CN115716712B - GO@Ni-SnO based2Gas sensor of micro-nano porous sensitive film, preparation method and application - Google Patents
GO@Ni-SnO based2Gas sensor of micro-nano porous sensitive film, preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 113
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
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- 238000004140 cleaning Methods 0.000 claims description 11
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011550 stock solution Substances 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 5
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- 238000004519 manufacturing process Methods 0.000 claims 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
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- 238000001514 detection method Methods 0.000 abstract description 7
- 150000001298 alcohols Chemical class 0.000 abstract description 6
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- 230000009286 beneficial effect Effects 0.000 abstract description 3
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- 239000012855 volatile organic compound Substances 0.000 description 32
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
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- 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
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- -1 salt pentahydrate Chemical class 0.000 description 1
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Abstract
The invention belongs to the technical field of gas sensing materials, and particularly relates to a gas sensor based on a GO@Ni-SnO 2 micro-nano porous sensitive film, a preparation method and application of the gas sensor in detecting various VOC gases. According to the invention, a mixed solution containing various precursors is prepared firstly, a GO@Ni-SnO 2 micro-nano sensitive film with a large specific surface area and an ordered pore diameter is prepared based on a template dipping method, the porous characteristic is beneficial to improving the surface adsorption site and the gas diffusion speed of the film, so that high sensitivity is obtained, and the selectivity of the sensor to VOC gas can be increased by doping Ni and Graphene Oxide (GO). The prepared gas sensor has higher sensitivity and better selectivity to VOC gases (such as alcohols, aldehydes, benzenes and ketones), the minimum detection limit can reach 5ppb, and the gas sensor has no response to interference gases such as methane, H 2、CO、NO、NO2 and the like.
Description
Technical Field
The invention belongs to the technical field of gas sensing materials, and particularly relates to a preparation method of a gas sensor based on a GO@Ni-SnO 2 micro-nano porous sensitive film, and the gas sensor and application thereof in detecting various VOC gases.
Background
VOCs are various organic compounds with boiling points between 50 ℃ and 260 ℃ that directly or indirectly lead to the generation of haze, photochemical smog and greenhouse effect and to skin allergies, immunological disorders in humans and even increased cancer risk. The concentration values of various VOCs in the air, namely the air quality evaluation, are obtained, and the method has important application value in devices such as air conditioners, fresh air, purification and the like. Traditional spectroscopy methods for detecting VOCs comprise spectrum, gas chromatography, mass spectrum, gas chromatography-mass spectrometry and the like, and are mainly characterized by high sensitivity and high selectivity, but require precise large-scale instruments, so that the operation and maintenance cost is high, and quick and portable detection is difficult to realize. The semiconductor sensor has the typical characteristics of simple structure, low price and small volume, and is easy to realize the real-time monitoring of the net points. For example, priya S and the like are adopted to prepare SnO 2 hollow nano particles by a microemulsion method, so that low-concentration and rapid response to ethanol gas is realized. However, the sensor obtained by the method has high sensitivity response to ethanol gas only, and cannot monitor various common VOCs gases in daily life at the same time. Tian J and the like synthesize flower-shaped SnO 2 microspheres loaded with noble metal pd by adopting a solvothermal method, and the flower-shaped SnO 2 microspheres are used for detecting toluene, but have poor selectivity, strong response to conventional redox gases and long recovery time (400 seconds). So that it is difficult to achieve the high sensitivity and fast response detection of various VOCs at the same time by the conventional semiconductor sensor.
