CN102944597A - Deliquescent-polyelectrolyte-based full-solid-state ethanol gas sensor enzyme electrode and manufacturing method thereof - Google Patents
Deliquescent-polyelectrolyte-based full-solid-state ethanol gas sensor enzyme electrode and manufacturing method thereof Download PDFInfo
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- CN102944597A CN102944597A CN2012105328850A CN201210532885A CN102944597A CN 102944597 A CN102944597 A CN 102944597A CN 2012105328850 A CN2012105328850 A CN 2012105328850A CN 201210532885 A CN201210532885 A CN 201210532885A CN 102944597 A CN102944597 A CN 102944597A
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Abstract
The invention relates to a deliquescent-polyelectrolyte-based full-solid-state ethanol gas sensor enzyme electrode and a manufacturing method thereof. The manufacturing method comprises the following steps: on a matrix made of an insulating material, preparing a printed electrode composed of a working electrode, a reference electrode and a counter electrode by screen printing technology; coating a polycarbonate insulator on the surfaces in the middle; coating a reaction layer composed of graphene, deliquescent polyelectrolyte and alcohol oxidase on the working electrode; and coating a deliquescent solid polymer film among the working electrode, counter electrode and reference electrode to obtain the biological enzyme electrode. The invention provides an enzyme electrode for gas-state ethanol detection; and the enzyme electrode can implement high-selectivity detection of ethanol gas without using any liquid electrolyte in the use process, thereby integrally enhancing the properties and practicality of the ethanol gas biosensor.
Description
Technical field
The present invention relates to a kind of all solid state alcohol gas sensor enzyme electrode based on deliquescence type polyelectrolyte and preparation method thereof.
Background technology
Along with the mankind deepen day by day to the attention degree of self health with to the concern of ecologic environment, Monitoring and Controlling to gas is had higher requirement, this research for gas sensor, development and production provide opportunities and challenges, have also proposed new research topic to gas sensor.In order to satisfy these requirements, gas sensor must have higher sensitivity and selectivity, and repeatability and good stability can manufacture, the cost performance high.But traditional gas sensor is because the restriction of itself material, the specific selectivity of pure gas sensor is all poor, only has the gas sensor array of seldom counting, with the method for neural network as the late time data disposal system, can realize to a certain extent the selectivity identification to gas, even so its overall performance still depends on the performance of single-sensor element, and the selectivity of sensor array is greatly limited.Therefore, improve the gas sensor specificity, significant for applying of gas sensor.
The most outstanding characteristics of biology sensor are specificitys, and biological identification molecule is combined with gas sensor, will be expected to obtain the gas sensor of high specific.In the biogas sensor research, the enzymic catalytic reaction that also mainly depends on the gas/liquid interface at present carries out (Anal.Chem, (1994), 66,3297-3302; Sens.Actuators B, (2002), 83, (1-3), 35-40; Sens.Actuators B, (2005), 108, (1-2), 639-645; Sens.Actuators B, (2000), 70, (1-3), 182-187; Biosens.﹠amp; Bioelectron., (2002), 17, (5), 389-394; Biosens.Bioelectron., (2002), 17, (5), 427-432; Sens.Actuators B, (2001), 81, (1), 107-114; Biosens.Bioelectron., (2002), 17, (9), 789-796), really do not realize the detection of gaseous sample in the gas phase, electrolyte evaporation or leakage can occur in these methods inevitably, decay (the Sens.Actuators B that causes sensor signal, (2005), 107,812-817), and the device preparation is complicated, is unfavorable for microminiaturization, intelligent and integrated.We utilize the serigraphy three-electrode system in conjunction with solid polymer electrolyte, made up all solid state alcohol gas sensor (20111046159.8), realized the detection of alcohol gas on gas/liquid/solid interface, but the response of biogas sensor still is subject to the restriction of moisture, utilization of the present invention has the polyelectrolyte of deliquescence character and is fixation support and the solid electrolyte of enzyme, keep the higher catalytic activity of enzyme molecule, charge transfer in the simultaneously realization response process has made up the new bio gas sensor.
