CN114113241A - Double-layer-structure SnO resistant to HMDSO poisoning2Methane sensor and preparation method thereof - Google Patents
Double-layer-structure SnO resistant to HMDSO poisoning2Methane sensor and preparation method thereof Download PDFInfo
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- CN114113241A CN114113241A CN202111420069.6A CN202111420069A CN114113241A CN 114113241 A CN114113241 A CN 114113241A CN 202111420069 A CN202111420069 A CN 202111420069A CN 114113241 A CN114113241 A CN 114113241A
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- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 72
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 49
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000001147 anti-toxic effect Effects 0.000 claims abstract description 44
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 239000010931 gold Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052737 gold Inorganic materials 0.000 claims abstract description 21
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 18
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 17
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 239000002574 poison Substances 0.000 claims abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910001868 water Inorganic materials 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 230000002155 anti-virotic effect Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 6
- 238000011068 loading method Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 230000000607 poisoning effect Effects 0.000 abstract description 14
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 42
- 208000005374 Poisoning Diseases 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 231100000572 poisoning Toxicity 0.000 description 12
- 230000008859 change Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 229910019020 PtO2 Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- DDYSHSNGZNCTKB-UHFFFAOYSA-N gold(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Au+3].[Au+3] DDYSHSNGZNCTKB-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000012694 precious metal precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 206010017740 Gas poisoning Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
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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
Abstract
The invention belongs to the technical field of preparation of methane sensors, and discloses a double-layer SnO (stannic oxide) resistant to HMDSO (high molecular weight differential decomposition) poisoning2A methane sensor and a preparation method thereof. The sensor is indirectly heated sensor made of Al2O3The device comprises a ceramic tube, two annular gold electrodes, four platinum wire leads, a sensitive inner layer, an anti-poison outer layer, a chromium-nickel heating wire and a six-pin tube seat; wherein the sensitive inner layer material is SiO2Surface graft modified SnO2The outer antitoxic layer is loaded SnO2Alumina fibers of (2). The preparation method comprises the following steps: (1) preparing sensitive inner layer material-SiO2Surface graft modified SnO2(ii) a (2) Preparing the antitoxic outer layer material-loaded SnO2Alumina fibers of (a); (3) firstly coating a sensitive inner layer material and then coating an anti-toxic outer layer material according to the preparation process of the indirectly heated sensor to prepare SnO with a double-layer structure2A methane-based sensor. The sensor element prepared by the invention can effectively resist the poisoning effect of HMDSO, and is used in V0、Vg、SRAnd the stability can be kept on various indexes.
Description
Technical Field
The invention belongs to the technical field of preparation of methane sensors, and particularly relates to double-layer SnO with an anti-HMDSO poisoning structure2A methane sensor and a preparation method thereof.
Background
Methane is an important fossil fuel, is a main component of natural gas and coal gas layers, hardly generates any waste during combustion, and is an excellent fuel for power generation, industry, chemical industry and residential life. Methane is a flammable and explosive gas, has an explosion range of 5% -16% in air, and is very easy to explode when exposed to open fire. Because natural gas is continuously popularized in the life of residents, explosion and poisoning accidents caused by natural gas leakage are increased, and high attention is paid to people for safe gas utilization. Therefore, the demand for real-time and effective monitoring of methane is also increasing, and gas monitoring technology is rapidly developing.
The gas sensing technology is widely applied to the fields of industrial production, automobile industry, medical application, indoor air quality detection, environmental research and the like, and provides powerful guarantee for safety production and daily life of people. Among them, the semiconductor oxide sensor is an important branch of gas sensing technology, and has a large share in the gas sensor market with its excellent performance and low price. The most widely used semiconductor gas-sensitive material at home and abroad at present has SnO2、ZnO、WO3、Fe2O3、In2O3Etc., in which SnO2Has the most extensive application, and shows higher sensitivity and shorter response recovery time to various common gases.
The gas-sensitive material of the sensor is very easily subjected to halogen, organic silicon and NO2And chemical pollutants containing S compounds and the like are poisoned and inactivated, so that the performance of the sensor is deteriorated, an alarm signal cannot be timely and accurately transmitted, and great potential safety hazards are brought to production and life. Hexamethyldisiloxane (HMDSO), a representative semiconductor gas sensor poison, has found widespread use in industrial environments such as industrial dyes, adhesives, lubricants, and polishing agents, etc., as well as household products such as silicone rubbers, aerosol sprays, etc. In this regard, several organizations and countries in the world place certain requirements on the gas poisoning resistance of sensor elements, such as ISO 26142: 2010. EN50194-1-2009 and the like. The new national standard GB 15322.2-2019 of a combustible gas detector released in 2019 in China specifies that: will senseThe vessel was placed at a 1% LEL (500 ppm CH) concentration of combustible vapor4) And 10 ppm HMDSO for 40 min, and then recovering for 20 min in a normal air range, wherein the absolute value of the difference between the alarm action value and the alarm set value of the detector is not more than 10% LEL. According to some previous reports, hexamethyldisiloxane is mainly adsorbed on a gas-sensitive material and further cracked into organosilicon, silicate and SiO2Etc., which block active sites on the surface of the gas sensitive material, thereby reducing the response performance of the sensor. However, there is a limited literature on how to design specific gas sensitive materials, optimizing sensors to be resistant to silicone poisoning. Therefore, it is urgent to develop a methane gas sensor that can resist silicon poisoning and can be normally monitored for use in an atmosphere containing organic silicon vapor.
