CN109030588B - Preparation method of ozone gas sensor array - Google Patents
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- CN109030588B CN109030588B CN201810520398.XA CN201810520398A CN109030588B CN 109030588 B CN109030588 B CN 109030588B CN 201810520398 A CN201810520398 A CN 201810520398A CN 109030588 B CN109030588 B CN 109030588B
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Abstract
The invention relates to a preparation method of an ozone gas sensor array. A method of making an ozone gas sensor array, comprising: (1) preparing a modifier solution; (2) preparing a carbon nanotube dispersion liquid; (3) standing and centrifuging the carbon nano tube dispersion liquid to obtain a precipitate; (4) mixing the precipitate with water, coating the mixture on the interdigital electrode, and drying to obtain a sensing chip; manufacturing a sensor chip into a sensor to obtain a sensor 1; (5) repeating the steps (1) to (4) for 5 times to obtain a sensor 2 to 6; (6) and electrifying and aging the sensors 1-6 to form a sensor array, thereby obtaining the ozone gas sensor array. According to the preparation method of the ozone gas sensor array, disclosed by the invention, the carbonyl multi-walled carbon nano-tubes are physically modified by using various micromolecular modifiers, so that the carbon nano-tube-based sensor array is prepared, and high sensitivity and identification and detection of ozone and common interferents thereof at room temperature are realized.
Description
Technical Field
The invention belongs to the technical field of gas-sensitive sensing detection, and particularly relates to a preparation method of an ozone gas-sensitive sensor array.
Background
According to the information issued by the central station of environmental monitoring in China, the ozone concentrations of Jingjin Ji and Long triangle have remarkable year-by-year rising trends in three key areas (Jingjin Ji, Long triangle and bead triangle) since 2013, and particularly the rising of the ozone concentrations of Jingjin Ji and Long triangle is most remarkable in 2017. And displaying subsequent monitoring data: in the 5 th month of 2017, the average exceeding-standard rate of ozone in 74 cities is 32.7%, and from the month, the first pollutants in the 74 cities, which continuously exceed the standard days for 5 months, are ozone. Since ozone comes mostly from a large number of artificial sources (nitrogen oxides NO)XAnd waveVolatile Organic Compounds (VOCs) generated through a series of photochemical reactions under the illumination condition, and the concentration of the secondary pollutants is closely related to the meteorological condition. The reaction is most severe under conditions of high temperature, strong sunlight, low humidity and calm wind, with ultraviolet radiation being the most critical factor. The Xinjiang area belongs to a typical continental arid climate, is rich in light and heat, dry in weather and strong in ultraviolet, and is not beneficial to the diffusion of pollutants due to the addition of the topographic characteristics of 'three mountains with two pots' in Xinjiang, so that the Xinjiang area faces a severe threat of ozone pollution. Ozone, as a major component of photochemical smog, severely affects local air quality, and increases in its concentration can directly harm human and animal health and plant growth. Furthermore, ozone can work in conjunction with other pollutants, for example, ozone can increase the harm of PM (respirable particulate matter) to humans, which can also increase the harm of ozone. In 2008, the national environmental protection agency stipulates: the average maximum value of ozone in 8h per day can not be higher than 75ppb, and the average maximum value of ozone in 8h per day in a room can not be higher than 50 ppb. This puts higher demands on the detection technology of ozone and ozone precursors. At present, the common methods for ozone detection mainly comprise: iodometry, spectrophotometry, electrochemistry, ultraviolet spectroscopy, etc. Among them, the ultraviolet spectroscopy is widely studied and applied because of its clear mechanism for ozone detection, mature technology, and stable and reliable performance. However, the uv spectroscopy has the disadvantages of large size, high cost, and single detection function, and its practical application range is limited.
A gas sensor is a device that measures the type, concentration, and composition of a gas. At present, the chemical resistance type gas sensor is widely applied due to the advantages of simple preparation, small volume, convenient integration, high sensitivity, low requirement on working environment and the like. Among them, the most typical metal oxide-based gas sensors have a wide enough band gap to react with many target gases, but such gas sensors have the defects of high operating temperature (200 ℃.), large power consumption, poor selectivity, etc. The conductive polymer sensor has the disadvantages of low sensitivity and selectivity, poor stability and weather resistance and long response time (generally about 2-10 minutes) to target gas although the cost is low. The carbon nano tube has the characteristics of large specific surface area, abundant reaction sites, good conductivity, weather resistance and stability and sensitivity to the environment, so that the carbon nano tube becomes an ideal gas-sensitive sensing material. Generally, the presence of various atmospheric pollutants, such as ethanol, formaldehyde and water vapor, can cause great interference in the highly sensitive detection of ozone.
