CN114965651A - ZnO-based methane sensor and preparation method and application thereof - Google Patents
ZnO-based methane sensor and preparation method and application thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 221
- 239000011787 zinc oxide Substances 0.000 claims abstract description 103
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002105 nanoparticle Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 23
- 239000004246 zinc acetate Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000005286 illumination Methods 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 238000004880 explosion Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004528 spin coating Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 13
- 238000001035 drying Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The invention relates to the technical field of methane gas detection, in particular to a ZnO-based methane sensor and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: firstly mixing zinc acetate, oxalic acid and water, carrying out coprecipitation reaction, and then carrying out heat treatment to obtain zinc oxide nano particles; secondly, mixing the zinc oxide nano particles with an alcohol organic solvent to obtain zinc oxide slurry; and coating the zinc oxide slurry on the surface of an electrode to form a film, and then sequentially carrying out annealing treatment and illumination to obtain the ZnO-based methane sensor. The ZnO-based methane sensor prepared by the preparation method does not need to increase the temperature of a device when detecting methane gas, and can avoid accidental explosion caused by increasing the temperature of the device when detecting methane gas.
Description
Technical Field
The invention relates to the technical field of methane gas detection, in particular to a ZnO-based methane sensor and a preparation method and application thereof.
Background
Methane is used as a basic energy source, is widely applied to the life and industry of people, brings great convenience to the life and social development of human beings, and is accompanied with great harm due to the characteristics of flammability, explosiveness and the like. The major accidents caused by methane explosion are rare every year, which cause huge property loss and casualties, and the accidents are caused by that the methane can not be detected in time and is gathered in a closed space to cause explosion. The methane has special properties, and a tetrahedrally symmetrical structure is formed by C-H bonds, and the bond energy of the C-H bonds is up to 434 kJ.mol -1 The activation of the C-H bond of methane becomes an important way for realizing methane detection of the traditional semiconductor sensor. In the traditional semiconductor sensor, the module is required to be added to provide high temperature for assisting the semiconductor to activate methane, so that the methane is detected, and the methane is used as combustible gas, so that the detection at high temperature undoubtedly increases the risk.
Disclosure of Invention
The ZnO-based methane sensor prepared by the preparation method does not need to increase the temperature of a device when detecting methane gas, and can avoid accidental explosion caused by increasing the temperature of the device when detecting methane gas.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a ZnO-based methane sensor, which comprises the following steps:
firstly mixing zinc acetate, oxalic acid and water, carrying out coprecipitation reaction, and then carrying out heat treatment to obtain zinc oxide nano particles;
secondly, mixing the zinc oxide nano particles with an alcohol organic solvent to obtain zinc oxide slurry;
and coating the zinc oxide slurry on the surface of an electrode to form a film, and then sequentially carrying out annealing treatment and illumination to obtain the ZnO-based methane sensor.
Preferably, the mass ratio of the zinc acetate to the oxalic acid to the water is (1-3): (0.5-2): 100.
preferably, the first mixed feedstock further comprises a soluble metal salt;
the metal elements in the soluble metal salt comprise one or more of Mn, Cu, Ru, Al, Ag and Fe.
Preferably, the mass ratio of the zinc acetate to the soluble metal salt is (0.01-10): 226.
preferably, the temperature of the heat treatment is 250-550 ℃, and the time is 1-10 h.
Preferably, the concentration of the zinc oxide slurry is 0.01-0.1 g/mol;
the annealing temperature is 200-400 ℃, and the time is 0-6 h.
Preferably, the wavelength of the illumination is 300-2500 nm, the power is 50-300W, and the time is 0.5-2 h.
The invention also provides the ZnO-based methane sensor prepared by the preparation method in the technical scheme, which comprises an electrode and a ZnO layer coated on the surface of the electrode.
Preferably, the ZnO in the ZnO layer is undoped ZnO or ZnO doped with a metal element;
the metal elements comprise one or more of Mn, Cu, Ru, Al, Ag and Fe.
The invention also provides the application of the ZnO-based methane sensor in the technical scheme in the field of methane gas detection.
