CN105021682B - A kind of needle-like chlorion sensor and preparation method thereof - Google Patents
A kind of needle-like chlorion sensor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of needle-like chlorion sensor, including reference electrode and electrodes selective, described electrodes selective includes filamentary silver and is coated on the silver chloride layer of filamentary silver one end；Described reference electrode includes wire and is coated on the solid-state electrolyte layer and reference film of the wire end surface successively.It is big that the needle-like chlorion sensor is directed to chlorion sensor bulk in traditional chlorine ion concentration detection, time-consuming, the shortcomings of can not detecting micro, chloride ion-selective electrode, outer reference electrode are fabricated to needle-like and integrated, in terms of can be with quick detection microorganism, micro blood, and be easy to carry, it is easy to operate.
Description
Technical field
The present invention relates to electrochemical sensor technology field, more particularly to a kind of needle-like chlorion sensor and its preparation side
Method.
Background technology
Chlorion is a kind of ion for being widely present in nature, is the presence of most abundant anion in organism.In people
In vivo, the cation such as chlorion and sodium ion is cooperatively to maintain the capacity and osmotic pressure of extracellular fluid, and help to maintain
Body fluid acid-base balance, while it helps internal carbon dioxide transport to lung to excrete.It will be further appreciated that, chlorine
Ion also participates in the effect of the absorption of formation, promotion vitamin B12 and the iron of human body hydrochloric acid in gastric juice, and can be by activating ptyalin
Promote starch-splitting, promote food digestion.Chlorion can also stimulate liver function, promote metabolic waste in liver to discharge, or even have
The effect of stable nervous cell membrane potential.
Chlorion is the indispensable ion of human body, and people typically obtain chlorion by meals, and its main source is chlorine
Change sodium, separately have and come from potassium chloride on a small quantity.Most common salt, flavouring like sauce all contain substantial amounts of chlorine element.It is irrational
Have a meal, or a large amount of perspiration, severe diarrhea, vomitings, or diuretics, in vivo serious dehydration person are needed to use because curing the disease, all may be used
Different degrees of chlorine can occur to lack.Chlorine, which lacks, can break people's cylinder electrolyte balance, and be often accompanied by sodium deficiency, when serious
Low chlorine metabolic alkalosis can be caused, stomach subacidity is easily caused, digests and assimilates bad, and aggravate alopecia, loss of tooth, even
Contraction of muscle is bad, influence is grown.Therefore it is also very necessary to chloride test in organism.
ISE is a kind of to the selective indicator electrode of certain specific ion, chlorion selectivity
Electrode is the electrode special that Chlorine in Solution ion concentration is detected using electrochemical principle.The detection of chlorion medical science, chemical industry,
Pharmacy, environmental protection have a wide range of applications with field of food, and especially the chloride test in human body fluid has important medical science
Clinical meaning.Current chlorion sensor is mostly used for industry spot, and patent 201310274636 discloses a kind of using complete
The chlorion sensor of Fibre Optical Sensor pattern, measurement process is complex, it is impossible to quickly and conveniently measure micro solution in chlorine from
Sub- content.
The content of the invention
The invention provides a kind of needle-like chlorion sensor and preparation method thereof, needle-like chlorion sensor detection speed
Degree is fast, can realize trace detection.
A kind of needle-like chlorion sensor, including reference electrode and electrodes selective, described electrodes selective include silver
Silk and the silver chloride layer for being coated on filamentary silver one end；
Described reference electrode includes wire and is coated on the solid-state electrolyte layer of the wire end surface successively
And reference film.
The present invention is big for chlorion sensor bulk in traditional chlorine ion concentration detection, and time-consuming, it is impossible to detects micro
The shortcomings of, Ag/AgCl is employed as chloride ion-selective electrode, and chloride ion-selective electrode, reference electrode are fabricated to pin
Shape is simultaneously integrated, can be with quick detection microorganism, micro blood in terms of, detection performance it is good, the interference being subject to is few.
