CN114113241B - HMDSO poisoning resistant double-layer structure SnO 2 Methyl hydride sensor and preparation method thereof - Google Patents
HMDSO poisoning resistant double-layer structure SnO 2 Methyl hydride sensor and preparation method thereof Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910006404 SnO 2 Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 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
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 29
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 62
- 230000001147 anti-toxic effect Effects 0.000 claims abstract description 45
- 239000000919 ceramic Substances 0.000 claims abstract description 34
- 239000010931 gold Substances 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims abstract description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 26
- 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 26
- 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
- 238000000034 method Methods 0.000 claims abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052737 gold Inorganic materials 0.000 claims abstract description 19
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 12
- 239000002574 poison Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 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 9
- 230000008569 process Effects 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 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
- 150000002440 hydroxy compounds Chemical class 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003466 welding Methods 0.000 claims description 3
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 32
- 208000005374 Poisoning Diseases 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- 238000003917 TEM image Methods 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 206010017740 Gas poisoning Diseases 0.000 description 1
- 244000208060 Lawsonia inermis Species 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention belongs to the technical field of methane sensor preparation, and discloses a double-layer structure SnO resisting HMDSO poisoning 2 Provided are a methyl hydride sensor and a preparation method thereof. The sensor is a bypass type sensor and is made of Al 2 O 3 The device comprises a ceramic tube, two annular gold electrodes, four platinum wire leads, a sensitive inner layer, an antitoxic outer layer, a chromium-nickel heating wire and a six-pin tube seat; wherein the sensitive inner layer material is SiO 2 Surface grafting modified SnO 2 The anti-poison outer layer material is loaded SnO 2 Is a fiber of alumina. The preparation method comprises the following steps: (1) Preparation of sensitive inner layer material- -SiO 2 Surface grafting modified SnO 2 The method comprises the steps of carrying out a first treatment on the surface of the (2) Preparation of antitoxic outer layer material-loaded SnO 2 Is a fiber of alumina; (3) Coating sensitive inner layer material and then anti-poison outer layer material according to the preparation process of the bypass type sensor to prepare the SnO with the double-layer structure 2 A methyl hydride sensor. The sensor element prepared by the invention can effectively resist the poisoning effect of HMDSO, and can be used for detecting the toxic effect of the HMDSO in V 0 、V g 、S R Can be kept stable in various indexes.
Description
Technical Field
The invention belongs to the technical field of methane sensor preparation, and particularly relates to an HMDSO poisoning resistant SnO with a double-layer structure 2 Provided are a methyl hydride sensor and a preparation method thereof.
Background
The gas sensing technology is generally 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 safe production and daily life of people. Among them, the semiconductor oxide sensor is an important branch of the gas sensing technology, and has a large share in the gas sensor market due to its excellent performance and low price. The semiconductor gas-sensitive material most widely used at home and abroad at present is SnO 2 、ZnO、WO 3 、Fe 2 O 3 、In 2 O 3 Etc., in which SnO is used 2 Is most widely used inMany common gases exhibit higher sensitivity and shorter response recovery times.
Various organizations and countries in the world have placed certain demands on the resistance of sensor elements to gas poisoning, such as ISO26142: 2010. EN50194-1-2009, etc. The new national standard for flammable gas detectors published in 2019 of China GB 15322.2-2019 specifies: the sensor was placed at a flammable vapor concentration of 1% LEL (500 ppm CH 4 ) And 10 ppm HMDSO for 40 min, and then recovering for 20 min in the 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. It has been reported in some prior literature that hexamethyldisiloxane is mainly adsorbed on gas sensitive materials and further cleaved into organosilicon, silicate, siO 2 Etc., blocking the active sites on the surface of the gas sensitive material, thereby degrading the response performance of the sensor. However, there are few documents on how to design a specific gas sensitive material, optimize the sensor so that it can resist silicone poisoning. Thus, there is an urgent need to develop a methane gas sensor that is resistant to silicon poisoning and can be used for normal monitoring in a gas atmosphere containing silicone vapors.