The invention provides a preparation method of a ZnO-based methane sensor, which comprises the following steps: firstly mixing zinc acetate, oxalic acid and water, carrying out coprecipitation reaction, and then carrying out heat treatment to obtain zinc oxide nanoparticles; secondly, mixing the zinc oxide nano particles with an alcohol organic solvent to obtain zinc oxide slurry; and coating the zinc oxide slurry on the surface of an electrode to form a film, and then sequentially carrying out annealing treatment and illumination to obtain the ZnO-based methane sensor.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) the preparation method provided by the invention has the advantages of simple process, low manufacturing cost and good controllability;
2) according to the invention, ZnO is prepared on the surface of the electrode, and continuous illumination is carried out, so that charge transfer caused by catalytic decomposition of methane in the ZnO semiconductor in the photocatalysis process is converted into electric signals of the sensor through the semiconductor sensitivity effect to be output, accidental explosion caused by increasing the temperature of a device when methane gas is detected can be avoided, the prepared sensor has high sensitivity, and the safety of methane concentration detection of the sensor in industrial production, mines and household life is improved.
Drawings
FIG. 1 is a test curve of the sensitivity of a ZnO-based methane gas sensor to methane according to example 2 of the present invention;
FIG. 2 is a stability test curve of the ZnO-based methane gas sensor according to example 2 of the present invention;
FIG. 3 is a schematic structural view of a ZnO-based methane gas sensor according to embodiments 1 to 2 of the present invention, including a 1-ZnO layer and a 2-Au finger electrode.
Detailed Description
The invention provides a preparation method of a ZnO-based methane sensor, which comprises the following steps:
firstly mixing zinc acetate, oxalic acid and water, carrying out coprecipitation reaction, and then carrying out heat treatment to obtain zinc oxide nano particles;
secondly, mixing the zinc oxide nano particles with an alcohol organic solvent to obtain zinc oxide slurry;
and coating the zinc oxide slurry on the surface of an electrode to form a film, and then sequentially carrying out annealing treatment and illumination to obtain the ZnO-based methane sensor.
In the present invention, all the starting materials for the preparation are commercially available products well known to those skilled in the art, unless otherwise specified.
According to the invention, zinc acetate, oxalic acid and water are firstly mixed, and heat treatment is carried out after coprecipitation reaction to obtain the zinc oxide nano-particles.
In the present invention, the zinc acetate is preferably zinc acetate dihydrate; the oxalic acid is preferably oxalic acid dihydrate; the water is preferably deionized water.
In the invention, the mass ratio of the zinc acetate to the oxalic acid to the water is preferably (1-3): (0.5-2): 100, more preferably (1 to 1.5): (0.5-1): 100, most preferably 1.0976:0.6304: 100.
In the present invention, the first mixing is preferably performed under stirring or ultrasonic conditions, and the stirring or ultrasonic process is not particularly limited in the present invention, and the zinc acetate and the oxalic acid are all dissolved in water by a process well known to those skilled in the art.
In the present invention, the first mixed preparation raw material further preferably includes a soluble metal salt; the metal elements in the soluble metal salt comprise one or more of Mn, Cu, Ru, Al, Ag and Fe. In the present invention, the soluble metal salt preferably includes a soluble chloride salt, a soluble nitrate salt or a soluble organic salt.
In the invention, the mass ratio of the zinc acetate to the soluble metal salt is preferably (0.01-10): 226, more preferably (0.05 to 5): 226, most preferably (1-2): 226.
in the present invention, the first mixing process is preferably performed by mixing zinc acetate and water and then adding oxalic acid; the oxalic acid is preferably added dropwise, and the adding process is not limited in any way and can be carried out by adopting a process well known to a person skilled in the art. In the invention, during the dripping of the oxalic acid, the oxalic acid and the zinc acetate are subjected to precipitation reaction. After the completion of the dropwise addition, the present invention also preferably includes a precipitation reaction which proceeds. In the present invention, the precipitation reaction is preferably carried out under stirring or ultrasonic conditions, and the stirring or ultrasonic process is not particularly limited, and the zinc acetate and the oxalic acid are all dissolved in water by a process known to those skilled in the art.
When the first mixed raw material includes a soluble metal salt, the first mixing process is preferably performed by mixing zinc acetate and water and then sequentially adding a soluble metal solution and oxalic acid.
After the coprecipitation reaction is finished, the method also preferably comprises suction filtration and washing; the detergent adopted for suction filtration washing is preferably deionized water; the present invention does not have any particular limitation on the specific process of the suction filtration washing, and the process known to those skilled in the art can be adopted.
