CN108828033A - A kind of solid ionic electrodes selective and preparation method based on single corner electrode - Google Patents

A kind of solid ionic electrodes selective and preparation method based on single corner electrode Download PDF

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CN108828033A
CN108828033A CN201810261671.1A CN201810261671A CN108828033A CN 108828033 A CN108828033 A CN 108828033A CN 201810261671 A CN201810261671 A CN 201810261671A CN 108828033 A CN108828033 A CN 108828033A
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electrode
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single angle
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平建峰
姜成美
姚瑶
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Zhejiang University ZJU
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    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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    • G01N27/333—Ion-selective electrodes or membranes
    • G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes

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Abstract

The invention discloses a kind of solid ionic electrodes selectives and preparation method based on single corner electrode, the solid ionic electrodes selective includes electrode basement and the ion selectivity polymer film coated in electrode basement surface, and the electrode basement is the electrode for having single cornea doped with single angle or surface modification.Compared to the ion selective electrode containing internal-filling liquid, solid ionic electrodes selective of the invention not only has comparable sensitivity and selectivity, but also can develop to microelectrode direction.

Description

It is a kind of based on the solid ionic electrodes selective of single corner electrode and preparation Method
Technical field
The present invention relates to electrochemical sensor technology field more particularly to a kind of solid-states based on single corner electrode Ion selective electrode and preparation method.
Background technique
Ion selective electrode is the electrochemical sensing of a kind of activity using membrane potential measurement effects of ion or concentration Device generates and the ionic activity in its sensitive membrane and the phase interface of solution when it and containing when the contact of the solution of measured ion Direct related membrane potential.As one kind can quickly, in accurate, conveniently, selective measurement complex sample certain ion contains The analysis testing tool of amount, ion selective electrode be widely used to environmental monitoring, biomedical detection, Chemical Manufacture, The fields such as quality detection.Traditional ion selective electrode is made of sensitive membrane, internal-filling liquid and conducting element.However, being filled due to interior The presence of liquid, so that this sensor develops without normal direction micromation direction.
It is in the prior art, electrode coated that with it, preparation is simple, is easy to be miniaturized and have and conventional ion electrodes selective The features such as similar sensitivity and selectivity, is widely used in ion selective electrode preparation.It is electrode coated to be selected by Coating Ions The metal wire of selecting property polymeric membrane is made.However, due to being easily formed one layer of very thin water layer, thus electrode between film and metal Serious potential drifting can be generated, reproducibility is bad.Oxidation-reduction process in water layer is mainly the reduction of dissolved oxygen, electrode Potential drifting is mainly as caused by the change of pH in sample and dissolved oxygen.Therefore, in order to make Coating Ions electrodes selective have There is preferable stability, it is necessary to choose that hydrophobicity is stronger, while there is the substrate of swift electron delivery rate to be used to prepare ion Electrodes selective.
Carbon materials have stronger hydrophobicity, while low in cost, therefore may be used as the base of ion selective electrode Bottom.However, conventional carbon materials such as graphite, glass carbon etc., electronics conduction velocity is slower, based on these materials as substrate Electrode coated sensitivity is poor.
Summary of the invention
The present invention provides a kind of solid ionic electrodes selective based on single corner electrode, has high current potential Stability, sensitivity and selectivity.
The present invention provides following technical solutions：
A kind of solid ionic electrodes selective based on single corner electrode, including electrode basement and be coated in electrode The ion selectivity polymer film of substrate surface, the electrode basement are to have list doped with single angle or surface modification The electrode of wall carbon nano-tube cornea.
The diameter at single angle (SWNHs) is 2~5nm, and length is 40~50nm, after form is similar to truncation Single-walled carbon nanotube, but one end has unique pyramidal structure.Single angle has high than table capacitor and high electronics biography The characteristic of rate is led, while there is stronger hydrophobicity, the solid ionic prepared using single corner electrode as electrode basement Electrodes selective has high potential stability, sensitivity and selectivity.
Doped with single angle electrode be single angle carbon paste electrode, single angle carbon paste electrode by The mass ratio of single angle and adhesive composition, the single angle and adhesive is 7: 1~7: 7；
The adhesive is at least one of paraffin oil, triphenylamine and ionic liquid；Further preferably, the ion Liquid is hexafluorophosphate based on imidazoles or based on pyridine.
The electrode that surface modification has single cornea is the screen printing being surface modified using single angle Brush electrode or glass-carbon electrode.