Disclosure of Invention
In view of the above-mentioned drawbacks and disadvantages of the prior art, an object of the present invention is to provide a double-layer SnO with HMDSO poisoning resistance 2 Provided are a methyl hydride sensor and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
HMDSO poisoning resistant double-layer structure SnO 2 The sensor is a bypass type sensor and is made of Al 2 O 3 The device comprises a ceramic tube (1), two annular gold electrodes (2), four platinum wire leads (3), a sensitive inner layer (4), an antitoxic outer layer (5), a chromium-nickel heating wire (6) and a six-pin tube seat (7); two annular gold electrodes (2) are arranged at intervals in parallel on Al 2 O 3 Each gold electrode (2) is connected with two platinum wire leads (3) on the ceramic tube (1), and a sensitive inner layer (4) is coated on Al 2 O 3 Ceramic tube (1) and gold electrode (2)An antitoxic outer layer (5) is coated on the outer surface of the sensitive inner layer (4), and a chromium-nickel heating wire (6) passes through Al 2 O 3 Inside the ceramic tube (1), two ends of a chromium-nickel heating wire (6) and Al 2 O 3 Four 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 SiO 2 Surface grafting modified SnO 2 The anti-poison outer layer (5) is made of loaded SnO 2 Is a fiber of alumina.
Preferably, siO in the material of the sensitive inner layer (4) 2 The grafting ratio of (2) is 1-3 wt%; snO in the anti-poison outer layer (5) material 2 Is 30-70 wt% { loading = SnO 2 mass/(SnO) 2 Mass + alumina fiber mass) × 100% }.
Preferably, the thickness of the sensitive inner layer (4) is 0.05-0.2. 0.2 mm; the thickness of the antitoxic outer layer (5) is 0.05-0.3 mm.
Further, the material of the sensitive inner layer (4) and/or the material of the anti-poison outer layer (5) also comprises a noble metal, which is present in its oxidized form; the noble metal is one or more of metal Pt, metal Pd and metal Au; in the sensitive inner layer (4) material or the antitoxic outer layer (5) material, each noble metal is metered by the simple substance, and the dosage is SnO in the corresponding material 2 0.5-2. 2 wt% of the weight.
The preparation method comprises the following steps of:
(1) Preparation of sensitive inner layer material- -SiO 2 Surface grafting modified SnO 2 ；
(2) Preparation of antitoxic outer layer material-loaded SnO 2 Is a fiber of alumina: 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 parts by mass, adding 1-3 parts by mass of alumina fibers, and stirring for 2-3 h parts again; after the solution is naturally cooled to room temperature, ammonia water is used for regulating the pH value of the solution to 7-9, the solution is separated, washed and dried, and calcined at 450-600 ℃ for 1-2 h after grinding, thus preparing the antitoxic outer layer material, namely the loaded SnO 2 Is a fiber of alumina;
(3) Preparation of double-layer SnO 2 Nail baseAn alkane sensor:
(3.1) at Al 2 O 3 Two 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 1 to form 0.25-0.5 part by volume of mixed solution, preparing into paste, and uniformly coating the paste on Al obtained in the step (3.1) 2 O 3 The outer surface of the ceramic tube (1) is calcined after natural air drying in the air, and at the moment, al is added in the ceramic tube 2 O 3 The outer surface of the ceramic tube (1) is provided with a sensitive inner layer (4); wherein, the calcination conditions are as follows: calcining at 60-150deg.C for 0.5-2 h, and then heating to 450-600deg.C at a heating rate of 5-10deg.C/min 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 a mixed solution consisting of water and absolute ethyl alcohol according to the mass ratio of (2-5) to 1, preparing into paste, uniformly coating on the outer surface of the sensitive inner layer (4) obtained in the step (3.2), and then adopting the same air drying and calcining steps as those in the step (3.2), wherein the process is characterized in that the process comprises the following steps of 2 O 3 The outer surface of the sensitive inner layer (4) of the outer surface of the ceramic tube (1) is provided with an antitoxic outer layer (5);
(3.4) passing a chromium-nickel heating wire (6) through the Al obtained in the step (3.3) 2 O 3 And (3) welding the two ends of the chromium-nickel heating wire (6) and the four platinum wire leads (3) on the six-pin tube seat (7) together in the ceramic tube (1) to prepare the target sensor.
Further, in the step (3.2), the sensitive inner layer material is ground and then added with a noble metal precursor solution with the concentration of 2.5-8 and wt percent, and then added with a mixed solution consisting of water and absolute ethyl alcohol to be prepared into paste; the noble metal is one or more of metal Pt, metal Pd and metal Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and the consumption of each noble metal precursor solution ensures that the noble metal simple substance provided by each noble metal precursor solution accounts for SnO in the sensitive inner layer material 2 0.5-2. 2 wt% of the weight.
Further, in the step (3.3), after the anti-toxin outer layer material is ground, adding a noble metal precursor solution with the concentration of 2.5-8 and 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 metal Pt, metal Pd and metal Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and the consumption of each noble metal precursor solution ensures that the noble metal simple substance provided by each noble metal precursor solution accounts for SnO in the antitoxic outer layer material 2 0.5-2. 2 wt% of the weight.