In the invention, the temperature of the heat treatment is preferably 250-550 ℃, more preferably 300-450 ℃, and most preferably 350 ℃; the time is preferably 1 to 10 hours, more preferably 4 to 8 hours, and most preferably 6 hours.
In the invention, when the first mixed preparation raw material comprises soluble metal salt, the zinc oxide nanoparticles are metal element doped zinc oxide nanoparticles; the metal element-doped zinc oxide nanoparticles preferably comprise metal element-doped zinc oxide nanoparticles; the doping metal in the zinc oxide nano-particles doped with the metal element is preferably one or more of Mn, Cu, Ru, Al, Ag and Fe.
In the invention, the particle size of the zinc oxide nanoparticles is preferably 10-20 nm, more preferably 12-18 nm, and most preferably 14-16 nm. In the invention, when the zinc oxide nanoparticles are metal element-doped zinc oxide nanoparticles, the doping amount of metal in the metal element-doped zinc oxide nanoparticles is preferably 0.01 to 10.0%, more preferably 0.5 to 8%, and most preferably 1 to 3%.
After obtaining the zinc oxide nano-particles, mixing the zinc oxide nano-particles and an alcohol organic solvent for the second time to obtain the zinc oxide slurry.
The kind of the alcohol organic solvent used in the present invention is not particularly limited, and those known to those skilled in the art can be used. In a specific embodiment of the present invention, the alcohol organic solvent is specifically methanol.
The process of the second mixing is not particularly limited, and may be performed by a process known to those skilled in the art.
In the invention, the concentration of the zinc oxide slurry is preferably 0.01-0.1 g/mL, more preferably 0.02-0.08 g/mL, and most preferably 0.04-0.05 g/mL.
After the zinc oxide slurry is obtained, the zinc oxide slurry is coated on the surface of an electrode to form a film, and then annealing treatment and illumination are sequentially carried out to obtain the ZnO-based methane sensor.
In the present invention, the electrodes are preferably interdigitated electrodes or MEMS electrodes; the interdigital electrodes are preferably ceramic wafer-based interdigital electrodes. In the present invention, the finger width of the interdigital electrode is preferably 300 μm, and the width between two adjacent interdigital electrodes is 300 μm. In the present invention, the interdigital electrode is preferably a gold interdigital electrode (as shown in fig. 3).
In the present invention, the coating method is preferably spin coating. In the present invention, the spin coating preferably includes first spin coating and second spin coating which are sequentially performed; the rotating speed of the first spin coating is preferably 100-1500 rpm, more preferably 300-1300 rmp, and most preferably 500-1000 rpm; the time is preferably 1 to 10s, more preferably 2 to 8s, and most preferably 6 s; the rotation speed of the second spin coating is preferably 2000-5000 rmp, more preferably 2500-4500 rpm, and most preferably 3000-4000 rpm; the time is preferably 10 to 40 seconds, more preferably 15 to 35 seconds, and most preferably 20 to 30 seconds. In the present invention, after the second spin coating is completed, the process of repeating the first spin coating and the second spin coating is also preferably included; the number of repetitions is preferably 3 to 6, and more preferably 5. In the invention, the first spin coating has the function of rotating speed glue homogenizing; the second spin coating functions to volatilize into a film.
After the film formation is completed, the present invention also preferably includes drying. The drying temperature is preferably 60 ℃ and the drying time is preferably 30 min. In the present invention, the drying is preferably performed in an oven.
In the invention, the annealing treatment temperature is preferably 200-400 ℃, more preferably 250-350 ℃, and most preferably 280-320 ℃; the time is preferably 0 to 6 hours, more preferably 1 to 3 hours, and most preferably 1 hour.
After the annealing treatment is completed, the present invention preferably further includes cooling, and the cooling process is not particularly limited in the present invention and may be performed by a process known to those skilled in the art. In a particular embodiment of the invention, the cooling is preferably natural cooling.
In the invention, the wavelength of the illumination is preferably 300-2500 nm, more preferably 350-600 nm, most preferably 365nm, the power is preferably 50-300W, more preferably 150-300W, most preferably 300W, and the time is preferably 0.5-2 h, more preferably 1.0-1.5 h.
In the invention, the organic matter adsorbed on the surface can be catalytically decomposed by the illumination treatment.