The ion selectivity polymer film can polymerize for calcium ion selective polymer film or potassium ion selective Object film.
The present invention also provides the preparation method of the above-mentioned solid ionic electrodes selective based on single corner electrode, Include the following steps：
(1) electrode basement is prepared；
(2) in the electrode basement surface drop coating ion selectivity polymer film solution, described consolidate is obtained after dry State ion selective electrode.
Preferably, the preparation method of electrode basement is：
Single angle is uniformly mixed with adhesive, is filled in electrode casing, is compacted, conducting wire is inserted into, is obtained after dry To the electrode basement doped with single angle；
Or, coating single angle stragging liquid on the surface of screen printing electrode or glass-carbon electrode, table is obtained after dry Face is modified with the electrode basement of single cornea.
The single angle can be used the prior art and be prepared, for example, can refer to bibliography (Nan Li, Zhiyong Wang, Keke Zhao, Zujin Shi, Zhennan Gu, Shukun Xu, Carbon, 2010,4,1580- 1585.) it is prepared using the method for arc discharge.
In step (2), ion selectivity polymer film solution is made of solute and solvent, and the solute includes that ion carries Body, polymer, plasticizer and lipophilicity macromolecular.Ion selectivity polymer film solution drop coating is in electrode basement, after dry Become ion selectivity polymer film.
Preferably, by percentage to the quality, the solute includes：
The ionophore can be Calcium ionophore or potassium ion carrier；Ion selectivity polymer film solution is dry Corresponding calcium ion selective polymer film or potassium ion selective polymer film can be formed respectively afterwards.
The Calcium ionophore is bis- [(octadecylamino formoxyl) the methoxyl group acetyl of ETH 1001,10,19- Base]-Isosorbide-5-Nitrae, 7,13,16- five oxa- -10,19- diazacyclo heneicosanes (the 21203 of such as Fluka), (-)-(R, R)-N, N ' - Two-[11- (carbethoxyl group) undecyl]-N, N ', 4,5- tetramethyl -3,6- dioxaoctane-diamides, diethyl N, N ' - [(4R, 5R) -4,5- dimethyl -1,8- dioxo -3,6- dioxa octamethylene] bis- (12- methylamino laurate) (such as Fluka 21192), N, N, N ', [cyclohexyl] diglycolic acid of N '-four diamides, N, N, N ',-four cyclohexyl -3- oxa- glutaramide of N ' In (the 21193 of such as Fluka), tert-butyl-cup [4] aromatic hydrocarbons four [2- (diphenylphosphoryl) ether] (the 72385 of such as Fluka) It is a kind of.
The potassium ion carrier be valinomycins (Valinomycin, such as the V0627 of Sigma), 4- tert-butyl -2,2, 14,14- tetraethyl substitution -2a, 14a, two oxygen bridge cup [4] aromatic hydrocarbons-tetraacethyl, four tert-butyl ester (the 60396 of such as Fluka), bis- [(benzene And -15- crown- 5) -4 '-ylmethyl] pimelate (the 60401 of such as Fluka), 2- dodecyl -2- methyl-1,3- glyceryl pair One of [N- [5 '-nitros (Benzo15crown5 derivatives) -4 '-yl] carbamate] (60397 of such as Fluka).
The polymer is polyvinyl chloride (PVC) and/or polymethyl methacrylate (PMMA).
At least one of described plasticizer dinitrobenzene Octyl Ether, dioctyl adipate and butyl phthalate.
Plasticizer can improve the plasticity of ion selectivity polymer film.
The lipophilicity macromolecular is tetrachlorobenzene boronation potassium and/or tetraphenylboron sodium.
Lipophilicity macromolecular can exclude interference of the lipophilic anion to ionophore in real solution, improve electrode Sensitivity, and reduce the impedance of film.
In ion selectivity polymer film solution, the quality of organic solvent is 4-10 times of solute gross mass.
Preferably, the organic solvent is tetrahydrofuran.
Compared with prior art, beneficial effects of the present invention are：
Electrode coated compared to traditional metal, solid ionic electrodes selective of the invention is low in cost, and prepares letter It is single；Compared to the ion selective electrode containing internal-filling liquid, solid ionic electrodes selective of the invention not only has comparable Sensitivity and selectivity, but also can develop to microelectrode direction.
Detailed description of the invention
Fig. 1 is electrochemical impedance spectrogram of the electrode in the calcium chloride solution of 0.1mol/L, wherein：A is the preparation of embodiment 3 Solid ionic electrodes selective response curve, b be comparative example 1 prepare electrode response curve；
Fig. 2 is the dynamic response figure of solid ionic electrodes selective prepared by embodiment 10；
Fig. 3 is the water layer test chart of solid ionic electrodes selective prepared by embodiment 14.
