CN108362741B - Preparation method and use method of gas sensor based on metal phthalocyanine - Google Patents
Preparation method and use method of gas sensor based on metal phthalocyanine Download PDFInfo
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- CN108362741B CN108362741B CN201810162282.3A CN201810162282A CN108362741B CN 108362741 B CN108362741 B CN 108362741B CN 201810162282 A CN201810162282 A CN 201810162282A CN 108362741 B CN108362741 B CN 108362741B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
The invention provides a preparation method and a use method of a gas sensor based on metal phthalocyanine. The invention also provides a using method of the metal phthalocyanine-based gas sensor, the using method comprises the steps of placing the sensor in a closed cavity, filling detection gas with preset concentration in the closed cavity and maintaining the atmosphere of the gas with the preset concentration, filling dry air or nitrogen in the closed cavity during recovery, and irradiating the sensor with laser to desorb the detection gas.
Description
Technical Field
The invention belongs to the field of gas detection, and particularly relates to a preparation method and a use method of a gas sensor.
Background
At present, commercial gas sensors mainly comprise traditional metal oxide semiconductor sensors and solid electrolyte sensors, the detection concentration of the gas sensors is in the order of one Part Per Million (ppm), and the gas sensors have the problems of high power consumption, low sensitivity, poor interference resistance and the like due to the need of working at higher temperature.
Metal Phthalocyanine (MPc) has a unique macrocyclic conjugated structure, is an organic semiconductor material with excellent performance, and can be used as a sensitive material to prepare an organic gas sensor. Compared with the traditional metal oxide semiconductor sensor and the solid electrolyte sensor, the MPC gas sensor has the advantages of rich raw material sources, low cost, simple film making process, easy compatibility with other technologies and the like. More importantly, the MPc molecules have structure tailorability, and can controllably adjust central metal, conjugated plane electron cloud and peripheral substituent groups in the MPc molecules, so that the MPc molecules have high detection sensitivity and good selectivity at room temperature for specific gas molecules.
However, the response and recovery time of metal phthalocyanine is long, and even the metal phthalocyanine cannot be recovered to the starting position, as compared with a metal semiconductor type gas sensor, which poses a great problem for its commercial application. In addition, the gas sensor based on the metal phthalocyanine also needs to be heated properly to show excellent response performance, which brings about no small difficulty in manufacturing the sensor.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a preparation method of a gas sensor based on metal phthalocyanine and a use method thereof, which are used for solving the problems that the metal phthalocyanine gas sensor in the prior art is slow in response and recovery speed and cannot be detected at normal temperature.
To achieve the above and other related objects, the present invention provides a method for preparing a metal phthalocyanine-based gas sensor, comprising: dissolving metal phthalocyanine in a mixed solution of N, N-Dimethylformamide (DMF) and water, dripping the mixed solution on the surface of an electrode, and drying to form a metal phthalocyanine film covering the electrode; the electrodes are interdigital electrodes.
Preferably, the average film thickness of the metal phthalocyanine film is 50-500 nm, the metal phthalocyanine film is composed of nanofibers, and the average length of the nanofibers is 50-500 nm.
Preferably, the mass ratio of DMF to water is 0.1-10: 1.
Preferably, the preparation of the metal phthalocyanine comprises the following steps:
step 1: mixing and grinding trimellitic anhydride, urea, divalent metal chloride and ammonium molybdate into powder, adding the ground powder into a container, heating to 180-250 ℃, and keeping for 6-24 hours;
step 2: soaking the product obtained in the step 1 in 0.5-2 mol/L hydrochloric acid solution for 12-24 hours, and filtering and washing to enable the pH value of the product to reach 6-8;
and step 3: transferring the product obtained in the step 2 into a container, boiling the product for 20-120 minutes by using a sodium hydroxide solution with the concentration of 0.5-2 mol/L, and filtering or centrifuging the product to obtain a solid product;
and 4, step 4: transferring the solid product obtained in the step 3 into a container, adding a saturated sodium chloride solution containing 0.5-2 mol/L of sodium hydroxide, and refluxing for 6-12 hours at the temperature of 80-100 ℃;
and 5: after the solution is cooled, adding the solution into distilled water, and removing insoluble substances by filtration or centrifugation;
step 6: and (3) dropwise adding hydrochloric acid into the solution obtained in the step (5), adjusting the pH to be below 3, standing for 8-48 hours, filtering out precipitates in the solution, washing with methanol and distilled water, and finally drying to obtain the metal phthalocyanine.
