CN116794118A - In-based 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 Sensor and preparation method thereof - Google Patents
In-based 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 Sensor and preparation method thereof Download PDFInfo
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 48
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical group [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000011258 core-shell material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 47
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- 238000010438 heat treatment Methods 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 9
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- FTLHORLYDROOSU-UHFFFAOYSA-N indium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FTLHORLYDROOSU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011895 specific detection Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 9
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000004693 imidazolium salts Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000007443 Neurasthenia Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- LECSHJWIACEDPZ-UHFFFAOYSA-N ethane-1,2-diamine naphthalene hydrochloride Chemical compound C(CN)N.C1=CC=CC2=CC=CC=C12.Cl LECSHJWIACEDPZ-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 230000000241 respiratory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
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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
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a method based on In 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor and a preparation method thereof relate to the technical field of semiconductor gas sensors. NO (NO) 2 The sensor is made of Al with the size of 10mm multiplied by 10mm 2 O 3 The ceramic substrate, the Au interdigital electrode and the sensitive material coated on the Au interdigital electrode are composed, wherein the sensitive material is In 2 O 3 ZIF-8 core-shell nanocube composite material. In (In) 2 O 3 The side length of the nanocube is about 30-40 nm, and the ZIF-8 filter film is coated on In 2 O 3 The thickness of the surface of the nanocube is about 5-10 nm. The invention utilizes microscopic regulation and control of In 2 O 3 The nano cube size enhances the surface activity, and the ZIF-8 filter film is coated on the surface to effectively improve the NO of the sensor 2 Is a specific recognition sensitive property of (a). In addition, the device of the invention has simple process and small volume, and is suitable for mass productionThus in a specific detection microenvironment NO 2 The concentration field has wide application prospect.
Description
Technical Field
The invention relates to the technical field of semiconductor gas sensors, in particular to an In-based gas sensor 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor and a method for manufacturing the same.
Background
In recent years, rapid developments in the urban, industrial and transportation industries have resulted in serious air pollution. Nitrogen dioxide (NO) 2 ) Is six typical Pollutants (PM) of the atmosphere 2.5 、PM 10 、O 3 、SO 2 、NO 2 CO) is a toxic, pungent and highly corrosive gas, and is widely derived from fossil fuel combustion, industrial tail gas and automobile tail gas. NO (NO) 2 The gas can disturb the atmospheric components, bring extreme weather such as acid rain, and the like, and cause serious damage to the ecological environment and corrosion of buildings. In addition, NO 2 The gas also can cause great harm to human health, breathe trace NO 2 The gas stimulates the respiratory tract and causes dry cough or pharyngeal discomfort. If the human body is exposed to NO 2 The gas exceeds 15 minutes, which can lead to chronic respiratory inflammation, neurasthenia syndrome and other diseases. No is regulated by the maximum allowable concentration file of harmful substances in the atmosphere in living areas of China 2 The concentration cannot exceed 0.15 mg/m 3 . Thus, monitoring NO in the atmosphere in real time 2 The concentration has important significance for protecting urban ecological environment and human health.
At present, NO in urban atmosphere 2 The concentration is determined mainly by naphthalene ethylenediamine hydrochloride spectrophotometry. Although the method has the advantages of high sensitivity, good selectivity and the like, the Gao Angjia grid of the precise instrument greatly increases the detection cost, and the complicated measurement steps consume excessive manpower and cannot detect the air pollution condition in real time. Compared with gas sensors such as infrared spectrum, gas chromatography and electrochemistry, the chemical resistance type gas sensor based on the semiconductor oxide has the advantages of miniaturization, low cost, excellent gas sensitivity performance, real-time detection and the likeThe advantages are widely researched and focused, and the method has great application potential in the field of urban atmospheric environment detection. But the further development is still limited by the defects of high working temperature, poor selectivity and the like.
