CN110672670A - Planar flexible room temperature NO based on three-dimensional MXene folded ball/ZnO composite material2Sensor and preparation method thereof - Google Patents
Planar flexible room temperature NO based on three-dimensional MXene folded ball/ZnO composite material2Sensor and preparation method thereof Download PDFInfo
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Abstract
Planar flexible room temperature NO based on three-dimensional MXene folded ball/ZnO composite material2A sensor and a preparation method thereof belong to the technical field of gas sensors. The sensor consists of a polyimide flexible substrate with an Au interdigital electrode and a three-dimensional MXene fold ball/ZnO composite material sensitive electrode prepared on the interdigital electrode and the substrate. The anti-aggregation three-dimensional MXene folded ball is prepared by treating MXene through an ultrasonic spraying method on the basis of an MXene material, so that the advantages of preventing aggregation and maintaining the large specific surface area of MXene to the maximum are achieved, meanwhile, the composite oxidability is realized, ZnO nanoparticles are added on the surface of the three-dimensional MXene folded ball, the sensing sites are increased, and compared with two-dimensional MXene and pure three-dimensional MXene folded ball, the sensor prepared on the basis of the three-dimensional MXene folded ball/ZnO composite material obtains higher NO2Sensing performance, and has good selectivity, recoverability and flexibility.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a planar flexible room temperature NO composite material with three-dimensional MXene folded spheres/ZnO composite material as a sensitive electrode2The sensor and the preparation method thereof are mainly used for detecting wearable nitrogen dioxide.
Background
MXenes is a new class of two-dimensional materials, and is a short name for two-dimensional transition Au metal carbides, nitrides and carbonitrides, and the name comes from the preparation process and the performance of the MXenes. MAX ceramic materials are used as raw materials (M represents transition Au, such as titanium, vanadium, chromium and manganese, A represents an intermediate sacrificial layer, and X represents C or N element), and the sacrificial layer A is removed by etching with a strong acid corrosive liquid, so as to obtain MX. By ion intercalation and sonication, "MX" is dispersed into two-dimensional flakes, eventually with the suffix "ene" added due to similar properties as graphene. MXene prepared has the general formula Mn+1XnTzT represents a group such as O2-、OH-、F-And Cl-Has a great influence on the electrical and chemical properties of MXene. Currently, MXenes has very excellent performance in lithium and sodium ion energy storage systems, water purification and electromagnetic shielding, and has the advantages of good flexibility, simple preparation and high conductivity.
Due to the rise of human-computer interaction in the internet of things and wearable equipment, the demand for high-sensitivity flexible room-temperature gas sensors is increasing day by day. In previous reports, the conductivity of MXene varies with humidity and gas in the environment, which shows broad prospects as a gas and humidity sensor. By utilizing the flexibility and the conductivity of MXene, a novel gas sensor can be manufactured, has the advantages of room-temperature operation and low power consumption, and can play an important role in the fields of air and food quality monitoring, medical diagnosis and production safety. Consumption and abrasion resistance. According to the work of the Hee-Tae Jung topic group, MXene-based gas sensors have a superior signal-to-noise ratio compared to other two-dimensional materials (e.g., black phosphorus, transition Au metal disulfide, graphene). The anti-interference performance of MXene is very valuable for high conductivity room temperature gas sensors, however, the response of gas sensors based on Au metal MXene needs to be further improved to make them more practical.
Some efforts have been made by researchers to improve the gas sensing performance of MXene. These modifications can be divided into two types: increase of surface active sites and construction of specific forms. In our previous work, we used alkaline treatment to increase the surface oxygen termination and thus enhance the response to ammonia gas, and the group of Hee-Tae Jung used a similar approach to increase the selectivity to ethanol by modulating the insertion of Au metal ions. In addition, it has been reported that organ-like MXene is compounded with polyaniline and MXene and TiO2Compounding to improve the gas-sensitive property of MXene. The above work can be considered to augment sensitivity by increasing MXene surface active sites. For another modification, professor in my work, they used electrospinning techniques to construct a three-dimensional MXene framework to reduce the detection limit concentration of VOCs. However, in these reports, both high response and high selectivity cannot be satisfied, and the detected gas is limited to VOC only.
