CN103308563A - Gas sensitive element by taking single-walled carbon nanotube/phthalocyanine composite material as ammonia-sensitive material and preparation method thereof - Google Patents
Gas sensitive element by taking single-walled carbon nanotube/phthalocyanine composite material as ammonia-sensitive material and preparation method thereof Download PDFInfo
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Abstract
一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件及其制备方法，它涉及一种测量氨气浓度的气敏元件及其制备方法。本发明是要解决单一单壁碳纳米管为氨敏材料的气敏元件可逆性较差和金属酞菁为氨敏材料的气敏元件电阻值较高的问题。一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件由叉指电极和单壁碳纳米管/酞菁复合材料构成。制备方法：一、制备羧基化单壁碳纳米管；二、制备单壁碳纳米管/酞菁复合材料；三、滴涂；即得到以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件。本发明可用于制备以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件。
A gas sensor using single-wall carbon nanotube/phthalocyanine composite material as an ammonia sensitive material and a preparation method thereof, which relates to a gas sensor for measuring the concentration of ammonia gas and a preparation method thereof. The invention aims to solve the problems of poor reversibility of the gas sensor with single single wall carbon nanotube as ammonia sensitive material and high resistance value of the gas sensor with metal phthalocyanine as ammonia sensitive material. A gas sensor using a single-wall carbon nanotube/phthalocyanine composite material as an ammonia-sensitive material is composed of an interdigital electrode and a single-wall carbon nanotube/phthalocyanine composite material. Preparation method: 1. Preparation of carboxylated single-wall carbon nanotubes; 2. Preparation of single-wall carbon nanotube/phthalocyanine composite materials; gas sensor. The invention can be used to prepare the gas sensor with the single-wall carbon nanotube/phthalocyanine composite material as the ammonia sensitive material.
Description
技术领域technical field
本发明涉及一种测量氨气浓度的气敏元件及其制备方法。The invention relates to a gas sensor for measuring ammonia concentration and a preparation method thereof.
背景技术Background technique
随着人类对可持续发展战略认识的不断深入，环境污染和气候变化问题已引起了世界各国的高度重视。同时人们在生产和生活中所使用和产生的气体种类和数量却逐年增加，其中的有害气体，不仅污染环境和影响气候，而且有产生***、火灾和使人中毒的危险。气体传感器作为有害气体检测的最有效途径之一，近年来受到了世界各国企业集团和研究机构的广泛关注。传统的基于半导体金属氧化物材料(如ZnO，SnO2和Fe2O3等)的传感器，以其材料成本低廉、制造简单、灵敏度较高(通常检测范围为1ppm～1000ppm)以及寿命较长等优点已经被广泛用来检测含氮有害气体。这些传感器的不足之处在于工作温度高(几百甚至上千摄氏度)、功率要求高，成膜设备成本高、对气体的选择性差、而且当探测到某些气体(如硫化物)时，还容易中毒。由于碳纳米管独特的准一维纳米结构、巨大的比表面积、丰富的孔隙结构、特殊的电子能带结构、相当高的电导率和稳定的理化性质，成为了近年来气体传感器领域国内外争相研究的热点之一。但是其所表现出的恢复时间慢、选择性较差、溶解性和分散性不理想以及成膜性手段受限等问题目前亟待解决。以酞菁为代表的有机半导体材料，以其特有的性能，如高选择性、高灵敏度、较快的响应恢复速度、分子结构可设计、可在常温或接近常温下工作以及可用成本低廉的液相法(如旋凃和提拉法)成膜等，在气体传感器领域中占有重要的地位。然而，此类气体传感器表现出来的测量电阻值高(>10GΩ)和长期稳定性较差等问题，又成为限制其实用化而必须要解决的问题。With the continuous deepening of human understanding of sustainable development strategies, environmental pollution and climate change issues have attracted great attention from all over the world. At the same time, the types and quantities of gases used and produced by people in production and life are increasing year by year. The harmful gases in them not only pollute the environment and affect the climate, but also have the danger of explosion, fire and poisoning. As one of the most effective ways to detect harmful gases, gas sensors have attracted extensive attention from business groups and research institutions around the world in recent years. Traditional sensors based on semiconductor metal oxide materials (such as ZnO, SnO 2 and Fe 2 O 3 , etc.) are characterized by low material cost, simple manufacture, high sensitivity (usually the detection range is 1ppm to 1000ppm) and long life. Advantages It has been widely used to detect harmful gases containing nitrogen. The disadvantages of these sensors are high operating temperature (hundreds or even thousands of degrees Celsius), high power requirements, high cost of film-forming equipment, poor selectivity to gases, and when certain gases (such as sulfides) are detected, the Easily poisoned. Due to the unique quasi-one-dimensional nanostructure, huge specific surface area, rich pore structure, special electronic band structure, relatively high electrical conductivity and stable physical and chemical properties of carbon nanotubes, it has become a hot topic in the field of gas sensors in recent years. One of the hot spots of phase research. However, its problems such as slow recovery time, poor selectivity, unsatisfactory solubility and dispersion, and limited film-forming methods need to be solved urgently. Organic semiconductor materials represented by phthalocyanine, with their unique properties, such as high selectivity, high sensitivity, fast response and recovery speed, molecular structure can be designed, can work at room temperature or near room temperature, and can use low-cost liquid Phase methods (such as spin coating and pulling method) film formation, etc., occupy an important position in the field of gas sensors. However, the problems of high measurement resistance (>10GΩ) and poor long-term stability of this type of gas sensor have become problems that limit its practical application and must be solved.
发明内容Contents of the invention
本发明是要解决单一单壁碳纳米管为氨敏材料的气敏元件可逆性较差和金属酞菁为氨敏材料的气敏元件电阻值较高的问题，而提供一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件及其制备方法。The present invention aims to solve the problem of poor reversibility of the gas sensor with a single single-walled carbon nanotube as the ammonia-sensitive material and the relatively high resistance value of the gas sensor with metal phthalocyanine as the ammonia-sensitive material, and provides a single-walled carbon The nanotube/phthalocyanine composite material is an ammonia-sensitive gas sensor and a preparation method thereof.
本发明一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件由叉指电极和单壁碳纳米管/酞菁复合材料构成；其中所述的单壁碳纳米管/酞菁复合材料中的酞菁为戊烷氧基金属酞菁。A gas sensor using single-wall carbon nanotube/phthalocyanine composite material as ammonia-sensitive material in the present invention is composed of interdigital electrodes and single-wall carbon nanotube/phthalocyanine composite material; wherein said single-wall carbon nanotube/phthalocyanine composite material The phthalocyanine in the phthalocyanine composite material is a pentyloxy metal phthalocyanine.