Preferably, the noble metal-containing acid is H 2 PtCl 6 ·H 2 O、HAuCl 4 The water-soluble salt containing noble metal is (NH) 4 ) 2 PdCl 4 。
In step (1), siO 2 Surface grafting modified SnO 2 Can be prepared according to the prior art, preferably the process is as follows:
(1.1) preparation of nano SnO 2 Powder;
(1.2) taking 2 to 5 parts by mass of nano SnO prepared in the step (1.1) 2 3-5 parts by volume of hydrogen peroxide, 3-5 parts by volume of ammonia water and 6-10 parts by volume of water, performing ultrasonic vibration at 50-70 ℃ for 30-60 min, separating, and drying to obtain SnO 2 A hydroxy compound intermediate;
(1.3) taking 2 to 5 parts by mass of nano SnO prepared in the step (1.2) 2 Preparing a sensitive inner layer material, namely SiO, by magnetically stirring 3-5 h, separating, drying, and calcining 1-2 h at 500-800 ℃ with 0.2-0.6 part by mass of 3-aminopropyl triethoxysilane and 10-15 parts by mass of toluene 2 Surface grafting modified SnO 2 。
In the step (1.1), nano SnO 2 The 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 parts to obtain gel, separating, washing, drying, grinding, and calcining at 450-600 ℃ for 1-2 h parts to obtain nano SnO 2 And (3) powder.
The invention has the beneficial effects that:
(1) The sensitive inner layer of the invention is SiO 2 Modified nano SnO 2 By nano SnO 2 Surface modification is carried out, and a layer of SiO is grafted on the surface 2 The presence of the surface modification layer limits nano SnO at high temperatures 2 Is to agglomerate and modify nano SnO 2 The particle size is only 5-15 nm, the distribution is uniform, and the catalyst has excellent response performance to methane;
(2) The invention explores an anti-poisoning material, namely, a certain mass fraction of SnO is loaded 2 Is made of fiber cotton Al 2 O 3 Due to Al 2 O 3 The characteristic of low conductivity is that the resistance of the antitoxic outer layer is far greater than that of the sensitive inner layer, and the SnO caused by HMDSO 2 /Al 2 O 3 The resistance change of the outer layer does not affect the whole element resistance; in addition, al 2 O 3 The HMDSO can 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 invention has extremely short response recovery time and extremely good short-term repeatability, maintains extremely high linearity for the concentration of methane in an extremely wide detection range of 3000-15000 ppm, and has the potential of semi-quantitatively detecting methane in a silicon-containing atmosphere;
(4) The sensor element prepared by the invention can effectively resist the poisoning effect of HMDSO, and is characterized in that V 0 、V g 、S R The stability can be kept on a plurality of indexes, and the requirements of the national standard GB 15322.2-2019 of the flammable gas detector on poisoning resistance are far exceeded;
(5) The raw materials adopted by the invention are cheap and easy to obtain, nontoxic and harmless, and the sensor element has simple preparation process and can be produced in a large scale and industrialized way.
Drawings
Fig. 1: the invention relates to a double-layer structure SnO resisting HMDSO poisoning 2 Schematic structure of the methyl hydride sensor.
Fig. 2: the sensitive inner layer material prepared in example 1- -SiO 2 Surface grafting modified SnO 2 Is a TEM image of (1).
Fig. 3: the antitoxic outer layer material prepared in example 1- -supported SnO 2 SEM image (a) and EDS analysis result (b) of the alumina fiber of (a).
Fig. 4: the sensors obtained in comparative example 1 and example 1 showed a change in resistance during recovery from poisoning.
Fig. 5: the sensors obtained in example 6, example 7 and example 9 show a change in resistance during recovery from poisoning.
Fig. 6: example 1 sensor at 10000 ppm CH 4 Short-term repeatability test results repeated 6 times under pulse.
Fig. 7: example 1 sensor resistance sensitivity S R Relationship to methane concentration.
Fig. 8: comparative example 1 and example 1 sensors were used for methane, acetone, CO, NH 3 Resistance sensitivity of the gas.