In view of this, the invention provides a high-sensitivity carbon nanotube-based ozone gas sensor array and a preparation method thereof, and the gas sensor array can identify and detect ozone and common interferent thereof at room temperature.
Disclosure of Invention
The invention aims to provide a preparation method of an ozone gas sensor array, which is simple, the prepared ozone gas sensor array can be used for identifying and detecting ozone and common interferents at room temperature, and the sensitivity is high.
In order to realize the purpose, the adopted technical scheme is as follows:
a preparation method of an ozone gas sensor array comprises the following steps:
(1) dissolving a micromolecular modifier in deionized water, and performing ultrasonic dispersion to obtain a modifier solution with the molar concentration of 0.8-1.2 mmol/L; wherein the micromolecular modifier is hydroxylamine hydrochloride;
(2) mixing the carboxylated carbon nanotube powder and the modifier solution according to the weight ratio of 0.02 g: 3-5ml of the carbon nano tube dispersion liquid is obtained by uniformly mixing the components in a mass-volume ratio;
(3) standing the carbon nano tube dispersion liquid at room temperature for 46-50h, and centrifuging to obtain a precipitate;
(4) uniformly mixing the precipitate and deionized water according to the mass ratio of 1:3.5-4.5 to obtain paste;
uniformly coating the paste on the interdigital electrode, and drying at room temperature for 12-24h to obtain a sensing chip;
manufacturing a sensor chip into a sensor to obtain a sensor 1;
(5) repeating the steps (1) to (4) for 5 times to obtain a sensor 2, a sensor 3, a sensor 4, a sensor 5 and a sensor 6 in sequence; wherein the micromolecule modifier is composed of aminoacetic acid, succinic acid, hexadecyl trimethyl ammonium bromide, 8-hydroxy quinaldine and pyrene in sequence;
(6) and continuously applying a voltage of 0.1V to the two ends of the sensors 1-6, electrifying and aging for 22-26h to form a sensor array, thus obtaining the ozone gas sensor array.
Further, in the step (1), the time of ultrasonic dispersion is 8-12 min.
Still further, in the step (1), the molar concentration of the modifier solution is 1 mmol/L;
the time of ultrasonic dispersion is 10 min.
Further, in the step (2), the carbon nanotube dispersion liquid is obtained by mixing the carboxylated carbon nanotube powder with the modifier solution and then performing ultrasonic dispersion for 30-60 min.
Still further, in the step (2), the ratio of the carbon nanotube powder and the modifier solution is in the range of 0.02 g: 4ml of the mixture was mixed at a mass/volume ratio.
Further, in the step (3), the carbon nanotube dispersion liquid is kept still at room temperature for 48 hours.
Further, in the step (4), the sensing chip serves as a substrate of the sensor.
Further, in the step (6), the voltage is a direct current voltage.
Still further, in the step (6), the aging time is 24 hours.
The invention also aims to provide a method for detecting ozone and common interferents thereof, wherein the method for detecting the ozone gas sensor array prepared by the preparation method combines kinetic and thermodynamic parameters to analyze and process data, and has the advantages of good stability, short response time and good selectivity.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the ozone gas sensor array, the carbonyl multi-walled carbon nano-tubes are physically modified by using various small-molecule modifiers under mild conditions, so that the carbon nano-tube-based ozone gas sensor array is prepared, high sensitivity and identification detection of ozone and common interferents thereof at room temperature are realized, and the prepared ozone gas sensor array has the advantages of good stability, short response time, good selectivity and strong anti-interference performance, and can be mainly used for measuring ozone and detecting interferents such as formaldehyde, alcohol, nitrogen dioxide and the like.
2. According to the method for detecting the ozone and the common interferents thereof, the ozone gas sensor array is utilized under mild conditions, high sensitivity and identification detection of the ozone and the common interferents thereof at room temperature are realized, and the method is good in stability, short in response time and good in selectivity.