Specific embodiment
The preparation of 1 single angle modified electrode substrate of embodiment
By dimethylformamide (DMF) dispersant liquid drop at single angle in glass-carbon electrode (or screen printing electrode) table Face, it is dry under room temperature (or infrared lamp), it is prepared into required single angle modified electrode.
The concentration at single angle is 2mg/ml in dispersion liquid；The dimethylformamide dispersion liquid at single angle Volume is 6-8 μ L.
Single angle can be prepared using the prior art, for example, can refer to the side that document uses arc discharge Method prepared (Nan Li, Zhiyong Wang, Keke Zhao, Zujin Shi, Zhennan Gu, Shukun Xu, Carbon, 2010,4,1580-1585.).
The preparation of 2 single angle carbon paste electrode substrate of embodiment
Single angle powder is mixed with paraffin oil, triphenylamine or ionic liquid with 7: 3 mass ratio, is sufficiently ground Mill, obtains uniform mixture；
Mixture is filled in clean electrode casing and is compacted, a copper wire is inserted into behind electrode as conducting wire, It is prepared into required carbon paste electrode.
The preparation of 3 Calcium signaling of embodiment
(1) single angle modified electrode (using glass-carbon electrode as substrate) is prepared according to the method for embodiment 1；
(2) upper 100 μ L calcium ion is dripped on the electrode basement surface that surface modification obtained above has single angle to gather Compound film solution is dried 24 hours at room temperature；
Calcium ion polymer film solution is by Calcium ionophore, polymer, plasticizer, lipophilicity macromolecular and solvent group At；
Calcium ionophore is N, N, N ', N '-four [cyclohexyl] diglycolic acid diamides, on the basis of the gross mass of solute, The mass percent concentration of Calcium ionophore is 1%；
Polymer is polymethyl methacrylate, on the basis of the gross mass of solute, the mass percent concentration of polymer It is 33%；
Plasticizer is butyl phthalate, and on the basis of the gross mass of solute, the mass percent concentration of plasticizer is 65.8%；
Lipophilic macromolecular is tetraphenylboron sodium, on the basis of the gross mass of solute, the mass percent concentration of lipophilic macromolecular It is 0.2%；
Organic solvent is tetrahydrofuran, and quality is 4 times of Solute mass.
The preparation of 4~9 Calcium signaling of embodiment
Compared with Example 3, the difference is that, it is bis- that Calcium ionophore is replaced with into ETH 1001,10,19- respectively [(octadecylamino formoxyl) Methoxyacetyl]-Isosorbide-5-Nitrae, 7,13,16- five oxa- -10,19- diazacyclo heneicosanes, (-)-(R, R)-N, N '-two-[11- (carbethoxyl group) undecyl]-N, N ', 4,-two acyl of 5- tetramethyl -3,6- dioxaoctane Amine, diethyl N, N '-[(4R, 5R) -4,5- dimethyl -1,8- dioxo -3,6- dioxa octamethylene] bis- (12- methylamino moons Cinnamic acid ester), N, N, N ',-four cyclohexyl -3- oxa- glutaramide of N ', four [2- (diphenylphosphoryl) of tert-butyl-cup [4] aromatic hydrocarbons Ether], other parameters are the same as embodiment 3.
Comparative example 1
Single angle modified electrode in embodiment 3 is substituted for the glass carbon electricity without the modification of single angle Pole, other are the same as embodiment 3.
The preparation of 10 potassium ion-selective electrode of embodiment
(1) single angle modified electrode (using glass-carbon electrode as substrate) is prepared according to the method for embodiment 1；
(2) upper 100 μ L potassium ion is dripped on the electrode basement surface that surface modification obtained above has single angle to gather Compound film solution is dried 24 hours at room temperature；
Potassium ion polymer film solution is by potassium ion carrier, polymer, plasticizer, lipophilicity macromolecular and solvent group At；
Potassium ion carrier is valinomycins (Valinomycin, such as the V0627 of Sigma), using the gross mass of solute as base Standard, the mass percent of potassium ion carrier are 1%；
Polymer is polyvinyl chloride, and on the basis of the gross mass of solute, the mass percent of polymer is 33%；
Plasticizer is dinitrobenzene Octyl Ether, and on the basis of the gross mass of solute, the mass percent of plasticizer is 65.8%；
Lipophilic macromolecular is tetrachlorobenzene boronation potassium, on the basis of the gross mass of solute, the mass percent of lipophilic macromolecular It is 0.2%；
Organic solvent is tetrahydrofuran, and quality is 4 times of Solute mass.