In the present invention, we use two improved methods to maximize the gas sensing properties of MXene. MXene (Ti)3C2Tx) It has good dispersibility in water, but MXene can be seriously aggregated after drying and lose its advantage of large specific surface area, which is not favorable for gas sensing. Anti-aggregation three-dimensional MXene (Ti) can be prepared by ultrasonic spray pyrolysis method3C2Tx) The sphere is corrugated to maintain its high specific surface area and improve gas sensing performance through topography building. Furthermore, we combined ZnO nanoparticles with three-dimensional MXene (Ti)3C2Tx) And (5) compounding the folded ball. Effecting reversible NO2And (6) responding. Based on a flexible PI substrate, we realized room temperature NO2Sensing, and response value, selectivity and recovery rate are obviously improved.
Disclosure of Invention
The invention aims to provide a method for preparing a liquid crystal displayThree-dimensional MXene (Ti)3C2Tx) Planar flexible room temperature nitrogen dioxide sensor made of composite material of folded ball/ZnO (T represents surface group terminal, x is in proportion of each terminal on surface), preparation method thereof and NO of sensor2Practical application in detection. The sensor obtained by the invention has the highest NO of the existing MXene sensor2Response, and has good selectivity, recoverability and flexibility.
The planar flexible room temperature nitrogen dioxide sensor disclosed by the invention is composed of a PI (polyimide) flexible substrate with an Au interdigital electrode and sensitive electrodes prepared on the interdigital electrode and the substrate as shown in figure 1, wherein the sensitive electrode material is a three-dimensional MXene folded ball/ZnO composite material, and is prepared by the following steps:
(1) weighing Ti3AlC2Slowly adding the powder into etching liquid formed by mixing concentrated hydrochloric acid (30-40 mass percent) and lithium fluoride, and adding Ti3AlC2The mass ratio of the powder to the lithium fluoride is 0.8-1: 1, Ti3AlC2The mass-volume ratio of the powder to the concentrated hydrochloric acid is 1 g: 30-50 mL; stirring and reacting for 20-24 hours in water bath at 40-60 ℃, repeatedly washing and centrifuging a product after the reaction is finished by using deionized water until the pH value of a supernatant is 6-7; then dispersing the washed product in 60-70 mL of deionized water, performing ultrasonic dispersion for 30-60 min, and centrifuging to obtain an upper-layer dispersion liquid to obtain an MXene colloidal dispersion liquid; taking 10-20 mL of dispersion liquid for suction filtration, drying to prepare an MXene film, weighing the mass of the MXene film, and calculating the concentration of the MXene dispersion liquid to be 4-6 mg/mL;
(2) taking 30-50 mL of MXene dispersion liquid, and then adding the MXene dispersion liquid into 10-30 mL of PVP-k30 aqueous solution, wherein the mass ratio of PVP-k30 to MXene is 0.9-1: 1, after fully stirring, slowly adding 30-50 mL of zinc acetate solution, wherein the mass ratio of zinc acetate to MXene is (1-1.1): 1, ultrasonic spraying after fully stirring; carrying the ultrasonic atomization product into a tube furnace with the temperature stabilized at 600-800 ℃ by using nitrogen with the flow velocity of 2-6L/min to obtain the three-dimensional MXene (Ti)3C2Tx) The wrinkled ball/ZnO composite powder is brought into a static collecting device by nitrogen and collected.
The invention relates to a preparation method of a planar flexible room temperature nitrogen dioxide sensor, which comprises the following steps:
(1) the PI flexible substrate with Au interdigitated electrodes was purchased from gigi sensing technologies, guangzhou, inc.