Preferably, the divalent metal chloride is CuCl2、FeCl2、NiCl2、CoCl2Or ZnCl2。
Preferably, the metal phthalocyanine is a tetracarboxyl metal phthalocyanine having the general formula MPC (COOH)4Wherein M is Cu, Fe, Ni, Co or Zn.
Preferably, the mixed molar ratio of the trimellitic anhydride, the urea, the divalent metal chloride and the ammonium molybdate is as follows: 400: 2000-4000: 100-200: 1 to 5.
The invention also provides a use method of the gas sensor based on the metal phthalocyanine, which comprises the following steps
Step 1: placing the gas sensor based on the metal phthalocyanine in a closed cavity, filling dry air or nitrogen, and applying voltage to the gas sensor based on the metal phthalocyanine;
step 2: filling detection gas with preset concentration into the closed cavity and maintaining the atmosphere of the gas with the preset concentration;
and step 3: and filling dry air or nitrogen into the closed cavity, and irradiating the metal phthalocyanine-based gas sensor by using laser to desorb the detection gas.
Preferably, the detection gas is NO2、NO、SO2、Cl2Or O3One or more of the above gases.
Preferably, the laser wavelength is 390-500 nm, and the laser power is 10-500 mW.
Preferably, the laser irradiation incidence angle is 0-60 degrees, and the laser irradiation distance is 0-30 cm.
As described above, the preparation method and the use method of the gas sensor based on the metal phthalocyanine provided by the invention have the following advantages:
1) the invention provides a simple film forming process, which is characterized in that metal phthalocyanine is dissolved in a mixed solution of DMF and water and then is dripped on an electrode to form a uniform film, and the phthalocyanine can be effectively crystallized into nanofibers to form a conductive network, thereby accelerating electronic conduction and improving the response speed of gas sensitivity.
2) Compared with the traditional phthalocyanine synthesis method, the method has the advantages of simple synthesis steps, high synthesis speed and high yield.
3) The invention provides a using method of a gas sensor, which uses laser irradiation to assist recovery and greatly increases the recovery speed of a metal phthalocyanine gas sensor.
4) The metal phthalocyanine gas-sensitive detection provided by the invention has low limit and good selectivity.
The conception, the specific technical solutions and the technical effects produced by the present invention will be further described with reference to the preferred embodiments so that the objects, the features and the effects of the present invention can be fully understood.
Drawings
FIG. 1 is a scanning electron microscope test chart of a synthesized metal phthalocyanine according to a preferred embodiment of the present invention;
FIG. 2 is a scanning electron microscope test chart of dropping metal phthalocyanine on interdigital electrodes according to a preferred embodiment of the present invention;
FIG. 3 shows a preferred embodiment of the present invention with the sensor placed at a concentration of 50ppm NO2A measured gas sensitive response plot in a gas;
FIG. 4 is a drawing of the present inventionThe sensor of the preferred embodiment is placed at a concentration of 50ppb to 50ppm NO2A measured gas sensitive response plot in a gas;
FIG. 5 is a gas-sensitive test chart of a sensor of a preferred embodiment of the present invention placed in an atmosphere of a plurality of different gases.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example 1:
the embodiment provides a preparation method of a gas sensor based on metal phthalocyanine, which comprises the following steps: dissolving metal phthalocyanine in a mixed solution of DMF and water with the mass ratio of 1:1, dripping the solution on an electrode to form a metal phthalocyanine film covered on the electrode, wherein the average film thickness of the film is 200 nm; the metal phthalocyanine film is composed of nano fibers, and the average length of the nano fibers is 200 nm; the electrodes are interdigital electrodes.
The preparation of the metal phthalocyanine comprises the following steps:
step 1: mixing trimellitic anhydride, urea and CoCl2Mixing ammonium molybdate according to the molar ratio of 400:2500:150:1, grinding into powder, adding the ground powder into a container, heating to 200 ℃, and keeping for 12 hours;
step 2: soaking the product obtained in the step 1 in 1mol/L hydrochloric acid for 14 hours, filtering and washing to ensure that the pH value of the product reaches 7;
and step 3: transferring the product obtained in the step 2 into a container, boiling the product for 60 minutes by using a sodium hydroxide solution with the concentration of 1mol/L, and filtering the product to obtain a solid product;
and 4, step 4: transferring the solid product obtained in the step 3 into a container, adding a saturated sodium chloride solution containing 1mol/L of sodium hydroxide, and refluxing at the temperature of 100 ℃ for 8 hours;
and 5: after the solution is cooled, adding the solution into distilled water, and removing insoluble substances by filtration;
step 6: dropwise adding hydrochloric acid into the solution obtained in the step 5, adjusting the pH to 2, standing for 14 hours, filtering out precipitates in the solution, washing with methanol and distilled water, and finally drying to obtain tetracarboxy cobalt phthalocyanine CoPc (COOH)4。
FIG. 1 is a scanning electron microscope test chart of the metal phthalocyanine synthesized in the present example; FIG. 2 is a scanning electron microscope test chart of the present example in which metal phthalocyanine is dropped on interdigital electrodes. It can be seen from the figure that the preparation method of the metal phthalocyanine of the embodiment has uniform film formation, good crystallinity in the mixed solution of DMF and water, and easy formation of a conductive network.
