CN104792645A - Normal temperature methane sensor and preparation method thereof - Google Patents
Normal temperature methane sensor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a normal temperature methane sensor and a preparation method thereof. The method comprises the following steps: taking mesoporous silica as a carrier, loading a precious metal/cerium oxide compound on the mesoporous silica with an immersion method, and thus preparing a precious metal/cerium oxide/mesoporous silica composite material; adding the dispersion liquid of the obtained composite material on the electrode surface of a quartz crystal microbalance drop by drop, and thus obtaining the normal temperature methane sensor based on the precious metal/cerium oxide/mesoporous silica composite material. The prepared normal temperature methane sensor has good selectivity and high sensitivity for methane, the preparation process is simple and is suitable for the mass production of gas sensors, and the normal temperature methane sensor can be used for detecting methane in natural gas, shale gas, marsh gas and mine gas.
Description
Technical field
The present invention relates to a kind of nano-sensor and preparation method thereof, be specifically related to a kind of normal temperature methane transducer and preparation method thereof.
Background technology
Day by day serious along with energy shortage and problem of environmental pollution, rock gas and shale gas are considered to more satisfactory clean and substitute energy with features such as its rich reserves, the high and low pollutions of the thermal efficiency.Methane is its principal ingredient, has inflammable and explosive property and greenhouse effect, and its greenhouse effect are equivalent volume CO
2decades of times, it is necessary and urgent for monitoring it and processing.
It is several that current methane transducer both domestic and external mainly contains catalytic combustion type, metal-oxide semiconductor (MOS) and infrared sensor etc.The J. Yu of Hong Kong University in 2013 etc. (Sensors and Actuators B 184 (2013) 118 – 129) utilize wolframic acid niobium nanometer rods schottky diode to detect methane, the method can obtain larger response at a room temperature and a high temperature, and this method of inspection can detect methane under blast limit.But use material price expensive, be difficult to real-time detection.Two kinds of conventional catalyst systems are carried in mesoporous rhodium oxide-alumina material and test methane by the people (Nanoscale, 2013,5,9720 – 9725) such as Chinese The 2nd Army Medical College subordinate Changhai hospital Jiacan Su in 2013.This material has meso-hole structure and larger specific surface area, and meanwhile, this material has high catalytic activity and anti-poisoning capability to methyl hydride combustion reaction.Use MEMS(MEMS (micro electro mechanical system)) sensor, this sensor response time is short, has relatively high signal to export, can realize Site Detection.But the less stable of this method senser element used, complicated process of preparation.
In sum, semiconductor and catalytic combustion type methane transducer working temperature higher, less stable.Infrared sensor cost is high.
Summary of the invention
An object of the present invention is to overcome problems of the prior art, provides a kind of normal temperature methane transducer.This sensor has highly sensitive, the feature such as selectivity and good stability.
Two of object of the present invention is the preparation method providing this sensor.
Single mesopore silicon oxide also exists poor selectivity, sensitivity is low and noise is large problem as methane sensitive material, be necessary mesopore silicon oxide and other materials phase compound, prepare compound substance, give full play to the advantage of compound substance, realize material function integration, will greatly improve the sensing capabilities of sensor.The oxygen flow ability powerful due to cerium oxide and the catalytic performance of noble metal, and preparation technology simple, be easy to and the feature such as other technologies are compatible, noble metal/cerium oxide compound demonstrates good application prospect as the methanation catalyst of excellence in Catalytic methane oxidation.Mesopore silicon oxide combines with noble metal/cerium oxide compound by the present invention, prepare a kind of normal temperature methane gas sensor, give full play to the advantage of bi-material performance, to the exploitation of normal temperature methane transducer and have very important significance in the application of the energy and security fields.
According to above-mentioned mechanism, the present invention adopts following technical scheme:
A kind of normal temperature methane transducer, it is characterized in that this sensor is coated with noble metal/cerium oxide/mesopore silicon oxide composite material film at QCM (Quartz Crystal Microbalance) electrode surface, the thickness of this film is: 1415 ng to 5400 ng compound substances; Described noble metal/cerium oxide/mesopore silicon oxide compound substance take mesopore silicon oxide as carrier, and load has noble metal and cerium oxide compound, and wherein the mass ratio of noble metal, cerium oxide and mesopore silicon oxide is: 0.053:0.949:(1 ~ 10).
Above-mentioned noble metal is: palladium, platinum, rhodium, gold.