(2) Drop coating of three-dimensional MXene (Ti)3C2Tx) Wrinkled ball/ZnO composite: repeatedly washing the PI flexible substrate with the Au interdigital electrode with deionized water and absolute ethyl alcohol, drying, and sticking the area around the electrode with an adhesive tape to perform masking, so that the dropping coating range is stabilized in the interdigital electrode area, and errors among sensors are reduced; weighing three-dimensional MXene (Ti)3C2Tx) The wrinkle ball/ZnO composite material powder and deionized water are mixed according to the weight ratio of (3-5) mg: uniformly mixing the components in a proportion of 1mL, uniformly dripping the components on a PI flexible substrate with an Au interdigital electrode after the components are fully dispersed, and drying the PI flexible substrate for 30-40 minutes at a temperature of 80-90 ℃ under a vacuum condition; removing the adhesive tape to prepare the planar flexible room temperature NO taking the novel three-dimensional MXene wrinkled ball/ZnO composite material as the sensitive electrode2A sensor.
The anti-aggregation three-dimensional MXene folded ball is prepared by treating MXene through an ultrasonic spraying method on the basis of an MXene material, so that the advantages of preventing aggregation and maintaining the large specific surface area of MXene to the maximum are achieved, meanwhile, the composite oxidability is realized, ZnO nanoparticles are added on the surface of the three-dimensional MXene folded ball, the sensing sites are increased, and compared with two-dimensional MXene and pure three-dimensional MXene folded ball, the sensor prepared on the basis of the three-dimensional MXene folded ball/ZnO composite material obtains higher NO2Sensing performance.
The invention has the advantages that:
(1) the sensor utilizes the wrinkled MXene and the composite ZnO to make NO2The sensing performance is greatly improved, and a feasible solution is provided for improving the gas-sensitive performance of the MXene material.
(2) The sensor works at room temperature, and has lower working temperature and lower power consumption than the traditional gas humidity-sensitive sensors such as solid electrolyte and the like.
(3) Sensor for detecting NO under experimental bending condition2Has certain bending resistance and is hopeful to be appliedThe wearable device is used.
Drawings
FIG. 1: the invention relates to a schematic manufacturing flow diagram of a planar flexible room temperature sensor device; the device comprises a flexible PI substrate, Au interdigital electrodes on the substrate, a mask adhesive tape and a powder material, wherein 1 is the flexible PI substrate, 2 is the Au interdigital electrodes on the substrate, 3 is the mask adhesive tape, and 4 is the drop-coated powder material.
As shown in fig. 1, the powder is coated and dried by dropping after passing through the mask, and a rectangular sensitive material layer with a regular shape can be obtained after removing the mask, so that the uniformity of each device is ensured.
FIG. 2: SEM picture, TEM picture and particle size distribution diagram of the three-dimensional MXene folded spheres prepared by the invention. Parts in the figure: SEM images of three-dimensional MXene pleated spheres (10000 times magnification a, 40000 times magnification c); the particle size distribution diagram b of the three-dimensional MXene folded spheres; TEM image of three-dimensional MXene wrinkled spheres (100000 magnification d, 400000 magnification e).
As shown in FIG. 2, wrinkles on the surface of MXene spheres were observed, and the particle size was mostly distributed around 1 μm.
FIG. 3: SEM picture and TEM picture of three-dimensional MXene wrinkle ball/ZnO prepared by the invention. Parts in the figure: SEM image of three-dimensional MXene wrinkled spheres/ZnO (10000 times magnification a, 50000 times magnification b); TEM image of three-dimensional MXene wrinkled spheres/ZnO (100000 magnification c, 400000 magnification d).
As shown in fig. 3, ZnO nanoparticles are uniformly attached to the surface of MXene pleated spheres.
FIG. 4: selectivity test charts of sensors based on two-dimensional MXene sheet (comparative example 1), three-dimensional MXene wrinkled beads (comparative example 2), and three-dimensional MXene wrinkled beads/ZnO composite (example 1) prepared by the present invention for 100ppm of ethanol, acetone, toluene, formaldehyde, ammonia, and nitrogen dioxide.
As shown in fig. 4, the response value of the two-dimensional MXene sheet to all test gases is lower than 1%, while the response value of the three-dimensional MXene corrugated ball to ammonia and nitrogen dioxide is significantly improved, and the selectivity of the three-dimensional MXene corrugated ball/ZnO composite material to nitrogen dioxide is further improved while the response value to nitrogen dioxide is improved.
