CN114456357B - 一种基于卟啉聚合物的三乙胺气敏材料 - Google Patents
一种基于卟啉聚合物的三乙胺气敏材料 Download PDFInfo
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 16
- 229920000642 polymer Polymers 0.000 title abstract description 6
- 229920000547 conjugated polymer Polymers 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 238000001514 detection method Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 230000004044 response Effects 0.000 claims abstract description 5
- -1 porphyrin compounds Chemical class 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- QRFALSDGOMLVIR-UHFFFAOYSA-N 1,2,3,4-tetrabromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1Br QRFALSDGOMLVIR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- RQFDSUDJQPEOIJ-UHFFFAOYSA-N BrC1=CC=C(C=C1)[Fe] Chemical compound BrC1=CC=C(C=C1)[Fe] RQFDSUDJQPEOIJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011540 sensing material Substances 0.000 abstract description 4
- 238000012544 monitoring process Methods 0.000 abstract description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 37
- 239000007789 gas Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 241000251468 Actinopterygii Species 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ULUNQYODBKLBOE-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)-1h-pyrrole Chemical compound C1=CNC(C=2NC=CC=2)=C1 ULUNQYODBKLBOE-UHFFFAOYSA-N 0.000 description 1
- UZQDUXAJFTWMDT-UHFFFAOYSA-N 4-(2-trimethylsilylethynyl)benzaldehyde Chemical compound C[Si](C)(C)C#CC1=CC=C(C=O)C=C1 UZQDUXAJFTWMDT-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 208000005577 Gastroenteritis Diseases 0.000 description 1
- 206010037423 Pulmonary oedema Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
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- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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Abstract
本发明提供了一种用于三乙胺检测的传感材料,是由四溴苯卟啉铁与对炔基苯卟啉铁通过Sonogashira偶合反应得到的一种卟啉共轭聚合物分子半导体材料。本申请将卟啉共轭聚合物分子半导体材料用于三乙胺传感检测,是首次采用卟啉共轭聚合物用于三乙胺检测,同时拓展了卟啉类化合物在传感领域的应用。制备过程将聚合物滴加到带有ITO叉指电极的玻璃基片上作为半导体活性层,实现了室温条件下对低浓度三乙胺灵敏快速检测,检测限为0.34ppm。该材料在室温下可以实现对三乙胺的灵敏响应,对于三乙胺的环境监测有着极高的实用价值。