The optimal working temperature can be effectively reduced by modification methods such as microcosmic morphology regulation and noble metal modification. The larger specific surface area can improve the surface activity of the sensing material, reduce the adsorption energy of gas molecules, and the chemical sensitization of noble metal can increase the number of negative oxygen species on the surface, thereby reducing the working temperature. The selectivity of the gas sensor can be improved by utilizing the specific recognition capability of noble metal or special semiconductor material to the target gas. However NO 2 The molecule is a typical macromolecular with pi-bond structure, and an unpaired electron is arranged outside the atomic nucleus and has stronger chemisorption capability, so that the traditional modification method is difficult to improve the NO of the semiconductor material 2 Is selected from the group consisting of (1). In recent years, researchers have found that the porous structure of Metal Organic Framework (MOF) materials can filter macromolecular interfering gases, thereby improving the selectivity of gas sensors. ZIFs are imidazolium salts (Im) or functional imidazolium salts formed by coordination of metal ions with nitrogen atoms, the pore size and adsorption properties of which can be controlled by adjusting the imidazole ligand species. However, the sensitivity is lower because the MOF filter layer reduces the contact area between the target gas and the sensitive material. On the basis of improving the selectivity of the MOF filter layer, the surface activity of the sensitive material is improved through microscopic morphology control, so that the dual improvement of the sensitivity and the selectivity is realized, and further research is still needed.
Disclosure of Invention
The invention aims to solve NO 2 In the preparation of the sensor, the porous structure of the Metal Organic Framework (MOF) material can filter macromolecular interference gas, improve the selectivity, but has lower sensitivity, and provide a sensor based on In 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor and a method for manufacturing the same.
The invention is realized by the following technical scheme: in-based 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 The sensor is used for detecting the position of the sensor,from Al of size 10mm ×10mm 2 O 3 Ceramic substrate, au interdigital electrode and sensitive material coated on the Au interdigital electrode, wherein the Au interdigital electrode and Al 2 O 3 The connection mode of the ceramic substrate is well known, and the sensitive material is In 2 O 3 ZIF-8 core-shell nanocube composite material. In (In) 2 O 3 The ZIF-8 core-shell nanocube composite material is prepared through the following steps.
(1) Dissolving 0.6-0.7 g of indium nitrate pentahydrate in 15 ml deionized water, magnetically stirring for 10-20 min, adding 15-ml n-butylamine, and continuously stirring for 1-h until complete mixing; transferring the obtained solution into a stainless steel autoclave lined with 50 ml polytetrafluoroethylene, performing solvothermal reaction for 5-7 hours at 120 ℃, respectively centrifugally washing 3 times by deionized water and absolute ethyl alcohol after the reaction is finished, and finally, placing the reaction product into a vacuum oven and drying for 6-h at 60 ℃; transferring the dried reaction product to a crucible, calcining at 400 ℃ in the atmosphere of air in a muffle furnace for 2 h, wherein the heating rate is 10 ℃/min; finally, in is obtained 2 O 3 A nanocube;
(2) Dissolving 0.08-0.10 g of dimethyl imidazole in a methanol solution of 20 ml, and magnetically stirring for 10 min; taking In prepared In step (1) of 0.277 and 0.277 g 2 O 3 Adding the nanocubes into a methanol solution in which dimethyl imidazole is dissolved, and continuously stirring for 20min to obtain a solution (1); simultaneously, 0.04 g zinc chloride is dissolved in 20 ml methanol solution, and the solution (2) is obtained by magnetic stirring for 10 min; then the solution (2) is slowly added into the solution (1) dropwise, the obtained mixed solution is stirred for 1 h and then is transferred into a stainless steel autoclave lined with 50 ml polytetrafluoroethylene for solvothermal reaction at 75 ℃ for 12 h; after cooling to room temperature, the product was centrifugally washed 3 times with methanol solution and dried 6 h In a vacuum oven at 60℃to give In 2 O 3 ZIF-8 core-shell nanocube composite material.