Detailed Description
The present invention will be described in further detail below for the purpose of making the present invention clearer and more specific. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
As shown in FIG. 1, a double-layer structure SnO resistant to HMDSO poisoning 2 The sensor is a bypass type sensor and is made of Al 2 O 3 The device comprises a ceramic tube 1, two annular gold electrodes 2, four platinum wire leads 3, a sensitive inner layer 4, an antitoxic outer layer 5, a chromium-nickel heating wire 6 and a six-pin tube seat 7; two annular gold electrodes 2 are arranged at intervals in parallel with Al 2 O 3 On the ceramic tube 1, two platinum wire leads 3 are connected to each gold electrode 2, and a sensitive inner layer 4 is coated on Al 2 O 3 The outer surface of the ceramic tube 1, the antitoxic outer layer 5 is coated on the outer surface of the sensitive inner layer 4, and the chromium-nickel heating wire 6 passes through Al 2 O 3 Inside the ceramic tube 1, both ends of the chromium-nickel heating wire 6 and Al 2 O 3 The four 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 SiO 2 Surface grafting modified SnO 2 、PtO 2 And PdO, the thickness of the sensitive inner layer 4 is 0.1 mm; the material of the antitoxic outer layer 5 is loaded SnO 2 The thickness of the poison resistant outer layer 5 is 0.15. 0.15 mm.
The preparation method comprises the following steps:
(1) Preparation of sensitive inner layer material- -SiO 2 Surface grafting modified SnO 2 ：
(1.1) preparation of nano SnO 2 Powder: adding 80 mL concentrated nitric acid into a three-necked bottle with a tail gas treatment device, continuously adding 20 g tin particles, stirring at room temperature for 3 h to obtain white gel, centrifuging, washing with deionized water to neutrality, drying at 105deg.C in a vacuum drying oven for 20 h, grinding, calcining at 450deg.C for 2 h, grinding the pale yellow solid to obtain nanometer SnO 2 Powder;
(1.2) taking 2.25 and g nano SnO prepared in the step (1.1) 2 Adding 0.35. 0.35 g parts by mass of 3-aminopropyl triethoxysilane and 15. 15 mL toluene into a 50 mL beaker, magnetically stirring for 5 h, centrifuging, drying, calcining at 500 ℃ for 2 h to obtain a sensitive inner layer material-SiO 2 Surface grafting modified SnO 2 The TEM image is shown in figure 2, the particle size is in the range of 5-15 and nm, the average particle size is 9.86 nm, and the distribution is uniform; detected by gas chromatography, siO 2 The grafting ratio of (2) was 1 wt%;
(2) Preparation of antitoxic outer layer material-loaded SnO 2 Is a fiber of alumina: adding 10 mL concentrated nitric acid into a three-necked bottle with a tail gas treatment device, continuously adding 1.5 g tin particles into the concentrated nitric acid, stirring at room temperature for 3 h, adding 2 g alumina fiber cotton into the dissolved mixed solution, and stirring for 2 h again; cooling the solution to room temperature, regulating the pH of the solution to 9 with ammonia water, filtering, cleaning with deionized water and methanol respectively for 3 times, drying at 105deg.C in a vacuum drying oven for 20 h, grinding, calcining at 450deg.C in a muffle furnace for 2 h to obtain the antitoxic outer layer material-loaded SnO 2 The SEM and EDS analysis results of the alumina fibers of (a) are shown in FIG. 3 (a) and FIG. 3 (b), respectively, and the SnO is clearly shown in FIG. 3 (a) 2 Are very uniformly dispersed in Al 2 O 3 So as not to affect HMDSO and SnO 2 Can also exert Al 2 O 3 As a function of the filter layer, the analysis result of EDS of FIG. 3 (b) also shows that SnO is supported on the alumina fiber 2 ；
(3) Preparation ofSnO with double-layer structure 2 A base methane sensor:
(3.1) at Al 2 O 3 Two 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 the sensitive inner layer material 1 g prepared in the step (1), fully grinding in an agate mortar, and dripping 0.25-mL mass concentration of 2.5% H 2 PtCl 6 ·H 2 An O aqueous solution and 0.25. 0.25 mL mass concentration of 2.5% (NH 4 ) 2 PdCl 4 Dripping water and absolute ethyl alcohol into the aqueous solution according to the mass ratio of 0.5:1 to form a mixed solution of 0.5: 0.5 mL, preparing into paste, uniformly coating the paste on Al obtained in the step (3.1) by using a fine hair pen 2 O 3 The outer surface of the ceramic tube 1 is naturally dried in air by 1 h and then is placed in a muffle furnace for calcination, and at the moment, the ceramic tube is made of Al 2 O 3 The outer surface of the ceramic tube 1 is provided with a sensitive inner layer 4; wherein, the calcination conditions are as follows: calcining at 60 ℃ for 1 h, and then heating to 600 ℃ at a heating rate of 7 ℃/min for 2 h;
(3.3) taking the antitoxic outer layer material 1 g prepared in the step (2), fully grinding in an agate mortar, dripping the mixed solution 0.5 mL composed 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 nap pen, and then adopting the same air drying and calcining steps as those of the step (3.1), wherein the process is carried out on Al 2 O 3 The outer surface of the sensitive inner layer 4 of the outer surface of the ceramic tube 4 is provided with an antitoxic outer layer 5;
(3.4) passing a chromium-nickel heating wire 6 through the Al obtained in the step (3.3) 2 O 3 And (3) welding two ends of the chromium-nickel heating wire 6 and four platinum wire leads 3 on the six-pin tube seat 7 together in the ceramic tube 1 to obtain the target sensor.