本发明一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件的制备方法，按以下步骤进行：A kind of preparation method of the gas sensor with single wall carbon nanotube/phthalocyanine composite material as the ammonia sensitive material of the present invention, carries out according to the following steps:
一、制备羧基化单壁碳纳米管：将单壁碳纳米管加入到浓度为2mol/L～3mol/L硝酸水溶液中，于80℃～90℃温度下回流反应36h～48h，过滤后得到滤饼，将滤饼分散于浓度为0.5mol/L～2mol/L盐酸水溶液中超声震荡10min～30min，过滤，得到纯化单壁碳纳米管，然后将得到的纯化单壁碳纳米管置于混酸中加热处理，得到反应后的溶液，向反应后的溶液中加入去离子水稀释，然后用0.20μm聚四氟乙烯过滤膜抽滤，得到羧基化单壁碳纳米管粗产物，对得到的羧基化单壁碳纳米管粗产物水洗至滤液呈中性，最后在真空干燥箱中于温度为80℃的条件下干燥1天，得到羧基化单壁碳纳米管；其中所述的单壁碳纳米管的质量与浓度为2mol/L～3mol/L硝酸水溶液的体积比为1g:(100～200)mL，所述的混酸由浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液混合而成，且浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液的体积比为3:1，所述的纯化单壁碳纳米管的质量与混酸的体积比为1g:(100～200)mL，所述的混酸与去离子水的体积比为1:(5～10)；1. Preparation of carboxylated single-walled carbon nanotubes: Add single-walled carbon nanotubes into an aqueous solution of nitric acid with a concentration of 2mol/L-3mol/L, reflux reaction at a temperature of 80°C-90°C for 36h-48h, and obtain filtered Cake, disperse the filter cake in a hydrochloric acid aqueous solution with a concentration of 0.5mol/L-2mol/L, vibrate ultrasonically for 10min-30min, filter to obtain purified single-walled carbon nanotubes, and then place the obtained purified single-walled carbon nanotubes in mixed acid Heat treatment to obtain the reacted solution, add deionized water to the reacted solution for dilution, and then filter with 0.20 μm polytetrafluoroethylene filter membrane to obtain the crude product of carboxylated single-walled carbon nanotubes. The crude product of single-walled carbon nanotubes is washed with water until the filtrate is neutral, and finally dried in a vacuum oven at a temperature of 80° C. for 1 day to obtain carboxylated single-walled carbon nanotubes; wherein the single-walled carbon nanotubes The mass and concentration of 2mol/L～3mol/L nitric acid aqueous solution volume ratio is 1g:(100～200)mL, and described mixed acid is mixed by the sulfuric acid aqueous solution that concentration is 18mol/L and the nitric acid aqueous solution that concentration is 16mol/L Forming, and concentration is that the sulfuric acid aqueous solution of 18mol/L and the volume ratio of the nitric acid aqueous solution of 16mol/L are 3:1, and the quality of described purifying single-walled carbon nanotubes and the volume ratio of mixed acid are 1g:(100 ～200) mL, the volume ratio of described mixed acid and deionized water is 1:(5～10);
二、制备单壁碳纳米管/酞菁复合材料：将步骤一得到的羧基化单壁碳纳米管在频率为40kHz的条件下超声分散于DMF中，得到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液，将浓度为10mg/mL的酞菁DMF溶液滴加到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液中，然后在频率为40kHz条件下避光超声震荡反应13h～48h，得到反应后的溶液，将反应后的溶液用0.20μm聚四氟乙烯过滤膜抽滤，得到单壁碳纳米管/酞菁复合材料粗产物，采用DMF对得到的单壁碳纳米管/酞菁复合材料粗产物离心洗涤至上层清液无色，然后采用氯仿离心洗涤至上层清液无色，最后采用乙醇离心洗涤3次，弃去清液，得到单壁碳纳米管/酞菁复合材料沉淀，然后将单壁碳纳米管/酞菁复合材料沉淀置于温度为60℃的真空干燥箱中干燥2h，得到单壁碳纳米管/酞菁复合材料；所述的浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液与浓度为10mg/mL的酞菁DMF溶液的体积比为1:(2～4)，所述的酞菁DMF溶液中的酞菁为戊烷氧基金属酞菁；2. Preparation of single-walled carbon nanotubes/phthalocyanine composites: the carboxylated single-walled carbon nanotubes obtained in step 1 were ultrasonically dispersed in DMF at a frequency of 40 kHz to obtain carboxylated single-walled carbon nanotubes with a concentration of 10 mg/mL Carbon nanotube DMF suspension, add the phthalocyanine DMF solution with a concentration of 10mg/mL dropwise to the carboxylated single-walled carbon nanotube DMF suspension with a concentration of 10mg/mL, and then oscillate in the dark at a frequency of 40kHz React for 13h to 48h to obtain the reacted solution, and filter the reacted solution with a 0.20μm polytetrafluoroethylene filter membrane to obtain a crude single-walled carbon nanotube/phthalocyanine composite material, and use DMF to treat the obtained single-walled carbon The crude product of the nanotube/phthalocyanine composite material was centrifugally washed until the supernatant was colorless, then centrifugally washed with chloroform until the supernatant was colorless, finally washed 3 times with ethanol, and the supernatant was discarded to obtain single-walled carbon nanotubes/ The phthalocyanine composite material is precipitated, and then the single-walled carbon nanotube/phthalocyanine composite material is precipitated and placed in a vacuum oven at a temperature of 60° C. for 2 hours to obtain a single-walled carbon nanotube/phthalocyanine composite material; the concentration is The volume ratio of the carboxylated single-walled carbon nanotube DMF suspension of 10mg/mL and the phthalocyanine DMF solution that concentration is 10mg/mL is 1:(2～4), and the phthalocyanine in the described phthalocyanine DMF solution is pentyl Alkoxy metal phthalocyanine;
三、滴涂：将步骤二得到的单壁碳纳米管/酞菁复合材料在频率为40kHz的条件下超声分散于DMF中，超声2h，得到浓度为0.1mg/mL～1.0mg/mL的单壁碳纳米管/酞菁复合材料DMF悬浮液，然后用注射器将浓度为0.1mg/mL～1.0mg/mL的单壁碳纳米管/酞菁复合材料DMF悬浮液1μL～30μL滴涂在叉指电极上，溶液蒸发后，将其放入真空干燥箱中，在温度为80℃的条件下干燥12h～48h，即得到以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件。3. Drop coating: ultrasonically disperse the single-walled carbon nanotube/phthalocyanine composite material obtained in step 2 in DMF at a frequency of 40 kHz, and ultrasonically for 2 hours to obtain a single-walled carbon nanotube/phthalocyanine composite material with a concentration of 0.1 mg/mL-1.0 mg/mL. Wall carbon nanotube/phthalocyanine composite DMF suspension, and then use a syringe to drop 1 μL to 30 μL of single-wall carbon nanotube/phthalocyanine composite DMF suspension with a concentration of 0.1 mg/mL to 1.0 mg/mL on the interdigital On the electrode, after the solution evaporates, put it in a vacuum drying oven, and dry it at a temperature of 80°C for 12h to 48h to obtain a gas sensor with single-walled carbon nanotube/phthalocyanine composite material as the ammonia sensitive material .