Preferably, described filamentary silver and a diameter of 0.1-0.6mm of wire, length are 4~5cm.The size
It is easy to carry.
One end that described electrodes selective is coated with silver chloride layer is test side, and the other end is output end, and is detected
End and the center section of output end are coated with insulating barrier；
It is test side that described reference electrode, which is coated with solid-state electrolyte layer and one end of reference film, and the other end is output
End, and test side and the center section of output end are coated with insulating barrier.
The outside of described insulating barrier is additionally provided with shell, and described insulating barrier stretches out from the two ends of described shell.
Present invention also offers a kind of preparation method of described needle-like chlorion sensor, comprise the following steps：
(1) aluminum oxide suspension, sulfuric acid solution, deionized water and surface-active are used into one end of filamentary silver and wire successively
The agent aqueous solution is handled；
Wherein, when aluminum oxide suspension is handled, polished 10~15 minutes using supersonic oscillations；
The concentration of sulfuric acid solution is 0.5~2mol/L, soaks filamentary silver and wire 3~5 minutes during processing；
(2) filamentary silver for treating step (1) uses electrochemical method by filamentary silver chlorination in the solution of chloride ion-containing, keeps away
Light is dried；
(3) conducting polymer is scattered in deionized water and is configured to suspension, then added inorganic agent and carboxymethyl is fine
The plain sodium of dimension or sodium hydroxyethyl cellulose, are configured to electrolyte slurry, wire are repeatedly dipped into electrolyte slurry, make electrolysis chylema
The surface that material is coated on wire forms solid-state electrolyte layer, and lucifuge is dried；
Concentration expressed in percentage by volume of the described conducting polymer in suspension is 1~5%；
Mass percentage concentration of the described inorganic agent in electrolyte slurry is 0.01~0.1%；
The mass percentage concentration of described sodium carboxymethylcellulose or sodium hydroxyethyl cellulose in electrolyte slurry is
1.5~5%；
(4) plasticizer, lipophilicity macromolecular, non-conductive polymer polymer are dissolved in cyclohexanone or tetrahydrofuran and matched somebody with somebody
Reference film liquid is made, the wire that step (3) is treated repeatedly dips the reference film liquid, dips reference film liquid time control solid-state
Dielectric substrate is not totally submerged by reference film liquid, and reference film liquid, which is coated on outside solid-state electrolyte layer, forms reference film, and lucifuge is done
It is dry；
In terms of the gross mass of solute, wherein the mass percent of plasticizer is 60.7~65.9%, lipophilicity macromolecular
Mass percent is 0.1~0.6%, and the mass percent of non-conductive polymer polymer is 32.8~36.4%；
(5) heat-shrink tube is respectively coated by chloride ion-selective electrode and reference electrode middle and upper part, is used as insulating barrier；
(6) by working electrode and reference electrode cage connection and it is fixed, obtains described needle-like chlorion sensing
Device.
Wire is spun gold, filamentary silver, platinum filament or copper wire.
In step (1), described aluminum oxide turbid liquid concentration is 60-100g/L, prepares the alumina powder of the suspension
A diameter of 0.5 micron to 50 nanometers of end；
Described aqueous surfactant solution is molten for 0.1-1% carboxymethylcellulose sodium solution or sodium hydroxyethyl cellulose
Liquid.
In step (2), the solution of described chloride ion-containing is the sodium chloride of 0.1~1 mol/L, potassium chloride, calcium chloride or
The aqueous solution of magnesium chloride.
Described electrochemical method is cyclic voltammetry or constant voltage method.
In step (3), described conducting polymer is selected from polypyrrole and its derivative, Polyaniline and its derivative or poly- thiophene
Fen and its derivative；
Described inorganic agent is polyethylene glycol to isooctyl phenyl ether.