Disclosure of Invention
In view of the above-mentioned drawbacks and disadvantages of the prior art, it is an object of the present invention to provide a double-layered SnO with resistance to HMDSO poisoning2A methane sensor and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
double-layer-structure SnO resistant to HMDSO poisoning2The methane sensor is an indirectly heated sensor made of Al2O3The device comprises a ceramic tube (1), two annular gold electrodes (2), four platinum wire leads (3), a sensitive inner layer (4), an anti-virus outer layer (5), a chromium-nickel heating wire (6) and a six-pin tube seat (7); two annular gold electrodes (2) are arranged on the Al at intervals in parallel2O3On the ceramic tube (1), each gold electrode (2) is connected with two platinum wire leads (3), and the sensitive inner layer (4) is coated on Al2O3The outer surfaces of the ceramic tube (1) and the gold electrode (2) and the anti-poison outer layer (5) are coated on the outer surface of the sensitive inner layer (4), and the chromium-nickel heating wire (6) penetrates through Al2O3The two ends of the chromium-nickel heating wire (6) and Al inside the ceramic tube (1)2O3Four platinum wire leads (3) of the ceramic tube (1) are welded on the six-pin tube seat (7) together; wherein the sensitive inner layer (4) is made of SiO2Surface graftingModified SnO2The material of the antitoxic outer layer (5) is loaded SnO2Alumina fibers of (2).
Preferably, the sensitive inner layer (4) is made of SiO2The grafting ratio of (A) is 1-3 wt%; SnO among materials of the antitoxic outer layer (5)2The load factor of (2) is 30-70 wt% { load factor = SnO2mass/(SnO)2Mass of (d) + mass of alumina fibers) 100%.
Preferably, the thickness of the sensitive inner layer (4) is 0.05-0.2 mm; the thickness of the antitoxic outer layer (5) is 0.05-0.3 mm.
Furthermore, the sensitive inner layer (4) material and/or the antitoxic outer layer (5) material also comprises noble metal, and the noble metal exists in the oxidation state; the noble metal is one or more of metal Pt, metal Pd and metal Au; in the material of the sensitive inner layer (4) or the material of the antitoxic outer layer (5), each noble metal is metered by the simple substance, and the dosage of each noble metal accounts for SnO in the corresponding material20.5-2 wt% of the mass.
The preparation method comprises the following steps of (by volume parts in mL) and (by mass parts in g):
(1) preparing sensitive inner layer material-SiO2Surface graft modified SnO2；
(2) Preparing the antitoxic outer layer material-loaded SnO2Alumina fiber of (a): stirring 1-3 parts by mass of tin particles and 5-20 parts by volume of concentrated nitric acid at room temperature for 2-5 h, adding 1-3 parts by mass of alumina fiber, and stirring again for 2-3 h; after the solution is naturally cooled to room temperature, ammonia water is used for adjusting the pH value of the solution to 7-9, separation, washing and drying are carried out, and after grinding, calcination is carried out at the temperature of 450-600 ℃ for 1-2 h, thus obtaining the antitoxic outer layer material-load SnO2Alumina fibers of (a);
(3) preparing SnO with double-layer structure2A methyl methane sensor:
(3.1) in Al2O3Two annular gold electrodes (2) are arranged on the ceramic tube (1) at intervals in parallel, and each gold electrode (2) is connected with two platinum wire leads (3);
(3.2) taking 0.5-1 part by mass of the sensitive inner layer material prepared in the step (1), grinding, adding water and absolute ethyl alcohol according to the mass ratio of (2-5) to 10.25-0.5 volume part of the mixed solution, prepared into paste, and then evenly coated on the Al obtained in the step (3.1)2O3The outer surface of the ceramic tube (1) is naturally dried in air and then calcined, and Al is added at the moment2O3Preparing a sensitive inner layer (4) on the outer surface of the ceramic tube (1); wherein, the calcining conditions are as follows: firstly calcining at 60-150 ℃ for 0.5-2 h, and then heating to 450-600 ℃ at the heating rate of 5-10 ℃/min for calcining for 1-2 h;
(3.3) taking 0.5-1 part by mass of the antitoxic outer layer material prepared in the step (2), grinding, adding 0.25-0.5 part by volume of mixed solution consisting of water and absolute ethyl alcohol according to the mass ratio of (2-5) to 1, preparing into paste, uniformly coating the paste on the outer surface of the sensitive inner layer (4) obtained in the step (3.2), and then carrying out air drying and calcining steps which are the same as the steps (3.2), wherein Al is added at the moment2O3Preparing an anti-virus outer layer (5) on the outer surface of the sensitive inner layer (4) on the outer surface of the ceramic tube (1);
(3.4) passing a chromium-nickel heating wire (6) through the Al obtained in the step (3.3)2O3And (3) welding two ends of a chromium-nickel heating wire (6) and four platinum wire leads (3) on a six-pin tube seat (7) together inside the ceramic tube (1) to obtain the target sensor.