本发明的优点：一、本发明利用无机材料优异的导电性和热、光与化学稳定性，有机材料分子可裁剪性、响应快、易加工等特点，将两者通过组分和结构的周期性变化形成复合材料，实现无机/有机材料的功能互补、优化和协同增强，从而提高单一气敏材料的气敏性能，以获得综合性能更加优异的气敏元件；二、本发明制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件，室温下，在0.6ppm～80ppmNH3浓度范围内具有较好的响应，而在0.6ppm～40ppm低浓度NH3范围内NH3浓度与响应间具有良好的线性关系，可以检测到600ppb级NH3；三、本发明制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件在不同浓度氨气中都具有良好的灵敏度、可逆性、稳定性，且对同浓度的CO2、CO、CH4和H2等气体没有响应，对NH3具有了良好的选择性；四、本发明制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件大大提高了单壁碳纳米管的气敏性能，可以对NH3进行检测。Advantages of the present invention: 1. The present invention utilizes the excellent electrical conductivity, heat, light and chemical stability of inorganic materials, and the molecular tailorability, fast response, and easy processing of organic materials, and combines the two through the cycles of components and structures. The composite material can be formed through the change of properties to realize the functional complementarity, optimization and synergistic enhancement of inorganic/organic materials, thereby improving the gas-sensing performance of a single gas-sensing material and obtaining a gas-sensing element with more excellent comprehensive performance; The wall carbon nanotube/phthalocyanine composite material is a gas sensor of ammonia sensitive material. At room temperature, it has a good response in the concentration range of 0.6ppm to 80ppmNH3 , and in the range of low concentration NH3 from 0.6ppm to 40ppm, NH3 There is a good linear relationship between the concentration and the response, and 600ppb NH3 can be detected; three, the gas sensor prepared by the present invention uses the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material in different concentrations of ammonia. It has good sensitivity, reversibility and stability, and has no response to gases such as CO 2 , CO, CH 4 and H 2 at the same concentration, and has good selectivity to NH 3 ; The carbon nanotube/phthalocyanine composite material is an ammonia-sensitive gas sensor that greatly improves the gas-sensing performance of single-walled carbon nanotubes, and can detect NH 3 .
附图说明Description of drawings
图1为本试验制备的以单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件的响应与氨气浓度关系曲线；Fig. 1 is the response and ammonia concentration curve of the gas sensor of ammonia sensitive material with single-walled carbon nanotube/tetra-3-isoamyloxyphthalocyanine copper composite material prepared by this test;
图2为本试验制备的以单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件在不同浓度氨气中的响应恢复曲线；Fig. 2 is the response recovery curve of the gas sensor of the ammonia-sensitive material with single-walled carbon nanotubes/tetra-3-isoamyloxyphthalocyanine copper composite material prepared in this test in different concentrations of ammonia;
图3为本试验制备的以单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件的响应与氨气浓度关系曲线；Fig. 3 is the response and the ammonia concentration curve of the gas sensor of the ammonia-sensitive material with the single-walled carbon nanotube/tetra-4-isoamyloxyphthalocyanine copper composite material prepared by this test;
图4为本试验制备的以单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件在不同浓度氨气中的响应恢复曲线；Fig. 4 is the response recovery curve of the gas sensor of the ammonia-sensitive material with single-walled carbon nanotube/tetra-4-isoamyloxyphthalocyanine copper composite material prepared in this test in different concentrations of ammonia;
图5为本试验制备的以单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料为氨敏材料的气敏元件的响应与氨气浓度关系曲线；Figure 5 shows the response of the gas sensor with single-walled carbon nanotubes/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite material as the ammonia sensitive material and the ammonia gas Concentration curve;
图6为本试验制备的以单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料为氨敏材料的气敏元件在不同浓度氨气中的响应恢复曲线。Figure 6 shows the gas sensor prepared in this experiment with single-walled carbon nanotube/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite material as the ammonia sensitive material under different concentrations of ammonia gas. The response recovery curve in .
具体实施方式Detailed ways
具体实施方式一：本实施方式一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件由叉指电极和单壁碳纳米管/酞菁复合材料构成；其中所述的单壁碳纳米管/酞菁复合材料中的酞菁为戊烷氧基金属酞菁。Specific Embodiment 1: In this embodiment, a gas sensor with single-wall carbon nanotube/phthalocyanine composite material as ammonia-sensitive material is composed of interdigital electrodes and single-wall carbon nanotube/phthalocyanine composite material; The phthalocyanine in the single-wall carbon nanotube/phthalocyanine composite material is a pentyloxy metal phthalocyanine.
本实施方式所述的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件室温下，在0.6ppm～80ppmNH3浓度范围内具有较好的响应，而在0.6ppm～40ppm低浓度NH3范围内NH3浓度与响应间具有良好的线性关系，可以检测到600ppb级NH3。The gas sensor using the single-wall carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material described in this embodiment has a good response in the range of 0.6ppm to 80ppm NH3 concentration at room temperature, and a low concentration of 0.6ppm to 40ppm. There is a good linear relationship between the NH 3 concentration and the response within the NH 3 concentration range, and 600ppb level NH 3 can be detected.
本实施方式所述的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件在不同浓度氨气中都具有良好的灵敏度、可逆性、稳定性，且对同浓度的CO2、CO、CH4和H2等气体没有响应，对NH3具有了良好的选择性。The gas sensor using the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensing material described in this embodiment has good sensitivity, reversibility, and stability in different concentrations of ammonia gas, and has good sensitivity to the same concentration of CO 2 , CO, CH 4 and H 2 have no response, and have good selectivity to NH 3 .
具体实施方式二：本实施方式与具体实施方式一不同的是：所述的戊烷氧基金属酞菁结构式为
具体实施方式三：本实施方式一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件的制备方法，按以下步骤进行：Specific embodiment three: In this embodiment, a method for preparing a gas sensor using a single-walled carbon nanotube/phthalocyanine composite material as an ammonia-sensitive material is carried out according to the following steps:
一、制备羧基化单壁碳纳米管：将单壁碳纳米管加入到浓度为2mol/L～3mol/L硝酸水溶液中，于80℃～90℃温度下回流反应36h～48h，过滤后得到滤饼，将滤饼分散于浓度为0.5mol/L～2mol/L盐酸水溶液中超声震荡10min～30min，过滤，得到纯化单壁碳纳米管，然后将得到的纯化单壁碳纳米管置于混酸中加热处理，得到反应后的溶液，向反应后的溶液中加入去离子水稀释，然后用0.20μm聚四氟乙烯过滤膜抽滤，得到羧基化单壁碳纳米管粗产物，对得到的羧基化单壁碳纳米管粗产物水洗至滤液呈中性，最后在真空干燥箱中于温度为80℃的条件下干燥1天，得到羧基化单壁碳纳米管；其中所述的单壁碳纳米管的质量与浓度为2mol/L～3mol/L硝酸水溶液的体积比为1g:(100～200)mL，所述的混酸由浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液混合而成，且浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液的体积比为3:1，所述的纯化单壁碳纳米管的质量与混酸的体积比为1g:(100～200)mL，所述的混酸与去离子水的体积比为1:(5～10)；1. Preparation of carboxylated single-walled carbon nanotubes: Add single-walled carbon nanotubes into an aqueous solution of nitric acid with a concentration of 2mol/L-3mol/L, reflux reaction at a temperature of 80°C-90°C for 36h-48h, and obtain filtered Cake, disperse the filter cake in a hydrochloric acid aqueous solution with a concentration of 0.5mol/L-2mol/L, vibrate ultrasonically for 10min-30min, filter to obtain purified single-walled carbon nanotubes, and then place the obtained purified single-walled carbon nanotubes in mixed acid Heat treatment to obtain the reacted solution, add deionized water to the reacted solution for dilution, and then filter with 0.20 μm polytetrafluoroethylene filter membrane to obtain the crude product of carboxylated single-walled carbon nanotubes. The crude product of single-walled carbon nanotubes is washed with water until the filtrate is neutral, and finally dried in a vacuum oven at a temperature of 80° C. for 1 day to obtain carboxylated single-walled carbon nanotubes; wherein the single-walled carbon nanotubes The mass and concentration of 2mol/L～3mol/L nitric acid aqueous solution volume ratio is 1g:(100～200)mL, and described mixed acid is mixed by the sulfuric acid aqueous solution that concentration is 18mol/L and the nitric acid aqueous solution that concentration is 16mol/L Forming, and concentration is that the sulfuric acid aqueous solution of 18mol/L and the volume ratio of the nitric acid aqueous solution of 16mol/L are 3:1, and the quality of described purifying single-walled carbon nanotubes and the volume ratio of mixed acid are 1g:(100 ~200) mL, the volume ratio of the mixed acid to deionized water is 1:(5~10);
二、制备单壁碳纳米管/酞菁复合材料：将步骤一得到的羧基化单壁碳纳米管在频率为40kHz的条件下超声分散于DMF中，得到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液，将浓度为10mg/mL的酞菁DMF溶液滴加到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液中，然后在频率为40kHz条件下避光超声震荡反应13h～48h，得到反应后的溶液，将反应后的溶液用0.20μm聚四氟乙烯过滤膜抽滤，得到单壁碳纳米管/酞菁复合材料粗产物，采用DMF对得到的单壁碳纳米管/酞菁复合材料粗产物离心洗涤至上层清液无色，然后采用氯仿离心洗涤至上层清液无色，最后采用乙醇离心洗涤3次，弃去清液，得到单壁碳纳米管/酞菁复合材料沉淀，然后将单壁碳纳米管/酞菁复合材料沉淀置于温度为60℃的真空干燥箱中干燥2h，得到单壁碳纳米管/酞菁复合材料；所述的浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液与浓度为10mg/mL的酞菁DMF溶液的体积比为1:(2～4)，所述的酞菁DMF溶液中的酞菁为戊烷氧基金属酞菁；2. Preparation of single-walled carbon nanotubes/phthalocyanine composites: the carboxylated single-walled carbon nanotubes obtained in step 1 were ultrasonically dispersed in DMF at a frequency of 40 kHz to obtain carboxylated single-walled carbon nanotubes with a concentration of 10 mg/mL Carbon nanotube DMF suspension, add the phthalocyanine DMF solution with a concentration of 10mg/mL dropwise to the carboxylated single-walled carbon nanotube DMF suspension with a concentration of 10mg/mL, and then oscillate in the dark at a frequency of 40kHz React for 13h to 48h to obtain the reacted solution, and filter the reacted solution with a 0.20μm polytetrafluoroethylene filter membrane to obtain a crude single-walled carbon nanotube/phthalocyanine composite material, and use DMF to treat the obtained single-walled carbon The crude product of the nanotube/phthalocyanine composite material was centrifugally washed until the supernatant was colorless, then centrifugally washed with chloroform until the supernatant was colorless, finally washed 3 times with ethanol, and the supernatant was discarded to obtain single-walled carbon nanotubes/ The phthalocyanine composite material is precipitated, and then the single-walled carbon nanotube/phthalocyanine composite material is precipitated and placed in a vacuum oven at a temperature of 60° C. for 2 hours to obtain a single-walled carbon nanotube/phthalocyanine composite material; the concentration is The volume ratio of the carboxylated single-walled carbon nanotube DMF suspension of 10mg/mL and the phthalocyanine DMF solution that concentration is 10mg/mL is 1:(2～4), and the phthalocyanine in the described phthalocyanine DMF solution is pentyl Alkoxy metal phthalocyanine;
三、滴涂：将步骤二得到的单壁碳纳米管/酞菁复合材料在频率为40kHz的条件下超声分散于DMF中，超声2h，得到浓度为0.1mg/mL～1.0mg/mL的单壁碳纳米管/酞菁复合材料DMF悬浮液，然后用注射器将浓度为0.1mg/mL～1.0mg/mL的单壁碳纳米管/酞菁复合材料DMF悬浮液1μL～30μL滴涂在叉指电极上，溶液蒸发后，将其放入真空干燥箱中，在温度为80℃的条件下干燥12h～48h，即得到以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件。3. Drop coating: ultrasonically disperse the single-walled carbon nanotube/phthalocyanine composite material obtained in step 2 in DMF at a frequency of 40 kHz, and ultrasonically for 2 hours to obtain a single-walled carbon nanotube/phthalocyanine composite material with a concentration of 0.1 mg/mL-1.0 mg/mL. Wall carbon nanotube/phthalocyanine composite DMF suspension, and then use a syringe to drop 1 μL to 30 μL of single-wall carbon nanotube/phthalocyanine composite DMF suspension with a concentration of 0.1 mg/mL to 1.0 mg/mL on the interdigital On the electrode, after the solution evaporates, put it in a vacuum drying oven, and dry it at a temperature of 80°C for 12h to 48h to obtain a gas sensor with single-walled carbon nanotube/phthalocyanine composite material as the ammonia sensitive material .
本实施方式利用无机材料优异的导电性和热、光与化学稳定性，有机材料分子可裁剪性、响应快、易加工等特点，将两者通过组分和结构的周期性变化形成复合材料，实现无机/有机材料的功能互补、优化和协同增强，从而提高单一气敏材料的气敏性能，以获得综合性能更加优异的气敏元件。This embodiment takes advantage of the excellent electrical conductivity, heat, light and chemical stability of inorganic materials, and the molecular tailorability, fast response, and easy processing of organic materials to form a composite material through periodic changes in components and structures. Realize the functional complementarity, optimization and synergistic enhancement of inorganic/organic materials, so as to improve the gas-sensing performance of a single gas-sensing material, and obtain a gas-sensing element with better comprehensive performance.
本实施方式制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件，室温下，在0.6ppm～80ppmNH3浓度范围内具有较好的响应，而在0.6ppm～40ppm低浓度NH3范围内NH3浓度与响应间具有良好的线性关系，可以检测到600ppb级NH3。The gas sensor prepared in this embodiment using the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material has a good response in the concentration range of 0.6ppm to 80ppmNH3 at room temperature, and has a good response in the concentration range of 0.6ppm to 40ppm. There is a good linear relationship between the NH 3 concentration and the response within the NH 3 concentration range, and 600ppb level NH 3 can be detected.
本实施方式制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件在不同浓度氨气中都具有良好的灵敏度、可逆性、稳定性，且对同浓度的CO2、CO、CH4和H2等气体没有响应，对NH3具有了良好的选择性。The gas sensor prepared in this embodiment using the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material has good sensitivity, reversibility, and stability in different concentrations of ammonia, and has good sensitivity to the same concentration of CO 2 , Gases such as CO, CH4 , and H2 had no response, and a good selectivity to NH3 was obtained.
本实施方式制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件大大提高了单壁碳纳米管的气敏性能，可以对NH3进行检测。The gas sensor prepared in this embodiment using the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material greatly improves the gas-sensing performance of the single-walled carbon nanotube, and can detect NH 3 .
具体实施方式四：本实施方式与具体实施方式三不同的是：步骤一中所述加热处理具体操作过程如下：在温度为40℃～60℃的条件下加热处理6h～12h。其它与具体实施方式三相同。Embodiment 4: This embodiment differs from Embodiment 3 in that: the specific operation process of the heat treatment in step 1 is as follows: heat treatment at a temperature of 40° C. to 60° C. for 6 hours to 12 hours. Others are the same as in the third embodiment.
