CN101986149B - Electrode material for measuring sulfur dioxide gas, sensor and preparation method thereof - Google Patents
Electrode material for measuring sulfur dioxide gas, sensor and preparation method thereof Download PDFInfo
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- CN101986149B CN101986149B CN 200910055547 CN200910055547A CN101986149B CN 101986149 B CN101986149 B CN 101986149B CN 200910055547 CN200910055547 CN 200910055547 CN 200910055547 A CN200910055547 A CN 200910055547A CN 101986149 B CN101986149 B CN 101986149B
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000007772 electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000010931 gold Substances 0.000 claims abstract description 60
- 239000004964 aerogel Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052737 gold Inorganic materials 0.000 claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 229920002313 fluoropolymer Polymers 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 29
- 239000004811 fluoropolymer Substances 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 24
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- 239000000839 emulsion Substances 0.000 claims description 20
- 239000004809 Teflon Substances 0.000 claims description 19
- 229920006362 Teflon® Polymers 0.000 claims description 19
- 230000002829 reductive effect Effects 0.000 claims description 19
- -1 polychlorotrifluoroethylene Polymers 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 6
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- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
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- 238000006722 reduction reaction Methods 0.000 claims description 4
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001263 FEMA 3042 Substances 0.000 claims description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
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- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
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Abstract
The invention discloses an electrode material for measuring sulfur dioxide gas, which comprises a substrate and a sulfur dioxide oxidization catalyst deposited on the substrate, wherein the sulfur dioxide oxidization catalyst comprises 3 to 10 weight percent of hydrophilic aerogel, 10 to 30 weight percent of hydrophobic fluorine-containing polymer bonding agent and 60 to 87 weight percent of gold. The invention also discloses the preparation method of the electrode material and a sensor using the electrode material.
Description
Technical field
The present invention relates to a kind of electrochemical electrode material that detects sulfur dioxide gas, contain sensor and this electrochemical electrode material preparation method of this electrode material.The electrochemical sensor that makes with electrochemical electrode material of the present invention under low wet environment has good Measurement sensibility.
Background technology
Sulphuric dioxide SO
2It is one of Air Pollutants of industrial discharging.Usually adopt the galvanochemistry SO 2 sensor to monitor the content of Sulfur Dioxide In The Atmosphere.The critical component of this galvanochemistry SO 2 sensor is electrolyte/electrode, specifically comprises electrolyte, potential electrode, to electrode and contrast electrode.
A kind of galvanochemistry SO 2 sensor that prior art is commonly used for example as shown in Figure 1.Shown in Figure 1 is a kind of three electrolysis type SO 2 sensor.As shown in Figure 1, sulfur dioxide gas body sensor 100 comprises potential electrode 3, to electrode 5 and contrast electrode 4.Usually apply zero-bias between potential electrode and contrast electrode, the current potential that is about to potential electrode is arranged to equal the current potential of contrast electrode.The shell of described sulfur dioxide gas body sensor 100 comprises housing 122 and cap 124, and in they were encapsulated in described electrode 3,4 and 5, this sensor 100 linked to each other with measuring equipment by stitch 110.
In sensor 100, cap 124 consists of intake assembly with dustproof membrane 126.Wherein, dustproof membrane 126 is positioned on the cap 124, can be used for preventing that dust and other particulate pollutant from entering sensor 100 by making such as materials such as porous Teflon plastic foils, and protection electrode 3 is not contaminated.Cap 124 has a pore 128, and pore 128 allows gas therefrom to pass through.
The critical component of sensor 100 is electrode and electrolytic solution, comprises described electrode 3,4 and 5 and acidic electrolysis bath sulfuric acid or phosphoric acid.
In the surveying work process, following oxidation reaction occurs on the potential electrode:
SO
2+2H
2O-------SO
4 2-+4H
++2e
-(1)
Following reduction reaction is occured in electrode:
O
2+4H
++4e
-------2H
2O (2)
Sulphuric dioxide is diffused into potential electrode by a pore, is combined with water there, and oxidation reaction occurs, and forms sulfate ion, hydrogen ion and electronics.On the other hand, to the electrode place, reduction reaction occurs and generates water in oxygen and the combination of hydrogen radical ion.In formed sulfate ion, hydrogen ion and the electronics, hydrogen ion arrives electrode by electrolyte on potential electrode, and electronics then reaches from potential electrode by an external circuit electrode is formed oxidation current.Sometimes between potential electrode and contrast electrode, apply the bias voltage of 0V by a potentiostatic circuit, for potential electrode 3 provides a zero potential.Under this current potential, potential electrode occurs suc as formula the oxidation reaction shown in (1), forms simultaneously oxidation current.Because oxidation current depends on the wear rate of sulphuric dioxide, so can determine the concentration of the sulphuric dioxide at potential electrode 3 places by measuring oxidation current.