Disclosure of Invention
The invention aims to provide a preparation method of a gas sensor based on a GO@Ni-SnO 2 micro-nano porous sensitive film, and the gas sensor prepared based on the method can be used for detecting various VOCs, can improve the electrical response of the sensor to various VOCs gases, and has important application value in the aspect of an air quality monitoring sensor.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a gas sensor based on GO@Ni-SnO2 micro-nano porous sensitive film comprises the following steps:
S1, dissolving tin tetrachloride pentahydrate, nickel nitrate, aluminum nitrate nonahydrate and graphene oxide serving as precursors in water, and then performing ultrasonic treatment until the precursor solution is completely dissolved to prepare a precursor solution;
S2, forming an orderly arranged single-layer organic colloid ball array layer on the flat substrate, immersing the flat substrate in the precursor solution, and separating the organic colloid ball array layer from the flat substrate and floating on the surface of the precursor solution;
s3, cleaning and hydrophilizing the surface of the gas sensor device, transferring the organic colloid ball array layer floating in the precursor solution to the surface of the gas sensor device, enabling the organic colloid ball array layer to completely cover the surface of the device, filling the precursor solution in gaps between the organic colloid ball array layer and the device and between adjacent organic colloid balls, and then placing the gaps in a drying oven at 50-60 ℃ for drying for 15-30min;
S4, annealing the dried gas sensor device at 400-450 ℃ for 1.5-2h to obtain the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film.
The preparation method of the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film is further improved:
Preferably, in the precursor solution, the molar concentration ratio of the tin tetrachloride pentahydrate, the nickel nitrate, the aluminum nitrate nonahydrate and the graphene oxide is 30:1:2:1, wherein the concentration of the tin tetrachloride pentahydrate is 2-3mol/L.
Preferably, the preparation method of the organic colloidal sphere array layer in step S2 is as follows:
S21, mixing an organic colloid sphere stock solution which takes water as a solvent and has the concentration of the organic colloid sphere of 10-15wt% with ethanol according to the volume ratio of 1:1 to obtain a mixed solution, wherein the diameter of the organic colloid sphere is 150-500nm;
S22, carrying out hydrophilic treatment on the surface of the flat substrate, slowly dripping the mixed solution onto the flat substrate from the edge of the flat substrate, self-assembling the organic colloid balls on an air-water interface, absorbing excessive moisture, and naturally drying to form an orderly arranged single-layer organic colloid ball array layer on the flat substrate.
Preferably, the specific steps of hydrophilic treatment of the flat substrate are as follows: and (3) placing the flat substrate in an ultraviolet ozone cleaning machine for irradiation for 15-20 minutes, removing organic impurities on the surface and obtaining the super-hydrophilic surface.
Preferably, the organic colloid sphere stock solution comprises organic colloid spheres, divinylbenzene, water, a surfactant, a dispersing agent and a preservative, wherein the organic colloid spheres are made of polystyrene microspheres, and the flat substrate is a glass slide.
Preferably, the organic colloid sphere stock solution is prepared by adding organic colloid spheres, divinylbenzene, a surfactant, a dispersing agent and a preservative into water according to a mass ratio of 35:7:1:1:1.
Preferably, the gas sensor device is placed in an ultraviolet ozone cleaning machine for irradiation to remove surface organic impurities and obtain a super hydrophilic surface.
Preferably, the gas sensor device is placed in an ultraviolet ozone cleaning machine for irradiation for cleaning and hydrophilic treatment.
Preferably, the specific steps of transferring the organic colloidal sphere array layer floating in the precursor solution to the surface of the gas sensor device are as follows: slowly immersing the gas sensor device into the precursor solution prepared in the step S1 at an angle of the bottom surface of the device and the water surface of the device being less than 30 degrees, and fishing out the floating organic colloid ball array layer.
The second purpose of the invention is to provide a gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film prepared by the preparation method.
The second purpose of the invention is to provide an application of the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film in detecting various VOC gases.
Compared with the prior art, the invention has the beneficial effects that:
1) The invention provides a preparation method of a gas sensor based on GO@Ni-SnO 2 micro-nano porous sensitive film, which is technically characterized in that a mixed solution containing various precursors is prepared firstly, the GO@Ni-SnO 2 micro-nano sensitive film with large specific surface area and ordered pore diameter is prepared based on a template dipping method, the porous characteristic is beneficial to improving the surface adsorption site and the gas diffusion speed of the film, so that high sensitivity is obtained, and the selectivity of the sensor to VOC gas can be increased by doping Ni and Graphene Oxide (GO).