Drawings
FIG. 1 is a scanning electron micrograph of an unmodified carbon nanotube used in the present invention;
FIG. 2 is a transmission electron micrograph of an unmodified carbon nanotube used in the present invention;
FIG. 3 is a graph showing the response of the sensor 1 of example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide;
FIG. 4 is a graph showing the response of the sensor 2 of example 1 to ozone, formaldehyde, alcohol, acetone, water vapor, and nitrogen dioxide;
FIG. 5 is a graph showing the response of the sensor 3 of example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide;
FIG. 6 is a graph showing the response of the sensor 4 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide in example 1;
FIG. 7 is a graph showing the response of the sensor 5 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide in example 1;
FIG. 8 is a graph showing the response of the sensor 6 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide in example 1;
FIG. 9 is a graph of fingerprint discrimination of a carbon nanotube-based ozone gas sensor array for 6 target analytes;
wherein, in fig. 3-8: 1 is ozone, 2 is formaldehyde, 3 is alcohol, 4 is acetone, 5 is water vapor, and 6 is nitrogen dioxide.
Detailed Description
In order to further illustrate the method for preparing an ozone gas sensor array according to the present invention and achieve the intended purpose, the following embodiments are combined to describe the method for preparing an ozone gas sensor array according to the present invention, and the detailed implementation, structure, features and efficacy thereof are described in detail. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Before describing the method for preparing the ozone gas sensor array in detail, it is necessary to further describe the raw materials mentioned in the present invention to achieve better effects.
Hydroxylamine hydrochloride with the molecular formula of ClH4NO, molecular weight 69.49, is colorless crystal, has strong hygroscopicity, is easy to deliquesce, and is white chemical substance soluble in water, ethanol, glycerol, and diethyl ether, and has density of 1.67g/cm3(17 ℃), is mainly used as a reducing agent and a developer, is used for preparing oxime in organic synthesis, and is also used as a raw material for synthesizing an anticancer drug (hydroxyurea), a sulfa drug (sulfamethoxazole) and a pesticide (methomyl).
The structural formula of the aminoacetic acid is NH2CH2COOH, commonly known as glycine, gum sugar, white monoclinic or hexagonal crystal, or white crystalline powder, is odorless, has special sweet taste, is easily soluble in water, is slightly soluble in methanol and ethanol, and is hardly soluble in acetone and diethyl ether.
Succinic acid, also known as succinic acid, having a molecular formula of C4H6O4Molecular weight of 118.09, colorless crystal, acid taste, combustibility, water solubility, and slightly solubility in ethanol, diethyl ether, acetone, and glycerol.
Cetyl trimethyl ammonium bromide (CTMAB for short), molecular formula C19H42BrN，The molecular weight is 364.446, and the white microcrystalline powder is a quaternary ammonium salt; it is hygroscopic and stable in acidic solution; soluble in 10 parts water, readily soluble in ethanol, slightly soluble in acetone, and practically insoluble in diethyl ether and benzene.
8-hydroxyquinaldine, also known as 8-hydroxy-2-methylquinoline, having the molecular formula C10H9NO, molecular weight 159.1846, white prismatic crystal, melting point 74 ℃, boiling point 266-.
Pyrene of formula C16H10The product has molecular weight of 202.26, light yellow monoclinic crystal (colorless pure product), aromatic property, boiling point of 393.5 deg.C, relative density of 1.271(22/4 deg.C), water insolubility, and easy dissolution in organic solvents such as ethanol, diethyl ether, carbon disulfide, benzene, toluene, tetrahydrofuran, etc. Pyrene is mainly present in the distillate of coal tar pitch. Pyrene is used as an organic synthetic raw material, can be oxidized to prepare 1, 4, 5, 8-naphthalene tetracarboxylic acid, and is used for dyes, synthetic resins, disperse dyes and engineering plastics; after acylation, vat dye brilliant orange GR and other various dyes can be prepared.
The scanning electron microscope image and the transmission electron microscope image of the carboxylated carbon nanotube powder adopted in the invention are shown in fig. 1-2, and the carbon nanotube has the characteristics of large specific surface area, abundant reaction sites and the like, and the characteristics enable the carbon nanotube to become an ideal gas-sensitive sensing material.