Example 2
According to example 1, the present implementation provides a method of using a metal phthalocyanine-based gas sensor, comprising the steps of:
step 1: placing the sensor in a closed cavity, charging dry air, and applying 0.5V voltage to the sensor;
step 2: 50ppm of NO is introduced into the closed cavity2Gas and maintaining the concentration gas atmosphere;
and step 3: filling dry air into the sealed cavity, and irradiating the sensor with laser with wavelength of 395nm and power of 50mW to make NO in the sealed cavity2And (4) desorption, wherein the laser irradiation incidence angle is 0 DEG, and the laser irradiation distance is 10 cm.
FIG. 3 shows the sensor of this example placed at a concentration of 50ppm NO2The recovery part adopts laser irradiation assistance to measure a gas-sensitive response graph in gas. Wherein Ig is the current value after the test gas is introduced, and Ia is the current value when the dry air is introduced; FIG. 4 shows the sensor of this example placed at a concentration of 50ppb to 50ppm of NO2A measured gas sensitive response plot in a gas; fig. 5 is a gas-sensitive test chart obtained by placing the sensor in the atmosphere of a plurality of different gases in the present embodiment. As can be seen from the figure, the gas sensor NO based on the metal phthalocyanine2The response sensitivity is high, the recovery speed is high under the assistance of laser irradiation, and the method has a lower response limit and excellent selectivity.
Example 3
The embodiment provides a preparation method of a gas sensor based on metal phthalocyanine, which comprises the following steps: dissolving metal phthalocyanine in a mixed solution of DMF and water with the mass ratio of 2:1, dripping the solution on an electrode to form a metal phthalocyanine film covered on the electrode, wherein the average film thickness of the film is 100 nm; the metal phthalocyanine film is composed of nano fibers, and the average length of the nano fibers is 100 nm; the electrodes are interdigital electrodes.
The preparation of the metal phthalocyanine comprises the following steps:
step 1: mixing trimellitic anhydride, urea and NiCl2Mixing and grinding ammonium molybdate according to the molar ratio of 400:3000:180:4 into powder, adding the ground powder into a container, heating to 220 ℃, and keeping for 18 hours;
step 2: soaking the product obtained in the step 1 in 1.5mol/L hydrochloric acid for 18 hours, filtering and washing to ensure that the pH value of the product reaches 7.5;
and step 3: transferring the product obtained in the step 2 into a container, boiling the product for 40 minutes by using a sodium hydroxide solution with the concentration of 1.5mol/L, and centrifuging the product to obtain a solid product;
and 4, step 4: transferring the solid product obtained in the step (3) into a container, adding a saturated sodium chloride solution containing 1.5mol/L sodium hydroxide, and refluxing at the temperature of 95 ℃ for 10 hours;
and 5: after the solution is cooled, adding the solution into distilled water, and removing insoluble substances through centrifugation;
step 6: dropwise adding hydrochloric acid into the solution obtained in the step 5, adjusting the pH to 1, standing for 18 hours, filtering out precipitates in the solution, washing with methanol and distilled water, and finally drying to obtain tetracarboxy nickel phthalocyanine NiPc (COOH)4。
Example 4
According to example 3, the present implementation provides a method of using a metal phthalocyanine-based gas sensor, comprising the steps of:
step 1: placing a sensor in a closed cavity, filling nitrogen, and applying 0.5V voltage to the sensor;
step 2: 50ppm of gas is introduced into the closed cavityNO of2Gas and maintaining the concentration gas atmosphere;
and step 3: filling nitrogen into the sealed cavity, and irradiating the sensor with laser with wavelength of 450nm and power of 100mW to make NO in the sealed cavity2And (4) desorption, wherein the laser irradiation incidence angle is 20 degrees, and the laser irradiation distance is 15 cm.