Comparative example 1
The structure of the sensor is different from that of the sensor of embodiment 1 in that: no antitoxic outer layer 5; correspondingly, step (2) and step (3.3), namely step (3.2), are omitted in the preparation method, and step (3.4) is performed by directly skipping step (3.3).
Example 2
The difference from example 1 is that: in the step (2), the amount of the alumina fiber cotton is 1 g. The procedure is as in example 1.
Example 3
The difference from example 1 is that: in the step (2), the amount of the alumina fiber cotton is 1.5. 1.5 g. The procedure is as in example 1.
Example 4
The difference from example 1 is that: in the step (2), the amount of the alumina fiber cotton is 2.5 and g. The procedure is as in example 1.
Example 5
The difference from example 1 is that: in the step (2), the amount of the alumina fiber cotton is 3 g. The procedure is as in example 1.
Example 6
The difference from example 1 is that: the material of the antitoxic outer layer 5 is loaded SnO 2 Alumina fibers and PtO of (a) 2 Correspondingly, in the step (3.3), after the anti-toxin outer layer material is sufficiently ground in an agate mortar, H with the mass concentration of 0.25 and mL percent of 2.5 percent is added 2 PtCl 6 ·H 2 O aqueous solution, then adding water and absolute ethanol to form a mixed solution to prepare into paste. The procedure is as in example 1.
Example 7
The difference from example 1 is that: the material of the antitoxic outer layer 5 is loaded SnO 2 In step (3.3), the anti-poison outer layer material was sufficiently ground in an agate mortar, and then (NH) was added at a concentration of 2.5% by mass of 0.25. 0.25 mL 4 ) 2 PdCl 4 The aqueous solution is then added dropwise with a mixed solution of water and absolute ethyl alcohol to prepare a paste. The procedure is as in example 1.
Example 8
The difference from example 1 is that: the material of the antitoxic outer layer 5 is loaded SnO 2 Alumina fibers and Au of (a) 2 O 3 Correspondingly, in the step (3.3), after the antitoxic outer layer material is sufficiently ground in an agate mortar, HAuCl with the mass concentration of 0.25 and mL and 2.5% is added 4 The aqueous solution is then added dropwise with a mixed solution of water and absolute ethyl alcohol to prepare a paste. The procedure is as in example 1.
Example 9
The difference from example 1 is that: the material of the antitoxic outer layer 5 is loaded SnO 2 Alumina fibers, ptO of (a) 2 And PdO, correspondingly, in the step (3.3), after the anti-toxin outer layer material is sufficiently ground in an agate mortar, 0.25 mL mass percent of H with the concentration of 2.5 percent is added 2 PtCl 6 ·H 2 An O aqueous solution and 0.25. 0.25 mL mass concentration of 2.5% (NH 4 ) 2 PdCl 4 The aqueous solution is then added dropwise with a mixed solution of water and absolute ethyl alcohol to prepare a paste. The procedure is as in example 1.
Example 10
The difference from example 1 is that: the material of the antitoxic outer layer 5 is loaded SnO 2 Alumina fibers, ptO of (a) 2 And Au (gold) 2 O 3 Correspondingly, in the step (3.3), after the anti-toxin outer layer material is sufficiently ground in an agate mortar, H with the mass concentration of 0.25 and mL percent of 2.5 percent is added 2 PtCl 6 ·H 2 O aqueous solution and HAuCl with mass concentration of 0.25 and mL of 2.5% 4 The aqueous solution is then added dropwise with a mixed solution of water and absolute ethyl alcohol to prepare a paste. The procedure is as in example 1.