Prior art has reported that various potential electrode detect SO
2Major part is gold electrode.
The people such as A.W.E.Hodgson (Anal.Chem.1999,71,2831-2837) reported golden reduce deposition in Nafion 117 (a kind of E.I.Du Pont Company produce fluoro-containing copolymer film) formation potential electrode, can detectable concentration be low to moderate the SO of 10ppb with this potential electrode
2Yet the conductivity of Nafion film depends on moisture, and is very responsive to humidity.So this type of all solid state electrolysis-type SO 2 sensor is only applicable to use in a humid environment, and easy dehydration when using under the environment of drying can cause measurement result unstable.This so that its application be very restricted.
United States Patent (USP) 4,042,464 disclose a kind of potential electrode, and this potential electrode carries that Au catalyst forms by being carried on the material with carbon element.This electrochemical sensor that carries Au catalyst that is carried on the material with carbon element that comprises also can be subject to the very large impact of humidity, in low wet environment (as being lower than 15%RH), and long-time the use, signal can very fast decay.The use of this potential electrode of result also has certain limitation.
Therefore, this area also needs to develop and a kind ofly has good Measurement sensibility be used for electrode material, this sulphuric dioxide of a kind of usefulness of needs exploitation that sulphuric dioxide measures and measure with the sulphuric dioxide survey sensor of electrode material formation and their manufacture method under low wet environment.
Summary of the invention
A goal of the invention of the present invention provides a kind of electrode material for the sulphuric dioxide measurement, and this sulphuric dioxide is measured the sensor that forms with electrode material and have good Measurement sensibility under low wet environment.
Another goal of the invention of the present invention provides a kind of sulphuric dioxide survey sensor that forms with electrode material with the above-mentioned sulphuric dioxide measurement of the present invention.
A further object of the present invention provides a kind of sulphuric dioxide of the present invention and measures the manufacture method of using electrode material.
Therefore, one aspect of the present invention provides a kind of electrode material for the sulfur dioxide gas electrochemical sensor, and it comprises:
Base material; With
Be deposited on the catalyst for oxidation of sulfur dioxide on the described base material, described catalyst for oxidation of sulfur dioxide comprises:
The hydrophilic aerogel of 3-10 % by weight;
The hydrophobic adhesion agent of 10-30 % by weight; With
The gold of 60-87 % by weight.
Another aspect of the present invention provides a kind of above-mentioned manufacture method for sulfur dioxide gas electrochemical sensor electrodes material, and it comprises:
Base material is provided;
Chlorauric acid solution is added in the hydrophilic aerogel that is dispersed in water;
Add reductive agent and form aerogel-Au catalyst;
Add fluoropolymer emulsion, with the described aerogel-Au catalyst that flocculates;
Place on the described base material described flocculate and sintering, obtain being deposited on the catalyst for oxidation of sulfur dioxide on the described base material, described catalyst for oxidation of sulfur dioxide comprises:
The hydrophilic aerogel of 3-10 % by weight;
The hydrophobic adhesion agent of 10-30 % by weight; With
The gold of 60-87 % by weight.
Description of drawings
Below in conjunction with description of drawings preferred embodiment of the present invention.In the accompanying drawing, identical or corresponding part uses identical Reference numeral to represent.
Fig. 1 is a kind of structural representation of prior art electrolysis-type sulfur dioxide gas body sensor;
Fig. 2 is the present invention makes potential electrode with superfine silicon dioxide aerogel Au catalyst SO
2Sensor to 5ppm SO
2In through normal temperature low humidity (about 15%RH), place for a long time the response change of about seven days front and back;
Fig. 3 be existing with carbon upload metal working electrode do the work electrode the SO2 sensor to 5ppmSO
2In through normal temperature low humidity (about 15%RH), place for a long time the response change of about seven days front and back.
Embodiment
In instructions of the present invention, except as otherwise noted, otherwise all terms all have and its identical implication in the art.