具体实施方式五：本实施方式与具体实施方式四不同的是：所述加热处理具体操作过程如下：在温度为60℃的条件下加热处理6h。其它与具体实施方式四相同。Embodiment 5: This embodiment is different from Embodiment 4 in that: the specific operation process of the heat treatment is as follows: heat treatment at a temperature of 60° C. for 6 hours. Others are the same as in Embodiment 4.
具体实施方式六：本实施方式与具体实施方式三至五之一不同的是：步骤一中所述的单壁碳纳米管的质量与浓度为2mol/L～3mol/L硝酸水溶液的体积比为1g:(150～200)mL。其它与具体实施方式三至五之一相同。Specific embodiment six: this embodiment is different from one of specific embodiments three to five in that: the quality and concentration of the single-walled carbon nanotubes described in step one are 2mol/L～3mol/L and the volume ratio of the nitric acid aqueous solution is 1g: (150-200) mL. Others are the same as one of the third to fifth specific embodiments.
具体实施方式七：本实施方式与具体实施方式三至六之一不同的是：步骤二中所述的戊烷氧基金属酞菁结构式为
具体实施方式八：本实施方式与具体实施方式三至七之一不同的是：步骤二中所述的浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液与浓度为10mg/mL的酞菁DMF溶液的体积比为1:2。其它与具体实施方式三至七之一相同。Embodiment 8: The difference between this embodiment and one of Embodiments 3 to 7 is that the carboxylated single-walled carbon nanotube DMF suspension with a concentration of 10 mg/mL and the concentration of 10 mg/mL described in step 2 are different. The volume ratio of phthalocyanine DMF solution is 1:2. Others are the same as one of the third to seventh embodiments.
具体实施方式九：本实施方式与具体实施方式三至八之一不同的是：步骤二中将浓度为10mg/mL的酞菁DMF溶液滴加到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液中，然后在频率为40kHz条件下避光超声震荡反应24h。其它与具体实施方式三至八之一相同。Specific embodiment nine: the difference between this embodiment and one of the specific embodiments three to eight is that in step 2, the phthalocyanine DMF solution with a concentration of 10 mg/mL is added dropwise to the carboxylated single-walled carbon nanometer with a concentration of 10 mg/mL. Tube DMF suspension, and then under the condition of frequency of 40kHz sonication reaction in the dark for 24h. Others are the same as one of the third to eighth specific embodiments.
具体实施方式十：本实施方式与具体实施方式三至九之一不同的是：步骤三中用注射器将浓度为0.5mg/mL的单壁碳纳米管/酞菁复合材料10μLDMF悬浮液滴涂在叉指电极上。其它与具体实施方式三至九之一相同。Embodiment 10: The difference between this embodiment and one of Embodiments 3 to 9 is that in
采用下述试验验证本发明的效果：Adopt following test to verify effect of the present invention:
试验一：一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件的制备方法，按以下步骤进行：Test 1: A method for preparing a gas sensor using a single-walled carbon nanotube/phthalocyanine composite material as an ammonia-sensitive material, according to the following steps:
一、制备羧基化单壁碳纳米管：将1g单壁碳纳米管加入到100mL浓度为2.6mol/L硝酸水溶液中，于90℃温度下回流反应48h，过滤后得到滤饼，将滤饼分散于浓度为1mol/L盐酸水溶液中超声震荡10min，过滤，得到纯化单壁碳纳米管，然后将得到的纯化单壁碳纳米管置于100mL混酸中加热处理，加热处理温度为60℃，加热处理时间为6h，得到反应后的溶液，向反应后的溶液中加入500mL去离子水稀释，然后用0.20μm聚四氟乙烯过滤膜抽滤，得到羧基化单壁碳纳米管粗产物，用去离子水对得到的羧基化单壁碳纳米管粗产物水洗至滤液呈中性，最后在真空干燥箱中于温度为80℃的条件下干燥1天，得到羧基化单壁碳纳米管；所述的混酸由浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液混合而成，且浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液的体积比为3:1；1. Preparation of carboxylated single-walled carbon nanotubes: Add 1 g of single-walled carbon nanotubes to 100 mL of 2.6 mol/L nitric acid aqueous solution, reflux at 90 ° C for 48 hours, filter to obtain a filter cake, and disperse the filter cake Ultrasonic vibration in 1mol/L hydrochloric acid aqueous solution for 10min, filtration to obtain purified single-walled carbon nanotubes, and then place the obtained purified single-walled carbon nanotubes in 100mL mixed acid for heat treatment, the heat treatment temperature is 60°C, heat treatment The time is 6h, the solution after the reaction is obtained, 500mL of deionized water is added to the solution after the reaction to dilute, and then suction filtration is performed with a 0.20 μm polytetrafluoroethylene filter membrane to obtain the crude product of carboxylated single-walled carbon nanotubes, which is washed with deionized washing the crude product of carboxylated single-walled carbon nanotubes with water until the filtrate is neutral, and finally drying in a vacuum oven at a temperature of 80° C. for 1 day to obtain carboxylated single-walled carbon nanotubes; The mixed acid is formed by mixing an aqueous solution of sulfuric acid with a concentration of 18mol/L and an aqueous solution of nitric acid with a concentration of 16mol/L, and the volume ratio of the aqueous solution of sulfuric acid with a concentration of 18mol/L and the aqueous solution of nitric acid with a concentration of 16mol/L is 3:1;
二、制备单壁碳纳米管/酞菁复合材料：将步骤一得到的羧基化单壁碳纳米管在频率为40kHz的条件下超声分散于DMF中，得到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液，将20mL浓度为10mg/mL的四-3-异戊氧基酞菁铜DMF溶液滴加到10mL浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液中，然后在频率为40kHz条件下避光超声震荡反应13h～48h，得到反应后的溶液，将反应后的溶液用0.20μm聚四氟乙烯过滤膜抽滤，得到单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料粗产物，采用DMF对得到的单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料粗产物离心洗涤至上层清液无色，然后采用氯仿离心洗涤至上层清液无色，最后采用乙醇离心洗涤3次，弃去清液，得到单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料沉淀，然后将单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料沉淀置于温度为60℃的真空干燥箱中干燥2h，得到单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料；2. Preparation of single-walled carbon nanotubes/phthalocyanine composites: the carboxylated single-walled carbon nanotubes obtained in step 1 were ultrasonically dispersed in DMF at a frequency of 40 kHz to obtain carboxylated single-walled carbon nanotubes with a concentration of 10 mg/mL Carbon nanotube DMF suspension, 20mL concentration is that 10mg/mL tetrakis-3-isopentyloxyphthalocyanine copper DMF solution is added dropwise to 10mL concentration is in the carboxylated single-walled carbon nanotube DMF suspension of 10mg/mL, Then, under the condition of 40kHz frequency, avoid light and ultrasonically oscillate for 13h to 48h to obtain the reacted solution, and filter the reacted solution with a 0.20μm polytetrafluoroethylene filter membrane to obtain single-walled carbon nanotube/tetrafluoroethylene The crude product of the isopentyloxy phthalocyanine copper composite material was centrifuged and washed with DMF to the obtained single-walled carbon nanotube/tetrakis-3-isoamyloxy phthalocyanine copper composite material until the supernatant was colorless, and then washed with chloroform Wash by centrifugation until the supernatant is colorless, and finally use ethanol to wash by centrifugation for 3 times, discard the supernatant, and obtain the single-walled carbon nanotube/tetrakis-3-isoamyloxyphthalocyanine copper composite material precipitation, and then the single-walled carbon nanotube The tube/tetrakis-3-isoamyloxyphthalocyanine copper composite precipitate was placed in a vacuum oven at a temperature of 60°C and dried for 2 hours to obtain a single-walled carbon nanotube/tetrakis-3-isoamyloxyphthalocyanine copper composite material ;
三、滴涂：将步骤二得到的单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料在频率为40kHz的条件下超声分散于DMF中，超声2h，得到浓度为0.5mg/mL的单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料DMF悬浮液，然后用注射器将浓度为0.5mg/mL的单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料DMF悬浮液10μL滴涂在叉指电极上，溶液蒸发后，将其放入真空干燥箱中，在温度为80℃的条件下干燥12h，即得到以单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件。3. Drop coating: ultrasonically disperse the single-walled carbon nanotube/tetrakis-3-isoamyloxyphthalocyanine copper composite material obtained in step 2 in DMF at a frequency of 40 kHz, and ultrasonically for 2 hours to obtain a concentration of 0.5 mg /mL of SWNT/tetrakis-3-isoamyloxyphthalocyanine copper composite DMF suspension, and then use a syringe to inject single-walled carbon nanotubes/tetrakis-3-amyloxyphthalocyanine at a concentration of 0.5mg/
气敏元件的响应为在氨气中电阻值的变化值与在空气中电阻值的比值的100倍，响应时间和恢复时间为气敏元件达到阻值变化最大值的90%所需的时间。The response of the gas sensor is 100 times the ratio of the resistance change in ammonia to the resistance in air, and the response time and recovery time are the time required for the gas sensor to reach 90% of the maximum resistance change.