Example 11
The difference from example 1 is that: the material of the antitoxic outer layer 5 is loaded SnO 2 Alumina fibers, pdO and Au of (a) 2 O 3 Correspondingly, in the step (3.3), after the anti-toxin outer layer material is sufficiently ground in an agate mortar, 0.25-mL mass concentration of 2.5 percent (NH) is added 4 ) 2 PdCl 4 Aqueous solution and HAuCl with a mass concentration of 2.5% of 0.25 mL 4 The aqueous solution is then added dropwise with a mixed solution of water and absolute ethyl alcohol to prepare a paste. The procedure is as in example 1.
Example 12
The difference from example 1 is that: the material of the antitoxic outer layer 5 is loaded SnO 2 Alumina fibers, ptO of (a) 2 PdO and Au 2 O 3 Correspondingly, in the step (3.3), after the anti-toxin outer layer material is sufficiently ground in an agate mortar, H with the mass concentration of 0.25 and mL percent of 2.5 percent is added 2 PtCl 6 ·H 2 O aqueous solution, 0.25. 0.25 mL mass concentration 2.5% (NH) 4 ) 2 PdCl 4 Aqueous solution and HAuCl with a mass concentration of 2.5% of 0.25 mL 4 The aqueous solution is then added dropwise with a mixed solution of water and absolute ethyl alcohol to prepare a paste. The procedure is as in example 1.
Performance testing
Sensor performance was tested by a gas sensor tester (WS-30A, zhengweisheng electronic technologies Co., ltd.) using static gas distribution. CH (CH) 4 Standard gas (99.99%) was purchased from henna source specialty gases limited.
Test one: the sensors obtained in comparative example 1 and example 1, example 6, example 7 and example 9 were stabilized in air by 120 s, 9 mL methane was injected into the air distribution box of 18L, 80. 80 s HMDSO was then injected into the air distribution box by 1.71. Mu.L, and the sensor element was re-exposed to the air environment after 40 min of time, and the change of the resistance of the sensor element during the experiment was recorded.
Fig. 4 shows the change in resistance of the sensors obtained in comparative example 1 and example 1 during recovery from poisoning. It can be seen that: comparative example 1 showed a relatively significant drop in resistance after introduction of HMDSO gas and could not be restored to the original state after restoration to the air atmosphere; whereas example 1 showed no significant change in resistance after exposure to HMDSO gas and was able to quickly recover to the original state after recovery to the air atmosphere, example 1 showed good resistance to silicone poisoning as compared to comparative example 1. The index examined in fig. 4 is the change in element resistance value, as can be readily seen in the figure: EXAMPLE 1R before and after poisoning a 、R g The two indexes hardly change (R a ，R g Resistance values of the sensor element in the air atmosphere and the target atmosphere, respectively); as can be seen from the circuit law of the series circuit, V of embodiment 1 a 、V g The two indexes are stable; according to formula S R =R a /R g It is understood that S of example 1 R It must also remain stable, indicating that: sensor R obtained in example 1 a 、R g 、V a 、V g 、S R The indexes can be kept stable before and after poisoning.
Fig. 5 shows the resistance change during poisoning recovery of the sensors obtained in example 6, example 7, and example 9. Similar to fig. 4, the sensors obtained in example 6, example 7 and example 9 showed no significant change in resistance after exposure to HMDSO gas and quickly recovered to the initial state after recovery to the air atmosphere, indicating that the sensors obtained in example 6, example 7 and example 9 also had good silicone poisoning resistance.
And (2) testing II: the sensor obtained in example 1 was alternately exposed to 10000 ppm CH 4 The atmosphere (180 mL methane was injected into the distribution box of 18L) was repeated 6 times in 120 s and 120 s air atmosphere, and the change of the voltage value during the experiment was recorded.
FIG. 6 shows the sensor of example 1 at 10000 ppm CH 4 Short-term repeatability test results repeated 6 times under pulse. It can be seen that: the sensor of example 1 has extremely short response recovery times and excellent short-term repeatability.
And (3) test III: the sensor obtained in example 1 was exposed to different concentrations of CH 4 120 s in atmosphere (each exposure to CH 4 After the atmosphere, the sensor was allowed to recover 120 s in an air atmosphere and then continued to be exposed to a higher concentration of CH 4 In atmosphere), CH 4 The gas concentration was increased by 1000 ppm each time starting from 3000 ppm (54 mL methane was injected into the gas distribution box of 18L) (18 mL methane was injected into the gas distribution box of 18L) to 15000 ppm (270 mL methane was injected into the gas distribution box of 18L); averaging the element resistance values read by the sensor test system according to the formula S R =R a /R g （R a ，R g The resistance values of the sensor element in the air atmosphere and the target atmosphere are respectively calculated, and the resistance sensitivity S of the sensor to methane with different concentrations is calculated R 。
FIG. 7 is a plot of sensor resistance sensitivity versus methane concentration for example 1. It can be seen that: the resistance sensitivity of the sensor of example 1 remained highly linear to methane concentration over an extremely wide detection range of 3000-15000 ppm, with the potential for semi-quantitative detection of methane in a silicon-containing atmosphere.