The electrode material that the present invention is used for the sulfur dioxide gas electrochemical sensor comprises base material.The suitable material as sulfur dioxide gas electrochemical sensor electrodes material base material is without particular limitation, can be any conventional substrate material known in the art.The indefiniteness example of suitable base material has, fluoro-containing copolymer film for example, for example applications as laminates of poly tetrafluoroethylene, polychlorotrifluoroethylene film, polyhexafluoropropylene film, poly-2,2-difluoride membranes or above-mentioned two or more films etc.
Thickness and manufacture method as the polymer film of base material are well-known in the art.In an example of the present invention, use poly tetrafluoroethylene as base material, the thickness of this base material is the 1-400 micron, preferably 10-300 micron, more preferably 100-250 micron.
In another example of the present invention, use available from the Mupor PTFE film of the porex base material as described electrode material.
The electrode material that the present invention is used for the sulfur dioxide gas electrochemical sensor also comprises the catalyst for oxidation of sulfur dioxide that is deposited on the described base material, and described catalyst for oxidation of sulfur dioxide comprises the hydrophilic aerogel, golden and hydrophobic fluoropolymer adhesion agent.
In the art, aerogel is called again xerogel.Sloughs most of solvent when gel, make in the gel content liquid than solids content much less, or the medium that is full of in the space reticulate texture of gel is gas that appearance is the solid shape, is xerogel, is also referred to as aerogel.The present invention adopts the hydrophilic aerogel to be used for carrying electric gold grain as carrier, and the sulphuric dioxide potential electrode that the result forms has good Measurement sensibility under low wet environment.
The hydrophilic aerogel that is applicable to sulfur dioxide gas electrochemical sensor electrodes material of the present invention is without particular limitation, can be any hydrophilic aerogel that helps to keep electrode humidity.The average primary particle diameter of this water wettability aerogel is usually less than 100 nanometers, better less than 50 nanometers, better less than 20 nanometers.
The specific surface area that is applicable to the hydrophilic aerogel of sulfur dioxide gas electrochemical sensor electrodes material of the present invention is generally 200-1000m
2/ g, preferably 250-600m
2/ g, more preferably 300-500m
2/ g.
In an example of the present invention, described hydrophilic aerogel is selected from the potpourri of hydrophilic aerosil, hydrophilic molecular sieve aerogel, the active alundum (Al2O3) aerogel of hydrophilic or above-mentioned two or more aerogels etc.
The hydrophilic aerogel that is applicable to sulfur dioxide gas electrochemical sensor electrodes material of the present invention also is commercially available, and for example, it can be the aerosil available from people chemical plant, Guangzhou.
In oxidation catalyst of the present invention, the content of the non-conductive hydrophilic carrier that is formed by the hydrophilic aerogel is between the 3-10 % by weight.If the consumption of non-conductive hydrophilic carrier very little, then it is not enough to the carrier band gold grain, can cause the gathering between the gold grain agglomerating; If the consumption of opposite non-conductive hydrophilic carrier is too many, then can make catalyzer electric conductivity variation.
In a better example of the present invention, in described catalyst for oxidation of sulfur dioxide, the amount of the non-conductive hydrophilic carrier that is formed by the hydrophilic aerogel is 5-8 % by weight, more preferably 6-7 % by weight preferably.
Contain gold grain in catalyst for oxidation of sulfur dioxide of the present invention, its content accounts for the 60-87 % by weight of total catalyst weight, better accounts for the 65-80 % by weight, better accounts for the 68-78 % by weight.
In a better example of the present invention, described gold grain is formed by the gold chloride in-situ reducing in hydrophilic aerogel solution.Obtain the compound of hydrophilic aerogel-Jin.Adopt this in-situ reducing method can prevent that gold grain from reuniting.
For improving the electric conductivity of electrode material, electrode material of the present invention also optionally contains the conductive particle except gold, better is conductive carbon particles.The resistance of used conductive carbon is 600-1200 Ω preferably, is 400-1000 Ω better, and specific surface area is generally 100-800m
2/ g is preferably 200-700m
2/ g.This conductive carbon particles is commercially available, and for example, it can be the vulcan XC-72.R conductive carbon particles available from Cabot company.
Described conductive particle (for example carbon granule) except gold can still join in the compound of described hydrophilic aerogel-Jin before adding hydrophobicity fluoropolymer adhesion agent before the gold chloride in-situ reducing or after the gold chloride in-situ reducing.Can adopt the dispersion means (such as mechanical raking, ultrasound wave dispersion, vibration etc.) of any routine to make it Uniform Dispersion after reinforced.