Quartz in the electrode of above-mentioned QCM (Quartz Crystal Microbalance) is AT cut type, namely become 35 ° of 15' to cut with quartz crystal primary optical axis, silver coating or gold on its two corresponding surfaces) layer is as electrode, quartz crystal is clipped in the middle of two plate electrodes and forms sandwich structure, and the frequency range of QCM (Quartz Crystal Microbalance) is 5 ~ 10 MHz.
Prepare a method for above-mentioned normal temperature methane transducer, it is characterized in that the concrete steps of the method are:
A. precious metal salt is soluble in water, add n-octyl ammonium bromide (TOABr), dichloromethane extraction, aqueous phase discarded; Sodium borohydride (NaBH is added in oil phase
4) methanol solution and Mercaptoundecanoic acid, react 30 minutes, obtain black solid, filter, washing, solid is dissolved in acidifying tetrahydrofuran, obtains noble metal precursor body; The mass ratio of described noble metal, n-octyl ammonium bromide, sodium borohydride and Mercaptoundecanoic acid is: (5 ~ 30): 65:30:9;
B. ammonium ceric nitrate and 1-decyl alcohol are dissolved in methanol solution by the mol ratio of 1:4, add the methanol solution of the sodium methoxide of catalyst amount, stirring reaction 4 h, revolve steaming, suction filtration, obtains cerium oxide precursor body, is dissolved in tetrahydrofuran by this cerium oxide precursor body;
C. step a gained noble metal precursor body, step b gained cerium oxide precursor body and lauric acid are dissolved in tetrahydrofuran by the mass ratio of 5:2, obtain noble metal/cerium oxide compound;
D. by step c gained noble metal/cerium oxide compound and mesoporous silicon oxide by 1:(1 ~ 10) mass ratio be scattered in 50 DEG C ~ 60 DEG C reaction 12 h in tetrahydrofuran solution, suction filtration, washing, namely obtains noble metal/cerium oxide/mesopore silicon oxide compound substance;
E. noble metal/cerium oxide/mesopore silicon oxide the compound substance of steps d gained is dispersed in organic solvent, form the dispersion liquid of 1 ~ 10mg/L, get 0.1 ~ 0.5 μ L dispersant liquid drop and be added to QCM (Quartz Crystal Microbalance) electrode surface, 60 ~ 150 DEG C of vacuum drying, obtain normal temperature methane gas sensor.
The preparation method of above-mentioned mesopore silicon oxide is: ethyl orthosilicate (TEOS) and polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer (P123) are pressed (1 ~ 5): the mol ratio of 0.017 is dissolved in 1 mol/L hydrochloric acid, after stirring reaction 24h, at 80 ~ 110 DEG C of reaction 24 h, suction filtration, washing, 500 DEG C of calcining 4 h obtain mesopore silicon oxide white powder.
Precious metal salt described in above-mentioned steps a is: potassium chloropalladate, palladium bichloride, chloroplatinic acid, potassium platinic chloride, potassium chloroplatinite, ammonium chloroplatinate, hydration pentachloro-rhodium acid ammonium, the acid of hydration pentachloro-rhodium ammonium, gold chloride, tetra chlorauric acid.Organic solvent described in above-mentioned steps f is one or more in ethanol, acetone, tetrahydrofuran, N, N-dimethyl formamide, N, N-dimethyl acetamide, N-methyl pyrrolidone.
The normal temperature methane transducer prepared by said method has excellent selectivity and high sensitivity to methane, and preparation technology is simple, is suitable for a large amount of productions of gas sensor, can be applicable to the detection of methane in rock gas, shale gas, biogas and methane gas.
Accompanying drawing explanation
Fig. 1 is the nitrogen adsorption/desorption figure of the noble metal/cerium oxide/meso-porous titanium dioxide silicon composite prepared by embodiment 1;
Fig. 2 is transmission electron microscope (TEM) figure of the noble metal/cerium oxide/meso-porous titanium dioxide silicon composite prepared by embodiment 1;
Fig. 3 is QCM (Quartz Crystal Microbalance) (QCM) methane and other gas air-sensitive test patterns of noble metal/cerium oxide/meso-porous titanium dioxide silicon composite;
Fig. 4 be noble metal/cerium oxide/meso-porous titanium dioxide silicon composite of being prepared by embodiment 1 to 100ppm, 70ppm, 50ppm(ppm: the continuous air-sensitive test pattern of methane gas 1,000,000/).
