CN101418080B - Method for preparing chitosan proton exchange membrane for hydrogen sensor - Google Patents
Method for preparing chitosan proton exchange membrane for hydrogen sensor Download PDFInfo
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- CN101418080B CN101418080B CN2008102265020A CN200810226502A CN101418080B CN 101418080 B CN101418080 B CN 101418080B CN 2008102265020 A CN2008102265020 A CN 2008102265020A CN 200810226502 A CN200810226502 A CN 200810226502A CN 101418080 B CN101418080 B CN 101418080B
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- chitosan
- exchange membrane
- proton exchange
- ammonium acetate
- acetic acid
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Abstract
The invention discloses a method for preparing a chitosan proton exchange membrane for hydrogen sensors. The method comprises the following steps of adding chitosan powder with the molecular weight between 40,000 and 60,000 and the deacetylation degree between 80 and 95 percent to an acetic acid solution with the concentration between 1 and 10 percent (V/V), well mixing the two, adding 1 to 70 wtpercent of ammonium acetate to the chitosan acetic acid solution and continuing to stir for 12 to 24 hours till the solution is uniform. The method adopts a casting-method membrane preparation process, puts the well-stirred solution into a polytetrafluoroethylene container, naturally evaporates the solution for preparing a membrane at a room temperature, and puts the membrane into a dryer for further drying. The proton conductivity of the ammonium acetate/chitosan proton exchange membrane at 25 DEG C is 1x10<-8> to 4x10<-4>Scm<-1>. The chitosan proton exchange membrane of the invention has the advantages that the membrane is extensive in source, simple in processing technology, low in production cost, friendly to environment and good in protonic selective permeability.
Description
Technical field
The invention belongs to the hydrogen sensor field, particularly a kind of preparation method of chitosan proton exchange membrane for hydrogen sensor.
Background technology
Exhaust the today of giving prominence to day by day at traditional energy, clean reproducible hydrogen energy source and be widely used in industrial production and daily life with environmental problem.Yet, hydrogen gas leakage and the necessary consideration of safety problem that produces by the material failure that hydrogen causes.
Solid electrolyte hydrogen sensor (solid electrolyte hydrogen sensor) is that a class is the electrochemical sensor of electrolytical portable online detection hydrogen with proton exchange membrane.As the core component of transmitter, proton conduction carrier proton exchange membrane must have superior thermostability and proton conductive.The proton exchange membrane that is used for the hydrogen sensor field at present is the Nafion series proton exchange membrane of du pont company, the production process complexity of this proton exchange membrane, cost an arm and a leg, the selection perviousness is relatively poor, and serviceability is poor under high temperature and the low humidity condition, need utilize water to come proton conducting as medium.
Chitosan [(1,4)-2 amino-2-deoxidation-B-D-dextran] is the product of chitin deacetylase base.It is water insoluble, is soluble in weak acid (acetate); Have characteristics such as good film-forming properties, moisture retention.Ring texture on the chitosan molecule has guaranteed the heat/chemical stability of chitosan film, and enough mechanical properties.Have numerous hydroxyls and amino on the chitosan molecule chain, be easy to it is carried out chemical modification; Simultaneously hydroxyl and the amino potentiality that chitosan film had be prepared into high-performance proton film that exist.At present chitosan is carried out acidification and prepare proton exchange membrane and possess some special knowledge, and the preparation that is used for hydrogen sensor chitosan high-performance proton exchange membrane be yet there are no report in fuel cell field.
Summary of the invention
The objective of the invention is to propose a kind of chitosan that adopts as the preparation method of hydrogen sensor with proton exchange membrane.The present invention is dissolved in acetic acid solution with chitosan, adopts the casting filming technology to prepare chitosan film, introduces the purpose that amido functional group is realized the conduction of proton by the doping ammonium acetate in chitosan compound.Chitosan proton exchange membrane material source of the present invention is extensive, and complete processing is simple, and low production cost is environmentally friendly, and proton selects perviousness good.
Preparation process of the present invention is as follows:
(1) under the normal temperature and pressure, be to add the chitosan powder in the acetic acid solution of 1%～10% (V/V) in concentration, every 100ml acetic acid solution adds 0.5～2g chitosan, fully stirs and makes the chitosan acetic acid solution;
(2) adding mass percent to the above-mentioned chitosan acetic acid solution that stirs is 10%～50% ammonium acetate, continue to stir 12～24 hours even to solution;
(3) adopt the teeming practice filming technology, the solution that stirs is moved into polytetrafluoroethylcontainer container, spontaneous evaporation forms ammonium acetate/chitosan film under the room temperature, moves into further drying of moisture eliminator.