With the above materials in mind, the method for preparing an ozone gas sensor array according to the present invention will be described in detail with reference to the following embodiments:
example 1.
The specific operation steps are as follows:
(1) dissolving a micromolecular modifier in deionized water, and performing ultrasonic dispersion for 10min to obtain a modifier solution with the molar concentration of 1 mmol/L; wherein the micromolecular modifier is hydroxylamine hydrochloride;
(2) adding 0.02g of carboxylated carbon nanotube powder into 4ml of modifier solution, uniformly mixing, and performing ultrasonic dispersion for 50min to obtain stable carbon nanotube dispersion liquid;
(3) standing the carbon nanotube dispersion liquid at room temperature for 48h, allowing the small molecular modifier to physically bond on the wall of the carbon nanotube through supermolecule action or adsorption action of the carbon nanotube to form the carbon nanotube physically modified by the small molecular modifier, centrifuging, and collecting the precipitate of the physically modified carbon nanotube to obtain a precipitate;
(4) uniformly mixing the precipitate with deionized water according to the mass ratio of 1:4, and grinding to form uniform paste to obtain paste;
dipping a little paste by using a sample brush, uniformly coating the paste on the interdigital electrode, and drying the interdigital electrode at room temperature for 18h to obtain a primary carbon nanotube-based sensing chip;
manufacturing a sensor chip into a sensor, and taking the sensor chip as a substrate of the sensor to obtain a sensor 1;
(5) repeating the steps (1) to (4) for 5 times to obtain a sensor 2, a sensor 3, a sensor 4, a sensor 5 and a sensor 6 in sequence; wherein the micromolecule modifier is composed of aminoacetic acid, succinic acid, hexadecyl trimethyl ammonium bromide, 8-hydroxy quinaldine and pyrene in sequence;
(6) and continuously applying a direct current voltage of 0.1V to the two ends of the sensors 1-6, electrifying and aging for 24h to obtain the carbon nano tube sensors with stable performance, and then forming a sensor array to obtain the ozone gas-sensitive sensor array which can be used for testing the gas-sensitive response performance of the ozone gas-sensitive sensor array to ozone, nitrogen dioxide and common interferents.
The sensors 1-6 prepared in example 1 were tested with an electrochemical workstation for their response curves to ozone, formaldehyde, alcohol, acetone, water vapor, nitrogen dioxide, as shown in figures 3-8.
A power supply of a chemical workstation is electrified, and under the bias of 0.1V, the response curve of the carbon nanotube-based ozone gas-sensitive sensor 1 prepared by taking hydroxylamine hydrochloride as the micromolecule dispersant and obtained in the example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide at room temperature (the temperature is 25 ℃ and the relative humidity is 25%) is tested, as shown in fig. 3, as can be seen from the response curve, the response sizes of the carbon nanotube-based ozone gas-sensitive sensor prepared by taking hydroxylamine hydrochloride as the micromolecule dispersant to ozone at room temperature respectively reach 19.91%, 20.99% and 22.07%; the response times were 22.7 seconds, 14.8 seconds, and 22.1 seconds, respectively. The response to formaldehyde reaches-15.67%, -16.25%, -17.60% respectively; the response times were 14.7 seconds, 11.7 seconds, and 13.4 seconds, respectively. The response to alcohol respectively reaches-49.24%, -48.58%, -46.99%; the response times were 6 seconds, 6.6 seconds, and 6.4 seconds, respectively. The response to acetone respectively reaches-4.07%, -4.62%, -5.09%; response times were 3.59 seconds, 3.83 seconds, 5.06 seconds, respectively: the response to water vapor reaches-0.19%, -0.17% respectively; the response times were 11.04 seconds, 5.59 seconds, and 7.28 seconds, respectively. The response to nitrogen dioxide respectively reaches 1.13%, 1.23% and 1.23%; the response times are respectively: 10.34 seconds, 8.5 seconds, 10.35 seconds.