Embodiment
The present invention's each raw material used all can be buied by market.
embodiment 1
1. getting polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer (P123) 1 g adds in 30 ml 2 M hydrochloric acid and 7.5 ml water, add ethyl orthosilicate 2.1 g, magnetic agitation 24 h, load 80 DEG C of reaction 24 h in polytetrafluoroethylkettle kettle, washing, calcining obtains white mesopore silicon oxide white powder.
2. in 5 ml water, dissolve potassium chloropalladate 25.8 mg, add n-octyl ammonium bromide (TOABr) and be transferred to by product in 15 ml methylene chloride, separatory, discards aqueous phase.Add methanol solution 10 ml having dissolved 30 mg sodium borohydrides, add Mercaptoundecanoic acid 9.1 mg, obtain black solid, be dissolved in the tetrahydrofuran of acidifying, obtain noble metal precursor body.
3. be dissolved in 50 ml methyl alcohol by 5 g ammonium ceric nitrates, add 1-decyl alcohol, add dissolving 5 g sodium methoxide, 6 ml methyl alcohol, stir 2 h, will obtain product and revolve steaming, and removing white solid, product is dissolved in 50 ml tetrahydrofurans, obtains cerium oxide precursor body.
4. noble metal precursor liquid solution 10ml described in step 2 is added in cerium oxide precursor liquid solution described in step 3, add lauric acid 360 mg, 1.2 ml water, 10 ml tetrahydrofurans, obtain noble metal/cerium oxide compound.
5. added by mesopore silicon oxide 1 g described in step 1 in noble metal/cerium oxide complex solution 50 ml described in step 4,60 DEG C of reaction 12 h, suction filtration, washing, obtains noble metal/cerium oxide/meso-porous titanium dioxide silicon composite.
6. be dispersed in ethanol by the noble metal/cerium oxide/meso-porous titanium dioxide silicon composite of step 5 gained, form the dispersion liquid of 1mg/L, get 0.1 μ L dispersant liquid drop and be added to electrode surface, 60 DEG C of vacuum drying, obtain normal temperature methane gas sensor.
See the nitrogen adsorption desorption figure that Fig. 1, Fig. 1 are noble metal/cerium oxide/meso-porous titanium dioxide silicon composite that the present invention synthesizes, characterization result shows: this compound substance is typical mesoporous species adsorbs type.Belong to H1 type hysteresis loop, interpret sample has the cylindrical of opening regular shape, and has narrower pore diameter distribution, and average pore size is approximately 4 nm.
See transmission electron microscope (TEM) figure that Fig. 2, Fig. 2 are noble metal/cerium oxide/meso-porous titanium dioxide silicon composite, as seen from the figure, this material duct is more homogeneous, and is typical hexagonal hole road.
See Fig. 3, Fig. 3 is QCM (Quartz Crystal Microbalance) (QCM) methane and other gas air-sensitive test patterns of noble metal/cerium oxide/meso-porous titanium dioxide silicon composite, can learn from figure, the response of mesoporous silicon oxide to methane of load palladium/cerium oxide compound is best, selectivity is the highest, the positive negative direction of response due to test gas is different, so the test of other gases to methane gas is noiseless.
See Fig. 4, Fig. 4 be noble metal/cerium oxide/meso-porous titanium dioxide silicon composite to 100ppm, 70ppm, 50ppm(ppm: the continuous air-sensitive test pattern of methane gas 1,000,000/), can learn, the sensitivity of this material to methane is higher, stability is better, can recycle.
embodiment 2
1. getting polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer (P123) 1 g adds in 30 ml 2 M hydrochloric acid and 7.5 ml water, add ethyl orthosilicate 4.2 g, magnetic agitation 24 h, load 80 DEG C of reaction 24 h in polytetrafluoroethylkettle kettle, washing, calcining obtains white mesopore silicon oxide white powder.
2. in 5 ml water, dissolve potassium chloropalladate 25.8 mg, add n-octyl ammonium bromide (TOABr) and product is transferred in 15 ml methylene chloride, separatory, aqueous phase discarded.Add methanol solution 10 ml having dissolved 30 mg sodium borohydrides, add Mercaptoundecanoic acid 9.1 mg, obtain black solid, be dissolved in the tetrahydrofuran of acidifying, obtain noble metal precursor body.
3. be dissolved in 50 ml methyl alcohol by 5 g ammonium ceric nitrates, add 1-decyl alcohol, add dissolving 5 g sodium methoxide, 6 ml methyl alcohol, stir 2 h, will obtain product and revolve steaming, and removing white solid, product is dissolved in 50 ml tetrahydrofurans, obtains cerium oxide precursor body.