The described addition of conductive particle except gold is without particular limitation, as long as can increase electric conductivity and other useful performance of final electrode material is had no adverse effect.In an example of the present invention, the addition of described conductive particle except gold by the general assembly (TW) of catalyst for oxidation of sulfur dioxide, is the 0-8 % by weight, preferably 1-6 % by weight, more preferably 2-5 % by weight.
The hydrophobicity fluoropolymer adhesion agent that is applicable to sulfur dioxide gas electrochemical sensor electrodes material of the present invention is without particular limitation, as long as it can flocculate above-mentioned hydrophilic gel and gold grain together.Be preferably, described fluoropolymer adhesion agent has identical material with fluoropolymer as base material.For example use with as the identical fluoropolymer emulsion of the fluoropolymer of base material as the fluoropolymer adhesion agent.
The indefiniteness example of described fluoropolymer binder has, for example ptfe emulsion, polychlorotrifluoroethylene emulsion, polyhexafluoropropylene emulsion, poly-2,2-difluoroethylene emulsion and two or more the potpourri etc. in them.
In a better example of the present invention, use poly tetrafluoroethylene as base material, and use ptfe emulsion as the fluoropolymer adhesion agent.
In sulfur dioxide gas electrochemical sensor electrodes material of the present invention (sometimes be also referred to as is that the non-conductive hydrophilic carrier carries gold electrode), the content of fluoropolymer adhesion agent is between the 10%-30 % by weight; If the content of fluoropolymer adhesion agent is too many, then the hydrophobicity of sensor can be too strong, makes the response time of sensor become large; On the contrary, if the content of fluoropolymer adhesion agent very little, then can make the water wettability of sensor too strong, catalyzer be flooded, thereby make sensitivity, not reach the sensitivity requirement.
In a better example of the present invention, by the general assembly (TW) of described catalyst for oxidation of sulfur dioxide, the content of described fluoropolymer adhesion agent is the 12-28 % by weight, preferably the 15-25 % by weight.
In addition, the atomic ratio of described hydrophilic aerogel and gold grain is preferably between 1～2, more preferably between the 1.2-1.8.
In an example of the present invention, use teflon as the fluoropolymer adhesion agent, the content of this teflon in the potential electrode of sulfur dioxide gas electrochemical sensor of the present invention is the 10-30 % by weight, preferably 12-28 % by weight, more preferably 15-25 % by weight.
Compare for the sensor of measuring sulfur dioxide gas with existing, the sulfur dioxide gas electrochemical sensor that forms with potential electrode of the present invention has good stability, (25 ℃ of normal temperature low humidities, 15% relative humidity) after lower 7 days, the sulphuric dioxide sensitivity of sensor of the present invention is original about 80%, and the sulphuric dioxide sensitivity of existing sensor only is original about 20%.
The present invention also provides a kind of manufacture method of described electrode material for the sulfur dioxide gas electrochemical sensor, and it comprises the step that base material is provided.
As previously described, the material of the suitable potential electrode base material that is used as the sulfur dioxide gas electrochemical sensor is without particular limitation, can be conventional base material known in the art.
The indefiniteness example of suitable base material has, and fluoro-containing copolymer film for example is such as applications as laminates of poly tetrafluoroethylene, polychlorotrifluoroethylene film, polyhexafluoropropylene film or above-mentioned two or more films etc.
Thickness and manufacture method as the polymer film of base material are well-known in the art.In an example of the present invention, use poly tetrafluoroethylene as base material, the thickness of this base material is the 1-400 micron, preferably 10-300 micron, more preferably 100-250 micron.
In another example of the present invention, use available from the Mupor PTFE film of the U.S. porex base material as described potential electrode.
The inventive method also comprises chlorauric acid solution is added to step in the described hydrophilic aerogel that is dispersed in water in advance.
The method that the hydrophilic aerogel is dispersed in water that is applicable to the inventive method is without particular limitation, can be any conventional method known in the art.For improving the dispersion efficiency of hydrophilic aerogel in water, improve dispersing uniformity, when disperseing, can adopt the aid dispersion means, for example, can adopt the methods such as mechanical raking, ultrasound wave dispersion, vibration, the method that better adopts ultrasound wave to stir improves the dispersion efficiency of hydrophilic aerogel in water, improves dispersing uniformity.
In the dispersed system of described hydrophilic aerogel-water, the weight ratio of hydrophilic aerogel and water is without particular limitation, as long as this hydrophilic gel can be well dispersed in the water.In an example of the present invention, the weight ratio of described hydrophilic gel and water is 1: 800-1500, preferably 1: 900-1200.