The power supply of the electrochemical workstation is switched on, and under the bias of 0.1V, the response curve of the carbon nanotube-based ozone gas-sensitive sensor 2 prepared by using aminoacetic acid as the small-molecule dispersant in example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide at room temperature (the temperature is 25 ℃ and the relative humidity is 25%) is tested, as shown in fig. 4, it can be seen from the response curve that the response magnitudes of the carbon nanotube-based ozone gas-sensitive sensor prepared by using aminoacetic acid as the small-molecule dispersant to ozone at room temperature respectively reach 6.10%, 6.21% and 6.76%; the response times were 29.5 seconds, 23.2 seconds, and 29.5 seconds, respectively. The response to formaldehyde reaches-2.87%, -3.01%, -2.98% respectively; the response times were 3.6 seconds, 3.4 seconds, and 3 seconds, respectively. The response to alcohol respectively reaches-25.12%, -24.76%, -24.26%; the response times were 8.1 seconds, 8.4 seconds, and 8.7 seconds, respectively. The response to acetone reaches-4.71%, -4.94%, -4.96% respectively; the response times were 3.62 seconds, 8.39 seconds, and 10.98 seconds, respectively. The response to water vapor respectively reaches the following values: -0.63%, -0.62%, 0.17%. Response times were 8.59 seconds, 5.0 seconds, 5.89 seconds, respectively: the response to the nitrogen dioxide respectively reaches 0.81 percent, 0.81 percent and 0.94 percent; the response times are respectively: 8.0 seconds, 10.63 seconds, 10.69 seconds.
The power supply of the electrochemical workstation is switched on, and under the bias of 0.1V, the response curve of the carbon nanotube-based ozone gas-sensitive sensor 3 prepared by using succinic acid as the small-molecule dispersant and obtained in example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide at room temperature (the temperature is 25 ℃ and the relative humidity is 25%) is tested, as shown in fig. 5, it can be seen from the response curve that the response of the carbon nanotube-based ozone gas-sensitive sensor prepared by using succinic acid as the small-molecule dispersant to ozone respectively reaches 16.62%, 15.71% and 16.14% at room temperature; the response times were 6.6 seconds, 7.8 seconds, and 5.3 seconds, respectively. The response to formaldehyde reaches-5.98%, -5.91%, -5.74% respectively; the response times were 8.7 seconds, and 7.4 seconds, respectively. The response to alcohol reaches-22.68%, -21.85%, -22.44% respectively; the response times were 4.6 seconds, 5.3 seconds, and 4.6 seconds, respectively. The response to acetone reaches-5.25%, -4.97%, -4.79% respectively; the response times were 6.67 seconds, 6.33 seconds, and 5.47 seconds, respectively. The response to water vapor reaches-0.29%, -0.40%, -0.46 respectively; the response times are respectively: 8.81 seconds, 5.17 seconds, 4.29 seconds. The response to nitrogen dioxide respectively reaches 1.77%, 1.57% and 1.84%; the response times are respectively: 12.3 seconds, 4.9 seconds, 4.6 seconds.
The power supply of the electrochemical workstation is switched on, and under the bias of 0.1V, the response curve of the carbon nanotube-based ozone gas-sensitive sensor 4 prepared by using the hexadecyl trimethyl ammonium bromide as the small molecular dispersant in the example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide at room temperature (the temperature is 25 ℃ and the relative humidity is 25%) is tested, as shown in fig. 6, and as can be seen from the response curve, the response of the carbon nanotube-based ozone gas-sensitive sensor prepared by using the hexadecyl trimethyl ammonium bromide as the small molecular dispersant to ozone reaches 29.24%, 29.10% and 29.99% respectively at room temperature; the response times were 14.3 seconds, 11.2 seconds, and 12.4 seconds, respectively. The response to formaldehyde reaches-6.07%, -6.15%, -6.91% respectively; the response times were 16.4 seconds, 15 seconds, and 15.7 seconds, respectively. The response to alcohol respectively reaches-3.62%, -3.57%, -3.62%; the response times were 8.5 seconds, 5.9 seconds, and 4.9 seconds, respectively. The response to acetone reaches-4.54%, -4.65%, -4.54% respectively; the response times were 3.93 seconds, 10.81 seconds, and 8.91 seconds, respectively. The response to water vapor reaches 0.08%, 0.92% and 1.4% respectively; the response times are respectively: 6.07 seconds, 4.01 seconds, 5.15 seconds. The response to nitrogen dioxide respectively reaches 1.75%, 2.09% and 1.73%; the response times are respectively: 11.47 seconds, 10.27 seconds, 8.71 seconds.