Described chitosan powder is that molecular weight is 4～60,000, and deacetylation is 80～95% chitosan.
Its chitosan film thickness that is cast in the polytetrafluoroethylcontainer container is 120～370 μ m.Chitosan proton exchange membrane thickness depends on the volume that adopts solution in the casting filming technology immigration polytetrafluoroethylcontainer container.
The advantage of proton exchange membrane preparation method of the present invention is: (1) chitosan is the product of the solid waste chitin of aquatic products industry generations such as shrimp shell, crab shell through deacetylation, its proton exchange membrane of manufacturing hydrogen sensor can be economized on resources, turn waste into wealth, the means that make full use of the natural resources make production cost be minimized simultaneously; (2) preparation technology as proton exchange membrane is simple, easily realizes the industrialization batch process; (3) in the chitosan proton exchange membrane preparation process, do not relate to the generation of deleterious material, environmentally friendly; (4) chitosan proton exchange membrane is easily degraded as biomaterial, is a kind of good environment-friendly materials.(5) ammonium acetate/chitosan proton conduction performance excellence.
Description of drawings
Fig. 1 is the proton conductivity graphic representation of proton exchange membrane under 25 ℃～60 ℃ conditions of the chitosan of ammonium acetate content 40wt%.
Fig. 2 is the proton conduction rate curve under 25 ℃ of conditions of chitosan proton exchange membrane of ammonium acetate content 10%～50wt%.
Embodiment
Embodiment 1 system 40wt% ammonium acetate/chitosan proton exchange membrane
Under the normal temperature and pressure, with molecular weight is 50,000, deacetylation be 90% 1g chitosan powder to put into concentration be that the 100ml acetic acid solution of 1% (V/V) fully stirs, again the 40wt% ammonium acetate is added into the above-mentioned chitosan acetic acid solution that stirs, continue to stir 24 hours to evenly.Adopt casting filming technology system film, spontaneous evaporation film forming under the room temperature moves into further drying of moisture eliminator, and the film thickness of system is 140 μ m.
Cut area 1cm
2Chitosan proton exchange membrane adopts Schlumberger1255 spectral response analyser to carry out testing impedance, range of frequency 1Hz～1 * 10
6Hz, voltage magnitude is ± 5mV.At 30 ℃ proton conductivities is 3.22 * 10
-4, at 40 ℃ proton conductivities 4.64 * 10
-4, be 9.13 * 10 at 50 ℃ proton conductivities
-4, be 1.24 * 10 at 60 ℃ proton conductivities
-340wt% ammonium acetate/chitosan proton exchange membrane at the proton conduction rate curve of 25 ℃～60 ℃ of temperature as shown in Figure 1.
Embodiment 2 system 10wt% ammonium acetate/chitosan proton exchange membranes
Under the normal temperature and pressure, with molecular weight is 40,000, deacetylation be 90% 1.5g chitosan powder to put into concentration be that the 100ml acetic acid solution of 1% (V/V) fully stirs, again the 10wt% ammonium acetate is added into the above-mentioned chitosan acetic acid solution that stirs, continue to stir 24 hours to evenly.Adopt casting filming technology system film, spontaneous evaporation film forming under the room temperature moves into further drying of moisture eliminator, and the film thickness of system is 140 μ m.
Cut area 1cm
2Chitosan proton exchange membrane adopts Schlumberger 1255 spectral response analysers to carry out testing impedance, range of frequency 1Hz～1 * 10
6Hz, voltage magnitude is ± 5mV.Proton transfer rate under the 10wt% ammonium acetate chitosan proton exchange membrane differing temps is as shown in table 1:
The proton transfer rate of table 1 10wt% ammonium acetate/chitosan proton exchange membrane
Embodiment 3 system 50wt% ammonium acetate/chitosan proton exchange membranes
Under the normal temperature and pressure, with molecular weight is 60,000, deacetylation be 90% 2g chitosan powder to put into concentration be that the 100ml acetic acid solution of 1% (V/V) fully stirs, again the 50wt% ammonium acetate is added into the above-mentioned chitosan acetic acid solution that stirs, continue to stir 24 hours to evenly.Adopt casting filming technology system film, spontaneous evaporation film forming under the room temperature moves into further drying of moisture eliminator, and the film thickness of system is 140 μ m.