Further, in the step (3.2), after the sensitive inner layer material is ground, a precious metal precursor solution with the concentration of 2.5-8 wt% is added, and then a mixed solution consisting of water and absolute ethyl alcohol is added to be prepared into paste; the noble metal is one or more of Pt, Pd and Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and the dosage of each noble metal precursor solution ensures that the noble metal simple substance provided by the noble metal precursor solution accounts for SnO in the sensitive inner layer material20.5-2 wt% of the mass.
Further, in the step (3.3), the antitoxic outer layer material is ground, then a precious metal precursor solution with the concentration of 2.5-8 wt% is added, and then mixed liquid consisting of water and absolute ethyl alcohol is added to be prepared into paste; the noble metal is one or more of Pt, Pd and Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and each noble metal precursor solutionThe dosage of the noble metal ensures that the noble metal simple substance provided by the noble metal accounts for SnO in the antitoxic outer layer material20.5-2 wt% of the mass.
Preferably, the noble metal-containing acid is H2PtCl6·H2O、HAuCl4The water-soluble salt containing noble metal is (NH)4)2PdCl4。
In step (1), SiO2Surface graft modified SnO2Can be prepared according to the prior art, and preferably comprises the following steps:
(1.1) preparation of Nano SnO2Powder;
(1.2) taking 2-5 parts by mass of nano SnO prepared in the step (1.1)2Powder, 3-5 parts by volume of hydrogen peroxide, 3-5 parts by volume of ammonia water and 6-10 parts by volume of water, ultrasonic oscillation at 50-70 ℃ for 30-60 min, separation and drying to prepare SnO2A hydroxylate intermediate;
(1.3) taking 2-5 parts by mass of nano SnO prepared in the step (1.2)2The hydroxylate intermediate, 0.2-0.6 mass part of 3-aminopropyltriethoxysilane and 10-15 volume parts of toluene are magnetically stirred for 3-5 h, separated, dried and calcined at 800 ℃ for 1-2 h to prepare the sensitive inner layer material-SiO2Surface graft modified SnO2。
In step (1.1), nano SnO2The powder can be prepared according to the prior art, preferably: stirring 20-30 parts by mass of tin particles and 80-120 parts by volume of concentrated nitric acid at room temperature for 2-5 h to obtain gel, separating, washing, drying, grinding, calcining at 600 ℃ for 1-2 h to obtain nano SnO2And (3) powder.
The invention has the beneficial effects that:
(1) the sensitive inner layer of the invention is SiO2Modified nano SnO2By the reaction of nano SnO2Surface modification is carried out, and a layer of SiO is grafted on the surface2The existence of the surface modification layer limits the nano SnO at high temperature2Modified nano SnO2The particle size is only 5-15 nm, the distribution is uniform, and the response performance to methane is excellent;
(2) the invention explores an anti-poisoning material, namely a certain load massAmount fraction SnO2Cellucotton Al2O3Due to Al2O3Low conductivity, the resistance of the outer layer is far greater than that of the sensitive inner layer, and SnO caused by HMDSO2/Al2O3The resistance change of the outer layer does not influence the resistance of the whole element; further, Al2O3Can also be used as a filter layer to prevent HMDSO and decomposition products thereof from contacting the sensitive inner layer;
(3) the sensor element prepared by the method has extremely short response recovery time and excellent short-term repeatability, keeps very high linearity to the methane concentration in an extremely wide detection range of 3000-15000 ppm, and has the potential of semi-quantitative detection of methane in a silicon-containing atmosphere;
(4) the sensor element prepared by the invention can effectively resist the poisoning effect of HMDSO, and is used in V0、Vg、SRThe stability can be kept on various indexes, and the requirement of the anti-poisoning performance of the anti-poisoning gas detector is far exceeded by the national standard GB 15322.2-2019 of the combustible gas detector;
(5) the raw materials adopted by the invention are cheap and easily available, and the sensor element is non-toxic and harmless, has a simple preparation process, and can be produced industrially in a large scale.
Drawings
FIG. 1: the invention relates to double-layer SnO with HMDSO poisoning resistance2Schematic structure of methane sensor.
FIG. 2: example 1 sensitive inner layer Material- -SiO2Surface graft modified SnO2A TEM image of (a).