After the illumination is finished, the method also preferably comprises aging treatment, wherein the aging treatment is preferably performed in an illumination mode; the wavelength of the aging treatment is preferably 300-2500 nm, more preferably 350-600 nm, most preferably 365nm, the power is preferably 50-300W, more preferably 150-300W, most preferably 300W, and the time is preferably 12 h.
The invention also provides the ZnO-based methane sensor prepared by the preparation method in the technical scheme, which comprises an electrode and a ZnO layer coated on the surface of the electrode.
In the present invention, the electrodes are preferably interdigitated electrodes or MEMS electrodes; the interdigital electrodes are preferably interdigital electrodes based on ceramic sheets. In the present invention, the finger width of the interdigital electrode is preferably 300 μm, and the width between two adjacent interdigital electrodes is 300 μm. In the present invention, the interdigital electrode is preferably a gold interdigital electrode (as shown in fig. 3).
In the invention, ZnO in the ZnO layer is undoped ZnO or ZnO doped with metal elements; the metal element in the ZnO doped with the metal element comprises one or more of Mn, Cu, Ru, Al, Ag and Fe.
The invention also provides the application of the ZnO-based methane sensor in the technical scheme in the field of methane gas detection. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The ZnO-based methane sensor, the preparation method and the application thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1.0976g of zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) and 100mL of deionized water are stirred and dissolved until the solution is transparent, so as to obtain a zinc acetate solution;
0.6304g of oxalic acid dihydrate (C) 2 H 2 O 4 ·2H 2 O) and 100mL of deionized water are stirred until the solution is transparent, and an oxalic acid solution is obtained;
dropwise adding the oxalic acid solution into a zinc oxalate solution, obtaining a zinc oxalate precipitate after full reaction, and performing suction filtration and washing for 2-3 times by using deionized water to obtain the zinc oxalate precipitate;
putting the zinc oxalate precipitate into a tubular furnace, heating to 350 ℃ in air atmosphere, and calcining for 6h to obtain zinc oxide nano particles;
mixing the zinc oxide nano-particles with methanol to obtain a ZnO nano-particle solution with the concentration of 100 mg/mL;
and (3) dripping 25 mu L of ZnO nanoparticles onto the gold finger electrode shown in figure 3 by adopting a spin coating process, uniformly coating for 6s at the rotating speed of 1000rpm, and rotating for 30s at the rotating speed of 3000rpm to volatilize the ZnO nanoparticles into a film. Repeating the steps for 5 times, and drying in an oven at 60 ℃ for 30 minutes to obtain the ZnO film coated finger inserting electrode;
and annealing the finger-inserted electrode coated with the ZnO film for 1 hour at the temperature of 200 ℃, naturally cooling, and irradiating for 60 minutes under a 300W xenon lamp (with the wavelength of 300-2500 nm) to obtain the ZnO-based methane gas sensor.
Example 2
1.0976g of zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) and 100mL of deionized water are stirred and dissolved until the solution is transparent, so as to obtain a zinc acetate solution;
0.6304g of oxalic acid dihydrate (C) 2 H 2 O 4 ·2H 2 O) and 100mL of deionized water are stirred until the solution is transparent, and an oxalic acid solution is obtained;
dropwise adding the oxalic acid solution into a zinc oxalate solution, obtaining a zinc oxalate precipitate after full reaction, and performing suction filtration and washing for 2-3 times by using deionized water to obtain the zinc oxalate precipitate;
putting the zinc oxalate precipitate into a tubular furnace, heating to 350 ℃ in air atmosphere, and calcining for 6h to obtain zinc oxide nano particles;
mixing the zinc oxide nano-particles with methanol to obtain a ZnO nano-particle solution with the concentration of 100 mg/mL;
and (3) dripping 25 mu L of ZnO nanoparticles onto the gold finger electrode shown in figure 3 by adopting a spin coating process, uniformly coating for 6s at the rotating speed of 500rpm, and rotating for 20s at the rotating speed of 4000rpm to volatilize the ZnO nanoparticles into a film. Repeating the steps for 5 times, and drying in an oven at 60 ℃ for 30 minutes to obtain the ZnO film coated finger inserting electrode;
and annealing the finger-inserted electrode coated with the ZnO film for 1 hour at the temperature of 200 ℃, naturally cooling, and irradiating for 60 minutes under a 300W xenon lamp (with the wavelength of 300-2500 nm) to obtain the ZnO-based methane gas sensor.