FIG. 5: continuous gradient test patterns of sensors based on three-dimensional MXene corrugation spheres (comparative example 2) and three-dimensional MXene corrugation spheres/ZnO composite (example 1) prepared by the invention on 5ppm, 10ppm, 20ppm, 50ppm and 100ppm nitrogen dioxide. The three-dimensional MXene wrinkled ball sensor continuous gradient test chart is a, and the three-dimensional MXene wrinkled ball/ZnO sensor continuous gradient test chart is b.
As shown in fig. 5, the three-dimensional MXene wrinkle ball/ZnO sensor has a higher response value to various concentrations of nitrogen dioxide, and the recovery rate is much higher than that of the three-dimensional MXene wrinkle ball sensor.
FIG. 6: the gas-sensitive test chart of the sensor based on the three-dimensional MXene folded ball/ZnO is used for testing the gas sensitivity of 100ppm of nitrogen dioxide under the conditions of bending at 30 degrees, 60 degrees, 90 degrees and 120 degrees.
As shown in fig. 6, there is a slight attenuation in the response to 100ppm nitrogen dioxide with an increase in bend angle, with the decay rate of the response of the bend 120 ° test not exceeding 30%.
Detailed Description
Comparative example 1:
the method comprises the following steps of preparing a two-dimensional MXene material by using a hydrochloric acid/lithium fluoride etching method, preparing a planar flexible room temperature gas sensor by using the two-dimensional MXene material as a sensitive material, and testing the gas sensitivity of the sensor, wherein the specific process comprises the following steps:
(1) preparing a two-dimensional MXene material: weighing 1g of Ti3AlC2Slowly adding the concentrated hydrochloric acid (the mass fraction is 36%) 40mL and the LiF (1 g) in a PET bottle of 50mL, stirring and reacting for 24 hours in a water bath at 40 ℃, repeatedly washing and centrifuging the product after the reaction is finished by deionized water until the pH value of the supernatant is 6. Adding the lower-layer clay-like precipitate into 60mL of deionized water, carrying out ice bath ultrasonic treatment for 1 hour in a column type ultrasonic machine, finally centrifuging at the rotating speed of 3000 rpm for 1 hour, and taking the upper-layer liquid to obtain MXene dispersion liquid, wherein the concentration of MXene is 5 mg/mL.
(2) The PI flexible substrate with Au interdigitated electrodes was purchased from gigi sensing technologies, guangzhou, inc. The size of the substrate is 1cm x 1cm, the electrode width and the electrode gap are both 100nm, and the Au electrode deposition thickness is 100 nm.
(3) And (3) drop coating of two-dimensional MXene: and repeatedly washing the manufactured flexible PI substrate with the Au interdigital electrode by using deionized water and absolute ethyl alcohol, and drying. And (4) using the adhesive tape to stick all around the electrode for masking, so that the dispensing range is stabilized in the interdigital electrode area. MXene dispersion was measured in 500. mu.L, and was uniformly applied dropwise onto a flexible PI substrate, followed by placing in a vacuum oven at 80 ℃ for 30 minutes. Thereby preparing the planar flexible room temperature gas sensor taking two-dimensional MXene as a sensitive material.
Comparative example 2:
treating two-dimensional MXene by using an ultrasonic spray pyrolysis method to obtain a three-dimensional MXene folded ball, manufacturing a planar flexible room-temperature gas sensor by using the pure three-dimensional MXene folded ball as a sensitive material, and testing the gas-sensitive performance of the sensor, wherein the specific process comprises the following steps:
(1) preparing a two-dimensional MXene material: weighing 1g of Ti3AlC2Slowly adding the concentrated hydrochloric acid (the mass fraction is 36%) 40mL and LiF 1g in a 50mL PET bottle, stirring and reacting for 24 hours in a water bath at 40 ℃, repeatedly washing and centrifuging the product after the reaction is finished by deionized water until the pH value of the supernatant is 6. And adding the lower-layer clay-like precipitate into 60mL of deionized water, carrying out ice bath ultrasonic treatment for 1 hour in a column type ultrasonic machine, finally centrifuging at the rotating speed of 3000 revolutions per minute for 1 hour, and taking the upper-layer liquid to obtain MXene dispersion liquid. Weighing 10mL of MXene dispersion liquid, carrying out suction filtration, placing an MXene sheet obtained by suction filtration in a vacuum oven at 80 ℃ for drying to obtain an MXene film, weighing the weight of the MXene film, calculating to obtain the concentration of the MXene dispersion liquid to be 5mg/mL, and placing the MXene film in a refrigerator for low-temperature storage for later use.