FIG. 3: SnO Supported anti-toxic outer layer Material prepared in example 12SEM image (a) and EDS analysis result (b) of the alumina fiber of (1).
FIG. 4: the sensors obtained in comparative example 1 and example 1 showed a change in resistance during the poisoning recovery.
FIG. 5: the sensors obtained in example 6, example 7 and example 9 showed a change in resistance during the recovery from poisoning.
FIG. 6: example 1 sensor at 10000 ppm CH4And (5) repeating the short-term repeatability test result for 6 times under the pulse.
FIG. 7: fruit of Chinese wolfberryEXAMPLE 1 sensor resistance sensitivity SRCurve with methane concentration.
FIG. 8: comparative example 1 and example 1 sensor pairs for methane, acetone, CO, NH3The resistance sensitivity of the gas.
Detailed Description
In order to make the invention clearer and clearer, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
As shown in figure 1, a double-layer SnO resisting HMDSO poisoning2The methane sensor is an indirectly heated sensor made of Al2O3The device comprises a ceramic tube 1, two annular gold electrodes 2, four platinum wire leads 3, a sensitive inner layer 4, an anti-poison outer layer 5, a chromium-nickel heating wire 6 and a six-pin tube seat 7; two annular gold electrodes 2 are arranged in Al in parallel at intervals2O3Two platinum wire leads 3 are connected to each gold electrode 2 on the ceramic tube 1, and the sensitive inner layer 4 is coated on Al2O3The outer surface of the ceramic tube 1 and the outer antitoxic layer 5 are coated on the outer surface of the sensitive inner layer 4, and the chromium-nickel heating wire 6 penetrates through Al2O3Inside the ceramic tube 1, two ends of the chromium-nickel heating wire 6 and Al2O3Four platinum wire leads 3 of the ceramic tube 1 are welded on the six-pin tube seat 7 together; wherein the sensitive inner layer 4 is made of SiO2Surface graft modified SnO2、PtO2And PdO, the thickness of the sensitive inner layer 4 is 0.1 mm; the antitoxic outer layer 5 is made of loaded SnO2The thickness of the anti-poison outer layer 5 of the alumina fiber is 0.15 mm.
The preparation method comprises the following steps:
(1) preparing sensitive inner layer material-SiO2Surface graft modified SnO2：
(1.1) preparation of Nano SnO2Powder: adding 80 mL of concentrated nitric acid into a three-necked flask with tail gas treatment device, continuously adding 20 g of tin granules, stirring at room temperature for 3 h to obtain white gel, centrifuging, washing with deionized water to neutrality, and drying at 105 deg.C in a vacuum drying oven for 20 hh, calcining for 2 h at 450 ℃ after grinding, and grinding the obtained light yellow solid to obtain the nano SnO2Powder;
(1.2) taking 2.25 g of nano SnO prepared in the step (1.1)2Adding 0.35 g of 3-aminopropyltriethoxysilane and 15 mL of toluene into the powder in a 50 mL beaker, magnetically stirring for 5 h, centrifuging, drying, and calcining at 500 ℃ for 2 h to obtain a sensitive inner layer material-SiO2Surface graft modified SnO2The TEM image is shown in FIG. 2, the particle size is in the range of 5-15 nm, the average particle size is 9.86 nm, and the distribution is uniform; by gas chromatography detection, SiO2The graft ratio of (A) was 1 wt%;
(2) preparing the antitoxic outer layer material-loaded SnO2Alumina fiber of (a): adding 10 mL of concentrated nitric acid into a three-necked bottle with a tail gas treatment device, continuously adding 1.5 g of tin particles, stirring at room temperature for 3 h, adding 2 g of alumina cellucotton into the dissolved mixed solution, and stirring again for 2 h; cooling the solution to room temperature, adjusting pH to 9 with ammonia water, filtering, washing with deionized water and methanol for 3 times, drying at 105 deg.C for 20 hr in a vacuum drying oven, grinding, calcining at 450 deg.C in a muffle furnace for 2 hr to obtain an anti-toxic outer layer material-loaded SnO2The SEM image and EDS analysis results of the alumina fiber are respectively shown in FIG. 3 (a) and FIG. 3 (b), and the SnO can be clearly seen in FIG. 3 (a)2Is very uniformly dispersed in Al2O3So as not to affect both HMDSO and SnO2Can also exert Al2O3As a function of the filter layer, FIG. 3 (b) analysis of EDS also shows that SnO is supported on the alumina fiber2；
(3) Preparing SnO with double-layer structure2A methyl methane sensor:
(3.1) in Al2O3Two annular gold electrodes 2 are arranged on the ceramic tube 1 at intervals in parallel, and each gold electrode 2 is connected with two platinum wire leads 3;