Description
技术领域
本发明涉及三乙胺室温检测研究领域,具体涉及一种卟啉共轭聚合物气敏材料的制备及应用。将四溴苯卟啉铁与对炔基苯卟啉铁反应得到卟啉共轭聚合物,将其作为活性材料用于三乙胺的检测,该材料可以实现室温下对三乙胺的灵敏检测,对其实际应用有重要意义。
背景技术
如今,气体传感器是气体泄漏检测、公共安全、医疗诊断的必备设备,对环境空气质量实时监测的需求导致了气体传感器市场的迅速扩张。挥发性有机化合物(VOC)的蒸汽在现代生活中无处不在,因为它们是几种化学品和商品生产过程中不可或缺的一部分,并且在化石燃料燃烧过程中被广泛释放出来。挥发性有机化合物被认为是我们生活环境中的隐形杀手。由于三乙胺(TEA)被用作防腐剂、表面活性剂、有机溶剂、催化剂等,挥发的气体是无色的,有类似氨的气味。三乙胺具有腐蚀性,会刺激皮肤、呼吸系统和消化系统。当一个人长期接触高浓度的三乙胺时,可能会出现咳嗽、肠胃炎、肺水肿,甚至死亡。此外,三乙胺可以由降解死鱼和海鲜的微生物产生,可以作为监测鱼类新鲜度的化学标记物。
目前报道的对于三乙胺气体的传感材料,大多数都是基于金属氧化物,金属氧化物半导体具有易于制备、廉价和良好的稳定性等优点,使其成为三乙胺气体传感器的理想候选者。其中,基于ZnO的三乙胺气体传感器由于其形貌可控、电子迁移率快、化学稳定性好、生产成本低等优点而广受欢迎。然而,它们的实际应用受到工作温度高、灵敏度低和选择性差的限制。例如,GeyuLu等人制备的Pt-ZnO在工作温度200度下用于三乙胺检测,贵金属颗粒的修饰的氧化锌比单独的氧化锌相比,降低了工作温度,提升了检测三乙胺的响应,贵金属的加入提高了成本。然而,由于卟啉大的平面大环共轭分子结构和高的化学稳定性,以及分子结构的可修饰性,在生物化学、光电催化及气体传感等领域被广泛研究和应用。但是,卟啉分子的导电性较差,越来越多的研究选择将卟啉与其他材料复合进一步改进导电性进而气体传感性质,在这里将两种卟啉通过炔基键连接,扩大了卟啉的共轭程度,加快了电子的流动,有利于提高导电性,进而提升器件的灵敏响应,使用这种卟啉共轭聚合物对三乙胺检测还未见报道。
发明内容
针对上述现有技术中存在的问题,以及本研究领域的应用需求,本发明提供了一种成本低廉,制备工艺简单,可室温下实现三乙胺检测的传感材料的制备方法及应用。
四溴苯卟啉铁(左)和对炔基卟啉铁(右)分子结构如下:
四溴苯卟啉铁的合成:
步骤1:取300mg四溴苯自由卟啉和408mg氯化亚铁于250ml三口烧瓶中,加入80mlN,N-二甲基甲酰胺;
步骤2:加热至155摄氏度搅拌回流11小时后停止加热,冷却至室温;
步骤3:将反应后的液体倒入1000ml蒸馏水中,抽滤,收集固体;
步骤4:二氯甲烷/正己烷(体积比为1:1)过柱子,第一带即为产物带,旋蒸蒸干;
步骤5:用二氯甲烷/甲醇(体积比为1:6)进行重结晶,然后过滤,收集滤纸上深紫色沉淀,真空40摄氏度干燥一夜,得四溴苯卟啉铁,产率为30%。
对炔基卟啉铁的合成:
步骤1:取350mg双吡咯和420mg的4-[(三甲基硅基)乙炔基]苯甲醛于250ml三口瓶中,加入100ml二氯甲烷,室温搅拌,通氮气30分钟;
步骤2:加入77μL三氟乙酸,室温下继续搅拌3小时;
步骤3:称取680mg2,3-二氯-5,6-二氰对苯醌加入反应中,室温搅拌30分钟;
步骤4:加入2ml三乙胺,停止反应,去除溶剂,收集固体;
步骤5:二氯甲烷/正己烷(体积比为1:1)过柱子,第一带即为产物带,旋蒸蒸干;
步骤6:用二氯甲烷/甲醇(体积比为1:6)进行重结晶,然后过滤,收集滤纸上深紫色沉淀,真空40摄氏度干燥一夜;
步骤7:将100mg步骤6所得固体和183mg无水碳酸钾加入100ml三口瓶,加入20ml甲醇和30ml二氯甲烷,氮气保护,室温搅拌8h;
步骤8:旋蒸出去溶剂,固体用80ml二氯甲烷和100ml水进行萃取两次,有机相用无水硫酸钠干燥,蒸干去除二氯甲烷,得紫色粗产物;
步骤9:步骤8中紫色粗产物用二氯甲烷/正己烷(体积比为1:2)过柱子,第一带即为产物带,旋蒸蒸干,得对炔基自由卟啉,产率为90%;
步骤10:取300mg对炔基自由卟啉和408mg氯化亚铁于250ml三口烧瓶中,加入80mlN,N-二甲基甲酰胺,155摄氏度搅拌回流11小时后停止加热,冷却至室温;
步骤11:将反应后的液体倒入1000ml蒸馏水中,抽滤,收集固体;
步骤12:二氯甲烷/正己烷(体积比为1:1)过柱子,第一带即为产物带,旋蒸蒸干;
步骤5:用二氯甲烷/甲醇(体积比为1:6)进行重结晶,然后过滤,收集滤纸上深紫色沉淀,真空40摄氏度干燥一夜,得对炔基卟啉铁,产率为30%。
卟啉共轭聚合物的合成:
步骤1:分别取12.8mg四溴苯卟啉铁和20mg对炔基卟啉铁加入到含有三乙胺/四氢呋喃(1/3)40ml的100ml三口瓶中,通氮气15分钟;
步骤2:依次加入29mg三苯基膦,5mg乙酸钯,10.5mg碘化亚铜,76℃搅拌12小时,停止反应,冷却至室温;
步骤3:过滤,固体分别用水,甲醇,四氢呋喃,三氯甲烷和丙酮,采用索氏提取法各洗3次,最终得到卟啉共轭聚合物,产率为60%。
具有纳米片形貌的卟啉共轭聚合物的三乙胺气敏材料的制备方法,包括以下几个步骤:步骤1:将刻蚀ITO电极用洗洁精搓洗干净,然后分别用蒸馏水、无水乙醇、二氯甲烷超声处理各10分钟,氮气吹干,等待接下来使用;
步骤2:将卟啉共轭聚合物分散在无水乙醇中,超声3h;
步骤3:将制得分散液滴加到表面皿水层上,静置5分钟;
步骤4:采用竖直提拉法用刻蚀ITO电极蘸取表面皿水层上的聚合物。
其中聚集体的量为5mg,乙醇的量为2ml。
其中聚集体分散液的滴加量为20μL。
本发明的有益效果在于:发现一种新的材料可以用做三乙胺的气敏材料。该气敏器件的制备工艺及设备简单、易于实现工业化生产。通过炔基将卟啉连接成共轭聚合物,能够有效扩大卟啉的共轭程度,即提高电子迁移能力。以此构建的气敏器件的导电性以及灵敏度明显增加,而且通过采用竖直提拉的方法,将水面上卟啉共轭聚合物转移到洗净的ITO叉指电极的玻璃基片上作为半导体活性层,实现室温条件下对0.5-5.3ppm的三乙胺的灵敏快速响应。
附图说明
下面结合附图和实施例对本发明进一步说明。
图1是本发明制备过程示意图。从图中可以看出,1表示聚合物分散液滴加到含有蒸馏水的表面皿上,2表示采用竖直提拉法将卟啉共轭聚合物转移到刻蚀ITO电极上;
图2是四溴苯卟啉铁的质谱图;
图3是对炔基苯卟啉铁的质谱图;
图4是卟啉单体和卟啉聚合物紫外可见吸收光谱图,1为四溴苯卟啉铁在二氯甲烷溶液中紫外可见吸收光谱图,2为对炔基苯卟啉铁在二氯甲烷溶液中紫外可见吸收光谱图,3为卟啉共轭聚合物的紫外可见吸收光谱图;
图5是卟啉共轭聚合物的SEM图;
图6是卟啉共轭聚合物的I-V曲线;
图7是卟啉共轭聚合物对三乙胺的气敏测试图,图中可以看出,卟啉共轭聚合物对三乙胺具有良好的灵敏度,检测范围是0.5-5.3ppm,其最低检测限达到0.34ppm。
具体实施方式
实以卟啉共轭聚合物作为有机半导体材料,利用其检测室温条件下的三乙胺气体。首先将分散好的卟啉共轭聚合物用移液枪吸取20μL滴加到装有蒸馏水的表面皿上,静置5分钟,用刻蚀ITO电极采用竖直提拉法蘸取水层上的聚合物,如此反复制备传感器件。后将带有卟啉共轭聚合物的刻蚀ITO电极于Keysight B2912A仪器上进行气敏测试,最终得到卟啉共轭聚合物在室温条件下对三乙胺气体的检测情况。
本发明所合成的四溴苯卟啉铁和对炔基苯卟啉铁通过原始的丙酸法合成卟啉即可获得,通偶合反应得到卟啉共轭聚合物,不但大大简化工艺流程,而且制备条件温和、成本低、所需设备简单、生产安全性强,易于实现工业化生产。所合成的卟啉共轭聚合物能在室温条件下检测三乙胺气体,提高了气体传感器的应用范围。
以上所述,仅为本发明的较佳实施例而已,并非对本发明作任何形式上的限制;凡熟悉本专业的普通技术人员均可按说明书附图和以上所述而顺畅地实施本发明;但是,凡熟悉本专业的技术人员在不脱离本发明技术方案范围内,可利用以上所揭示的技术内容而作出的些许更改、修饰与演变的等同变化,均为本发明的等效实施例;同时,凡依据本发明的实施技术对以上实施例所作的任何等同变化的更动、修饰与演变等,均属于本发明的技术方案的保护范围之内。
Claims (4)
1.一种基于卟啉共轭聚合物的气敏材料,可以在室温下对三乙胺气体进行检测;其特征在于,利用四溴苯卟啉铁和对炔基苯卟啉铁反应得到卟啉共轭聚合物;5mg卟啉共轭聚合物和2ml乙醇超声分散,20μl分散液滴加到装有水的表面皿,静置5分钟,采用竖直提拉法将水面上卟啉共轭聚合物转移到洗净的ITO叉指电极的玻璃基片上,并将其作为半导体活性层,实现室温条件下对0.5-5.3ppm的三乙胺的灵敏快速响应。
2.根据权利要求1所述的基于卟啉共轭聚合物的气敏材料,其特征在于,所述卟啉共轭聚合物是由5,10,15,20-四(4-溴苯基)卟啉铁化合物与5,15-二(4-乙炔基苯基)-10,20-二苯基卟啉铁反应得到卟啉共轭聚合物。
3.根据权利要求1所述的基于卟啉共轭聚合物的气敏材料,其特征在于,所述静置过程中,随着乙醇挥发,卟啉共轭聚合物会在水面上平铺,采用竖直提拉法将水面上卟啉共轭聚合物转移到洗净的ITO叉指电极上。
4.根据权利要求1中所述的基于卟啉共轭聚合物的气敏材料,其特征在于,所述气敏材料可以在室温条件下实现对三乙胺气体进行检测,检测范围是0.5-5.3ppm,最低检测限为0.34ppm。
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