(2) Preparing three-dimensional MXene folded spheres: 60mL of deionized water was weighed into a 150mL beaker, 200mg of PVP-k30 powder was added, and after stirring for 10 minutes, 40mL of the prepared MXene dispersion was slowly added dropwise. Stirring for 30 minutes, carrying out ultrasonic atomization at 17MHz, introducing ultrasonic atomized water mist into a tubular furnace with the temperature stabilized at 800 ℃ by using nitrogen with the flow rate of 5L/min, and finally carrying out three-dimensional MXene Ti3C2TxThe pleated ball powder is brought into an electrostatic collection device to be collected.
(3) The PI flexible substrate with Au interdigitated electrodes was purchased from gigi sensing technologies, guangzhou, inc. The size of the substrate is 1cm x 1cm, the electrode width and the electrode gap are both 100nm, and the Au electrode deposition thickness is 100 nm.
(4) And (3) drop coating three-dimensional MXene wrinkle balls: and repeatedly washing the manufactured flexible PI substrate with the Au interdigital electrode by using deionized water and absolute ethyl alcohol, and drying. And (4) using the adhesive tape to stick all around the electrode for masking, so that the dispensing range is stabilized in the interdigital electrode area. Weighing 4mg of three-dimensional MXene folded sphere powder, uniformly mixing with 1mL of deionized water, uniformly dripping the mixture on a flexible PI substrate after fully dispersing, and then placing the flexible PI substrate in a vacuum drying oven at 80 ℃ for 30 minutes. Thereby preparing the planar flexible room temperature gas sensor taking the three-dimensional MXene folded ball as a sensitive material.
Example 1:
a planar flexible room temperature gas sensor is manufactured by taking a three-dimensional MXene folded ball/ZnO composite material as a sensitive electrode material, and the manufacturing process comprises the following steps:
(1) preparing a two-dimensional MXene material: weighing 1g of Ti3AlC2Slowly adding 40mL of concentrated hydrochloric acid (the mass fraction is 36%) and 1g of LiF in a 50mL PET bottle, stirring and reacting for 24 hours in a water bath at 40 ℃, repeatedly washing and centrifuging a product after the reaction is finished by deionized water until the pH value of a supernatant is 6. And adding the lower-layer clay-like precipitate into 60mL of deionized water, carrying out ice bath ultrasonic treatment for 1 hour in a column type ultrasonic machine, finally centrifuging at the rotating speed of 3000 revolutions per minute for 1 hour, and taking the upper-layer liquid to obtain MXene dispersion liquid. Weighing 10mL of MXene dispersion liquid, carrying out suction filtration, placing an MXene sheet obtained by suction filtration in a vacuum oven at 80 ℃ for drying to obtain an MXene film, weighing the weight of the MXene film, calculating to obtain the concentration of the MXene dispersion liquid to be 5mg/mL, and placing the MXene film in a refrigerator for low-temperature storage for later use.
(2) Preparing a three-dimensional MXene folded ball/ZnO composite material: 50mL of deionized water was measured and placed in a 100mL beaker, and 0.675 grams of zinc acetate dihydrate was added and stirred for 10 minutes. 20mL of deionized water was weighed into a 150mL beaker, 200mg of PVP-k30 powder was added, stirred for 10 minutes, then 40mL of the prepared MXene dispersion was slowly added dropwise, and stirred for 30 minutes. Then measuring 40mL of zinc acetate solution, slowly adding the zinc acetate solution into the MXene dispersion liquid, stirring for 30 minutes, carrying out ultrasonic atomization at 17MHz, and then carrying the atomized water mist into a pipe with the temperature stabilized at 800 ℃ by using nitrogen with the flow rate of 5L/minIn a furnace, final three-dimensional MXeneTi3C2TxThe wrinkled ball/ZnO composite material powder is carried into an electrostatic collecting device to be collected.