(3.2) taking 1 g of the sensitive inner layer material prepared in the step (1), fully grinding in an agate mortar, and dropwise adding 0.25 mL of H with the mass concentration of 2.5%2PtCl6·H2O aqueous solution and 0.25 mL of 25% of (NH)4)2PdCl4Adding 0.5 mL of mixed solution of water and absolute ethyl alcohol dropwise according to the mass ratio of 2.5: 1 into the aqueous solution, preparing into paste, and uniformly coating Al obtained in the step (3.1) by using fine hairbrush2O3The outer surface of the ceramic tube 1 is naturally dried in air for 1 h, and then is placed in a muffle furnace for calcination, and Al is added at the moment2O3Preparing a sensitive inner layer 4 on the outer surface of the ceramic tube 1; wherein, the calcining conditions are as follows: firstly calcining at 60 ℃ for 1 h, and then heating to 600 ℃ at the heating rate of 7 ℃/min for 2 h;
(3.3) taking 1 g of the antitoxic outer layer material prepared in the step (2) to fully grind in an agate mortar, dripping 0.5 mL of mixed solution consisting of water and absolute ethyl alcohol according to the mass ratio of 2.5: 1, preparing into paste, uniformly coating the paste on the outer surface of the sensitive inner layer 4 obtained in the step (3.2) by using a fine hair pen, and then adopting the same air drying and calcining steps as the step (3.1), wherein Al is adopted at the moment2O3Preparing an antitoxic outer layer 5 on the outer surface of the sensitive inner layer 4 on the outer surface of the ceramic tube 4;
(3.4) passing a chromium-nickel heating wire 6 through the Al obtained in the step (3.3)2O3And (3) welding two ends of a chromium-nickel heating wire 6 and four platinum wire lead wires 3 together on a six-pin tube seat 7 in the ceramic tube 1 to obtain the target sensor.
Comparative example 1
The structure of the sensor differs from that of the sensor of embodiment 1 in that: no outer layer 5 of antitoxic; correspondingly, step (2) and step (3.3) are omitted from the preparation method, namely step (3.2) is directly skipped to step (3.3) and step (3.4) is carried out.
Example 2
The difference from example 1 is that: in the step (2), the amount of the alumina cellucotton is 1 g. Otherwise, the same procedure as in example 1 was repeated.
Example 3
The difference from example 1 is that: in the step (2), the amount of the alumina cellucotton is 1.5 g. Otherwise, the same procedure as in example 1 was repeated.
Example 4
The difference from example 1 is that: in the step (2), the amount of the alumina cellucotton is 2.5 g. Otherwise, the same procedure as in example 1 was repeated.
Example 5
The difference from example 1 is that: in the step (2), the amount of the alumina cellucotton is 3 g. Otherwise, the same procedure as in example 1 was repeated.
Example 6
The difference from example 1 is that: the antitoxic outer layer 5 is made of loaded SnO2Alumina fiber and PtO2Correspondingly, in step (3.3), after the antitoxic outer layer material is fully ground in an agate mortar, 0.25 mL of H with the mass concentration of 2.5 percent is added2PtCl6·H2And (3) adding a water solution O, and then dropwise adding a mixed solution consisting of water and absolute ethyl alcohol to prepare a paste. Otherwise, the same procedure as in example 1 was repeated.
Example 7
The difference from example 1 is that: the antitoxic outer layer 5 is made of loaded SnO2The alumina fiber and PdO of (1) were, correspondingly, in step (3.3), sufficiently ground in an agate mortar and then added with 0.25 mL of (NH) having a mass concentration of 2.5%4)2PdCl4The aqueous solution is added with a mixed solution of water and absolute ethyl alcohol dropwise to prepare a paste. Otherwise, the same procedure as in example 1 was repeated.
Example 8
The difference from example 1 is that: the antitoxic outer layer 5 is made of loaded SnO2Alumina fiber of (5) and Au2O3Correspondingly, in step (3.3), after the antitoxic outer layer material is sufficiently ground in an agate mortar, 0.25 mL of HAuCl with the mass concentration of 2.5% is added4The aqueous solution is added with a mixed solution of water and absolute ethyl alcohol dropwise to prepare a paste. Otherwise, the same procedure as in example 1 was repeated.
Example 9
The difference from example 1 is that: the antitoxic outer layer 5 is made of loaded SnO2Alumina fiber of (2), PtO2And PdO, correspondingly, in the step (3.3), after the antitoxic outer layer material is fully ground in an agate mortar, 0.25 mL of H with the mass concentration of 2.5 percent is added2PtCl6·H2Aqueous O and 0.25 mL of 2.5% by mass (NH)4)2PdCl4The aqueous solution is added with a mixed solution of water and absolute ethyl alcohol dropwise to prepare a paste. Otherwise, the same procedure as in example 1 was repeated.