The preparation of 11~13 potassium ion-selective electrode of embodiment
Compared with Example 10, the difference is that, potassium ion carrier is replaced with into 4- tert-butyl -2,2 respectively, 14, Four tert-butyl ester of 14- tetraethyl substitution -2a, 14a, two oxygen bridge cup [4] aromatic hydrocarbons-tetraacethyl, bis- [(Benzo15crown5 derivatives) -4 '-Ji Jia Base] pimelate, 2- dodecyl -2- methyl-1, bis- [N- [5 '-nitros (Benzo15crown5 derivatives) -4 '-yl] ammonia of 3- glyceryl Carbamate], other parameters are the same as embodiment 10.
The preparation of 14 potassium ion-selective electrode of embodiment
(1) according to the method for embodiment 2, single wall carbon is prepared with 0.3g paraffin oil using 0.7g single angle powder and is received Rice angle carbon paste electrode；
(2) upper 30 μ L potassium ion polymer film solution is dripped on carbon paste electrode surface obtained above, it is small dries 24 at room temperature When；
Potassium ion polymer film solution is by potassium ion carrier, polymer, plasticizer, lipophilicity macromolecular and solvent group At；
Potassium ion carrier is valinomycins (Valinomycin, such as the V0627 of Sigma), using the gross mass of solute as base Standard, the mass percent of potassium ion carrier are 1%；
Polymer is polyvinyl chloride, and on the basis of the gross mass of solute, the mass percent of polymer is 33%；
Plasticizer is dinitrobenzene Octyl Ether, and on the basis of the gross mass of solute, the mass percent of plasticizer is 65.8%；
Lipophilic macromolecular is tetrachlorobenzene boronation potassium, on the basis of the gross mass of solute, the mass percent of lipophilic macromolecular It is 0.2%；
Organic solvent is tetrahydrofuran, and quality is 4 times of Solute mass.
The preparation of 15~17 potassium ion-selective electrode of embodiment
Compared with embodiment 14, the difference is that, potassium ion carrier is replaced with into 4- tert-butyl -2,2 respectively, 14, Four tert-butyl ester of 14- tetraethyl substitution -2a, 14a, two oxygen bridge cup [4] aromatic hydrocarbons-tetraacethyl, bis- [(Benzo15crown5 derivatives) -4 '-Ji Jia Base] pimelate, 2- dodecyl -2- methyl-1, bis- [N- [5 '-nitros (Benzo15crown5 derivatives) -4 '-yl] ammonia of 3- glyceryl Carbamate], other parameters are the same as embodiment 14.
Test case
Electrode prepared by embodiment 3 and comparative example 1 activates 24 hours in the calcium chloride solution of 0.01mol/L.Then Electrode is placed in the calcium chloride solution of 0.1mol/L and observes the response of its electrochemical impedance, the result is shown in Figure 1.
From figure 1 it appears that single corner electrode has faster electron transmission speed compared to glass-carbon electrode Rate.
Potassium ion-selective electrode prepared by embodiment 10 is placed under room temperature environment after drying 24 hours, in 0.01mol/ It is activated 24 hours in the Klorvess Liquid of L.Then the potassium ion-selective electrode after activation is placed in 10-6The potassium chloride of mol/L In solution, potassium concentration is incrementally increased, observes its potential response, as a result as shown in Figure 2.
As shown in Fig. 2, potential response is successively increased with the increase of potassium concentration, at the same the response time within 10s, Illustrate that there is high electronic conduction ability by the potassium ion-selective electrode of substrate of single corner electrode.
Potassium ion-selective electrode prepared by embodiment 14 is placed under room temperature environment after drying 24 hours, in 0.01mol/ It is activated 24 hours in the Klorvess Liquid of L.Then potassium ion-selective electrode after activation is placed in the potassium chloride of 0.1mol/L In solution, its response is observed, then electrode is placed in the sodium chloride solution of 0.1mol/L again, observes its potential response, finally It is placed it in the Klorvess Liquid of 0.1mol/L again, observes potential response, as a result as shown in Figure 3.
As shown in figure 3, potassium ion-selective electrode after these steps, is still able to maintain extremely stable current potential Response and repeatability.