(3) The PI flexible substrate with Au interdigitated electrodes was purchased from gigi sensing technologies, guangzhou, inc. The size of the substrate is 1cm x 1cm, the electrode width and the electrode gap are both 100nm, and the Au electrode deposition thickness is 100 nm.
(4) And (3) drop coating of a three-dimensional MXene wrinkle ball/ZnO composite material: and repeatedly washing the manufactured flexible PI substrate with the Au interdigital electrode by using deionized water and absolute ethyl alcohol, and drying. And (4) using the adhesive tape to stick all around the electrode for masking, so that the dispensing range is stabilized in the interdigital electrode area. Weighing 4mg of three-dimensional MXene folded ball/ZnO composite material powder, uniformly mixing with 1mL of deionized water, uniformly dripping the mixture on a flexible PI substrate after full dispersion, and then placing the flexible PI substrate in a vacuum drying oven at 80 ℃ for 30 minutes. Thereby preparing the planar flexible room temperature gas sensor taking the three-dimensional MXene folded ball/ZnO composite material as a sensitive material.
Gas-sensitive test:
(1) connecting the sensor to a Fluke signal tester, and respectively placing a two-dimensional MXene sensor, a three-dimensional MXene wrinkle ball sensor and a three-dimensional MXene wrinkle ball/ZnO composite material sensor in 100ppm ethanol, acetone, toluene, formaldehyde, ammonia gas and NO2The resistance signal test is performed in the atmosphere of (2). The test method of the sensor adopts a traditional static test method, and comprises the following specific processes:
1. connecting the sensor to a Fluke signal tester, placing the sensor in a test bottle filled with air with the volume of 1L to achieve stability, namely, the resistance value (R) of the sensor in the airair)。
2. The sensor was quickly transferred to a test bottle containing 100ppm of the target gas until the response signal stabilized, i.e., the resistance value (R) of the sensor in the target gas.
3. And (4) transferring the sensor back to the empty gas cylinder until the sensor is stable, and finishing a response recovery process by the sensor. The ratio of the resistance difference value | Δ R | of the sensor in the target gas and in the air to the resistance value in the air (| Δ R |/R |)air100%) is the sameThe response value of the sensor to the ammonia gas with the concentration.
(2) Connecting the sensors to a Fluke signal tester, and respectively placing the three-dimensional MXene wrinkled ball sensor and the three-dimensional MXene wrinkled ball/ZnO composite material sensor in air, 5ppm, 10ppm, 20ppm, 50ppm and 100ppm of NO2The resistance signal test is performed in the atmosphere of (2). The test method of the sensor adopts a traditional static test method, and comprises the following specific processes:
1. connecting the sensor to a Fluke signal tester, placing the sensor in a test bottle filled with air with the volume of 1L to achieve stability, namely, the resistance value (R) of the sensor in the airair)。
2. Rapidly transferring the sensor to the container with NO to be measured2Until the response signal is stable, i.e. the sensor is NO2Resistance value (R) in (1).
3. And (4) transferring the sensor back to the empty gas cylinder until the sensor is stable, and finishing a response recovery process by the sensor. Sensor in NO2And the ratio of the resistance difference value | Δ R | in the air to the resistance value in the air (| Δ R |/R |)air100%) is the response value of the sensor to the ammonia gas with the concentration.
(3) Connecting the sensor on a Fluke signal tester, and respectively bending the three-dimensional MXene folded ball/ZnO composite material sensor by 30 degrees, 60 degrees, 90 degrees and 120 degrees and placing the sensors in 100ppmNO2And (5) carrying out resistance signal test. The test method of the sensor adopts a traditional static test method, and comprises the following specific processes:
1. connecting the sensor to a Fluke signal tester, placing the sensor bent by 30 degrees in a test bottle filled with air and having a volume of 1L to achieve stability, namely, the resistance value (R) of the sensor in the airair)。
2. Rapid transfer of a bent 30 ℃ sensor to a cell containing 100ppm NO2Until the response signal is stable, i.e. the sensor is NO2Resistance value (R) in (1).