Example 3
1.0976g of zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) and 100mL of deionized water are stirred and dissolved until the solution is transparent, so as to obtain a zinc acetate solution;
0.6304g of oxalic acid dihydrate (C) 2 H 2 O 4 ·2H 2 O) and 100mL of deionized water are stirred until the solution is transparent, and an oxalic acid solution is obtained;
dropwise adding the oxalic acid solution into a zinc oxalate solution, obtaining a zinc oxalate precipitate after full reaction, and performing suction filtration and washing for 2-3 times by using deionized water to obtain the zinc oxalate precipitate;
putting the zinc oxalate precipitate into a tubular furnace, heating to 350 ℃ in air atmosphere, and calcining for 6h to obtain zinc oxide nano particles;
mixing the zinc oxide nano-particles with methanol to obtain a ZnO nano-particle solution with the concentration of 100 mg/mL;
and (3) dripping 25 mu L of ZnO nanoparticles onto the gold finger electrode by adopting a spin coating process, uniformly coating for 6s at the rotating speed of 1000rpm, and rotating for 30s at the rotating speed of 3000rpm to volatilize the ZnO nanoparticles into a film. Repeating the steps for 5 times, and drying in an oven at 60 ℃ for 30 minutes to obtain the ZnO film coated finger inserting electrode;
and annealing the ZnO film coated finger-inserting electrode for 1 hour at the temperature of 200 ℃, naturally cooling, irradiating for 60 minutes under a 300W xenon lamp (with the wavelength of 300-2500 nm), and then continuously irradiating for 12 hours under the 300W xenon lamp (with the wavelength of 300-2500 nm) for aging to obtain the ZnO-based methane gas sensor.
Example 4
2.6967g of zinc acetate dihydrate (Zn (CH) 3 COO) 2 ·2H 2 O) and 50mL of deionized water are stirred and dissolved until the solution is transparent, so as to obtain a zinc acetate solution;
1g of manganese acetate tetrahydrate 4 H 14 MnO 8 ) Stirring the solution and 50mL of deionized water until the solution is transparent to obtain a manganese acetate solution;
223.06 mu L of the manganese acetate solution is added into the zinc acetate solution, and the mixture is stirred to be fully mixed;
5g of oxalic acid dihydrate (C) 2 H 2 O 4 ·2H 2 O) pouring the mixture into the mixed solution, stirring for 1h, carrying out suction filtration on a reaction product, washing with water, drying at 70 ℃ for 5h, and grinding in a mortar for 30min to obtain a mixture of zinc oxalate and manganese oxalate;
putting the mixture into a tube furnace, heating to 350 ℃ in an air atmosphere, and calcining for 6h to obtain manganese-doped zinc oxide nanoparticles with the mass fraction of 0.5%;
mixing the zinc oxide nanoparticles with methanol to obtain ZnO nanoparticle slurry with the concentration of 100 mg/mL;
and (3) dropping 25 mu L of ZnO nanoparticle slurry onto the gold finger electrode by adopting a spin coating process, uniformly gluing for 6s at the rotating speed of 1000rpm, and rotating for 30s at the rotating speed of 3000rpm to volatilize the ZnO nanoparticle slurry into a film. Repeating the steps for 5 times, and drying in an oven at 60 ℃ for 30 minutes to obtain the ZnO film coated finger inserting electrode;
and annealing the ZnO film coated finger-inserting electrode for 1 hour at the temperature of 200 ℃, naturally cooling, irradiating for 60 minutes under a 300W xenon lamp (with the wavelength of 300-2500 nm), and then continuously irradiating for 12 hours under the 300W xenon lamp (with the wavelength of 300-2500 nm) for aging to obtain the ZnO-based methane gas sensor.