Example 10
The difference from example 1 is that: the antitoxic outer layer 5 is made of loaded SnO2Alumina fiber of (2), PtO2And Au2O3Correspondingly, in step (3.3), after the antitoxic outer layer material is fully ground in an agate mortar, 0.25 mL of H with the mass concentration of 2.5 percent is added2PtCl6·H2O aqueous solution and 0.25 mL of 2.5% HAuCl4The aqueous solution is added with a mixed solution of water and absolute ethyl alcohol dropwise to prepare a paste. Otherwise, the same procedure as in example 1 was repeated.
Example 11
The difference from example 1 is that: the antitoxic outer layer 5 is made of loaded SnO2Alumina fiber of (2), PdO and Au2O3Correspondingly, in step (3.3), after the antitoxic outer layer material is sufficiently ground in an agate mortar, 0.25 mL of (NH) with a mass concentration of 2.5% is added4)2PdCl4Aqueous solution and 0.25 mL of 2.5% HAuCl4The aqueous solution is added with a mixed solution of water and absolute ethyl alcohol dropwise to prepare a paste. Otherwise, the same procedure as in example 1 was repeated.
Example 12
The difference from example 1 is that: the antitoxic outer layer 5 is made of loaded SnO2Alumina fiber of (2), PtO2PdO and Au2O3Correspondingly, in step (3.3), after the antitoxic outer layer material is fully ground in an agate mortar, 0.25 mL of H with the mass concentration of 2.5 percent is added2PtCl6·H2O aqueous solution, 0.25 mL of 2.5% by mass (NH)4)2PdCl4Aqueous solution and 0.25 mL of 2.5% HAuCl4The aqueous solution is added with a mixed solution of water and absolute ethyl alcohol dropwise to prepare a paste. Otherwise, the same procedure as in example 1 was repeated.
Performance testing
By static gas distribution methodA gas sensor tester (WS-30A, Zhengzhou Weisheng electronics technology Co., Ltd.) tests the performance of the sensor. CH (CH)4Standard gas (99.99%) was purchased from special gases limited, source, south of hewn.
Test one: after the sensors obtained in comparative example 1, example 6, example 7 and example 9 were stabilized in air for 120 s, 9 mL of methane was injected into an 18L air distribution box, and after 80 s, 1.71. mu.L of HMDSO was injected into the air distribution box, and after timing for 40 min, the sensor element was re-exposed to the air environment, and the change of the resistance of the sensor element during the experiment was recorded.
FIG. 4 is a graph showing the change in resistance during the poisoning recovery process of the sensors obtained in comparative example 1 and example 1. Therefore, the following steps are carried out: comparative example 1 showed a relatively significant drop in resistance after the HMDSO gas was introduced and failed to return to the initial state after returning to the air atmosphere; example 1, however, showed no significant change in resistance after exposure to HMDSO gas and quickly returned to the initial state after returning to the air atmosphere, indicating that example 1 had good resistance to silicone poisoning compared to comparative example 1. The index examined in fig. 4 is the variation in the element resistance value, and it can be easily seen from the figure that: example 1R before and after poisoninga、RgBoth indices show almost no change (R)a，RgResistance values of the sensor element in an air atmosphere and a target atmosphere, respectively); from the circuit rule of the series circuit, V of example 1a、VgBoth indexes will remain stable; according to the formula SR=Ra/RgAs can be seen, S in example 1RIt must also remain stable, indicating that: sensor R obtained in example 1a、Rg、Va、Vg、SRAnd the like can be kept stable before and after poisoning.
FIG. 5 shows the resistance change during the poisoning recovery process of the sensors obtained in example 6, example 7 and example 9. Similar to fig. 4, the sensors obtained in examples 6, 7 and 9 showed no significant change in resistance after exposure to HMDSO gas and were able to recover quickly to the initial state after returning to the air atmosphere, indicating that the sensors obtained in examples 6, 7 and 9 also had good resistance to silicone poisoning.
And (2) test II: the sensor obtained in example 1 was exposed alternately to 10000 ppm CH4The experiment was repeated 6 times in 120 s of atmosphere (180 mL of methane was injected into the gas distribution box of 18L) and 120 s of air atmosphere, and the change in voltage value during the experiment was recorded.
FIG. 6 shows the sensor of example 1 at 10000 ppm CH4And (5) repeating the short-term repeatability test result for 6 times under the pulse. Therefore, the following steps are carried out: the sensor of example 1 has an extremely short response recovery time and excellent short-term reproducibility.
And (3) test III: the sensors obtained in example 1 were exposed to different concentrations of CH4Atmosphere 120 s (each exposure to CH)4After the atmosphere, the sensor was allowed to recover 120 s in air atmosphere and then continued to be exposed to a higher concentration of CH4In atmosphere) CH4The gas concentration started at 3000 ppm (54 mL methane injected in the 18L gas box) and increased by 1000 ppm each time (18 mL methane injected in the 18L gas box) until 15000 ppm (270 mL methane injected in the 18L gas box); averaging the resistance values of the elements read by the sensor test system according to the formula SR=Ra/Rg（Ra，RgThe resistance values of the sensor element in the air atmosphere and the target atmosphere, respectively), the resistance sensitivity S of the sensor to methane of different concentrations is calculatedR。
FIG. 7 is a plot of the resistance sensitivity of the sensor of example 1 versus methane concentration. Therefore, the following steps are carried out: the resistance sensitivity of the sensor in example 1 keeps high linearity to the methane concentration in the extremely wide detection range of 3000-15000 ppm, and the sensor has the potential of semi-quantitative detection of methane in a silicon-containing atmosphere.