Turning on a power supply of an electrochemical workstation, testing response curves of the carbon nanotube-based ozone gas-sensitive sensor 5 prepared by using 8-hydroxyquinaldine as a small molecular dispersant and obtained in example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide at room temperature (the temperature is 25 ℃ and the relative humidity is 25%) under the bias of 0.1V, as shown in fig. 7, it can be seen from the response curves that the carbon nanotube-based ozone gas-sensitive sensor prepared by using 8-hydroxyquinaldine as a small molecular dispersant has response values to ozone of 31.01%, 28.74% and 26.93% respectively at room temperature; the response times were 9.2 seconds, 9.4 seconds, and 10.7 seconds, respectively. The response to formaldehyde reaches-26.61%, -27.93%, -30.32% respectively; the response times were 12.2 seconds, 13.7 seconds, and 12.1 seconds, respectively. The response to alcohol respectively reaches-18.10%, -17.20%, -16.71%; the response times were 8.2 seconds, 8.4 seconds, and 9.3 seconds, respectively. The response to acetone reaches-6.56%, -6.38% respectively; the response times were 3.1 seconds, 3.0 seconds, and 2.8 seconds, respectively. The response to water vapor reaches 0.31%, 0.59% and 0.94% respectively; the response times are respectively: 3.08 seconds, 9.47 seconds, 11.29 seconds. The response to nitrogen dioxide respectively reaches 1.44%, 1.47% and 1.44%; the response times are respectively: 9.73 seconds, 10.57 seconds, 11.49 seconds.
The power supply of the electrochemical workstation is switched on, and under the bias of 0.1V, the response curve of the carbon nanotube-based ozone gas-sensitive sensor 6 prepared by taking pyrene as the small molecular dispersant and obtained in example 1 to ozone, formaldehyde, alcohol, acetone, water vapor and nitrogen dioxide at room temperature (the temperature is 25 ℃ and the relative humidity is 25%) is tested, as shown in fig. 8, it can be seen from the response curve that at room temperature, the response magnitudes of the carbon nanotube-based ozone gas-sensitive sensor prepared by taking pyrene as the small molecular dispersant to ozone respectively reach 32.28%, 35.63% and 35.31%; the response times were 19 seconds, 14.8 seconds, and 21.3 seconds, respectively. The response to formaldehyde reaches-13.10%, -13.96%, -14.41% respectively; the response times were 16.5 seconds, 15.7 seconds, and 15.0 seconds, respectively. The response to alcohol respectively reaches-4.55%, -4.76%, -4.56%; the response times were 10.1 seconds, 11.9 seconds, and 12.5 seconds, respectively. The response to acetone reaches-8.94%, -8.90%, -8.79% respectively; the response times were 2.79 seconds, 3.3 seconds, and 3.1 seconds, respectively. The response to water vapor reaches 0.04 percent, 0.05 percent and 0.58 percent respectively; the response times are respectively: 6.11 seconds, 8.33 seconds, 2.92 seconds. The response to nitrogen dioxide respectively reaches 1.22%, 1.42% and 1.44%; the response times are respectively: 0.91 second, 1.98 second, 4.85 second.
According to the preparation method of the ozone gas sensor array, the carbonyl multi-walled carbon nano-tubes are physically modified by using a plurality of small molecule modifiers under mild conditions, so that the carbon nano-tube-based ozone gas sensor array is prepared, high sensitivity and identification detection of ozone and common interferents thereof at room temperature are realized, and the prepared ozone gas sensor array is good in stability, short in response time and good in selectivity.
Example 2.