4. noble metal precursor liquid solution 10 ml described in step 2 is added in cerium oxide precursor liquid solution described in step 3, add lauric acid 360 mg, 1.2 ml water, 10 ml tetrahydrofurans, obtain noble metal/cerium oxide compound.
5. added by mesopore silicon oxide 1 g described in step 1 in noble metal/cerium oxide complex solution 50 ml described in step 4,60 DEG C of reaction 12 h, suction filtration, washing, obtains noble metal/cerium oxide/meso-porous titanium dioxide silicon composite.
6. be dispersed in ethanol by the noble metal/cerium oxide/meso-porous titanium dioxide silicon composite of step 5 gained, form the dispersion liquid of 1mg/L, get 0.1 μ L dispersant liquid drop and be added to electrode surface, 60 DEG C of vacuum drying, obtain normal temperature methane gas sensor.
embodiment 3
1. getting polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer (P123) 1 g adds in 30 ml 2 M hydrochloric acid and 7.5 ml water, add ethyl orthosilicate 2.1 g, magnetic agitation 24 h, load 80 DEG C of reaction 24 h in polytetrafluoroethylkettle kettle, washing, calcining obtains white mesopore silicon oxide white powder.
2. in 5 ml water, dissolve potassium chloropalladate 25.8 mg, add n-octyl ammonium bromide (TOABr) and product is transferred in 15 ml methylene chloride, separatory, aqueous phase discarded.Add methanol solution 10 ml having dissolved 30 mg sodium borohydrides, add Mercaptoundecanoic acid 9.1 mg, obtain black solid, be dissolved in the tetrahydrofuran of acidifying, obtain noble metal precursor body.
3. be dissolved in 50 ml methyl alcohol by 5 g ammonium ceric nitrates, add 1-decyl alcohol, add dissolving 5 g sodium methoxide, 6 ml methyl alcohol, stir 2 h, will obtain product and revolve steaming, and removing white solid, product is dissolved in 50 ml tetrahydrofurans, obtains cerium oxide precursor body.
4. noble metal precursor liquid solution 10 ml described in step 2 is added in cerium oxide precursor liquid solution described in step 3, add lauric acid 360 mg, 1.2 ml water, 10 ml tetrahydrofurans, obtain noble metal/cerium oxide compound.
5. added by mesopore silicon oxide 1 g described in step 1 in noble metal/cerium oxide complex solution 100 ml described in step 4,60 DEG C of reaction 12 h, suction filtration, washing, obtains noble metal/cerium oxide/meso-porous titanium dioxide silicon composite.
6. be dispersed in ethanol by the noble metal/cerium oxide/meso-porous titanium dioxide silicon composite of step 5 gained, form the dispersion liquid of 1mg/L, get 0.1 μ L dispersant liquid drop and be added to electrode surface, 60 DEG C of vacuum drying, obtain normal temperature methane gas sensor.
embodiment 4
1. getting polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer (P123) 1 g adds in 30 ml 2 M hydrochloric acid and 7.5 ml water, add ethyl orthosilicate 2.1 g, magnetic agitation 24 h, load 80 DEG C of reaction 24 h in polytetrafluoroethylkettle kettle, washing, calcining obtains white mesopore silicon oxide white powder.
2. in 5 ml water, dissolve potassium chloropalladate 25.8 mg, add n-octyl ammonium bromide (TOABr) and product is transferred in 15 ml methylene chloride, separatory, aqueous phase discarded.Add methanol solution 10 ml having dissolved 30 mg sodium borohydrides, add Mercaptoundecanoic acid 9.1 mg, obtain black solid, be dissolved in the tetrahydrofuran of acidifying, obtain noble metal precursor body.
3. be dissolved in 50 ml methyl alcohol by 5 g ammonium ceric nitrates, add 1-decyl alcohol, add dissolving 5 g sodium methoxide, 6 ml methyl alcohol, stir 2 h, will obtain product and revolve steaming, and removing white solid, product is dissolved in 50 ml tetrahydrofurans, obtains cerium oxide precursor body.
4. noble metal precursor liquid solution 10 ml described in step 2 is added in cerium oxide precursor liquid solution described in step 3, add lauric acid 360 mg, 1.2 ml water, 10 ml tetrahydrofurans, obtain noble metal/cerium oxide compound.
