自然科学基金项目(22133006和21771192);山东省泰山学者计划项目(ts201712019)资助。

摘　　要：有机半导体材料在气体传感领域具有广泛应用。本文通过扩展三明治型卟啉酞菁配合物中卟啉环的共轭结构,设计并合成了具有半导体性质的三明治型卟啉酞菁铕配合物,分别为[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Por-phenyl](1),[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Por-biphenyl](2)和[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Porpyrenephenyl](3)。并使用操作简单、成本较低的QLS方法将配合物薄膜修饰在ITO电极表面,随着共轭结构从配合物1,2到3依次增大,其聚集体形貌颗粒尺寸减小,活性位点暴漏的越多,增大了与气体的相互作用。利用XRD和UV-vis和Polarized UV-vis等多种表征手段对配合物分子在薄膜内的排列方式进行表征,揭示配合物分子在ITO电极表面的聚集模式为H聚集。对三种配合物进行I-V测试,导电性依次为:3>2>1。将配合物薄膜修饰的ITO电极在室温下暴露于(0.5~2.5)ppm NH3气体浓度下进行测试,发现三种配合物对(0.5~2.5)ppm NH3都具有响应,灵敏度依次为:0.8%·ppm^(-1),1.0%·ppm^(-1)和2.0%·ppm^(-1)。结果表明材料共轭结构大,电导率高的[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Por-pyrenephenyl](3)对NH3具有最高的灵敏度,最低检测限为0.12 ppm。本研究结果为分子设计并结合一种低成本的方法获得高性能的室温气体传感器提供了一种新的策略。Organic semiconductor materials are widely used in the field of gas sensing.In this paper,by extending the conjugated porphyrin ringins and sandwich(porphyrina-to)(phthalocyaninato)europiumtriple-decker complex,three complexes were designed and synthesized,i.e.[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Por-phenyl](1),[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Por-biphenyl](2)and[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Por-pyrenephenyl](3),respectively.And they were prepared for the self-assembled films by using a simple QLS method.By SEM observation,it finds that,as the conjugate structure increases from 1,2 to 3,the uniformity of microscopic particles increases and the size decreases,which are beneficial to the exposure of more activesites,thus increasing the adsorption of the gas.XRD,UV-vis and polarized UV-vis measurements reveal the H-aggregates formed of the triple-decker molecules in the QLS films.The electrical conductivity of the complexes in the QLS films is determined as follows:3>2>1 by the I-V curves.The ITO electrodes modified by the three kinds of films show the sensitive responsibility to(0.5~2.5)ppm NH3at room temperature with sensitivities of 0.8%·ppm^(-1),1.0%·ppm^(-1)and 2.0%·ppm^(-1)for 1,2 and 3,respectively.Consequently,[Pc(SC_(2)H_(5))_(8)]_(2)Eu[Por-pyrenephenyl](3)has the highest sensitivity,and the lowest detection limit of 0.12 ppm.The result provides a new strategy for molecular design combined with a low-cost approach to obtain high performance room-temperature gas sensors.

关 键 词：三明治型卟啉酞菁铕配合物 氨气 气体传感 

分 类 号：O625.6[理学—有机化学]