The concentration of chlorauric acid solution that is applicable to the inventive method is without particular limitation, as long as the gold chloride that adds is enough to reduce the gold grain that produces effective dose, namely in gold grain content range of the present invention and so that hydrophilic aerogel and golden atomic ratio are between 1～2.In an example of the present invention, the concentration of described chlorauric acid solution is 0.02-0.03M, 0.025M preferably, and by the weighing scale of 100 milligrams of hydrophilic gels, the addition of described concentration chlorauric acid solution is 250-750ml, preferably 500ml.
The inventive method also comprises and adds reductive agent forms aerogel-Au catalyst with original position step in the potpourri of described gold chloride/hydrophilic aerogel solution.The reductive agent that is used for gold chloride is reduced into gold grain is without particular limitation, as long as can reduce gold chloride and can final electrode not being had a negative impact.The indefiniteness example of described reductive agent has, such as: citric acid and salt thereof (such as sodium citrate, potassium citrate, lemon acid amide etc.), sodium borohydride, white phosphorus, tannic acid, ascorbic acid etc.
In order to improve the speed of reduction reaction, before adding reductive agent or after adding reductive agent, be preferably in before the adding reductive agent, the inventive method also optionally comprises the step with the aerocolloidal aqueous solution heating of described gold chloride/hydrophilic.Heating-up temperature is generally 50-80 ℃, preferably 50-70 ℃, is preferably 55-65 ℃.
The inventive method comprises that also the adding fluoropolymer emulsion is with the step of the described hydrophilic aerogel-Au catalyst that flocculates.The fluoropolymer adhesion agent of described hydrophilic aerogel-Au composite of being suitable for flocculating is without particular limitation, can be any fluorochemicals known in the art.Its indefiniteness example has, for example ptfe emulsion, polychlorotrifluoroethylene emulsion, polyhexafluoropropylene emulsion, poly-2,2-difluoroethylene emulsion and two or more the potpourri etc. in them.
In an example of the present invention, described fluoropolymer have with as the identical composition of the fluoropolymer of base material.
In the methods of the invention, the addition of the aqueous solution of described hydrophilic aerogel, chlorauric acid solution and fluoropolymer emulsion is without particular limitation, as long as they can make the catalyst for oxidation of sulfur dioxide of final formation have foregoing composition.
After with described hydrophilic aerogel-Au composite flocculation sediment, described flocculate can be filtered and cleans.Suitable filtration and cleaning method are without particular limitation, can be any filtration known in the art and cleaning method.Suitable clean-out system is water.
The inventive method also comprise with described flocculate (especially after filtration with clean after flocculate) place on the described base material and the step of sintering.Placing the method on the described base material without particular limitation described flocculate, can be the method for any routine known in the art.In an example of the present invention, described flocculate placed method on the described base material to comprise to be tiled in equably described flocculate on the described base material or with the even blade coating of described flocculate on the surface of described base material.The sintering temperature of the sintering step of the inventive method is 275-320 ℃, preferably 280-310 ℃.
In a better example of the present invention, described preparation method comprises the steps:
At first the hydrophilic aerogel is disperseed with ultrasound wave in 1: 1000 (w/w) water, then adds chlorauric acid solution, be heated to 60 ℃ after, add reductive agent, prepare the aerogel Au catalyst; Then in this aerogel Au catalyst solution, add the Teflon emulsion, thereby under superfine silicon dioxide aerogel-Au catalyzer and Teflon flocculates deposit in solution.Then by with the catalyzer of flocculation sediment with washed with de-ionized water after, shift on hydrophobic Teflon film, behind 275 ℃ of-320 ℃ of sintering, namely form a gas-diffusion electrode again, this gas-diffusion electrode can be used to do the gold electrode of electrochemical sensor.
Can use electrode material assembling sulfur dioxide gas body sensor of the present invention, it comprises: potential electrode, contrast electrode is to electrode and electrolytic solution.In sulfur dioxide gas body sensor of the present invention, described electrolytic solution can be sulfuric acid or phosphoric acid, and sulfur dioxide gas body sensor of the present invention can also comprise the first hydrophilic imbibition material layer, and it is arranged between described potential electrode and the described contrast electrode.Can also comprise the second hydrophilic imbibition material layer, it is arranged on described contrast electrode and described between the electrode.Can also comprise reservoir, described reservoir is positioned at described opposite side to electrode, and comprises the hydrophilic imbibition material which can retain moisture that discharges moisture content, is used for helping to regulate described electrolytical humidity.