3. And (4) transferring the sensor back to the empty gas cylinder until the sensor is stable, and finishing a response recovery process by the sensor. Sensor in NO2And difference in resistance | Δ in airRatio of R to resistance in air (| DeltaR |/R)air100%) is the response value of the sensor to the ammonia gas with the concentration.
4. Bending the sensor by 60 degrees, 90 degrees and 120 degrees in sequence, repeating the process of 1-3, and testing 100NO under different bending angles2In response to (2).
Table 1: two-dimensional MXene sensor, three-dimensional MXene fold ball sensor and | delta R |/R of three-dimensional MXene fold ball/ZnO composite material sensorairData of change with target gas of 100%
Table 2: three-dimensional MXene fold ball sensor and | delta R |/R of three-dimensional MXene fold ball/ZnO composite material sensorair100% with NO2Data on the change in concentration
Table 3: three-dimensional MXene folded ball/ZnO composite material sensor pair 100ppmNO2Is | Δ R |/Rair100% change data with bend angle
The ratio of the difference between the resistance value of a planar flexible room temperature gas sensor made of two-dimensional MXene, three-dimensional MXene wrinkled ball and three-dimensional MXene wrinkled ball/ZnO composite material in different gases with the concentration of 100ppm and the resistance value in the air to the air resistance value is listed in Table 1. As can be seen from the table, the response values of the three-dimensional MXene wrinkled spheres to the gases are increased compared with the two-dimensional MXene, but the NO is increased2The response of the composite ZnO is obviously improved, and the composite ZnO can react with NO after forming three-dimensional MXene wrinkle balls/ZnO2The response value of (2) is further improved, and the selectivity is more prominent.
Table 2 lists plane soft materials made of three-dimensional MXene wrinkle balls and three-dimensional MXene wrinkle ball/ZnO composite materialsDifferent concentration NO of sexual room temperature gas sensor2The ratio of the difference between the resistance value in air and the resistance value in air to the resistance value in air is dependent on NO2The value of the change in concentration. As can be seen from the table, after compounding ZnO, NO2The response of the device is greatly improved.
Table 3 lists the bending angles of the planar flexible room temperature gas sensor made of three-dimensional MXene wrinkled ball/ZnO composite material at 100ppmNO2And the ratio of the difference between the resistance value in air and the resistance value in air to the resistance value in air. It can be seen that after bending over a large angle, the sensor pair NO2Good response values can still be maintained.
Therefore, the planar flexible room temperature gas sensor which is prepared based on the three-dimensional MXene wrinkled ball/ZnO composite material and developed by the inventor shows NO2The high response value, high selectivity and high recoverability of the flexible test strip can meet the designed room temperature working condition and realize the flexible test.
Claims (2)
1. A planar flexible room temperature nitrogen dioxide sensor based on a three-dimensional MXene folded ball/ZnO composite material comprises a polyimide flexible substrate with an Au interdigital electrode and sensitive electrodes prepared on the substrate and the interdigital electrode, wherein the sensitive electrode material is the three-dimensional MXene folded ball/ZnO composite material and is prepared by the following steps,
(1) weighing Ti3AlC2Slowly adding the powder into etching liquid formed by mixing concentrated hydrochloric acid with the mass fraction of 30-40% and lithium fluoride, and adding Ti3AlC2The mass ratio of the powder to the lithium fluoride is 0.8-1: 1, Ti3AlC2The mass-volume ratio of the powder to the concentrated hydrochloric acid is 1 g: 30-50 mL; stirring and reacting for 20-24 hours in water bath at 40-60 ℃, repeatedly washing and centrifuging a product after the reaction is finished by using deionized water until the pH value of a supernatant is 6-7; then dispersing the washed product in 60-70 mL of deionized water, performing ultrasonic dispersion for 30-60 min, centrifuging to obtain an upper-layer dispersion liquid to obtain an MXene colloid dispersion liquid, wherein the concentration of MXene colloid in the dispersion liquid is 4-6 mg/mL;
(2) taking 30-50 mL of MXene dispersion liquid, and then adding the MXene dispersion liquid into 10-30 mL of PVP-k30 aqueous solution, wherein the mass ratio of PVP-k30 to MXene is 0.9-1: 1, after fully stirring, slowly adding 30-50 mL of zinc acetate solution, wherein the mass ratio of zinc acetate to MXene is (1-1.1): 1, ultrasonic spraying after fully stirring; and (3) introducing the ultrasonic atomization product into a tubular furnace with the temperature stabilized at 600-800 ℃ by using nitrogen with the flow speed of 2-6L/min, and introducing the obtained three-dimensional MXene folded ball/ZnO composite material powder into an electrostatic collection device by using the nitrogen for collection.