According to the preparation method, tin tetrachloride pentahydrate, nickel nitrate, aluminum nitrate nonahydrate and graphene oxide are taken as precursors to be dissolved in water, so that a precursor solution is prepared;
Slowly immersing the flat substrate attached with the organic colloid ball array layer into a precursor solution, wherein the organic colloid ball array layer gradually breaks away from the substrate and floats on the surface of the precursor solution due to the difference of wettability and the action of the surface tension of the solution;
Then carrying out hydrophilic treatment on the surface of the gas sensor device, fishing out a floating organic colloid ball array layer to completely cover the surface of the device, filling precursor solution in gaps between the organic colloid ball array layer and the device and between adjacent organic colloid balls due to capillary action, carrying out oxidation reaction on tin tetrachloride metal salt pentahydrate in precursor solution on the surface of the device and oxygen in air under high-temperature annealing to generate tin oxide, wherein nickel nitrate has low content, and the atomic radius of Ni atoms is similar to that of Sn atoms, so that Ni replaces a small part of Sn atoms in SnO 2 crystal lattice, thereby forming Ni doped SnO 2, and graphene oxide remains in a bulk phase of SnO 2 due to high temperature resistance, and the organic colloid balls are decomposed and removed due to intolerance of high temperature, so that a regular and ordered bowl-shaped porous structure is left, and finally the GO@Ni-SnO 2 micro-nano porous film is formed;
2) The gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film can be used for detecting ethanol, toluene, formaldehyde and acetone gases, and the minimum detection limit can reach 5ppb. The sensitivity to VOC gases (such as alcohols, aldehydes, benzenes and ketones) is higher, the selectivity is better, and the catalyst has no response to methane, H 2、CO、NO、NO2 and other interference gases.
Drawings
FIG. 1 is an SEM typical morphology diagram of a GO@Ni-SnO 2 micro-nano porous sensitive film prepared in example 1; .
FIG. 2 is a graph showing the concentration gradient response of the GO@Ni-SnO 2 micro-nano porous sensitive film based on the prepared film in example 1 when the VOCs gas sensor is used for detecting ethanol gas;
FIG. 3 is a graph of the selective gas-sensitive performance of the VOCs gas sensor based on GO@Ni-SnO 2 micro-nano porous sensitive film prepared in example 1;
FIG. 4 is a graph showing the concentration gradient response of the GO@Ni-SnO 2 micro-nano porous sensitive film based on the prepared film in example 2 when the VOCs gas sensor is used for detecting ethanol gas;
FIG. 5 is a graph for testing the selective gas-sensitive performance of the VOCs gas sensor based on GO@Ni-SnO 2 micro-nano porous sensitive film prepared in example 2;
FIG. 6 is a graph showing the concentration gradient response of the GO@Ni-SnO 2 micro-nano porous sensitive film based on the prepared film in example 3 when the VOCs gas sensor is used for detecting ethanol gas;
FIG. 7 is a graph showing the selective gas-sensitive performance of the VOCs gas sensor based on GO@Ni-SnO 2 micro-nano porous sensitive film prepared in example 3.
Detailed Description
The present invention will be further described in detail with reference to the following examples, in order to make the objects, technical solutions and advantages of the present invention more apparent, and all other examples obtained by those skilled in the art without making any inventive effort are within the scope of the present invention based on the examples in the present invention.