And (3) testing four: the sensors of comparative example 1 and example 1 were exposed to 10000 ppm methane (180. 180 mL methane in an air distribution box of 18L), 100 ppm acetone (5.8. Mu.L acetone in an air distribution box of 18L), 100 ppm CO (1.8 mL CO in an air distribution box of 18L), 100 ppm NH, respectively 3 (12. Mu.L NH was injected into the gas distribution tank of 18L) 3 ·H 2 O) 120S in the atmosphere, averaging the element resistance values read by the sensor test system, and determining the average value according to the formula S R =R a /R g （R a ，R g The resistance values of the sensor element in the air atmosphere and the target atmosphere, respectively), the resistance sensitivities S of the sensor 1 in comparative example 1 and example 1 to different kinds of gases were calculated R 。
FIG. 8 is a graph of the sensors of comparative example 1 and example 1 versus methane, acetone, CO, NH 3 Resistance sensitivity of the gas. It can be seen that: the sensors of comparative example 1 and example 1 have high selectivity for methane gas and high selectivity for interfering gases (acetone, CO, NH 3 ) Is relatively low and the response of example 1 to acetone gas is significantly lower than that of comparative example 1.
Claims (8)
1. HMDSO poisoning resistant double-layer structure SnO 2 A methyl hydride sensor, characterized in that: the sensor is a bypass type sensor and is made of Al 2 O 3 The device comprises a ceramic tube (1), two annular gold electrodes (2), four platinum wire leads (3), a sensitive inner layer (4), an antitoxic outer layer (5), a chromium-nickel heating wire (6) and a six-pin tube seat (7); two annular gold electrodes (2) are arranged at intervals in parallel on Al 2 O 3 Each gold electrode (2) is connected with two platinum wire leads (3) on the ceramic tube (1), and a sensitive inner layer (4) is coated on Al 2 O 3 The outer surfaces of the ceramic tube (1) and the gold electrode (2), the antitoxic outer layer (5) is coated on the outer surface of the sensitive inner layer (4), and the chromium-nickel heating wire (6) passes through Al 2 O 3 Ceramic tube(1) Inside, both ends of the chromium-nickel heating wire (6) and Al 2 O 3 Four 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 SiO 2 Surface grafting modified SnO 2 The anti-poison outer layer (5) is made of loaded SnO 2 Is a fiber of alumina; in the sensitive inner layer (4) material, siO 2 The grafting ratio of (2) is 1-3 wt%; snO in the anti-poison outer layer (5) material 2 The load rate of (2) is 30-70 wt%; the thickness of the sensitive inner layer (4) is 0.05-0.2 and mm, and the thickness of the anti-toxin outer layer (5) is 0.05-0.3 and mm.
2. HMDSO poisoning resistant bilayer structure SnO of claim 1 2 A methyl hydride sensor, characterized in that: the sensitive inner layer (4) material and/or the anti-poison outer layer (5) material also comprises a noble metal, which is present in its oxidized form; the noble metal is one or more of metal Pt, metal Pd and metal Au; in the sensitive inner layer (4) material or the antitoxic outer layer (5) material, each noble metal is metered by the simple substance, and the dosage is SnO in the corresponding material 2 0.5-2. 2 wt% of the weight.