The preparation method comprises the step (1) of preparing In 2 O 3 A nanocube with a side length of 30-40 nm; therefore, has larger specific surface area and is beneficial to improving In 2 O 3 Nano material surface activity for raising negative oxygen ion on surfaceThe number of sub-species increases the subsequent gas-sensitive redox active sites. In obtained In the step (2) 2 O 3 The ZIF-8 core-shell nanocube composite material is prepared by coating a ZIF-8 filter film on In 2 O 3 The thickness of the ZIF-8 filter film on the surface of the nanocube is 5-10 nm. In (In) 2 O 3 The ZIF-8 filter film with the surface modified on the nanocube can effectively reduce NO caused by macromolecular interference gases such as ethanol, acetone and the like 2 To achieve dual enhancement of sensitivity and selectivity.
In prepared based on the above preparation method 2 O 3 ZIF-8 core-shell nanocube composite material, NO 2 The preparation method of the sensor specifically comprises the following steps: 0.05 to 0.1 g of In 2 O 3 Mixing the ZIF-8 core-shell nanocube composite material with 0.5-1 ml of absolute ethyl alcohol, grinding In a mortar to form adhesive slurry, dipping the adhesive slurry by using a brush, uniformly coating the adhesive slurry on an Au interdigital electrode, placing the Au interdigital electrode on a heating table, baking at 80 ℃ for 20-30 min, and obtaining the In-based adhesive material after the adhesive slurry is dried 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor.
Compared with the prior art, the invention has the following beneficial effects: the invention provides an In-based liquid crystal display device 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor and a preparation method thereof are provided:
(1) The ZIF-8 filter film modified In is prepared by a simple solvothermal method and an In-situ growth method 2 O 3 The nano cube composite material has simple synthesis method and low cost;
(2) In control by micro-morphology modulation 2 O 3 The dimension of the nanocube greatly improves the specific surface area, increases the amount of oxygen adsorbed on the surface of the material and improves the NO ratio 2 And has a fast response recovery speed. On the basis, the ZIF-8 filter film coated on the surface can effectively inhibit the cross sensitivity of macromolecular interference gas and improve the selectivity. Thus, the sensor can detect NO in specific recognition 2 The field has wide application prospect;
(3) The invention has simple manufacturing process and small volume, is beneficial to industrial mass production and has important application value.
Drawings
FIG. 1 is a TEM morphology of comparative example 1 and example 2 of the present invention; wherein fig. 1 (a) is a TEM image of comparative example 1, and fig. 1 (b) is a TEM image of example 2.
Figure 2 is an XRD pattern of comparative example 1 and example 2 prepared according to the present invention.
FIG. 3 shows the results of the sensors of comparative example 1, example 2, example 3 according to the invention for 1 ppm NO at different test temperatures 2 Sensitivity contrast curve of (2).
FIG. 4 shows the sensor of example 2 of the present invention for different concentrations of NO at optimal operating temperature 2 Is a dynamic resistance curve of (a).
FIG. 5 shows the sensor of comparative example 1 and example 2 of the present invention at different NO 2 Gas-sensitive response at concentration.
FIG. 6 shows the responsiveness of the sensor of comparative example 1 and example 2 of the present invention to 200 ppm of other gases at 125 ℃.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Comparative example 1
(1) 0.65g of indium nitrate pentahydrate was dissolved in 15 ml deionized water, and after 20min magnetic stirring, 15 ml of n-butylamine was added and stirring was continued for 1 h until complete mixing. Then the obtained solution is transferred to a stainless steel autoclave lined with 50 ml polytetrafluoroethylene for solvothermal reaction at 120 ℃ for 6 h, after the reaction is finished, deionized water and absolute ethyl alcohol are respectively used for centrifugal washing for 3 times, and finally the reaction product is placed in a vacuum oven for drying at 60 ℃ for 6 h. And (3) transferring the dried reaction product to a crucible, and calcining at 400 ℃ in an air atmosphere in a muffle furnace for 2 h, wherein the heating rate is 10 ℃/min. Finally, in is obtained 2 O 3 Nanocubes.