Example 1
The embodiment provides a preparation method of a gas sensor based on a GO@Ni-SnO 2 micro-nano porous sensitive film, which comprises the following specific steps:
s1, the precursor is crystalline tin tetrachloride pentahydrate, nickel nitrate, aluminum nitrate nonahydrate and Graphene Oxide (GO). Dissolving four precursors in 50mL of distilled water, wherein the concentration of tin tetrachloride pentahydrate is 2mol/L, the concentration of nickel nitrate is 0.067mol/L, the concentration of aluminum nitrate nonahydrate is 0.134mol/L, the concentration of graphene oxide is 0.067mol/L (by adding a graphene oxide solution with the concentration of2 mg/mL), and then completely dissolving the precursor by ultrasonic treatment to prepare a precursor solution;
S2, adding polystyrene PS organic colloid spheres with the diameter of 500nm, divinylbenzene, a surfactant, a dispersing agent and a preservative into water according to the mass ratio of 35:7:1:1:1 to prepare an organic colloid sphere stock solution with the concentration of 10wt% of the organic colloid spheres, and mixing the organic colloid sphere stock solution with ethanol according to the volume ratio of 1:1 to obtain a mixed solution; carrying out hydrophilic treatment on the surface of the flat substrate (placing the flat substrate in an ultraviolet ozone cleaning machine for irradiation for 15 minutes), slowly dripping the mixed solution onto the flat substrate from the edge of the flat substrate, absorbing water by using filter paper, and naturally drying to form an orderly arranged single-layer organic colloid sphere array layer on the flat substrate;
then slowly immersing the flat substrate attached with the organic colloid ball array layer into the precursor solution prepared in the step S1, wherein the organic colloid ball array layer gradually breaks away from the substrate and floats on the surface of the precursor solution due to the difference of wettability and the action of the surface tension of the solution;
S3, placing the gas sensor device in an ultraviolet ozone cleaning machine for irradiation to remove organic impurities on the surface and obtain a clean and hydrophilic surface;
Then slowly immersing the gas sensor device into the precursor solution prepared in the step S1 from one side at a small angle (the included angle between the bottom surface of the device and the water surface is 20 degrees), fishing out the floating organic colloid ball array layer, enabling the organic colloid ball array layer to completely cover the surface of the device, filling the precursor solution in gaps between the organic colloid ball array layer and the device and between adjacent organic colloid balls, and drying in an oven at 60 ℃ for 30min;
and S4, placing the dried gas sensor device at 400 ℃ for annealing for 2 hours, and forming a GO@Ni-SnO 2 micro-nano porous sensitive film on the surface of the gas sensor to obtain the gas sensor 1 based on the GO@Ni-SnO 2 micro-nano porous sensitive film.
Fig. 1 is an SEM typical morphology diagram of the obtained go@ni-SnO 2 micro-nano porous sensitive film, and as can be seen from fig. 1, the surface of the film is in a regular and ordered bowl-shaped porous structure, the film is complete in structure, large in area and free of cracking, and has a micro-nano ordered porous structure with a pore diameter of about 500nm. The bottom four panels are mapping diagrams of the film, and the elemental distributions of which are seen as O, sn, ni and C.
The concentration gradient response diagram of the gas sensor 1 when used for detecting ethanol gas is tested by adopting a source meter test method, adopting an STP4 intelligent gas-sensitive analysis system (Nanjing Wei Xin Co., ltd.) to carry out gas-sensitive experiments under the conditions of room temperature (20 ℃) and RH 50%. First, the prepared sensor is connected to a test instrument, and then VOCs gas having an original concentration of 100ppm is injected into a test chamber by a syringe to reach a specific concentration of a target gas. In verifying the gas-sensitive properties of the film material, gas-sensitive tests were performed on ethanol as representative of typical VOCs, with a minimum detection limit of up to 5ppb as shown in fig. 2.