And (4) testing: the sensors of comparative example 1 and example 1 were exposed to 10000 ppm methane (180 mL methane in an 18L gas box), 100 ppm acetone (5.8 μ L acetone in an 18L gas box), 100 ppm CO (1.8 mL CO in an 18L gas box), and 100 ppm NH, respectively3(18L gas distribution Box filled with 12. mu.L NH3·H2O) atmosphere120S, averaging the resistance values of the elements read by the sensor test system, and calculating the average value according to the formula SR=Ra/Rg（Ra，RgResistance values of the sensor element in the air atmosphere and the target atmosphere, respectively), the resistance sensitivity S of the sensor 1 in comparative example 1 and example 1 to different kinds of gases was calculatedR。
FIG. 8 shows the sensor pairs for methane, acetone, CO, NH of comparative example 1 and example 13The resistance sensitivity of the gas. Therefore, the following steps are carried out: the sensors of the comparative example 1 and the example 1 have high selectivity to methane gas and interference gases (acetone, CO and NH)3) The relative sensitivity of (a) is low and the response of example 1 to acetone gas is significantly lower than that of comparative example 1.
Claims (10)
1. Double-layer-structure SnO resistant to HMDSO poisoning2Methane sensor, its characterized in that: the sensor is indirectly heated sensor made of Al2O3The device comprises a ceramic tube (1), two annular gold electrodes (2), four platinum wire leads (3), a sensitive inner layer (4), an anti-virus outer layer (5), a chromium-nickel heating wire (6) and a six-pin tube seat (7); two annular gold electrodes (2) are arranged on the Al at intervals in parallel2O3On the ceramic tube (1), each gold electrode (2) is connected with two platinum wire leads (3), and the sensitive inner layer (4) is coated on Al2O3The outer surfaces of the ceramic tube (1) and the gold electrode (2) and the anti-poison outer layer (5) are coated on the outer surface of the sensitive inner layer (4), and the chromium-nickel heating wire (6) penetrates through Al2O3The two ends of the chromium-nickel heating wire (6) and Al inside the ceramic tube (1)2O3Four platinum wire leads (3) of the ceramic tube (1) are welded on the six-pin tube seat (7) together; wherein the sensitive inner layer (4) is made of SiO2Surface graft modified SnO2The material of the antitoxic outer layer (5) is loaded SnO2Alumina fibers of (2).
2. The bilayer SnO of claim 1 resistant to HMDSO poisoning2Methane sensor, its characterized in that: sensitive inner layer (4) materialIn, SiO2The grafting ratio of (A) is 1-3 wt%; SnO among materials of the antitoxic outer layer (5)2The loading rate of (B) is 30-70 wt%.
3. The bilayer SnO of claim 1 resistant to HMDSO poisoning2Methane sensor, its characterized in that: the thickness of the sensitive inner layer (4) is 0.05-0.2 mm; the thickness of the antitoxic outer layer (5) is 0.05-0.3 mm.
4. The bilayer SnO as claimed in any one of claims 1 to 3 resistant to HMDSO poisoning2Methane sensor, its characterized in that: the material of the sensitive inner layer (4) and/or the material of the antitoxic outer layer (5) also comprises noble metal, and the noble metal exists in the oxidation state; the noble metal is one or more of metal Pt, metal Pd and metal Au; in the material of the sensitive inner layer (4) or the material of the antitoxic outer layer (5), each noble metal is metered by the simple substance, and the dosage of each noble metal accounts for SnO in the corresponding material20.5-2 wt% of the mass.