The dynamic response and water layer for the solid ionic electrodes selective that respectively prepared by testing example 11~13,15~17 are surveyed Performance is tried, it is consistent with electrode performance prepared by embodiment 10 and embodiment 14.
Technical solution of the present invention and beneficial effect is described in detail in embodiment described above, it should be understood that Above is only a specific embodiment of the present invention, it is not intended to restrict the invention, it is all to be done in spirit of the invention Any modification, supplementary, and equivalent replacement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of solid ionic electrodes selective based on single corner electrode, which is characterized in that including electrode basement and Ion selectivity polymer film coated in electrode basement surface, the electrode basement are doped with single angle or table Face is modified with the electrode of single cornea.
2. solid ionic electrodes selective according to claim 1, which is characterized in that doped with the electricity at single angle Extremely single angle carbon paste electrode, single angle carbon paste electrode is made of single angle and adhesive, described Single angle and adhesive mass ratio be 7: 1~7: 7；
The electrode that surface modification has single cornea is the silk-screen printing electricity being surface modified using single angle Pole or glass-carbon electrode.
3. solid ionic electrodes selective according to claim 1, which is characterized in that the ion selectivity polymer Film is calcium ion selective polymer film or potassium ion selective polymer film.
4. one kind is according to claim 1 or the preparation method of 2 described in any item solid ionic electrodes selectives, feature exist In including the following steps：
(1) electrode basement is prepared；
(2) in the electrode basement surface drop coating ion selectivity polymer film solution, obtained after dry the solid-state from Sub- electrodes selective.
5. the preparation method of solid ionic electrodes selective according to claim 4, which is characterized in that the system of electrode basement Preparation Method is：
Single angle is uniformly mixed with adhesive, is filled in electrode casing, is compacted, conducting wire is inserted into, is mixed after dry The miscellaneous electrode basement for having single angle；
Or, coating single angle stragging liquid on the surface of screen printing electrode or glass-carbon electrode, obtains after dry and repaired to surface It is decorated with the electrode basement of single cornea.
6. the preparation method of solid ionic electrodes selective according to claim 4, which is characterized in that in step (2), from Sub- selective polymerisation object coating solution is made of solute and solvent, and the solute includes ionophore, polymer, plasticizer and parent Lipid macromolecular.
7. the preparation method of solid ionic electrodes selective according to claim 6, which is characterized in that with mass percent Meter, the solute include：
8. the preparation method of the described in any item solid ionic electrodes selectives of according to claim 6 or 7, which is characterized in that institute The ionophore stated can be Calcium ionophore or potassium ion carrier；
The Calcium ionophore is bis- [(octadecylamino formoxyl) Methoxyacetyls] -1 of ETH 1001,10,19-, 4,7,13,16- five oxa- -10,19- diazacyclo heneicosanes, (-)-(R, R)-N, N '-two-[11- (carbethoxyl group) 11 Alkyl]-N, N ', 4,5- tetramethyl -3,6- dioxaoctane-diamides, diethyl N, N '-[dimethyl -1 (4R, 5R) -4,5-, 8- dioxo -3,6- dioxa octamethylene] bis- (12- methylamino laurates), N, N, N ', N '-four [cyclohexyl] diglycolic acid Diamides, N, N, N ',-four cyclohexyl -3- oxa- glutaramide of N ', four [2- (diphenylphosphoryl) of tert-butyl-cup [4] aromatic hydrocarbons One of ether]；
The potassium ion carrier is valinomycins, 4- tert-butyl -2,2,14,14- tetraethyl substitution -2a, 14a, two oxygen bridge cups [4] four tert-butyl ester of aromatic hydrocarbons-tetraacethyl, bis- [(Benzo15crown5 derivatives) -4 '-ylmethyl] pimelates, 2- dodecyl -2- first One of base -1,3- glyceryl bis- [N- [5 '-nitros (Benzo15crown5 derivatives) -4 '-yl] carbamates].
9. the preparation method of the described in any item solid ionic electrodes selectives of according to claim 6 or 7, which is characterized in that institute The polymer stated is polyvinyl chloride and/or polymethyl methacrylate.
10. the preparation method of the described in any item solid ionic electrodes selectives of according to claim 6 or 7, which is characterized in that institute The lipophilicity macromolecular stated is tetrachlorobenzene boronation potassium and/or tetraphenylboron sodium.
CN201810261671.1A 2017-12-19 2018-03-27 A kind of solid ionic electrodes selective and preparation method based on single corner electrode Pending CN108828033A (en)

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