The sensitivity of the gas sensor 1 to VOC gases (such as alcohols, aldehydes, benzenes and ketones) is tested by a source meter test method under the conditions of room temperature (20 ℃) and RH 50% and by using an STP4 intelligent gas-sensitive analysis system (Nanjing Wei Xin Co., ltd.). First, the prepared sensor is attached to a test instrument. VOCs gas having an original concentration of 100ppm is then injected into the test chamber with a syringe to achieve a specific concentration of the target gas. In verifying the gas-sensitive performance of the film material, gas-sensitive tests were performed with ethanol as representative of typical VOCs, and selective tests were performed with methane, hydrogen, carbon monoxide, nitric oxide and nitrogen dioxide as interfering gases. In the laboratory, two electric fans were installed to accelerate the dispersion of the gas, obtaining a uniform test gas mixture. Fig. 3 shows the result of a selective gas-sensitive performance test on VOCs sensing devices, and it can be seen from the figure that the SnO 2 sensor doped with Ni and graphene oxide has higher sensitivity and better selectivity to VOC gases (such as alcohols, aldehydes, benzenes and ketones) and basically has no response to interference gases such as methane, H 2、CO、NO、NO2 and the like.
Example 2
The embodiment provides a preparation method of a gas sensor based on GO@Ni-SnO 2 micro-nano porous sensitive film and capable of detecting various VOCs, which specifically comprises the following steps of, referring to embodiment 1: in the precursor solution, the molar concentration ratio of tin tetrachloride pentahydrate, nickel nitrate, aluminum nitrate nonahydrate and graphene oxide is 30:1:2:1, wherein the concentration of the tin tetrachloride pentahydrate is 3mol/L, the concentration of the nickel nitrate is 0.1mol/L, the concentration of the aluminum nitrate nonahydrate is 0.2mol/L, and the concentration of the graphene oxide is 0.1mol/L (by adding a graphene oxide solution with the concentration of 2 mg/mL); and (3) preparing the gas sensor 2 based on the GO@Ni-SnO 2 micro-nano porous sensitive film.
FIG. 4 is a concentration gradient response chart of the prepared GO@Ni-SnO 2 micro-nano porous sensitive film material VOCs gas sensor for detecting ethanol gas, wherein the minimum detection limit can reach 5ppb.
Fig. 5 shows the result of a selective gas-sensitive performance test on VOCs sensing devices, and it can be seen from the figure that the SnO 2 sensor doped with Ni and graphene oxide has higher sensitivity and better selectivity to VOC gases (such as alcohols, aldehydes, benzenes and ketones) and basically has no response to interference gases such as methane, H 2、CO、NO、NO2 and the like.
Example 3
The embodiment provides a preparation method of a gas sensor based on GO@Ni-SnO 2 micro-nano porous sensitive film and capable of detecting various VOCs, which specifically comprises the following steps of, referring to embodiment 1: and (3) annealing at 450 ℃ for 1.5 hours in the step (S4) to obtain the gas sensor 3 based on the GO@Ni-SnO 2 micro-nano porous sensitive film.
FIG. 6 is a concentration gradient response chart of the prepared GO@Ni-SnO 2 micro-nano porous sensitive film material VOCs gas sensor for detecting ethanol gas, wherein the minimum detection limit can reach 5ppb.
Fig. 7 shows the result of a selective gas-sensitive performance test on VOCs sensing devices, and it can be seen from the figure that the SnO 2 sensor doped with Ni and graphene oxide has higher sensitivity and better selectivity to VOC gases (such as alcohols, aldehydes, benzenes and ketones) and basically has no response to interference gases such as methane, H 2、CO、NO、NO2 and the like.
Those skilled in the art will appreciate that the foregoing is merely a few, but not all, embodiments of the invention. It should be noted that many variations and modifications can be made by those skilled in the art, and all variations and modifications which do not depart from the scope of the invention as defined in the appended claims are intended to be protected.