The specific operation steps are as follows:
(1) dissolving a micromolecular modifier in deionized water, and performing ultrasonic dispersion for 8min to obtain a modifier solution with the molar concentration of 0.8 mmol/L; wherein the micromolecular modifier is hydroxylamine hydrochloride;
(2) adding 0.02g of carboxylated carbon nanotube powder into 5ml of modifier solution, uniformly mixing, and performing ultrasonic dispersion for 30min to obtain stable carbon nanotube dispersion liquid;
(3) standing the carbon nanotube dispersion liquid at room temperature for 46h, allowing the small molecular modifier to physically bond on the wall of the carbon nanotube through supermolecule action or adsorption action of the carbon nanotube to form the carbon nanotube physically modified by the small molecular modifier, centrifuging, and collecting the precipitate of the physically modified carbon nanotube to obtain a precipitate;
(4) uniformly mixing the precipitate with deionized water according to the mass ratio of 1:3.5, and grinding to form uniform paste to obtain paste;
dipping a little paste by using a sample brush, uniformly coating the paste on the interdigital electrode, and drying the interdigital electrode at room temperature for 12 hours to obtain a primary carbon nanotube-based sensing chip;
manufacturing a sensor chip into a sensor, and taking the sensor chip as a substrate of the sensor to obtain a sensor 1;
(5) repeating the steps (1) to (4) for 5 times to obtain a sensor 2, a sensor 3, a sensor 4, a sensor 5 and a sensor 6 in sequence; wherein the micromolecule modifier is composed of aminoacetic acid, succinic acid, hexadecyl trimethyl ammonium bromide, 8-hydroxy quinaldine and pyrene in sequence;
(6) and continuously applying a direct current voltage of 0.1V to the two ends of the sensors 1-6, electrifying and aging for 22h to obtain the carbon nanotube sensor with stable performance, and forming a sensor array to obtain the ozone gas sensor array which can be used for testing the gas-sensitive response performance of the ozone gas sensor array to ozone, nitrogen dioxide and common interferents.
According to the preparation method of the ozone gas sensor array, the carbonyl multi-walled carbon nano-tubes are physically modified by using a plurality of small molecule modifiers under mild conditions, so that the carbon nano-tube-based gas sensor array is prepared, high sensitivity and identification detection of ozone and common interferents thereof at room temperature are realized, and the prepared ozone gas sensor array is good in stability, short in response time and good in selectivity.
Example 3.
The specific operation steps are as follows:
(1) dissolving a small molecular modifier in deionized water, and performing ultrasonic dispersion for 12min to obtain a modifier solution with the molar concentration of 1.2 mmol/L; wherein the micromolecular modifier is hydroxylamine hydrochloride;
(2) adding 0.02g of carboxylated carbon nanotube powder into 3ml of modifier solution, uniformly mixing, and performing ultrasonic dispersion for 60min to obtain stable carbon nanotube dispersion liquid;
(3) standing the carbon nanotube dispersion liquid at room temperature for 50h, allowing the small molecular modifier to physically bond on the wall of the carbon nanotube through supermolecule action or adsorption action of the carbon nanotube to form the carbon nanotube physically modified by the small molecular modifier, centrifuging, and collecting the precipitate of the physically modified carbon nanotube to obtain a precipitate;
(4) uniformly mixing the precipitate with deionized water according to the mass ratio of 1:4.5, and grinding to form uniform paste to obtain paste;
dipping a little paste by using a sample brush, uniformly coating the paste on the interdigital electrode, and drying the interdigital electrode at room temperature for 24 hours to obtain a primary carbon nanotube-based sensing chip;
manufacturing a sensor chip into a sensor, and taking the sensor chip as a substrate of the sensor to obtain a sensor 1;
(5) repeating the steps (1) to (4) for 5 times to obtain a sensor 2, a sensor 3, a sensor 4, a sensor 5 and a sensor 6 in sequence; wherein the micromolecule modifier is composed of aminoacetic acid, succinic acid, hexadecyl trimethyl ammonium bromide, 8-hydroxy quinaldine and pyrene in sequence;
(6) and continuously applying a direct current voltage of 0.1V to the two ends of the sensors 1-6, electrifying and aging for 26h to obtain the carbon nano tube sensors with stable performance, and then forming a sensor array to obtain the ozone gas-sensitive sensor array which can be used for testing the gas-sensitive response performance of the ozone gas-sensitive sensor array to ozone, nitrogen dioxide and common interferents.
According to the preparation method of the ozone gas sensor array, the carbonyl multi-walled carbon nano-tubes are physically modified by using a plurality of small molecule modifiers under mild conditions, so that the carbon nano-tube-based gas sensor array is prepared, high sensitivity and identification detection of ozone and common interferents thereof at room temperature are realized, and the prepared ozone gas sensor array is good in stability, short in response time and good in selectivity.