Test example
The ZnO-based methane gas sensor described in example 2 was tested, the test procedure being: placing the ZnO-based methane gas sensor on two poles of a self-made chamber and fixing; opening a solenoid valve switch and controlling the air inlet rate and proportion of different gases, thereby controlling the concentration of the target gas to be 1 ppm-50000 ppm; applying a voltage of 3.3V to two poles of the interdigital electrode, collecting an interdigital electrode resistance signal by using Keithley6400 (the test conditions are room temperature; the target gas humidity is 0%; 365nm ultraviolet illumination and the power is 30mW), and calculating the sensitivity according to the resistance value of the interdigital electrode in methane gas, wherein the calculation formula is as follows: the sensitivity S of the sensor to the target gas (the resistance of the sensor in air-the resistance of the sensor under the target gas)/the resistance of the sensor in air; as shown in FIG. 1, it can be seen from FIG. 1 that the ZnO-based methane sensor has good sensitivity at a methane concentration of 50-10000 ppm, and the response result follows the Langmuir isothermal adsorption model, with the change in the range of 35-85%;
referring to the test procedure described above, except that the target gas was cycled through 5 times, FIG. 2 shows the results of the sensor's operating stability to methane gas; the test result is shown in fig. 2, and as can be seen from fig. 2, the baseline of the ZnO-based methane gas sensor does not move obviously in 5 gas cycle releases, which indicates that the sensor has higher stability in the detection process.
Examples 1 and 3 were subjected to the same test, and the test results were similar to those of example 2.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a ZnO-based methane sensor is characterized by comprising the following steps:
firstly mixing zinc acetate, oxalic acid and water, carrying out coprecipitation reaction, and then carrying out heat treatment to obtain zinc oxide nano particles;
secondly, mixing the zinc oxide nano particles with an alcohol organic solvent to obtain zinc oxide slurry;
and coating the zinc oxide slurry on the surface of an electrode to form a film, and then sequentially carrying out annealing treatment and illumination to obtain the ZnO-based methane sensor.
2. The preparation method according to claim 1, wherein the mass ratio of the zinc acetate to the oxalic acid to the water is (1-3): (0.5-2): 100.
3. the method of claim 1 or 2, wherein the first mixed feedstock further comprises a soluble metal salt;
the metal elements in the soluble metal salt comprise one or more of Mn, Cu, Ru, Al, Ag and Fe.
4. The method according to claim 3, wherein the mass ratio of the zinc acetate to the soluble metal salt is (0.01-10): 226.
5. the method according to claim 1, wherein the heat treatment is carried out at a temperature of 250 to 550 ℃ for 1 to 10 hours.
6. The method according to claim 1, wherein the concentration of the zinc oxide slurry is 0.01 to 0.1 g/mol;
the annealing temperature is 200-400 ℃, and the time is 0-6 h.
7. The method according to claim 1, wherein the wavelength of the light is 300 to 2500nm, the power is 50 to 300W, and the time is 0.5 to 2 hours.
8. The ZnO-based methane sensor prepared by the preparation method of any one of claims 1 to 7, which is characterized by comprising an electrode and a ZnO layer coated on the surface of the electrode.
9. The ZnO-based methane sensor according to claim 8, wherein the ZnO in the ZnO layer is undoped ZnO or metallic element doped ZnO;
the metal elements comprise one or more of Mn, Cu, Ru, Al, Ag and Fe.
10. Use of the ZnO-based methane sensor according to claim 8 or 9 in the field of methane gas detection.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115463542A (en) * | 2022-10-08 | 2022-12-13 | 南京大学 | Method for efficiently photocatalytic degradation of hydrocarbon micromolecular gas or formaldehyde by using metal monoatomic modified zinc oxide nanoparticles |
| CN115784630A (en) * | 2022-11-15 | 2023-03-14 | 湖北大学 | Heterojunction composite film, preparation method and application thereof, and methane gas sensor |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11183420A (en) * | 1997-12-17 | 1999-07-09 | Fuji Electric Co Ltd | Thin film gas sensor |