5. added by mesopore silicon oxide 1 g described in step 1 in noble metal/cerium oxide complex solution 50 ml described in step 4,60 DEG C of reaction 12 h, suction filtration, washing, obtains noble metal/cerium oxide/meso-porous titanium dioxide silicon composite.
6. be dispersed in ethanol by the noble metal/cerium oxide/meso-porous titanium dioxide silicon composite of step 5 gained, form the dispersion liquid of 1 mg/L, get 0.2 μ L dispersant liquid drop and be added to electrode surface, 60 DEG C of vacuum drying, obtain normal temperature methane gas sensor.
embodiment 5
1. getting polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer (P123) 1 g adds in 30 ml 2 M hydrochloric acid and 7.5 ml water, add ethyl orthosilicate 2.1 g, magnetic agitation 24 h, load 80 DEG C of reaction 24 h in polytetrafluoroethylkettle kettle, washing, calcining obtains white mesopore silicon oxide white powder.
2. in 5 ml water, dissolve potassium chloropalladate 25.8 mg, add n-octyl ammonium bromide (TOABr) and product is transferred in 15 ml methylene chloride, separatory, aqueous phase discarded.Add methanol solution 10 ml having dissolved 30 mg sodium borohydrides, add Mercaptoundecanoic acid 9.1 mg, obtain black solid, be dissolved in the tetrahydrofuran of acidifying, obtain noble metal precursor body.
3. be dissolved in 50 ml methyl alcohol by 5 g ammonium ceric nitrates, add 1-decyl alcohol, add dissolving 5 g sodium methoxide, 6 ml methyl alcohol, stir 2 h, will obtain product and revolve steaming, and removing white solid, product is dissolved in 50 ml tetrahydrofurans, obtains cerium oxide precursor body.
4. noble metal precursor liquid solution 10 ml described in step 2 is added in cerium oxide precursor liquid solution described in step 3, add lauric acid 360 mg, 1.2 ml water, 10 ml tetrahydrofurans, obtain noble metal/cerium oxide compound.
5. added by mesopore silicon oxide 1 g described in step 1 in noble metal/cerium oxide complex solution 50 ml described in step 4,60 DEG C of reaction 12 h, suction filtration, washing, obtains noble metal/cerium oxide/meso-porous titanium dioxide silicon composite.
6. be dispersed in ethanol by the noble metal/cerium oxide/meso-porous titanium dioxide silicon composite of step 5 gained, form the dispersion liquid of 5 mg/L, get 0.1 μ L dispersant liquid drop and be added to electrode surface, 60 DEG C of vacuum drying, obtain normal temperature methane gas sensor.
In sum, the normal temperature methane gas sensor prepared by said method has excellent sensing capabilities to methane, and this preparation method's technique is simple, is suitable for a large amount of preparations of gas sensor.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.Any Reference numeral in claim should be considered as the claim involved by limiting.
In addition, be to be understood that, although this instructions is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of instructions is only for clarity sake, those skilled in the art should by instructions integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (7)
1. a normal temperature methane transducer, it is characterized in that this sensor is coated with noble metal/cerium oxide/mesopore silicon oxide composite material film at QCM (Quartz Crystal Microbalance) electrode surface, the thickness of this film is: 1415 ng to 5400 ng compound substances; Described noble metal/cerium oxide/mesopore silicon oxide compound substance take mesopore silicon oxide as carrier, and load has noble metal and cerium oxide compound, and wherein the mass ratio of noble metal, cerium oxide and mesopore silicon oxide is: 0.053:0.949:(1 ~ 10).
2. normal temperature methane transducer according to claim 1, is characterized in that described noble metal is: palladium, platinum, rhodium, gold.
3. method according to claim 1, it is characterized in that the quartz in the electrode of described QCM (Quartz Crystal Microbalance) is AT cut type, namely become 35 ° of 15' to cut with quartz crystal primary optical axis, silver coating or gold on its two corresponding surfaces) layer is as electrode, quartz crystal is clipped in the middle of two plate electrodes and forms sandwich structure, and the frequency range of QCM (Quartz Crystal Microbalance) is 5 ~ 10 MHz.