Example 4.
A method for detecting ozone and common interferents thereof comprises the following steps:
by using a radar fingerprint analysis method, the sensors 1, 2, 3, 4, 5, and 6 in the ozone gas sensor array of embodiment 1 are used to detect ozone, formaldehyde, alcohol, acetone, water vapor, and nitrogen dioxide, and then a principal component analysis method is used to analyze and process data, that is, kinetic and thermodynamic parameters are combined to analyze and process data (radar map analysis method), specifically: the thermodynamic parameter response of each analyte by 6 sensors is divided by the kinetic parameter response time, the response size and the response time are processed, high sensitivity and identification and detection of ozone and common interferents are achieved, and radar fingerprint spectrums of the 6 analytes are obtained.
According to the fingerprint, the ozone, the formaldehyde, the alcohol, the acetone, the water vapor and the nitrogen dioxide can be distinguished, and as shown in fig. 9, the ozone gas sensor array prepared in the embodiment 1 can identify and detect the ozone, the formaldehyde, the alcohol, the acetone, the water vapor and the nitrogen dioxide at room temperature, and has the advantages of strong anti-interference performance, high sensitivity and high selectivity.
The detection method of ozone and common interferents thereof, provided by the embodiment of the invention, is mainly used for anti-interference, identification and detection of atmospheric pollutant ozone and detection of interferents such as formaldehyde, alcohol, nitrogen dioxide, water vapor and the like, and high sensitivity and identification and detection of ozone and common interferents thereof at room temperature are realized by using the gas sensor array under a mild condition.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of an ozone gas sensor array is characterized by comprising the following steps:
(1) dissolving a micromolecular modifier in deionized water, and performing ultrasonic dispersion to obtain a modifier solution with the molar concentration of 0.8-1.2 mmol/L; wherein the micromolecular modifier is hydroxylamine hydrochloride;
(2) mixing the carboxylated carbon nanotube powder and the modifier solution according to the weight ratio of 0.02 g: 3-5ml of the carbon nano tube dispersion liquid is obtained after the mixing and 30-60min of ultrasonic dispersion;
(3) standing the carbon nanotube dispersion liquid at room temperature for 46-50h, and centrifuging to obtain a precipitate;
(4) uniformly mixing the precipitate and deionized water according to the mass ratio of 1:3.5-4.5 to obtain paste;
uniformly coating the paste on the interdigital electrode, and drying at room temperature for 12-24h to obtain a sensing chip;
manufacturing a sensor chip into a sensor to obtain a sensor 1;
(5) repeating the steps (1) to (4) for 5 times to obtain a sensor 2, a sensor 3, a sensor 4, a sensor 5 and a sensor 6 in sequence; wherein the micromolecule modifier is composed of aminoacetic acid, succinic acid, hexadecyl trimethyl ammonium bromide, 8-hydroxy quinaldine and pyrene in sequence;
(6) and continuously applying a voltage of 0.1V to the two ends of the sensors 1-6, electrifying and aging for 22-26h to form a sensor array, thus obtaining the ozone gas sensor array.
2. The method according to claim 1, wherein,
in the step (1), the ultrasonic dispersion time is 8-12 min.
3. The method according to claim 2, wherein,
in the step (1), the molar concentration of the modifier solution is 1 mmol/L;
the time of ultrasonic dispersion is 10 min.
4. The method according to claim 1, wherein,
in the step (2), the ratio of the carbon nanotube powder to the modifier solution is 0.02 g: 4ml of the mixture was mixed at a mass/volume ratio.
5. The method according to claim 1, wherein,
in the step (3), the carbon nanotube dispersion liquid is placed at a standstill at room temperature for 48 hours.
6. The method according to claim 1, wherein,
in the step (4), the sensing chip is used as a substrate of the sensor.
7. The method according to claim 1, wherein,
in the step (6), the voltage is a direct current voltage.
8. The method according to claim 7, wherein,
in the step (6), the aging time is 24 h.
9. The method for detecting ozone and common interferents thereof is characterized in that the ozone gas sensor array prepared by the preparation method of any one of claims 1 to 8 is used for analyzing and processing data by combining kinetic and thermodynamic parameters.
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