图1为本试验制备的以单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件的响应与氨气浓度关系曲线，从图1可以看出本试验制备的以单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件在0.6ppm～80ppmNH3浓度范围内具有较好的响应，而在低浓度2.5ppm～20ppmNH3范围NH3浓度与响应间具有良好的线性关系。Fig. 1 is the response and the ammonia concentration relation curve of the gas sensor with the single-walled carbon nanotube/tetra-3-isoamyloxyphthalocyanine copper composite material prepared in this test as the ammonia-sensitive material, as can be seen from Fig. 1 The gas sensor prepared in this experiment with the single-wall carbon nanotube/tetra-3-isoamyloxyphthalocyanine copper composite material as the ammonia-sensitive material has a good response in the range of 0.6ppm to 80ppmNH3 concentration, and at low There is a good linear relationship between the NH 3 concentration and the response in the range of 2.5ppm to 20ppmNH 3 .
图2为本试验制备的以单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件在不同浓度氨气中的响应恢复曲线，从图2可以看出本试验制备的以单壁碳纳米管/四-3-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件大大提高了单壁碳纳米管的恢复特性，室温下在不同浓度氨气中都具有良好的恢复性能，恢复时间为550s。Fig. 2 is the response recovery curve of the gas sensor of the ammonia-sensitive material in different concentrations of ammonia with the single-walled carbon nanotube/tetra-3-isoamyloxyphthalocyanine copper composite material prepared in this test, from Fig. 2 It can be seen that the gas sensor with single-walled carbon nanotubes/tetrakis-3-isoamyloxyphthalocyanine copper composite material prepared in this test as the ammonia-sensitive material has greatly improved the recovery characteristics of single-walled carbon nanotubes. It has good recovery performance even in concentrated ammonia gas, and the recovery time is 550s.
试验二：一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件的制备方法，按以下步骤进行：Experiment 2: A method for preparing a gas sensor using a single-walled carbon nanotube/phthalocyanine composite material as an ammonia-sensitive material, according to the following steps:
一、制备羧基化单壁碳纳米管：将1g单壁碳纳米管加入到100mL浓度为2.6mol/L硝酸水溶液中，于90℃温度下回流反应48h，过滤后得到滤饼，将滤饼分散于浓度为1mol/L盐酸水溶液中超声震荡10min，过滤，得到纯化单壁碳纳米管，然后将得到的纯化单壁碳纳米管置于100mL混酸中加热处理，加热处理温度为60℃，加热处理时间为6h，得到反应后的溶液，向反应后的溶液中加入500mL去离子水稀释，然后用0.20μm聚四氟乙烯过滤膜抽滤，得到羧基化单壁碳纳米管粗产物，用去离子水对得到的羧基化单壁碳纳米管粗产物水洗至滤液呈中性，最后在真空干燥箱中于温度为80℃的条件下干燥1天，得到羧基化单壁碳纳米管；所述的混酸由浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液混合而成，且浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液的体积比为3:1；1. Preparation of carboxylated single-walled carbon nanotubes: Add 1 g of single-walled carbon nanotubes to 100 mL of 2.6 mol/L nitric acid aqueous solution, reflux at 90 ° C for 48 hours, filter to obtain a filter cake, and disperse the filter cake Ultrasonic vibration in 1mol/L hydrochloric acid aqueous solution for 10min, filtration to obtain purified single-walled carbon nanotubes, and then place the obtained purified single-walled carbon nanotubes in 100mL mixed acid for heat treatment, the heat treatment temperature is 60°C, heat treatment The time is 6h, the solution after the reaction is obtained, 500mL of deionized water is added to the solution after the reaction to dilute, and then suction filtration is performed with a 0.20 μm polytetrafluoroethylene filter membrane to obtain the crude product of carboxylated single-walled carbon nanotubes, which is washed with deionized washing the crude product of carboxylated single-walled carbon nanotubes with water until the filtrate is neutral, and finally drying in a vacuum oven at a temperature of 80° C. for 1 day to obtain carboxylated single-walled carbon nanotubes; The mixed acid is formed by mixing an aqueous solution of sulfuric acid with a concentration of 18mol/L and an aqueous solution of nitric acid with a concentration of 16mol/L, and the volume ratio of the aqueous solution of sulfuric acid with a concentration of 18mol/L and the aqueous solution of nitric acid with a concentration of 16mol/L is 3:1;
二、制备单壁碳纳米管/酞菁复合材料：将步骤一得到的羧基化单壁碳纳米管在频率为40kHz的条件下超声分散于DMF中，得到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液，将20mL浓度为10mg/mL的四-4-异戊氧基酞菁铜DMF溶液滴加到10mL浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液中，然后在频率为40kHz条件下避光超声震荡反应13h～48h，得到反应后的溶液，将反应后的溶液用0.20μm聚四氟乙烯过滤膜抽滤，得到单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料粗产物，采用DMF对得到的单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料粗产物离心洗涤至上层清液无色，然后采用氯仿离心洗涤至上层清液无色，最后采用乙醇离心洗涤3次，弃去清液，得到单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料沉淀，然后将单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料沉淀置于温度为60℃的真空干燥箱中干燥2h，得到单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料；2. Preparation of single-walled carbon nanotubes/phthalocyanine composites: the carboxylated single-walled carbon nanotubes obtained in step 1 were ultrasonically dispersed in DMF at a frequency of 40 kHz to obtain carboxylated single-walled carbon nanotubes with a concentration of 10 mg/mL Carbon nanotube DMF suspension, the tetrakis-4-isoamyloxyphthalocyanine copper DMF solution that 20mL concentration is 10mg/mL is added dropwise in the carboxylated single-walled carbon nanotube DMF suspension that 10mL concentration is 10mg/mL, Then, under the condition of frequency 40kHz, avoid light and ultrasonically oscillate for 13h to 48h to obtain the reacted solution, and filter the reacted solution with a 0.20μm polytetrafluoroethylene filter membrane to obtain single-walled carbon nanotubes/tetrafluoroethylene The crude product of the isopentyloxyphthalocyanine copper composite material was centrifuged and washed with DMF to obtain the crude product of the single-walled carbon nanotube/tetrakis-4-isoamyloxyphthalocyanine copper composite material until the supernatant was colorless, and then washed with chloroform Wash by centrifugation until the supernatant is colorless, and finally use ethanol to wash by centrifugation for 3 times, discard the supernatant, and obtain the single-walled carbon nanotube/tetrakis-4-isoamyloxyphthalocyanine copper composite material precipitation, and then the single-walled carbon nanotube The tube/tetrakis-4-isoamyloxyphthalocyanine copper composite precipitate was placed in a vacuum oven at a temperature of 60°C and dried for 2 hours to obtain a single-walled carbon nanotube/tetrakis-4-isoamyloxyphthalocyanine copper composite material ;