Summary of the invention
The deficiency that in detection, exists in order to overcome existing alcohol gas biology sensor, the purpose of this invention is to provide a kind of all solid state alcohol gas sensor enzyme electrode based on deliquescence type polyelectrolyte and preparation method thereof, the enzyme electrode that makes with the method has improved properties and the practicality of biology sensor on the whole.
The technical solution adopted in the present invention is as follows:
The enzyme electrode that all-solid ethanol gas biosensor of the present invention is used has the insulating material matrix, be brushed with working electrode, contrast electrode and to electrode at the matrix surface screen printing, apply one deck carbonic ester insulator in the middle of the electrode, be coated with the responding layer that is formed by Graphene, deliquescence type polyelectrolyte and alcohol oxidase on the working electrode, then apply deliquescence type polyelectrolyte membrane at working electrode, contrast electrode with between to electrode.
The method for making of the enzyme electrode that all-solid ethanol gas biosensor is used may further comprise the steps:
1) preparation of deliquescence type polyelectrolyte
A. in the 100mL there-necked flask, (mol: ratio mol) joined diethylenetriamine and methyl acrylate in a certain amount of methyl alcohol, reaction 12h according to 1: 1; Then under decompression state, be warming up to 30 ℃ of reaction 1h, at 60 ℃ of lower reaction 1h, at 100 ℃ of lower reaction 2h, at 120 ℃ of lower reaction 3h, 140 ℃ of lower Depressor response 2h, reaction is diluted with absolute ethyl alcohol after finishing, and in a large amount of ether, wash, precipitate, vacuum drying obtains ultrabranching polyamide;
B. in the 100mL there-necked flask, with ultrabranching polyamide and deionized water, formic acid, formaldehyde according to 1: 10: 7: the ratio of 7 (g/g) is mixed, and then 75 ℃ of back flow reaction certain hours repeatedly wash, precipitate with ether, vacuum drying;
C. the product among the above-mentioned b is dissolved in the 50mL methyl alcohol, then adds a certain amount of halogenated alkane, 50 ℃ of reaction certain hours, product dissolves through methyl alcohol, and ether sedimentation is repeatedly purified, and vacuum drying obtains deliquescence type polyelectrolyte.
2) clean surface has working electrode, contrast electrode and to pottery or the PVC base system of electrode, dry for standby;
3) be that 2% glutaraldehyde concussion mixes with Graphene, 5～20mg/mL deliquescence type polyelectrolyte and the volume ratio of the alcohol oxidase of 3～6mg/mL, 0.5～3mg/mL, then getting 3～10 μ L drips and is coated in working electrode surface, naturally dry, form responding layer;
4) be that the poly-electrolytic solution of 2～5% deliquescence type evenly is coated in working electrode, contrast electrode and between the electrode, obtains enzyme electrode after naturally drying with volume ratio.
Advantage of the present invention is:
1) chooses working electrode, contrast electrode and electrode is printed on three-electrode system on the same matrix, be convenient to microminiaturization, the intellectuality and integrated of sensor electrode;
2) use of Graphene has improved the response sensitivity of sensor;
3) alcohol oxidase has improved the response selectivity of sensor greatly as the recognition component of ethanol molecule;
4) utilize solid-state polyelectrolyte as the electric charge transport vehicle in the electrochemical reaction process, avoid using liquid electrolyte, improve the stability of sensor signal;
5) deliquescence type polyelectrolyte can be enzymic catalytic reaction sufficiently high water activity is provided as the fixation support of enzyme, significantly improves response signal;
6) to have a volume little for enzyme electrode of the present invention, low cost, the advantage such as easy to use.And response sensitivity is high, and stability better responds the selectivity height, can be used for accurate measurement and the control of ethanol gas concentration.
Description of drawings
Fig. 1 is the structural representation of enzyme electrode of the present invention.