| CN1865963A (en) * | 2006-06-15 | 2006-11-22 | 武汉工程大学 | Combustible gas sensor preparing method |
| JP2007017422A (en) * | 2004-11-12 | 2007-01-25 | Canon Inc | Sensor and manufacturing method thereof |
| CN104391006A (en) * | 2014-11-13 | 2015-03-04 | 无锡信大气象传感网科技有限公司 | Preparation method of gas sensor |
| CN104407033A (en) * | 2014-11-13 | 2015-03-11 | 无锡信大气象传感网科技有限公司 | Preparation method of thin film chip gas-sensor |
| CN104458825A (en) * | 2014-10-22 | 2015-03-25 | 武汉工程大学 | Oxygen gas sensitive element and detection method thereof |
| WO2017020859A1 (en) * | 2015-08-06 | 2017-02-09 | 北京大学 | Stannum-doped photocatalysized formaldehyde sensing material and preparation method thereof, and formaldehyde sensor |
| US20170038326A1 (en) * | 2012-04-13 | 2017-02-09 | University Of Maryland, College Park | Highly Selective Nanostructure Sensors and Methods of Detecting Target Analytes |
| CN110208326A (en) * | 2019-06-25 | 2019-09-06 | 天津大学 | Work in the preparation method of the metal composite oxide base ethyl alcohol gas sensor under low temperature |
| CN111545197A (en) * | 2020-05-15 | 2020-08-18 | 湖北大学 | Ru-ZnO photocatalyst and preparation method and application thereof |
| CN111624236A (en) * | 2020-01-14 | 2020-09-04 | 黄辉 | Semiconductor film gas sensor and preparation method thereof |
| CN113621924A (en) * | 2021-07-30 | 2021-11-09 | 中国矿业大学 | Au modified ZnO methane sensitive material for MEMS gas sensor and preparation method thereof |
-
2022
- 2022-05-19 CN CN202210552582.9A patent/CN114965651A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11183420A (en) * | 1997-12-17 | 1999-07-09 | Fuji Electric Co Ltd | Thin film gas sensor |
| JP2007017422A (en) * | 2004-11-12 | 2007-01-25 | Canon Inc | Sensor and manufacturing method thereof |
| CN1865963A (en) * | 2006-06-15 | 2006-11-22 | 武汉工程大学 | Combustible gas sensor preparing method |
| US20170038326A1 (en) * | 2012-04-13 | 2017-02-09 | University Of Maryland, College Park | Highly Selective Nanostructure Sensors and Methods of Detecting Target Analytes |
| CN104458825A (en) * | 2014-10-22 | 2015-03-25 | 武汉工程大学 | Oxygen gas sensitive element and detection method thereof |
| CN104391006A (en) * | 2014-11-13 | 2015-03-04 | 无锡信大气象传感网科技有限公司 | Preparation method of gas sensor |
| CN104407033A (en) * | 2014-11-13 | 2015-03-11 | 无锡信大气象传感网科技有限公司 | Preparation method of thin film chip gas-sensor |
| WO2017020859A1 (en) * | 2015-08-06 | 2017-02-09 | 北京大学 | Stannum-doped photocatalysized formaldehyde sensing material and preparation method thereof, and formaldehyde sensor |
| CN110208326A (en) * | 2019-06-25 | 2019-09-06 | 天津大学 | Work in the preparation method of the metal composite oxide base ethyl alcohol gas sensor under low temperature |
| CN111624236A (en) * | 2020-01-14 | 2020-09-04 | 黄辉 | Semiconductor film gas sensor and preparation method thereof |
| CN111545197A (en) * | 2020-05-15 | 2020-08-18 | 湖北大学 | Ru-ZnO photocatalyst and preparation method and application thereof |
| CN113621924A (en) * | 2021-07-30 | 2021-11-09 | 中国矿业大学 | Au modified ZnO methane sensitive material for MEMS gas sensor and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王晓飞 等: "材料的化学制备与性能测试实验教程", vol. 1, 华中科技大学出版社, pages: 259 - 263 * |
| 章天金 等: "金属氧化物气敏传感器的研究现状及其发展趋势", 材料导报, vol. 12, no. 6, pages 38 - 44 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115463542A (en) * | 2022-10-08 | 2022-12-13 | 南京大学 | Method for efficiently photocatalytic degradation of hydrocarbon micromolecular gas or formaldehyde by using metal monoatomic modified zinc oxide nanoparticles |
| CN115463542B (en) * | 2022-10-08 | 2023-10-27 | 南京大学 | Method for efficiently catalyzing degradation of hydrocarbon micromolecular gas or formaldehyde by utilizing zinc oxide nano particles modified by metal monoatoms |
| CN115784630A (en) * | 2022-11-15 | 2023-03-14 | 湖北大学 | Heterojunction composite film, preparation method and application thereof, and methane gas sensor |
| CN115784630B (en) * | 2022-11-15 | 2024-03-29 | 湖北大学 | Heterojunction composite film, preparation method and application thereof, and methane gas sensor |
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