三、滴涂：将步骤二得到的单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料在频率为40kHz的条件下超声分散于DMF中，超声2h，得到浓度为0.5mg/mL的单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料DMF悬浮液，然后用注射器将浓度为0.5mg/mL的单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料DMF悬浮液10μL滴涂在叉指电极上，溶液蒸发后，将其放入真空干燥箱中，在温度为80℃的条件下干燥12h，即得到以单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件。3. Drop coating: ultrasonically disperse the single-walled carbon nanotube/tetrakis-4-isoamyloxyphthalocyanine copper composite material obtained in step 2 in DMF at a frequency of 40 kHz, and ultrasonically for 2 hours to obtain a concentration of 0.5 mg /mL of SWNT/tetrakis-4-isoamyloxyphthalocyanine copper composite DMF suspension, and then use a syringe to inject single-walled carbon nanotubes/tetrakis-4-isoamyloxyphthalocyanine at a concentration of 0.5mg/
气敏元件的响应为在氨气中电阻值的变化值与在空气中电阻值的比值的100倍，响应时间和恢复时间为气敏元件达到阻值变化最大值的90%所需的时间。The response of the gas sensor is 100 times the ratio of the resistance change in ammonia to the resistance in air, and the response time and recovery time are the time required for the gas sensor to reach 90% of the maximum resistance change.
图3为本试验制备的以单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件的响应与氨气浓度关系曲线，从图3可以看出气敏元件在0.15ppm～80ppmNH3浓度范围内具有较好的响应，而在低浓度0.15ppm～2.5ppmNH3范围NH3浓度与响应间具有良好的线性关系。Fig. 3 is the response curve of the gas sensor with single-walled carbon nanotubes/tetra-4-isoamyloxyphthalocyanine copper composite material as the ammonia-sensitive material and the relationship curve of ammonia gas concentration prepared in this test. It can be seen from Fig. 3 that the gas The sensitive element has a good response in the concentration range of 0.15ppm-80ppmNH 3 , and has a good linear relationship between the concentration of NH 3 and the response in the range of low concentration 0.15ppm-2.5ppmNH 3 .
图4为本试验制备的以单壁碳纳米管/四-4-异戊氧基酞菁铜复合材料为氨敏材料的气敏元件在不同浓度氨气中的响应恢复曲线，从图4可以看出复合材料气敏元件大大提高了单壁碳纳米管的恢复特性，室温下在不同浓度氨气中都具有良好的恢复性能，恢复时间为900s。Fig. 4 is the response recovery curve of the gas sensor of the ammonia-sensitive material with single-walled carbon nanotubes/tetra-4-isoamyloxyphthalocyanine copper composite material prepared in this test in different concentrations of ammonia, from Fig. 4 It can be seen that the composite material gas sensor greatly improves the recovery characteristics of single-walled carbon nanotubes, and has good recovery performance in different concentrations of ammonia at room temperature, and the recovery time is 900s.
试验三：一种以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件的制备方法，按以下步骤进行：Experiment 3: A method for preparing a gas sensor using a single-walled carbon nanotube/phthalocyanine composite material as an ammonia-sensitive material, according to the following steps:
一、制备羧基化单壁碳纳米管：将1g单壁碳纳米管加入到100mL浓度为2.6mol/L硝酸水溶液中，于90℃温度下回流反应48h，过滤后得到滤饼，将滤饼分散于浓度为1mol/L盐酸水溶液中超声震荡10min，过滤，得到纯化单壁碳纳米管，然后将得到的纯化单壁碳纳米管置于100mL混酸中加热处理，加热处理温度为60℃，加热处理时间为6h，得到反应后的溶液，向反应后的溶液中加入500mL去离子水稀释，然后用0.20μm聚四氟乙烯过滤膜抽滤，得到羧基化单壁碳纳米管粗产物，用去离子水对得到的羧基化单壁碳纳米管粗产物水洗至滤液呈中性，最后在真空干燥箱中于温度为80℃的条件下干燥1天，得到羧基化单壁碳纳米管；所述的混酸由浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液混合而成，且浓度为18mol/L的硫酸水溶液和浓度为16mol/L的硝酸水溶液的体积比为3:1；1. Preparation of carboxylated single-walled carbon nanotubes: Add 1 g of single-walled carbon nanotubes to 100 mL of 2.6 mol/L nitric acid aqueous solution, reflux at 90 ° C for 48 hours, filter to obtain a filter cake, and disperse the filter cake Ultrasonic vibration in 1mol/L hydrochloric acid aqueous solution for 10min, filtration to obtain purified single-walled carbon nanotubes, and then place the obtained purified single-walled carbon nanotubes in 100mL mixed acid for heat treatment, the heat treatment temperature is 60°C, heat treatment The time is 6h, the solution after the reaction is obtained, 500mL of deionized water is added to the solution after the reaction to dilute, and then suction filtration is performed with a 0.20 μm polytetrafluoroethylene filter membrane to obtain the crude product of carboxylated single-walled carbon nanotubes, which is washed with deionized washing the crude product of carboxylated single-walled carbon nanotubes with water until the filtrate is neutral, and finally drying in a vacuum oven at a temperature of 80° C. for 1 day to obtain carboxylated single-walled carbon nanotubes; The mixed acid is formed by mixing an aqueous solution of sulfuric acid with a concentration of 18mol/L and an aqueous solution of nitric acid with a concentration of 16mol/L, and the volume ratio of the aqueous solution of sulfuric acid with a concentration of 18mol/L and the aqueous solution of nitric acid with a concentration of 16mol/L is 3:1;
二、制备单壁碳纳米管/酞菁复合材料：将步骤一得到的羧基化单壁碳纳米管在频率为40kHz的条件下超声分散于DMF中，得到浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液，将20mL浓度为10mg/mL的四-3-2,2,4三甲基-3-戊氧基酞菁铜DMF溶液滴加到10mL浓度为10mg/mL的羧基化单壁碳纳米管DMF悬浮液中，然后在频率为40kHz条件下避光超声震荡反应13h～48h，得到反应后的溶液，将反应后的溶液用0.20μm聚四氟乙烯过滤膜抽滤，得到单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料粗产物，采用DMF对得到的单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料粗产物离心洗涤至上层清液无色，然后采用氯仿离心洗涤至上层清液无色，最后采用乙醇离心洗涤3次，弃去清液，得到单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料沉淀，然后将单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料沉淀置于温度为60℃的真空干燥箱中干燥2h，得到单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料；2. Preparation of single-walled carbon nanotubes/phthalocyanine composites: the carboxylated single-walled carbon nanotubes obtained in step 1 were ultrasonically dispersed in DMF at a frequency of 40 kHz to obtain carboxylated single-walled carbon nanotubes with a concentration of 10 mg/mL Carbon nanotube DMF suspension, 20mL tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper DMF solution with a concentration of 10mg/mL was added dropwise to 10mL carboxylation solution with a concentration of 10mg/mL Single-walled carbon nanotube DMF suspension, and then under the condition of frequency of 40kHz, avoid light and ultrasonic shock for 13h to 48h to obtain the reacted solution, and filter the reacted solution with a 0.20μm polytetrafluoroethylene filter membrane to obtain The crude product of single-walled carbon nanotubes/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite material, using DMF to obtain single-walled carbon nanotubes/tetrakis-3-2,2 , 4 The crude product of trimethyl-3-pentyloxyphthalocyanine copper composite material was centrifugally washed until the supernatant was colorless, then centrifugally washed with chloroform until the supernatant was colorless, finally washed 3 times by ethanol centrifugally, and the supernatant was discarded. solution, to obtain single-walled carbon nanotubes/tetra-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite material precipitation, and then single-walled carbon nanotubes/tetra-3-2,2, 4 The precipitation of trimethyl-3-pentyloxyphthalocyanine copper composite material was placed in a vacuum drying oven at a temperature of 60°C and dried for 2 hours to obtain single-walled carbon nanotubes/tetra-3-2,2,4 trimethyl- 3-pentyloxyphthalocyanine copper composite material;