In step (4), described non-conductive polymer polymer is selected from polyvinyl chloride or polyurethane；
Described lipophilicity macromolecular is selected from tetraphenylboron sodium, four (4- chlorphenyls) boric acid chlorine and the four [(fluoroforms of 3,5- bis-
Base) phenyl] potassium borate；
Described plasticizer is selected from double (2- ethylhexyls) adipic acid, 2- nitrobenzene octyl ether, phthalic acid ester, adipic acids
Dioctyl ester, di-n-octyl sebacate or adipic acid propane diols.
The concentration of non-conductive polymer polymer in a solvent is 72.6~140.0mg/mL in described reference film liquid.
In actually measurement, by under chloride ion-selective electrode and outer reference electrode in all solid state chlorion sensor
End be immersed in Chloride Solution to be measured, by wire upper end with periphery detection circuit be connected, you can detect Chlorine in Solution from
Sub- concentration.
Chloride ion-selective electrode is silver/silver chloride electrode in the present invention, is used under normal circumstances as reference electrode, special
It is not that in the case of liquid electrode, internal-filling liquid selection saturation potassium chloride, is common business reference electrode.Chlorine in Solution ion
With silver chlorate one dynamic equilibrium of formation, when solution concentration change, silver/silver chloride electrode current potential also changes, and meets energy therewith
This special formula journey.And reference electrode stablizes constant in the solution, the electrical potential difference of measurement therebetween can extrapolate Chlorine in Solution
Ion concentration.
Because the present invention is all solid-state electrode, it is not necessary to carry bulky liquid electrode, detection is got up convenient and swift.And
And sensor is extremely miniaturized, the chlorion prepare liquid of micro volume, such as detection of microorganism chlorion or clinic can be detected
The blood chloride detection of medical science.Also multiple sensor groups into sensor array, multi-channel measurement can be carried out side by side.
Brief description of the drawings
Fig. 1 is the structural representation of the needle-like chlorion sensor of the present invention；
Fig. 2 is the structural representation of the chloride ion-selective electrode of the needle-like chlorion sensor shown in Fig. 1；
Fig. 3 is the structural representation of the reference electrode of the needle-like chlorion sensor shown in Fig. 1；
Fig. 4 is response curve of the voltage to concentration for the needle-like chlorion sensor that the embodiment of the present invention 1 is obtained；
Fig. 5 is response curve of the voltage to concentration for the needle-like chlorion sensor that the embodiment of the present invention 2 is obtained.
Embodiment
Knowable to the structural representation of needle-like chlorion sensor as shown in Figure 1, the needle-like chlorion sensor, including chlorine
ISE, reference electrode, insulating barrier 6, shell 7.
The structural representation of chloride ion-selective electrode as shown in Figure 2 understands that the chloride ion-selective electrode includes silver
Silk 1 and silver chloride layer 2, wherein silver chloride layer 2 are covered in the latter half of filamentary silver 1.
Reference electrode as shown in Figure 3 understands that the reference electrode includes wire 3, solid-state electrolyte layer 4 and reference film 5,
Wherein, solid-state electrolyte layer 4 is coated on the latter half of wire 3, and reference film 5 is coated on solid electrolyte layer surface, and
The upper end of solid-state electrolyte layer 4 reserves one section and not covered by reference film 5.Insulating barrier 6 is coated on chloride ion-selective electrode and ginseng
Than on the outside of electrode, shell 7 is in the outside of insulating barrier 6 and is slightly less than insulating barrier 6, chlorine ion electrode is fixed and phase with reference electrode
It is mutually parallel.