In conclusion, the preparation method of the metal phthalocyanine provided by the embodiment of the invention has the advantages that the film is formed uniformly, the crystallization property in the mixed solution of DMF and water is good, and a conductive network is easy to form; gas sensor NO based on the metal phthalocyanine2The response sensitivity is high, the recovery speed is high under the assistance of laser irradiation, and the method has a lower response limit and excellent selectivity.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (5)
1. The preparation method of the gas sensor based on the metal phthalocyanine is characterized by dissolving the metal phthalocyanine in a mixed solution of N, N-dimethylformamide and water, dripping the mixed solution on the surface of an electrode, drying the mixed solution to form a metal phthalocyanine film covering the electrode, wherein the mass ratio of the N, N-dimethylformamide to the water in the mixed solution is 1-2: 1, the average film thickness of the metal phthalocyanine film is 100-200 nm, the metal phthalocyanine film is composed of nanofibers, the average length of the nanofibers is 100-200 nm, and the electrode is an interdigital electrode.
2. The method for preparing a gas sensor based on metal phthalocyanine according to claim 1, wherein the metal phthalocyanine is prepared by the following method, specifically comprising:
step 1: mixing trimellitic anhydride, urea, divalent metal chloride and ammonium molybdate according to a molar ratio of 400: 2500-3000: 150-180: 1-4, grinding into powder, adding the ground powder into a container, heating to 200-220 ℃, and keeping for 12-18 hours; wherein the divalent metal chloride is NiCl2 or CoCl 2; the metal phthalocyanine is tetracarboxyl metal phthalocyanine with a general formula of MPC (COOH)4, wherein M is Ni or Co;
step 2: soaking the product obtained in the step 1 in 1-1.5 mol/L hydrochloric acid solution for 14-18 hours, filtering and washing to enable the pH value of the product to reach 7-7.5;
and step 3: transferring the product obtained in the step 2 into a container, boiling the product for 40-60 minutes by using a sodium hydroxide solution with the concentration of 1-1.5 mol/L, and filtering or centrifuging the product to obtain a solid product;
and 4, step 4: transferring the solid product obtained in the step 3 into a container, adding a saturated sodium chloride solution containing 1-1.5 mol/L of sodium hydroxide, and refluxing at the temperature of 95-100 ℃ for 8-10 hours;
and 5: after the solution is cooled, adding the solution into distilled water, and removing insoluble substances by filtration or centrifugation;
step 6: and (3) dropwise adding hydrochloric acid into the solution obtained in the step (5), adjusting the pH to be below 1-2, standing for 14-18 hours, filtering out precipitates in the solution, washing with methanol and distilled water, and finally drying to obtain the metal phthalocyanine.
3. A method for using a metal phthalocyanine-based gas sensor manufactured by the manufacturing method according to any one of claims 1 to 2, comprising the steps of:
step 1: placing the gas sensor based on the metal phthalocyanine in a closed cavity, filling dry air or nitrogen, and applying voltage to the gas sensor based on the metal phthalocyanine;
step 2: filling detection gas with preset concentration into the closed cavity and maintaining the atmosphere of the gas with the preset concentration;
and step 3: and filling dry air or nitrogen into the closed cavity, and irradiating the metal phthalocyanine-based gas sensor by using laser to desorb the detection gas.
4. The method of claim 3, wherein the detection gas is NO2、NO、SO2、Cl2And O3One or more of the above gases.
5. The method of claim 3, wherein the laser wavelength is 390 to 500nm, the laser power is 10 to 500mW, the laser irradiation angle is 0 to 60 °, and the laser irradiation distance is 0 to 30 cm.
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| TWI675197B (en) * | 2018-12-27 | 2019-10-21 | 國立交通大學 | Gas-sensing apparatus |
| CN109828003B (en) * | 2019-02-18 | 2021-07-23 | 中国石油大学(华东) | Inorganic doping modification method for phthalocyanine molecular semiconductor material containing crown ether based on cadmium sulfide |
| CN111721812A (en) * | 2019-12-18 | 2020-09-29 | 中国科学院上海微***与信息技术研究所 | Sensor material, preparation method thereof, sensor and application of sensor in CO detection |
| CN113029239A (en) * | 2021-03-11 | 2021-06-25 | 昆山联鲸仪智能科技有限公司 | Multifunctional sensor and preparation method thereof |
| CN113777137A (en) * | 2021-09-24 | 2021-12-10 | 昆明学院 | Gas sensor based on chromium phthalocyanine monomolecular layer film and preparation method and application thereof |
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