The SO 2 sensor that adopts water wettability aerogel gold electrode material of the present invention to make to make can go up the sensor of uploading Au catalyst than carbon at dry resistance and have greatly improved.
Below, further specify in conjunction with the embodiments the present invention.
40 milligrams of hydrophilic ultrafine aerosils (available from people chemical plant, Guangzhou) are disperseed with ultrasound wave in 500 gram water, form the hydrophilic aerogel dispersion liquid that disperses.Adding 100ml concentration in this dispersion liquid is the gold chloride of 0.025M, is heated 60 ℃ after stirring, and then adds sodium citrate as reductive agent in the dispersion liquid of heating, prepares aerosil-Au catalyst.
Add 0.12 milliliter of Teflon emulsion (available from Dupont 30A) in this aerosil-Au catalyst solution, thereby under superfine silicon dioxide aerogel-Au catalyst and Teflon flocculates deposit in solution.Leach flocculate, after the washed with de-ionized water, shift on hydrophobic Teflon garden film (diameter 18mm) and with its even tiling, after 300 ℃ of sintering 15-20 minutes, obtain forming gas-diffusion electrode again.
With the gold electrode of this gas-diffusion electrode as electrochemical sensor, by preparation sulphuric dioxide survey sensor shown in Figure 1, contrast electrode and to electrode Pt/ air electrode.The acidic electrolysis bath of this sulphuric dioxide electrochemical sensor is phosphoric acid or sulfuric acid.The potential difference (PD) that to apply relative Pt/ air electrode between the work of this galvanochemistry SO 2 sensor and contrast electrode be 0mV.
It is that the simulating atmospheric environment of 5ppm is measured test that this sulphuric dioxide survey sensor is placed sulfur dioxide concentration, the result as shown in Figure 2, this sensor can provide stable test signal.
This sensor was placed 7 days under low wet environment (15%RH), be placed on subsequently in the simulating atmospheric environment that sulfur dioxide concentration is 5ppm and measure test, the result, as shown in Figure 2, through (25 ℃ of normal temperature low humidities, 15%RH) after 7 days, it is original about 80% that sensitivity can remain on, and shows that it has preferably dry resistance energy.
Comparative example 1
Such as United States Patent (USP) 4,042, year Au catalyst on the described preparation material with carbon element of 464 embodiment (Fig. 2 example) is as potential electrode, with the electrode of this potential electrode as electrochemical sensor, by preparation sulphuric dioxide survey sensor shown in Figure 1, contrast electrode and to electrode Pt/ air electrode.The acidic electrolysis bath of this sulphuric dioxide electrochemical sensor is phosphoric acid or sulfuric acid.The potential difference (PD) that to apply relative Pt/ air electrode between the work of this galvanochemistry SO 2 sensor and contrast electrode be 0mV.
It is that the simulating atmospheric environment of 5ppm is measured test that this sulphuric dioxide survey sensor is placed sulfur dioxide concentration, the result is as shown in Figure 3. through (25 ℃ of normal temperature low humidities, 15%RH) after 7 days, the sensitivity of this sensor is reduced to and original is reduced to originally about 20%, and showing it, anti-to do ability relatively poor.
30 milligrams of hydrophilic ultrafine aerosils (available from people chemical plant, Guangzhou) are disperseed with ultrasound wave in 500 gram water, form the hydrophilic aerogel dispersion liquid that disperses.Adding 120ml concentration in this dispersion liquid is the gold chloride of 0.025M, is heated after stirring and is heated to 60 ℃, then adds sodium citrate as reductive agent in the dispersion liquid of heating, prepares aerosil-Au catalyst.
Add 0.12 milliliter of Teflon emulsion (available from Dupont) in this aerosil-Au catalyst solution, thereby under superfine silicon dioxide aerogel-Au catalyst and Teflon flocculates deposit in solution.Leach flocculate, after the washed with de-ionized water, shift on hydrophobic Teflon garden film (diameter 18mm) and with its even tiling, after 300 ℃ of sintering 15-20 minutes, obtain forming gas-diffusion electrode again.
With the gold electrode of this gas-diffusion electrode as electrochemical sensor, by preparation sulphuric dioxide survey sensor shown in Figure 1, contrast electrode and to electrode Pt/ air electrode.The acidic electrolysis bath of this sulphuric dioxide electrochemical sensor is phosphoric acid or sulfuric acid.The potential difference (PD) that to apply relative Pt/ air electrode between the work of this galvanochemistry SO 2 sensor and contrast electrode be 0mV.