Fig. 2 is the deliquescence procedure chart of the deliquescence type polyelectrolyte of the embodiment of the invention 1 making, A: drying regime, B:40% relative humidity deliquescence 1h, C:40% relative humidity deliquescence 2h, D: state of saturation.
Fig. 3 is the deliquescence procedure chart that the embodiment of the invention 2 is made deliquescence type polyelectrolyte, A: drying regime, B:40% relative humidity deliquescence 1h, C:40% relative humidity deliquescence 2h, D: state of saturation.
Fig. 4 is that the enzyme electrode of the embodiment of the invention 2 making is to the response curve of alcohol vapour.
Embodiment
Further specify the present invention below in conjunction with drawings and Examples:
With reference to accompanying drawing 1, the enzyme electrode that all-solid ethanol gas biosensor is used has insulating body (8), be brushed with working electrode (1), contrast electrode (2) and to electrode (3) at the matrix surface screen printing, scribble one deck coated electrode table on their the center section face and polycarbonate insulator (4).Working electrode (1), contrast electrode (2) and electrode (3) is corresponded respectively to pin (5), (6) and (7) of base end.Working electrode is coated with the responding layer that is comprised of bioactive materials, nano material, alcohol oxidase on (1), then applies polyelectrolyte membrane at working electrode (1), contrast electrode (2) with between to electrode (3).
Described working electrode (1) is circular, and diameter is 2～4mm, and material is platinum, and contrast electrode is silver/silver chloride, is platinum to electrode.
Embodiment 1:
1) preparation of deliquescence type polyelectrolyte
A. in the 100mL there-necked flask, the diethylenetriamine of 0.2mol and the methyl acrylate of 0.2mol are joined in the 25mL methyl alcohol reaction 12h; Then under decompression state, be warming up to 30 ℃ of reaction 1h, at 60 ℃ of lower reaction 1h, at 100 ℃ of lower reaction 2h, at 120 ℃ of lower reaction 3h, 140 ℃ of lower Depressor response 2h, reaction is diluted with absolute ethyl alcohol after finishing, and in a large amount of ether, wash, precipitate, vacuum drying obtains ultrabranching polyamide;
B. in the 100mL there-necked flask, the 5g ultrabranching polyamide is mixed with 50mL deionized water, 35g formic acid and 35g formaldehyde, then 75 ℃ of back flow reaction certain hours repeatedly wash, precipitate vacuum drying with ether;
C. the product among the above-mentioned b is dissolved in the 50mL methyl alcohol, then adds the 10.32g bromination of n-butane, 50 ℃ of reaction 48h, product dissolves through methyl alcohol, and ether sedimentation is repeatedly purified, and vacuum drying obtains deliquescence type polyelectrolyte.
2) clean surface has working electrode (diameter 4mm), silver/silver chloride contrast electrode and platinum to the ceramic matrix of electrode, dry for standby;
3) be that 2% glutaraldehyde concussion mixes with Graphene, 10mg/mL deliquescence type polyelectrolyte and the volume ratio of the alcohol oxidase of 6mg/mL, 1mg/mL, then get 6 μ L and drip and be coated in working electrode surface, naturally dry the formation responding layer;
4) be that the poly-electrolytic solution of 3% deliquescence type evenly is coated in working electrode, contrast electrode and between the electrode, obtains enzyme electrode after naturally drying with volume ratio.