(2) Will be 0.1 In 0.1 g 2 O 3 Nanocube material and 1 ml absolute ethyl alcoholMixing, grinding In a mortar to form adhesive slurry, dipping a small amount of adhesive slurry with a brush, uniformly coating on the Au interdigital electrode, placing the Au interdigital electrode on a heating table, baking at 80deg.C for 25 min, and drying the sensitive material to obtain the In-based material 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor.
Example 1
(1) 0.65g of indium nitrate pentahydrate was dissolved in 15 ml deionized water, and after 20min magnetic stirring, 15 ml of n-butylamine was added and stirring was continued for 1 h until complete mixing. Then the obtained solution is transferred to a stainless steel autoclave lined with 50 ml polytetrafluoroethylene for solvothermal reaction at 120 ℃ for 6 h, after the reaction is finished, deionized water and absolute ethyl alcohol are respectively used for centrifugal washing for 3 times, and finally the reaction product is placed in a vacuum oven for drying at 60 ℃ for 6 h. And (3) transferring the dried reaction product to a crucible, and calcining at 400 ℃ in an air atmosphere in a muffle furnace for 2 h, wherein the heating rate is 10 ℃/min. Finally, in is obtained 2 O 3 Nanocubes.
(2) 0.08 g of dimethylimidazole was dissolved in 20 ml of methanol solution and magnetically stirred for 10 min. Taking In prepared In step (1) of 0.277 and 0.277 g 2 O 3 Adding nanocubes into the above solution, and stirring for 20min to obtain solution (1). Meanwhile, 0.04. 0.04 g of zinc chloride is dissolved in 20 ml of methanol solution, and the solution (2) is obtained by magnetic stirring for 10 min. Solution (2) was then slowly added dropwise to solution (1), and the resulting mixture was stirred for 1 h and transferred to a 50 ml teflon lined stainless steel autoclave for solvothermal reaction at 75 ℃ 12 h. After cooling to room temperature, the product was centrifugally washed 3 times with methanol solution and dried 6 h In a vacuum oven at 60℃to give In 2 O 3 ZIF-8 core-shell nanocube composite material.
(3) Will be 0.1 In 0.1 g 2 O 3 Mixing ZIF-8 core-shell nanocube composite material with 1 ml absolute ethyl alcohol, grinding in a mortar to form viscous slurry, dipping a small amount of viscous slurry by using a brush, uniformly coating the viscous slurry on an Au interdigital electrode, placing the interdigital electrode on a heating table, baking at 80 ℃ for 25 min, and drying the viscous slurryThe material becomes sensitive material, and is based on In 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor.
Example 2
(1) 0.6 g indium nitrate pentahydrate was dissolved in 15 ml deionized water, and after 15 min magnetic stirring, 15 ml n-butylamine was added and stirring was continued for 1 h until complete mixing. And then transferring the obtained solution into a stainless steel autoclave lined with 50 ml polytetrafluoroethylene, performing solvothermal reaction for 5-7 hours at 120 ℃, respectively centrifugally washing 3 times by using deionized water and absolute ethyl alcohol after the reaction is finished, and finally, placing the reaction product into a vacuum oven and drying for 6-h at 60 ℃. And (3) transferring the dried reaction product to a crucible, and calcining at 400 ℃ in an air atmosphere in a muffle furnace for 2 h, wherein the heating rate is 10 ℃/min. Finally, in is obtained 2 O 3 Nanocubes.
(2) 0.09 g of dimethylimidazole was dissolved in 20 ml of methanol solution and magnetically stirred for 10 min. Taking In prepared In step (1) of 0.277 and 0.277 g 2 O 3 Adding nanocubes into the above solution, and stirring for 20min to obtain solution (1). Meanwhile, 0.04. 0.04 g of zinc chloride is dissolved in 20 ml of methanol solution, and the solution (2) is obtained by magnetic stirring for 10 min. Solution (2) was then slowly added dropwise to solution (1), and the resulting mixture was stirred for 1 h and transferred to a 50 ml teflon lined stainless steel autoclave for solvothermal reaction at 75 ℃ 12 h. After cooling to room temperature, the product was centrifugally washed 3 times with methanol solution and dried 6 h In a vacuum oven at 60℃to give In 2 O 3 ZIF-8 core-shell nanocube composite material.