It is that the simulating atmospheric environment of 5ppm is measured test that this sulphuric dioxide survey sensor is placed sulfur dioxide concentration, and this sensor can provide stable test signal as a result.
This sensor was placed 7 days under low wet environment (15%RH), be placed on subsequently in the simulating atmospheric environment that sulfur dioxide concentration is 5ppm and measure test, the result, through (25 ℃ of normal temperature low humidities, 15%RH) after 7 days, it is original about 80% that sensitivity can remain on, and shows that it has preferably dry resistance energy.
60 milligrams of hydrophilic ultrafine aerosils (available from people chemical plant, Guangzhou) are disperseed with ultrasound wave in 500 gram water, form the hydrophilic aerogel dispersion liquid that disperses.Adding 110ml concentration in this dispersion liquid is the gold chloride of 0.025M, is heated after stirring and is heated to 60 ℃, then adds sodium citrate as reductive agent in the dispersion liquid of heating, prepares aerosil-Au catalyst.
Add 0.25 milliliter of Teflon emulsion (available from Dupont) in this aerosil-Au catalyst solution, thereby under superfine silicon dioxide aerogel-Au catalyst and Teflon flocculates deposit in solution.Leach flocculate, after the washed with de-ionized water, shift on hydrophobic Teflon garden film (diameter 18mm) and with its even tiling, after 300 ℃ of sintering 15-20 minutes, obtain forming gas-diffusion electrode again.
With the gold electrode of this gas-diffusion electrode as electrochemical sensor, by preparation sulphuric dioxide survey sensor shown in Figure 1, contrast electrode and to electrode Pt/ air electrode.The acidic electrolysis bath of this sulphuric dioxide electrochemical sensor is phosphoric acid or sulfuric acid.The potential difference (PD) that to apply relative Pt/ air electrode between the work of this galvanochemistry SO 2 sensor and contrast electrode be 0mV.
It is that the simulating atmospheric environment of 5ppm is measured test that this sulphuric dioxide survey sensor is placed sulfur dioxide concentration, and this sensor can provide stable test signal as a result.
This sensor was placed 7 days under low wet environment (15%RH), be placed on subsequently in the simulating atmospheric environment that sulfur dioxide concentration is 5ppm and measure test, the result, through (25 ℃ of normal temperature low humidities, 15%RH) after 7 days, it is original about 80% that sensitivity can remain on, and shows that it has preferably dry resistance energy.
40 milligrams of hydrophilic ultrafine aerosils (available from people chemical plant, Guangzhou) are disperseed with ultrasound wave in 500 gram water, form the hydrophilic aerogel dispersion liquid that disperses.Adding 110ml concentration in this dispersion liquid is the gold chloride of 0.025M, is heated after stirring and is heated to 60 ℃, then adds sodium citrate as reductive agent in the dispersion liquid of heating, prepares aerosil-Au catalyst.
Add the 80mg mean grain size in this aerosil-Au catalyst solution and be 35 microns carbon granule, add 0.25 milliliter of Teflon emulsion (available from Dupont) after mixing, thereby under superfine silicon dioxide aerogel-Au catalyst and Teflon flocculates deposit in solution.Leach flocculate, after the washed with de-ionized water, shift on hydrophobic Teflon garden film (diameter 18mm) and with its even tiling, after 300 ℃ of sintering 15-20 minutes, obtain forming gas-diffusion electrode again.
With the gold electrode of this gas-diffusion electrode as electrochemical sensor, by preparation sulphuric dioxide survey sensor shown in Figure 1, contrast electrode and to electrode Pt/ air electrode.The acidic electrolysis bath of this sulphuric dioxide electrochemical sensor is phosphoric acid or sulfuric acid.The potential difference (PD) that to apply relative Pt/ air electrode between the work of this galvanochemistry SO 2 sensor and contrast electrode be 0mV.
It is that the simulating atmospheric environment of 5ppm is measured test that this sulphuric dioxide survey sensor is placed sulfur dioxide concentration, and this sensor can provide stable test signal as a result.
This sensor was placed 7 days under low wet environment (15%RH), be placed on subsequently in the simulating atmospheric environment that sulfur dioxide concentration is 5ppm and measure test, the result, through (25 ℃ of normal temperature low humidities, 15%RH) after 7 days, it is original about 80% that sensitivity can remain on, and shows that it has preferably dry resistance energy.