Embodiment 1
(1) a diameter of 0.5mm is chosen, length is 5cm filamentary silver two, is respectively labeled as 1 and 2；Prepare 70g/L aluminum oxide
Aqueous suspension, filamentary silver is inserted in aluminum oxide suspension, is polished 10 minutes using supersonic oscillations；Then the filamentary silver is used successively
0.8mol/L dilution heat of sulfuric acid soaks 3 minutes, uses deionized water rinsing；
(2) filamentary silver is cleaned with 0.3% sodium carboxymethyl cellulose solution；
(3) treated filamentary silver 1 is used into constant voltage method in 250mmol/L sodium chloride solutions, voltage is 0.22V, when
Between be 30 seconds.By filamentary silver chlorination, lucifuge is dried；
(4) PEDOT/PSS [poly- (3,4- ethene dioxythiophenes)-polystyrolsulfon acid] is taken:Water=1:99 mass ratio is matched somebody with somebody
Mixed liquor processed, adds the polyethylene glycol of mixed liquor gross mass 0.05% to isooctyl phenyl ether, adds 3% carboxymethyl cellulose
Plain sodium, is configured to electrolyte slurry；Filamentary silver is dipped into electrolyte slurry more than 2 times, it is coated on filamentary silver surface, solid-state electricity is formed
Solve matter layer；
(5) 166uL2- nitrobenzene octyl ether, 1.425mg tetra- (4- chlorphenyls) potassium borate, 103.74mg polyvinyl chloride are dissolved
Viscous solution is configured in 1mL tetrahydrofurans, reference film liquid is used as；The filamentary silver that step (3) is treated dips the ginseng more than 2 times
Than film liquid, it is set to be coated on outside solid-state electrolyte layer, and slightly below solid-state electrolyte layer, lucifuge drying；
(6) heat-shrink tube is respectively coated by working electrode and reference electrode upper end, needle-like chloride ion-selective electrode is made
With corresponding reference electrode；
(7) by working electrode and reference electrode cage connection and it is parallel be fixed on wherein, that is, needle-like chlorion is made and passes
Sensor.
The needle-like chlorion sensor prepared using this embodiment measures various concentrations Chloride Solution, obtains voltage pair
The response curve of concentration, as a result as shown in Figure 4.
Embodiment 2
(1) a diameter of 0.5mm is chosen, length is 5cm each 1 of filamentary silver, platinum filament, prepares 70g/L aluminum oxide suspensions, makes
Polished 10 minutes with supersonic oscillations, soaked 3 minutes with 0.8mol/L dilution heat of sulfuric acid, use deionized water rinsing；
(2) filamentary silver and platinum filament are cleaned with 0.3% sodium carboxymethylcellulose；
(3) treated filamentary silver is used into cyclic voltammetry in the solution of chloride ion-containing, voltage is from -1 to 1V, scanning speed
Rate is 0.1V/s, and scanning hop count is 12, and by filamentary silver chlorination, lucifuge is dried；
(4) PEDOT/PSS is taken:Water=1:99 mass ratio prepares mixed liquor, and the polyethylene glycol of addition 0.05% is to different pungent
Base phenyl ether, add 3% sodium carboxymethylcellulose, be configured to electrolyte slurry；Platinum filament is repeatedly dipped into electrolyte slurry,
It is coated on platinum filament surface, form solid-state electrolyte layer；
(5) 189uL di-n-octyl sebacates, 1.425mg tetraphenylboron sodiums, 103.74mg polyvinyl chloride are dissolved in 1mL hexamethylenes
Viscous solution is configured in ketone, reference film liquid is used as；The platinum filament that step (3) is treated repeatedly dips the reference film liquid, makes it
It is coated on outside solid-state electrolyte layer, and slightly below solid-state electrolyte layer, lucifuge drying；
(6) heat-shrink tube is respectively coated by working electrode and reference electrode upper end, needle-like chloride ion-selective electrode is made
With corresponding reference electrode；
(7) by working electrode and reference electrode cage connection and it is parallel be fixed on wherein, that is, needle-like chlorion is made and passes
Sensor.
The needle-like chlorion sensor prepared using this embodiment measures various concentrations Chloride Solution, obtains voltage pair
The response curve of concentration, as a result as shown in Figure 5.