(3) Will be 0.06 g In 2 O 3 Mixing the ZIF-8 core-shell nanocube composite material with 0.8 ml absolute ethyl alcohol, grinding In a mortar to form viscous slurry, dipping a small amount of viscous slurry by using a brush, uniformly coating the viscous slurry on an Au interdigital electrode, placing the interdigital electrode on a heating table, baking at 80 ℃ for 20-30 min, and obtaining the In-based material after the viscous slurry is dried 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor.
Example 3
(1) 0.7 g indium nitrate pentahydrate was dissolved in 15 ml deionized water, and after magnetic stirring for 10 min, 15 ml n-butylamine was added and stirring was continued for 1 h until complete mixing. Then the obtained solution is transferred to a stainless steel autoclave lined with 50 ml polytetrafluoroethylene for solvothermal reaction at 120 ℃ for 5.5 h, after the reaction is finished, the solution is respectively centrifugally washed for 3 times by deionized water and absolute ethyl alcohol, and finally the reaction product is placed in a vacuum oven for drying at 60 ℃ for 6 h. And (3) transferring the dried reaction product to a crucible, and calcining at 400 ℃ in an air atmosphere in a muffle furnace for 2 h, wherein the heating rate is 10 ℃/min. Finally, in is obtained 2 O 3 Nanocubes.
(2) 0.1. 0.1 g of dimethylimidazole was dissolved in 20. 20 ml of methanol solution and magnetically stirred for 10 min. Taking In prepared In step (1) of 0.277 and 0.277 g 2 O 3 Adding nanocubes into the above solution, and stirring for 20min to obtain solution (1). Meanwhile, 0.04. 0.04 g of zinc chloride is dissolved in 20 ml of methanol solution, and the solution (2) is obtained by magnetic stirring for 10 min. Solution (2) was then slowly added dropwise to solution (1), and the resulting mixture was stirred for 1 h and transferred to a 50 ml teflon lined stainless steel autoclave for solvothermal reaction at 75 ℃ 12 h. After cooling to room temperature, the product was centrifugally washed 3 times with methanol solution and dried 6 h In a vacuum oven at 60℃to give In 2 O 3 ZIF-8 core-shell nanocube composite material.
(3) Will be 0.08 g In 2 O 3 Mixing the ZIF-8 core-shell nanocube composite material with 0.5-1 ml of absolute ethyl alcohol, grinding In a mortar to form viscous slurry, dipping a small amount of viscous slurry by using a brush, uniformly coating the viscous slurry on an Au interdigital electrode, placing the interdigital electrode on a heating table, baking at 80 ℃ for 30 min, and obtaining the In-based material after the viscous slurry is dried, wherein the viscous slurry is a sensitive material 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor.
As shown In FIG. 1, in can be seen 2 O 3 The nano material is in a cube shape, and the side length is about 30-40 nm; ZIF-8 filter film is coated on In 2 O 3 Nano cube surface, thicknessThe degree is about 5 to 10nm.
As shown In FIG. 2, according to In 2 O 3 XRD spectrum of the ZIF-8 core-shell nanocube composite material can be seen In 2 O 3 And characteristic peaks of ZIF-8, indicating that the sample contains In 2 O 3 And ZIF-8 crystals.
As shown in FIG. 3, the optimal operating temperature for all sensors is 125℃and the sensor pair in example 2 is 1 ppm NO 2 The gas response is as high as 50.
As shown in FIG. 4, the amplitude of the sensor resistance change in example 2 was varied with NO at a device operating temperature of 125 DEG C 2 The increase in concentration increases.
As shown in FIG. 5, NO 2 The gas-sensitive response of the sensor in example 2 was higher than that of the sensor in comparative example 1 over the range of test concentrations.
As shown in fig. 6, the cross-responsiveness of example 2 to other gases is significantly lower than that of comparative example 1.