Above-described embodiment and comparative example confirm, catalyst for oxidation of sulfur dioxide of the present invention is owing to be to make with reductive agent in-situ reducing gold chloride in the aqueous solution that is dispersed with the hydrophilic gel, therefore the water holding capacity of this catalyzer is higher than the oxidation catalyst that existing carbon carries gold, obtains good effect.
Claims (12)
1. electrode material that is used for the sulfur dioxide gas electrochemical sensor, it comprises:
Base material; With
Be deposited on the catalyst for oxidation of sulfur dioxide on the described base material, described catalyst for oxidation of sulfur dioxide comprises:
The hydrophilic aerogel of 3-10 % by weight;
The hydrophobicity fluoropolymer adhesion agent of 10-30 % by weight; With
The gold of 60-87 % by weight;
Described hydrophilic aerogel is selected from aerosil, molecular sieve aerogel and active alundum (Al2O3) aerogel;
The average primary particle diameter of described hydrophilic aerogel is less than 100 nanometers, and specific surface area is 200-1000m
2/ g.
2. the electrode material for the sulfur dioxide gas electrochemical sensor as claimed in claim 1 is characterized in that described catalyst for oxidation of sulfur dioxide comprises:
The hydrophilic aerogel of 5-8 % by weight;
The hydrophobicity fluoropolymer adhesion agent of 12-28 % by weight; With
The gold of 65-80 % by weight; With
The carbon granule of 0-8 % by weight.
3. the electrode material for the sulfur dioxide gas electrochemical sensor as claimed in claim 2 is characterized in that described catalyst for oxidation of sulfur dioxide comprises:
The hydrophilic aerogel of 6-7 % by weight;
The hydrophobicity fluoropolymer adhesion agent of 15-25 % by weight;
The gold of 68-78 % by weight; With
The carbon granule of 1-6 % by weight.
4. such as each described electrode material for the sulfur dioxide gas electrochemical sensor among the claim 1-3, it is characterized in that described hydrophobicity fluoropolymer binder is selected from teflon, polychlorotrifluoroethylene, polyhexafluoropropylene, poly-2,2-difluoroethylene emulsion and two or more the potpourri in them.
5. such as each described electrode material for the sulfur dioxide gas electrochemical sensor among the claim 1-3, it is characterized in that described base material is selected from the applications as laminates of poly tetrafluoroethylene, polychlorotrifluoroethylene film, polyhexafluoropropylene film, poly-2,2-difluoride membranes or above-mentioned two or more films.
6. the electrode material for the sulfur dioxide gas electrochemical sensor as claimed in claim 5 is characterized in that described hydrophobicity fluoropolymer adhesion agent and described base material are identical fluorinated polymer materials.
7. such as each described electrode material for the sulfur dioxide gas electrochemical sensor among the claim 1-3, the atomic ratio that it is characterized in that described hydrophilic aerogel and gold grain is 1～2:1.
8. manufacture method such as each described electrode material among the claim 1-7, it comprises:
Base material is provided;
Chlorauric acid solution is added in the hydrophilic aerogel that is dispersed in water;
Add reductive agent and form aerogel-Au catalyst;
Add fluoropolymer emulsion, with the described aerogel-Au catalyst that flocculates, obtain flocculate;
Place on the described base material described flocculate and sintering, obtain being deposited on the catalyst for oxidation of sulfur dioxide on the described base material, described catalyst for oxidation of sulfur dioxide comprises:
The hydrophilic aerogel of 3-10 % by weight;
The hydrophobicity fluoropolymer adhesion agent of 10-30 % by weight; With
The gold of 60-87 % by weight;
Described hydrophilic aerogel is selected from aerosil, molecular sieve aerogel and active alundum (Al2O3) aerogel;
The average primary particle diameter of described hydrophilic aerogel is less than 100 nanometers, and specific surface area is 200-1000m
2/ g.
9. method as claimed in claim 8 is characterized in that described reductive agent is selected from citric acid, sodium citrate, sodium borohydride, white phosphorus, tannic acid, ascorbic acid and the potpourri of two or more thereof.
10. method as claimed in claim 8 is characterized in that the temperature of reaction when adding reductive agent carries out reduction reaction is 50～70 ℃.
11. such as each described method among the claim 8-10, the sintering temperature that it is characterized in that described sintering step is 275-320 ℃.
12. a sensor, it comprises the electrode that forms such as each described electrode material among the claim 1-7.
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