5. A bilayer SnO as claimed in any one of claims 1 to 3 resistant to HMDSO poisoning2The preparation method of the methyl sensor is characterized in that the preparation steps are as follows, wherein the volume parts are calculated by mL, and the mass parts are calculated by g:
(1) preparing sensitive inner layer material-SiO2Surface graft modified SnO2；
(2) Preparing the antitoxic outer layer material-loaded SnO2Alumina fiber of (a): stirring 1-3 parts by mass of tin particles and 5-20 parts by volume of concentrated nitric acid at room temperature for 2-5 h, adding 1-3 parts by mass of alumina fiber, and stirring again for 2-3 h; after the solution is naturally cooled to room temperature, ammonia water is used for adjusting the pH value of the solution to 7-9, separation, washing and drying are carried out, and after grinding, calcination is carried out at the temperature of 450-600 ℃ for 1-2 h, thus obtaining the antitoxic outer layer material-load SnO2Alumina fibers of (a);
(3) preparing SnO with double-layer structure2A methyl methane sensor:
(3.1) in Al2O3Two annular metals are arranged on the ceramic tube (1) in parallel at intervalsThe electrodes (2), each gold electrode (2) is connected with two platinum wire leads (3);
(3.2) taking 0.5-1 part by mass of the sensitive inner layer material prepared in the step (1), grinding, adding 0.25-0.5 part by volume of mixed solution consisting of water and absolute ethyl alcohol according to the mass ratio of (2-5) to 1, preparing into paste, and uniformly coating the paste on the Al obtained in the step (3.1)2O3The outer surface of the ceramic tube (1) is naturally dried in air and then calcined, and Al is added at the moment2O3Preparing a sensitive inner layer (4) on the outer surface of the ceramic tube (1); wherein, the calcining conditions are as follows: firstly calcining at 60-150 ℃ for 0.5-2 h, and then heating to 450-600 ℃ at the heating rate of 5-10 ℃/min for calcining for 1-2 h;
(3.3) taking 0.5-1 part by mass of the antitoxic outer layer material prepared in the step (2), grinding, adding 0.25-0.5 part by volume of mixed solution consisting of water and absolute ethyl alcohol according to the mass ratio of (2-5) to 1, preparing into paste, uniformly coating the paste on the outer surface of the sensitive inner layer (4) obtained in the step (3.2), and then carrying out air drying and calcining steps which are the same as the steps (3.2), wherein Al is added at the moment2O3Preparing an anti-virus outer layer (5) on the outer surface of the sensitive inner layer (4) on the outer surface of the ceramic tube (1);
(3.4) passing a chromium-nickel heating wire (6) through the Al obtained in the step (3.3)2O3And (3) welding two ends of a chromium-nickel heating wire (6) and four platinum wire leads (3) on a six-pin tube seat (7) together inside the ceramic tube (1) to obtain the target sensor.
6. The bilayer SnO of claim 5 resistant to HMDSO poisoning2The preparation method of the methyl sensor is characterized by comprising the following steps: in the step (3.2), the sensitive inner layer material is ground, then noble metal precursor solution with the concentration of 2.5-8 wt% is added, and then mixed solution consisting of water and absolute ethyl alcohol is added to be prepared into paste; the noble metal is one or more of Pt, Pd and Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and the dosage of each noble metal precursor solution ensures that the noble metal simple substance provided by the noble metal precursor solution accounts for SnO in the sensitive inner layer material20.5-2 wt% of the mass.
7. The bilayer SnO of claim 5 resistant to HMDSO poisoning2The preparation method of the methyl sensor is characterized by comprising the following steps: in the step (3.3), grinding the antitoxic outer layer material, adding a noble metal precursor solution with the concentration of 2.5-8 wt%, and then adding a mixed solution consisting of water and absolute ethyl alcohol to prepare a paste; the noble metal is one or more of Pt, Pd and Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and the dosage of each noble metal precursor solution ensures that the noble metal simple substance provided by the noble metal precursor solution accounts for SnO in the antitoxic outer layer material20.5-2 wt% of the mass.
8. The bilayer SnO as claimed in claim 6 or 7 resistant to HMDSO poisoning2The preparation method of the methyl sensor is characterized by comprising the following steps: the acid containing noble metal is H2PtCl6·H2O、HAuCl4The water-soluble salt containing noble metal is (NH)4)2PdCl4。
9. The bilayer SnO of claim 5 resistant to HMDSO poisoning2The preparation method of the methyl sensor is characterized in that the process of the step (1) is as follows:
(1.1) preparation of Nano SnO2Powder;
(1.2) taking 2-5 parts by mass of nano SnO prepared in the step (1.1)2Powder, 3-5 parts by volume of hydrogen peroxide, 3-5 parts by volume of ammonia water and 6-10 parts by volume of water, ultrasonic oscillation at 50-70 ℃ for 30-60 min, separation and drying to prepare SnO2A hydroxylate intermediate;
(1.3) taking 2-5 parts by mass of nano SnO prepared in the step (1.2)2The hydroxylate intermediate, 0.2-0.6 mass part of 3-aminopropyltriethoxysilane and 10-15 volume parts of toluene are magnetically stirred for 3-5 h, separated, dried and calcined at 800 ℃ for 1-2 h to prepare the sensitive inner layer material-SiO2Surface graft modified SnO2。
10. The bilayer SnO of claim 9 resistant to HMDSO poisoning2The preparation method of the methyl sensor is characterized in that the process of the step (1.1) is as follows: stirring 20-30 parts by mass of tin particles and 80-120 parts by volume of concentrated nitric acid at room temperature for 2-5 h to obtain gel, separating, washing, drying, grinding, calcining at 600 ℃ for 1-2 h to obtain nano SnO2And (3) powder.
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