Embodiment 2:
1) preparation of deliquescence type polyelectrolyte
A. in there-necked flask, the diethylenetriamine of 0.4mol and the methyl acrylate of 0.4mol are joined in the 50mL methyl alcohol reaction 12h; Then under decompression state, be warming up to 30 ℃ of reaction 1h, at 60 ℃ of lower reaction 1h, at 100 ℃ of lower reaction 2h, at 120 ℃ of lower reaction 3h, 140 ℃ of lower Depressor response 2h, reaction is diluted with absolute ethyl alcohol after finishing, and in a large amount of ether, wash, precipitate, vacuum drying obtains ultrabranching polyamide;
B. in there-necked flask, the 10g ultrabranching polyamide is mixed with 100mL deionized water, 70g formic acid and 70g formaldehyde, then 75 ℃ of back flow reaction certain hours repeatedly wash, precipitate with ether, vacuum drying;
C. the product among the above-mentioned b is dissolved in the 100mL methyl alcohol, then adds 24.86g bromo normal hexane, 50 ℃ of reaction 24h, product dissolves through methyl alcohol, and ether sedimentation is repeatedly purified, and vacuum drying obtains deliquescence type polyelectrolyte.
2) clean surface has working electrode (diameter 4mm), silver/silver chloride contrast electrode and platinum to the ceramic matrix of electrode, dry for standby;
3) be that 2% glutaraldehyde concussion mixes with Graphene, 5mg/mL deliquescence type polyelectrolyte and the volume ratio of the alcohol oxidase of 3mg/mL, 0.5mg/mL, then get 10 μ L and drip and be coated in working electrode surface, naturally dry the formation responding layer;
4) be that the poly-electrolytic solution of 2% deliquescence type evenly is coated in working electrode, contrast electrode and between the electrode, obtains enzyme electrode after naturally drying with volume ratio.
Embodiment 3:
1) preparation of deliquescence type polyelectrolyte
A. in there-necked flask, the diethylenetriamine of 0.2mol and the methyl acrylate of 0.2mol are joined in the 25mL methyl alcohol, under agitation slowly drip the acrylic acid first vinegar of 0.2mol, reaction 12h; Then under decompression state, be warming up to 30 ℃ of reaction 1h, at 60 ℃ of lower reaction 1h, at 100 ℃ of lower reaction 2h, at 120 ℃ of lower reaction 3h, 140 ℃ of lower Depressor response 2h, reaction is diluted with absolute ethyl alcohol after finishing, and in a large amount of ether, wash, precipitate, vacuum drying obtains ultrabranching polyamide;
B. in there-necked flask, the 5g ultrabranching polyamide is mixed with 50mL deionized water, 35g formic acid and 35g formaldehyde, then 75 ℃ of back flow reaction certain hours repeatedly wash, precipitate with ether, vacuum drying;
C. the product among the above-mentioned b is dissolved in the 50mL methyl alcohol, then adds the 10.32g bromination of n-butane, 50 ℃ of reaction 72h, product dissolves through methyl alcohol, and ether sedimentation is repeatedly purified, and vacuum drying obtains deliquescence type polyelectrolyte.
2) clean surface has working electrode (diameter 2mm), silver/silver chloride contrast electrode and platinum to the ceramic matrix of electrode, dry for standby;
3) be that 2% glutaraldehyde concussion mixes with Graphene, 5mg/mL deliquescence type polyelectrolyte and the volume ratio of the alcohol oxidase of 5mg/mL, 1mg/mL, then get 8 μ L and drip and be coated in working electrode surface, naturally dry the formation responding layer;
4) be that the poly-electrolytic solution of 3% deliquescence type evenly is coated in working electrode, contrast electrode and between the electrode, obtains enzyme electrode after naturally drying with volume ratio.
Claims (7)
1. all solid state alcohol gas sensor enzyme electrode based on deliquescence type polyelectrolyte, it is characterized in that: it has the insulating material matrix, be brushed with working electrode, contrast electrode and to electrode at the matrix surface screen printing, apply one deck carbonic ester insulator in the middle of the electrode, be coated with the responding layer that is formed by Graphene, deliquescence type polyelectrolyte and alcohol oxidase on the working electrode, then apply deliquescence type polyelectrolyte membrane at working electrode, contrast electrode with between to electrode.