Claims (7)
1. a kind of needle-like chlorion sensor, including reference electrode and electrodes selective, it is characterised in that described selectivity electricity
Pole includes filamentary silver and is coated on the silver chloride layer of filamentary silver one end；
Described reference electrode includes wire and is coated on the solid-state electrolyte layer and ginseng of the wire end surface successively
Compare film；
Its preparation method comprises the following steps：
(1) aluminum oxide suspension, sulfuric acid solution, deionized water and surfactant water are used into one end of filamentary silver and wire successively
Solution is handled；
(2) water of the filamentary silver for treating step (1) in the sodium chloride of 0.1~1 mol/L, potassium chloride, calcium chloride or magnesium chloride
Using cyclic voltammetry or constant voltage method by filamentary silver chlorination in solution, lucifuge is dried；
(3) conducting polymer is scattered in deionized water and is configured to suspension, then add inorganic agent and carboxymethyl cellulose
Sodium or sodium hydroxyethyl cellulose, are configured to electrolyte slurry, and wire is repeatedly dipped into electrolyte slurry, apply electrolyte slurry
The surface for being overlying on wire forms solid-state electrolyte layer, and lucifuge is dried；
(4) plasticizer, lipophilicity macromolecular, non-conductive polymer polymer are dissolved in cyclohexanone or tetrahydrofuran and be configured to
Reference film liquid, the wire that step (3) is treated repeatedly dips the reference film liquid, dips reference film liquid time control solid state electrolysis
Matter layer is not totally submerged by reference film liquid, and reference film liquid, which is coated on outside solid-state electrolyte layer, forms reference film, and lucifuge is dried；
(5) heat-shrink tube is respectively coated by chloride ion-selective electrode and reference electrode middle and upper part, is used as insulating barrier；
(6) by electrodes selective and reference electrode cage connection and it is fixed, obtains described needle-like chlorion sensor.
2. needle-like chlorion sensor according to claim 1, it is characterised in that described electrodes selective is coated with chlorine
The one end for changing silver layer is test side, and the other end is output end, and test side and the center section of output end are coated with insulating barrier；
It is test side that described reference electrode, which is coated with solid-state electrolyte layer and one end of reference film, and the other end is output end, and
And test side and the center section of output end are coated with insulating barrier.
3. needle-like chlorion sensor according to claim 2, it is characterised in that the outside of described insulating barrier is additionally provided with
Shell, and described insulating barrier stretches out from the two ends of described shell.
4. needle-like chlorion sensor according to claim 1, it is characterised in that in step (1), described aluminum oxide hangs
Turbid liquid concentration is 60-100g/L, prepares a diameter of 0.5 micron to 50 nanometers of the alumina powder of the suspension；
Described aqueous surfactant solution is 0.1-1% carboxymethylcellulose sodium solution or sodium hydroxyethyl cellulose solution.
5. needle-like chlorion sensor according to claim 1, it is characterised in that in step (3), described conducting polymer
Thing is selected from polypyrrole and its derivative, Polyaniline and its derivative or polythiophene and its derivative；
Described inorganic agent is polyethylene glycol to isooctyl phenyl ether.
6. needle-like chlorion sensor according to claim 1, it is characterised in that in step (4), described non-conductive height
Molecularly Imprinted Polymer is selected from polyvinyl chloride or polyurethane；
Described lipophilicity macromolecular is selected from tetraphenylboron sodium, four (4- chlorphenyls) boric acid chlorine or four [3,5- bis- (trifluoromethyl) benzene
Base] potassium borate；
It is pungent that described plasticizer is selected from double (2- ethylhexyls) adipic acids, 2- nitrobenzene octyl ether, phthalic acid ester, adipic acid two
Ester, di-n-octyl sebacate or adipic acid propane diols.
7. needle-like chlorion sensor according to claim 6, it is characterised in that non-conductive height in described reference film liquid
The concentration of Molecularly Imprinted Polymer in a solvent is 72.6~140.0mg/mL.
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| CN1227524C (en) * | 2003-07-24 | 2005-11-16 | 中国科学院海洋研究所 | Full solid state reference electrode |
| CN100360928C (en) * | 2005-03-24 | 2008-01-09 | 厦门大学 | Composite scanning chlorion sensitive micro-probe and preparing process thereof |
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