三、滴涂：将步骤二得到的单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料在频率为40kHz的条件下超声分散于DMF中，超声2h，得到浓度为0.5mg/mL的单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料DMF悬浮液，然后用注射器将浓度为0.5mg/mL的单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料DMF悬浮液10μL滴涂在叉指电极上，溶液蒸发后，将其放入真空干燥箱中，在温度为80℃的条件下干燥12h，即得到以单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料为氨敏材料的气敏元件。3. Drop coating: ultrasonically disperse the single-walled carbon nanotube/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite material obtained in step 2 in DMF at a frequency of 40kHz , sonicate for 2 hours to obtain a single-walled carbon nanotube/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite DMF suspension with a concentration of 0.5 mg/mL, and then use a syringe to 10 μL of single-walled carbon nanotube/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite DMF suspension with a concentration of 0.5 mg/mL was drop-coated on the interdigitated electrode, and the solution was evaporated Afterwards, put it into a vacuum drying oven and dry it for 12 hours at a temperature of 80°C to obtain the The copper cyanine composite material is the gas sensor of the ammonia sensitive material.
气敏元件的响应为在氨气中电阻值的变化值与在空气中电阻值的比值的100倍，响应时间和恢复时间为气敏元件达到阻值变化最大值的90%所需的时间。The response of the gas sensor is 100 times the ratio of the resistance change in ammonia to the resistance in air, and the response time and recovery time are the time required for the gas sensor to reach 90% of the maximum resistance change.
图5为本试验制备的以单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料为氨敏材料的气敏元件的响应与氨气浓度关系曲线，从图5可以看出气敏元件在0.6ppm～80ppmNH3浓度范围内具有较好的响应，而在低浓度2.5ppm～40ppmNH3范围NH3浓度与响应间具有良好的线性关系。Figure 5 shows the response of the gas sensor with single-walled carbon nanotubes/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite material as the ammonia sensitive material and the ammonia gas Concentration relationship curve, it can be seen from Figure 5 that the gas sensor has a good response in the range of 0.6ppm to 80ppmNH 3 concentration, and a good linear relationship between NH 3 concentration and response in the low concentration range of 2.5ppm to 40ppmNH 3 .
图6为本试验制备的以单壁碳纳米管/四-3-2,2,4三甲基-3-戊氧基酞菁铜复合材料为氨敏材料的气敏元件在不同浓度氨气中的响应恢复曲线，从图6可以看出复合材料气敏元件大大提高了单壁碳纳米管的恢复特性，室温下在不同浓度氨气中都具有良好的恢复性能，恢复时间为200s。Figure 6 shows the gas sensor prepared in this experiment with single-walled carbon nanotube/tetrakis-3-2,2,4 trimethyl-3-pentyloxyphthalocyanine copper composite material as the ammonia sensitive material under different concentrations of ammonia gas. From the response recovery curve in Figure 6, it can be seen that the composite material gas sensor greatly improves the recovery characteristics of single-walled carbon nanotubes, and has good recovery performance in different concentrations of ammonia at room temperature, and the recovery time is 200s.
综上所述，室温下，本发明制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件对NH3具有了良好的选择性、灵敏度、可逆性和稳定性，通过单壁碳纳米管和酞菁材料的复合，实现了两者的功能互补、协同优化；本发明制备的以单壁碳纳米管/酞菁复合材料为氨敏材料的气敏元件可以检测0.6ppm～80ppm浓度范围NH3，适合作为氨敏元件，在实际生产、生活中具有广泛的应用前景。In summary, at room temperature, the gas sensor prepared by the present invention takes the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material to NH Good selectivity, sensitivity, reversibility and stability, through The combination of single-walled carbon nanotubes and phthalocyanine materials realizes the functional complementarity and synergistic optimization of the two; the gas sensor prepared by the present invention with single-walled carbon nanotubes/phthalocyanine composite materials as ammonia-sensitive materials can detect 0.6ppm NH 3 with a concentration range of ~80ppm is suitable as an ammonia sensitive element and has broad application prospects in actual production and life.
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| CN103616415A (en) * | 2013-12-19 | 2014-03-05 | 黑龙江大学 | Room-temperature oxidized graphene/phthalocyanin composite ammonia sensitive element and preparation method thereof |
| CN104176726A (en) * | 2014-09-05 | 2014-12-03 | 黑龙江大学 | Preparation method of N,N-dialkyl substituted metal phthalocyanine/carbon nanotube composite material |
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| CN103616415B (en) * | 2013-12-19 | 2016-04-13 | 黑龙江大学 | Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements and preparation method thereof |
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| CN108362741A (en) * | 2018-02-27 | 2018-08-03 | 上海交通大学 | A kind of preparation method and its application method of the gas sensor based on metal phthalocyanine |
| CN108362741B (en) * | 2018-02-27 | 2020-09-08 | 上海交通大学 | Preparation method and use method of gas sensor based on metal phthalocyanine |
| CN109030588A (en) * | 2018-05-28 | 2018-12-18 | 新疆大学 | A kind of preparation method of ozone gas sensor array |
| CN110927218A (en) * | 2019-12-10 | 2020-03-27 | 苏州慧闻纳米科技有限公司 | Preparation method of gas-sensitive material for detecting nitrogen dioxide and gas sensor |
| CN111721812A (en) * | 2019-12-18 | 2020-09-29 | 中国科学院上海微***与信息技术研究所 | A kind of sensor material and preparation method, sensor and application in CO detection |
| CN112047326A (en) * | 2020-09-14 | 2020-12-08 | 中国科学院长春光学精密机械与物理研究所 | Carbon nanotube phthalocyanine nanocomposite and preparation method and application thereof |
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