It should be noted that: the responsivity of the device is defined as its resistance value (R g ) And the resistance value in air (R a ) The ratio is S=R g /R a . During the test, a dynamic test system is used for testing. The device is placed in a gas chamber, a certain amount of gas to be detected is automatically injected by a dynamic gas distribution system, the resistance change is observed and recorded, and the corresponding sensitivity value is obtained through calculation.
The scope of the present invention is not limited to the above embodiments, and various modifications and alterations of the present invention will become apparent to those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (4)
1. In-based 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 The sensor is made of Al with the size of 10mm multiplied by 10mm 2 O 3 Ceramic substrate, au interdigital electrode and sensitive material coated on the Au interdigital electrodeThe method is characterized in that: the sensitive material is In 2 O 3 ZIF-8 core-shell nanocube composite material.
2. In-based 2 O 3 The preparation method of the ZIF-8 core-shell nanocube composite material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Dissolving 0.6-0.7 g of indium nitrate pentahydrate in 15 ml deionized water, magnetically stirring for 10-20 min, adding 15-ml n-butylamine, and continuously stirring for 1-h until complete mixing; transferring the obtained solution into a stainless steel autoclave lined with 50 ml polytetrafluoroethylene, performing solvothermal reaction for 5-7 hours at 120 ℃, respectively centrifugally washing 3 times by deionized water and absolute ethyl alcohol after the reaction is finished, and finally, placing the reaction product into a vacuum oven and drying for 6-h at 60 ℃; transferring the dried reaction product to a crucible, calcining at 400 ℃ in the atmosphere of air in a muffle furnace for 2 h, wherein the heating rate is 10 ℃/min; finally, in is obtained 2 O 3 A nanocube;
(2) Dissolving 0.08-0.10 g of dimethyl imidazole in a methanol solution of 20 ml, and magnetically stirring for 10 min; taking In prepared In step (1) of 0.277 and 0.277 g 2 O 3 Adding the nanocubes into a methanol solution in which dimethyl imidazole is dissolved, and continuously stirring for 20min to obtain a solution (1); simultaneously, 0.04 g zinc chloride is dissolved in 20 ml methanol solution, and the solution (2) is obtained by magnetic stirring for 10 min; then the solution (2) is slowly added into the solution (1) dropwise, the obtained mixed solution is stirred for 1 h and then is transferred into a stainless steel autoclave lined with 50 ml polytetrafluoroethylene for solvothermal reaction at 75 ℃ for 12 h; after cooling to room temperature, the product was centrifugally washed 3 times with methanol solution and dried 6 h In a vacuum oven at 60℃to give In 2 O 3 ZIF-8 core-shell nanocube composite material.
3. An In-based alloy as claimed In claim 2 2 O 3 The preparation method of the ZIF-8 core-shell nanocube composite material is characterized by comprising the following steps of: in obtained In step (1) 2 O 3 A nanocube with a side length of 30-40 nm; in obtained In the step (2) 2 O 3 The ZIF-8 core-shell nanocube composite material is prepared by coating a ZIF-8 filter film on In 2 O 3 The thickness of the ZIF-8 filter film on the surface of the nanocube is 5-10 nm.
4. In-based 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 The preparation method of the sensor is characterized by comprising the following steps of: in prepared by the method of claim 2 2 O 3 The ZIF-8 core-shell nanocube composite material comprises the following concrete processes: 0.05 to 0.1 g of In 2 O 3 Mixing the ZIF-8 core-shell nanocube composite material with 0.5-1 ml of absolute ethyl alcohol, grinding In a mortar to form adhesive slurry, dipping the adhesive slurry by using a brush, uniformly coating the adhesive slurry on an Au interdigital electrode, placing the Au interdigital electrode on a heating table, baking at 80 ℃ for 20-30 min, and obtaining the In-based adhesive material after the adhesive slurry is dried 2 O 3 NO of/ZIF-8 core-shell nanocube composite material 2 A sensor.
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