Cut area 1cm
2Chitosan proton exchange membrane adopts Schlumberger 1255 spectral response analysers to carry out testing impedance, range of frequency 1Hz～1 * 10
6Hz, voltage magnitude is ± 5mV.Proton transfer rate under the 50wt% ammonium acetate chitosan proton exchange membrane differing temps is as shown in table 2:
The proton transfer rate of table 2 50wt% ammonium acetate/chitosan proton exchange membrane
The proton conduction rate curve that 10wt%～50wt% ammonium acetate/chitosan proton exchange membrane is 25 ℃ as shown in Figure 2.Fig. 2 shows that the proton conduction performance of ammonium acetate/chitosan proton exchange membrane is relevant with the quality percentage composition that adds ammonium acetate, and the interpolation of 40wt% ammonium acetate can make the proton conductivity of proton exchange membrane reach maximum.
Claims (3)
1. the preparation method of a chitosan proton exchange membrane for hydrogen sensor is characterized in that, preparation process is as follows:
(1) under the normal temperature and pressure, be to add the chitosan powder in 1%～10% the acetic acid solution in volumetric concentration, every 100ml acetic acid solution adds 0.5～2g chitosan, fully stirs and makes the chitosan acetic acid solution;
(2) adding mass percent to the above-mentioned chitosan acetic acid solution that stirs is 10%～50% ammonium acetate, continue to stir 12～24 hours even to solution;
(3) adopt the teeming practice filming technology, the solution that stirs is moved into polytetrafluoroethylcontainer container, spontaneous evaporation forms ammonium acetate/chitosan film under the room temperature, moves into further drying of moisture eliminator.
2. the preparation method of chitosan proton exchange membrane according to claim 1 is characterized in that, described chitosan powder is that molecular weight is 4～60,000, and deacetylation is 80～95% chitosan.
3. the preparation method of chitosan proton exchange membrane according to claim 1 is characterized in that, the thickness of described formation ammonium acetate/chitosan film is 120～370 μ m.
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| CN2008102265020A CN101418080B (en) | 2008-11-13 | 2008-11-13 | Method for preparing chitosan proton exchange membrane for hydrogen sensor |
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| CN101418080B true CN101418080B (en) | 2011-06-22 |
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| CN105694088B (en) * | 2016-04-11 | 2018-06-15 | 福州大学 | A kind of preparation method and application of polyvinyl alcohol/chitosan solid electrolytic thin-membrane |
| CN108155406B (en) * | 2017-12-26 | 2021-04-06 | 中国科学院青岛生物能源与过程研究所 | Phosphosilicate glass doped chitosan intermediate-temperature proton exchange membrane and preparation method thereof |
| CN108659144A (en) * | 2018-05-31 | 2018-10-16 | 华南理工大学 | A kind of chitosan-based ion conductive material of purine-containing structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463989A (en) * | 2002-06-20 | 2003-12-31 | 中国科学院理化技术研究所 | Process for preparing low molecular weight chitosan using A.niger cellulase |
| CN1775838A (en) * | 2005-12-15 | 2006-05-24 | 北京航空航天大学 | Method for preparing chitose proton exchange membrance for fuel cell |
| WO2007108276A1 (en) * | 2006-03-20 | 2007-09-27 | Kabushiki Kaisha Atsumitec | Hydrogen sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463989A (en) * | 2002-06-20 | 2003-12-31 | 中国科学院理化技术研究所 | Process for preparing low molecular weight chitosan using A.niger cellulase |
| CN1775838A (en) * | 2005-12-15 | 2006-05-24 | 北京航空航天大学 | Method for preparing chitose proton exchange membrance for fuel cell |
| WO2007108276A1 (en) * | 2006-03-20 | 2007-09-27 | Kabushiki Kaisha Atsumitec | Hydrogen sensor |
Non-Patent Citations (2)
| Title |
|---|
| 崔峥 等.壳聚糖固体聚合物电池用膜.《化学进展》.2007,第19卷(第4期),第583-587页. |
| 崔峥等.壳聚糖固体聚合物电池用膜.《化学进展》.2007,第19卷(第4期),第583-587页. * |
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