2. The planar flexible room temperature nitrogen dioxide sensor based on the three-dimensional MXene wrinkled ball/ZnO composite material, according to claim 1, is characterized in that: repeatedly washing a polyimide flexible substrate with the Au interdigital electrode by using deionized water and absolute ethyl alcohol, drying, and sticking the area around the electrode by using an adhesive tape to perform masking, so that the dropping range is stabilized in the interdigital electrode area, and the error among sensors is reduced; weighing three-dimensional MXene folded ball/ZnO composite material powder and deionized water according to the weight ratio of (3-5): uniformly mixing 1mL of the mixture in proportion, uniformly and dropwisely coating the mixture on a polyimide flexible substrate with Au interdigital electrodes after fully dispersing, and then drying the polyimide flexible substrate for 30-40 minutes at 80-90 ℃ under a vacuum condition; removing the adhesive tape to prepare the planar flexible room temperature NO taking the three-dimensional MXene wrinkled ball/ZnO composite material as the sensitive electrode2A sensor.
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Cited By (12)
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| CN111307883A (en) * | 2020-03-19 | 2020-06-19 | 中国石油大学(华东) | Preparation method of ammonia gas sensor based on polyaniline-vanadium carbide, detection system and application thereof |
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| CN112254851A (en) * | 2020-10-16 | 2021-01-22 | 重庆大学 | Alk-Ti3C2Preparation method of PDMS flexible piezoresistive sensor |
| CN112382686A (en) * | 2020-10-27 | 2021-02-19 | 华南理工大学 | ZnO/Ti3C2TxLinear ultraviolet detector and preparation method thereof |
| CN112382686B (en) * | 2020-10-27 | 2023-03-21 | 华南理工大学 | ZnO/Ti 3 C 2 T x Linear ultraviolet detector and preparation method thereof |
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| CN112964754B (en) * | 2021-02-09 | 2024-01-26 | 上海应用技术大学 | Synthesis method of flexible ethanol sensor |
| CN113327775B (en) * | 2021-05-28 | 2022-04-29 | 河北工业大学 | Preparation method of potassium ion micro hybrid capacitor and electrode material |
| CN113327775A (en) * | 2021-05-28 | 2021-08-31 | 河北工业大学 | Preparation method of potassium ion micro hybrid capacitor and electrode material |
| CN113567510A (en) * | 2021-06-11 | 2021-10-29 | 厦门大学 | Preparation method of MXene-based composite metal nano-dot structure gas sensor |
| CN113804732A (en) * | 2021-08-24 | 2021-12-17 | 湘潭大学 | Wearable humidity sensing device for detecting human body sweating rate and manufacturing method thereof |
| CN113791126A (en) * | 2021-09-17 | 2021-12-14 | 吉林大学 | Degradable NO based on three-dimensional porous MXene folded spheres2Sensor and preparation method thereof |
| CN113791126B (en) * | 2021-09-17 | 2022-08-26 | 吉林大学 | Degradable NO based on three-dimensional porous MXene folded spheres 2 Sensor and preparation method thereof |
| CN114264702A (en) * | 2021-12-24 | 2022-04-01 | 安徽工业大学 | MXene @ Au self-repairing hydrogel gas-sensitive material, gas-sensitive element, gas sensor, preparation method and application of gas-sensitive element |
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