2. a kind of all solid state alcohol gas sensor enzyme electrode based on deliquescence type polyelectrolyte according to claim 1, it is characterized in that: the insulating material matrix is Polyvinylchloride or pottery, electrode adopts screen printing technique to print, described working electrode is circular, diameter is 2～4mm, material is platinum, and contrast electrode is silver/silver chloride, is platinum to electrode.
3. the method for making of a kind of all solid state alcohol gas sensor enzyme electrode based on deliquescence type polyelectrolyte according to claim 1 is characterized in that: comprise following a few step:
1) preparation of deliquescence type polyelectrolyte
A. in there-necked flask, according to 1: 1 ratio diethylenetriamine and methyl acrylate are joined in a certain amount of methyl alcohol, stir lower reaction 12h; Then under decompression state, be warming up to 30 ℃ of reaction 1h, at 60 ℃ of lower reaction 1h, at 100 ℃ of lower reaction 2h, at 120 ℃ of lower reaction 3h, 140 ℃ of lower Depressor response 2h, reaction is diluted with absolute ethyl alcohol after finishing, and in a large amount of ether, wash, precipitate, vacuum drying obtains ultrabranching polyamide;
B. in there-necked flask, with ultrabranching polyamide and deionized water, formic acid, formaldehyde according to 1: 10: 7: the ratio of 7 (g/g) is mixed, and then 75 ℃ of back flow reaction certain hours repeatedly wash, precipitate with ether, vacuum drying;
C. the product among the above-mentioned b is dissolved in the 50mL methyl alcohol, then adds a certain amount of halogenated alkane, 50 ℃ of reaction certain hours, product dissolves through methyl alcohol, and ether sedimentation is repeatedly purified, and vacuum drying obtains deliquescence type polyelectrolyte.
2) clean surface has working electrode, contrast electrode and to pottery or the PVC base system of electrode, dry for standby;
3) be that 2% glutaraldehyde concussion mixes with the deliquescence type polyelectrolyte of the Graphene of the alcohol oxidase of 3～6mg/mL, 0.5～3mg/mL, 5～20mg/mL and volume ratio, then getting 3～10 μ L drips and is coated in working electrode surface, naturally dry, form responding layer;
4) be that the poly-electrolytic solution of 2～5% deliquescence type evenly is coated in working electrode, contrast electrode and between the electrode, obtains enzyme electrode after naturally drying with volume ratio.
4. the method for making of a kind of all solid state alcohol gas sensor enzyme electrode based on Graphene according to claim 3 is characterized in that: used halogenated alkane is a kind of in bromination of n-butane, the bromo normal hexane.
5. the method for making of a kind of all solid state alcohol gas sensor enzyme electrode based on Graphene according to claim 3, it is characterized in that: in the preparation of deliquescence type polyelectrolyte, the reaction time in b step is 6～12h.
6. the method for making of a kind of all solid state alcohol gas sensor enzyme electrode based on Graphene according to claim 3, it is characterized in that: in the preparation of deliquescence type polyelectrolyte, the reaction time in c step is 6～72h.
7. the method for making of a kind of all solid state alcohol gas sensor enzyme electrode based on Graphene according to claim 3, it is characterized in that: described working electrode is for circular, and diameter is 2～4mm, and contrast electrode is silver/silver chloride, is platinum to electrode.
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| CN108398467A (en) * | 2018-03-06 | 2018-08-14 | 上海应用技术大学 | A kind of gas sensor and its construction method based on carbon nanotube and metal nanoparticle |
| WO2022110959A1 (en) * | 2020-11-27 | 2022-06-02 | 山东省科学院生物研究所 | Electrode system for quickly detecting ethanol, and ethanol detecting method using electrode system |
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| CN108398467A (en) * | 2018-03-06 | 2018-08-14 | 上海应用技术大学 | A kind of gas sensor and its construction method based on carbon nanotube and metal nanoparticle |
| WO2022110959A1 (en) * | 2020-11-27 | 2022-06-02 | 山东省科学院生物研究所 | Electrode system for quickly detecting ethanol, and ethanol detecting method using electrode system |
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