Claims (8)
1. The preparation method of the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film is characterized by comprising the following steps of:
S1, dissolving tin tetrachloride pentahydrate, nickel nitrate, aluminum nitrate nonahydrate and graphene oxide serving as precursors in water, and then performing ultrasonic treatment until the precursor solution is completely dissolved to prepare a precursor solution; in the precursor solution, the molar concentration ratio of the tin tetrachloride pentahydrate, the nickel nitrate, the aluminum nitrate nonahydrate and the graphene oxide is 30:1:2:1, wherein the concentration of the tin tetrachloride pentahydrate is 2-3mol/L;
s2, forming an orderly arranged single-layer organic colloid ball array layer on the flat substrate, wherein the diameter of the organic colloid balls is 150-500nm, immersing the flat substrate in the precursor solution, and separating the organic colloid ball array layer from the flat substrate and floating on the surface of the precursor solution;
s3, cleaning and hydrophilizing the surface of the gas sensor device, transferring the organic colloid ball array layer floating in the precursor solution to the surface of the gas sensor device, enabling the organic colloid ball array layer to completely cover the surface of the device, filling the precursor solution in gaps between the organic colloid ball array layer and the device and between adjacent organic colloid balls, and then placing the gaps in a drying oven at 50-60 ℃ for drying for 15-30min;
S4, annealing the dried gas sensor device at 400-450 ℃ for 1.5-2h to obtain the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film, wherein the gas sensor can be used for detecting various VOC gases.
2. The method for preparing a gas sensor based on a GO@Ni-SnO 2 micro-nano porous sensitive film according to claim 1, wherein the method for preparing the organic colloidal sphere array layer in the step S2 is as follows:
S21, mixing an organic colloid sphere stock solution which takes water as a solvent and has the concentration of the organic colloid sphere of 10-15wt% with ethanol according to the volume ratio of 1:1 to obtain a mixed solution;
S22, carrying out hydrophilic treatment on the surface of the flat substrate, slowly dripping the mixed solution onto the flat substrate from the edge of the flat substrate, self-assembling the organic colloid balls on an air-water interface, absorbing excessive moisture, and naturally drying to form an orderly arranged single-layer organic colloid ball array layer on the flat substrate.
3. The method for preparing the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film according to claim 2, wherein the specific steps of hydrophilic treatment of the flat substrate are as follows: and (3) placing the flat substrate in an ultraviolet ozone cleaning machine for irradiation for 15-20 minutes, removing organic impurities on the surface and obtaining the super-hydrophilic surface.
4. The method for preparing the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film according to claim 2, wherein the organic colloid sphere stock solution comprises organic colloid spheres, divinylbenzene, water, a surfactant, a dispersing agent and a preservative, the organic colloid spheres are made of polystyrene microspheres, and the flat substrate is a glass slide.
5. The method for preparing the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film according to claim 2 or 4, wherein the organic colloid sphere stock solution is prepared by adding organic colloid spheres, divinylbenzene, a surfactant, a dispersing agent and a preservative into water according to a mass ratio of 35:7:1:1:1.
6. The method for preparing the gas sensor based on the GO@Ni-SnO 2 micro-nano porous sensitive film according to claim 1, wherein the gas sensor device is placed in an ultraviolet ozone cleaning machine for irradiation so as to perform cleaning and hydrophilic treatment.
7. The method for preparing a gas sensor based on a GO@Ni-SnO 2 micro-nano porous sensitive film according to claim 1 or 6, wherein the specific steps of transferring an organic colloidal sphere array layer floating in a precursor solution to the surface of a gas sensor device are as follows: slowly immersing the gas sensor device into the precursor solution prepared in the step S1 at an angle of the bottom surface of the device and the water surface of the device being less than 30 degrees, and fishing out the floating organic colloid ball array layer.
8. A gas sensor based on go@ni-SnO 2 micro-nano porous sensitive film produced by the production method of any one of claims 1 to 7.
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| An electrochemical outlook upon the gaseous ethanol sensing by graphene oxide-SnO2 hybrid materials;E. Pargoletti等;Applied Surface Science;20190731;第483卷;第1081-1089页 * |
| Enhanced sensor response of Ni-doped SnO2 hollow spheres;Xianghong Liu等;Sensors and Actuators B: Chemical;20110301;第152卷(第2期);第162–167页 * |
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