3. An HMDSO poisoning resistant double-layer structure SnO as defined in claim 1 2 The preparation method of the methyl hydride sensor is characterized by comprising the following steps of:
(1) Preparation of sensitive inner layer material- -SiO 2 Surface grafting modified SnO 2 ；
(2) Preparation of antitoxic outer layer material-loaded SnO 2 Is a fiber of alumina: 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 parts by mass, adding 1-3 parts by mass of alumina fibers, and stirring for 2-3 h parts again; after the solution is naturally cooled to room temperature, ammonia water is used for regulating the pH value of the solution to 7-9, the solution is separated, washed and dried, and calcined at 450-600 ℃ for 1-2 h after grinding, thus preparing the antitoxic outer layer material, namely the loaded SnO 2 Is a fiber of alumina;
(3) Preparation of double-layer SnO 2 A base methane sensor:
(3.1) at Al 2 O 3 Two 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 1 to form 0.25-0.5 part by volume of mixed solution, preparing into paste, and uniformly coating the paste on Al obtained in the step (3.1) 2 O 3 The outer surface of the ceramic tube (1) is calcined after natural air drying in the air, and at the moment, al is added in the ceramic tube 2 O 3 The outer surface of the ceramic tube (1) is provided with a sensitive inner layer (4); wherein, the calcination conditions are as follows: calcining at 60-150deg.C for 0.5-2 h, and then heating to 450-600deg.C at a heating rate of 5-10deg.C/min 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 a mixed solution consisting of water and absolute ethyl alcohol according to the mass ratio of (2-5) to 1, preparing into paste, uniformly coating on the outer surface of the sensitive inner layer (4) obtained in the step (3.2), and then adopting the same air drying and calcining steps as those in the step (3.2), wherein the process is characterized in that the process comprises the following steps of 2 O 3 The outer surface of the sensitive inner layer (4) of the outer surface of the ceramic tube (1) is provided with an antitoxic outer layer (5);
(3.4) passing a chromium-nickel heating wire (6) through the Al obtained in the step (3.3) 2 O 3 And (3) welding the two ends of the chromium-nickel heating wire (6) and the four platinum wire leads (3) on the six-pin tube seat (7) together in the ceramic tube (1) to prepare the target sensor.
4. A HMDSO poisoning resistant bilayer structure SnO as claimed in claim 3 2 The preparation method of the methyl hydride sensor is characterized by comprising the following steps of: in the step (3.2), the sensitive inner layer material is grinded, then noble metal precursor solution with the concentration of 2.5-8 and wt percent is added, and then mixed solution consisting of water and absolute ethyl alcohol is added to prepare paste; the noble metal is one or more of metal Pt, metal Pd and metal Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and each of the noble metal precursors is an acid containing noble metalThe use amount of the 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 material 2 0.5-2. 2 wt% of the weight.
5. A HMDSO poisoning resistant bilayer structure SnO as claimed in claim 3 2 The preparation method of the methyl hydride sensor is characterized by comprising the following steps of: in the step (3.3), after the anti-toxin outer layer material is ground, adding a noble metal precursor solution with the concentration of 2.5-8 and 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 metal Pt, metal Pd and metal Au, the noble metal precursor is acid containing noble metal or water-soluble salt containing noble metal, and the consumption of each noble metal precursor solution ensures that the noble metal simple substance provided by each noble metal precursor solution accounts for SnO in the antitoxic outer layer material 2 0.5-2. 2 wt% of the weight.
6. HMDSO poisoning resistant bilayer structure SnO of claim 4 or 5 2 The preparation method of the methyl hydride sensor is characterized by comprising the following steps of: the acid containing noble metal is H 2 PtCl 6 ·H 2 O、HAuCl 4 The water-soluble salt containing noble metal is (NH) 4 ) 2 PdCl 4 。
7. A HMDSO poisoning resistant bilayer structure SnO as claimed in claim 3 2 The preparation method of the methyl hydride sensor is characterized in that the process of the step (1) is as follows:
(1.1) preparation of nano SnO 2 Powder;
(1.2) taking 2 to 5 parts by mass of nano SnO prepared in the step (1.1) 2 3-5 parts by volume of hydrogen peroxide, 3-5 parts by volume of ammonia water and 6-10 parts by volume of water, performing ultrasonic vibration at 50-70 ℃ for 30-60 min, separating, and drying to obtain SnO 2 A hydroxy compound intermediate;
(1.3) taking 2 to 5 parts by mass of nano SnO prepared in the step (1.2) 2 Preparing a sensitive product by magnetically stirring 3-5 h of a hydroxy compound intermediate, 0.2-0.6 part by mass of 3-aminopropyl triethoxysilane and 10-15 parts by mass of toluene, separating, drying, and calcining 1-2 h at 500-800 DEG CInner-sensing layer material-SiO 2 Surface grafting modified SnO 2 。
8. The HMDSO poisoning resistant bilayer structure SnO of claim 7 2 The preparation method of the methyl hydride 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 parts to obtain gel, separating, washing, drying, grinding, and calcining at 450-600 ℃ for 1-2 h parts to obtain nano SnO 2 And (3) powder.
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| CN107228927A (en) * | 2017-06-22 | 2017-10-03 | 云南大学 | A kind of high sensitivity methane gas sensitive material and preparation method and application |
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