4. prepare a method for the normal temperature methane transducer according to any one of claims 1 to 3, it is characterized in that the concrete steps of the method are:
A. precious metal salt is soluble in water, add n-octyl ammonium bromide (TOABr), dichloromethane extraction, aqueous phase discarded; Sodium borohydride (NaBH is added in oil phase
4) methanol solution and Mercaptoundecanoic acid, react 30 minutes, obtain black solid, filter, washing, solid is dissolved in acidifying tetrahydrofuran, obtains noble metal precursor body; The mass ratio of described noble metal, n-octyl ammonium bromide, sodium borohydride and Mercaptoundecanoic acid is: (5 ~ 30): 65:30:9;
B. ammonium ceric nitrate and 1-decyl alcohol are dissolved in methanol solution by the mol ratio of 1:4, add the methanol solution of the sodium methoxide of catalyst amount, stirring reaction 4 h, revolve steaming, suction filtration, obtains cerium oxide precursor body, is dissolved in tetrahydrofuran by this cerium oxide precursor body;
C. step a gained noble metal precursor body, step b gained cerium oxide precursor body and lauric acid are dissolved in tetrahydrofuran by the mass ratio of 5:2, obtain noble metal/cerium oxide compound;
D. by step c gained noble metal/cerium oxide compound and mesoporous silicon oxide by 1:(1 ~ 10) mass ratio be scattered in 50 DEG C ~ 60 DEG C reaction 12 h in tetrahydrofuran solution, suction filtration, washing, namely obtains noble metal/cerium oxide/mesopore silicon oxide compound substance;
E. noble metal/cerium oxide/mesopore silicon oxide the compound substance of steps d gained is dispersed in organic solvent, form the dispersion liquid of 1 ~ 10mg/L, get 0.1 ~ 0.5 μ L dispersant liquid drop and be added to QCM (Quartz Crystal Microbalance) electrode surface, 60 ~ 150 DEG C of vacuum drying, obtain normal temperature methane gas sensor.
5. method according to claim 3, it is characterized in that the preparation method of described mesopore silicon oxide is: ethyl orthosilicate (TEOS) and polyethylene oxide-polypropyleneoxide-polyethylene oxide triblock copolymer (P123) are pressed (1 ~ 5): the mol ratio of 0.017 is dissolved in 1 mol/L hydrochloric acid, after stirring reaction 24h, at 80 ~ 110 DEG C of reaction 24 h, suction filtration, washing, 500 DEG C of calcining 6 h obtain mesopore silicon oxide white powder.
6. method according to claim 3, is characterized in that the precious metal salt described in step a is: potassium chloropalladate, palladium bichloride, chloroplatinic acid, potassium platinic chloride, potassium chloroplatinite, ammonium chloroplatinate, hydration pentachloro-rhodium acid ammonium, the acid of hydration pentachloro-rhodium ammonium, gold chloride, tetra chlorauric acid.
7. method according to claim 1, is characterized in that: the organic solvent described in step f is one or more in ethanol, acetone, tetrahydrofuran, N, N-dimethyl formamide, N, N-dimethyl acetamide, N-methyl pyrrolidone.
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| CN106770546A (en) * | 2016-12-05 | 2017-05-31 | 河北工业大学 | For the preparation method of the catalysis type gas sensor of methane gas detection |
| CN110945341A (en) * | 2017-07-28 | 2020-03-31 | 富士胶片株式会社 | Resonant sensor |
| CN114324495A (en) * | 2021-12-08 | 2022-04-12 | 复旦大学 | Nano sensing material for methane detection, preparation method thereof and methane sensor |
| CN114324495B (en) * | 2021-12-08 | 2024-05-24 | 复旦大学 | Nano sensing material for methane detection, preparation method thereof and methane sensor |
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| CN1478201A (en) * | 2000-12-07 | 2004-02-25 | 松下电器产业株式会社 | Gas sensor and detection method and device for gas concentration |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770546A (en) * | 2016-12-05 | 2017-05-31 | 河北工业大学 | For the preparation method of the catalysis type gas sensor of methane gas detection |
| CN106770546B (en) * | 2016-12-05 | 2019-02-19 | 河北工业大学 | The production method of catalysis type gas sensor for methane gas detection |
| CN110945341A (en) * | 2017-07-28 | 2020-03-31 | 富士胶片株式会社 | Resonant sensor |
| CN110945341B (en) * | 2017-07-28 | 2022-09-09 | 富士胶片株式会社 | Resonant sensor |
| CN114324495A (en) * | 2021-12-08 | 2022-04-12 | 复旦大学 | Nano sensing material for methane detection, preparation method thereof and methane sensor |
| CN114324495B (en) * | 2021-12-08 | 2024-05-24 | 复旦大学 | Nano sensing material for methane detection, preparation method thereof and methane sensor |
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