CN109374710A - A kind of all solid state ion selective electrode and preparation method thereof based on conductive tungsten disulfide nano slices modified electrode - Google Patents
A kind of all solid state ion selective electrode and preparation method thereof based on conductive tungsten disulfide nano slices modified electrode Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The invention discloses a kind of all solid state ion selective electrode based on conductive tungsten disulfide nano slices modified electrode, conductive tungsten disulfide nano slices decorative layer and the ion selectivity polymer film including electrode basement and being successively coated in the electrode basement.The invention also discloses the preparation methods of all solid state ion selective electrode.The deficiencies of all solid state ion selective electrode based on conductive tungsten disulfide nano slices modified electrode of the invention overcomes unstable existing Coating Ions electrodes selective current potential and poor repeatability.
Description
Technical field
The present invention relates to electrochemical sensor technology fields, more particularly to a kind of conduction tungsten disulfide nano slices that are based on to modify
All solid state ion selective electrode of electrode and preparation method thereof.
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, polymer ions selective membrane is directly covered on basal electrode by this kind of electrode
Face, so that there is stability in use is poor for such electrode, and the interference vulnerable to extraneous factors such as light, oxygen gas and waters, meeting
Serious potential drifting is generated, reproducibility is bad.Therefore, in order to make Coating Ions electrodes selective that there is preferable stability,
People improve electron transport rate using intermediate decorative layer is increased between polymeric oxidizer film and electrode basement, subtract simultaneously
Few interference of the extraneous factor to electrode performance.
It has been closed extensively based on carbon-based and noble metal nanometer material as the solid ionic electrodes selective of intermediate decorative layer
Note, and obtained good chemical property.
The Chinese patent literature of Publication No. CN107449816A disclose a kind of all solid state ion selective electrode and its
Preparation method, which includes: matrix；And electronics conversion layer, institute's electronics conversion layer are arranged in institute
It states on the outer surface of matrix, the electronics conversion layer contains graphite oxide alkynes；And sensitive film layer, the sensitivity film layer setting exist
On the outer surface of the electronics conversion layer.Thus, it is possible to effectively improve the stability of all solid state ion selective electrode.
In electrochemical sensor field, tungsten disulfide nano slices have biggish specific surface area and good conductive characteristic,
Have become main material (Aixue Li, Jian Zhang, the Jichuan Qiu, Zhenhuan of research and development electrochemical capacitance
Zhao, Cheng Wang, Chunjiang Zhao, Hong Liu, Talanta, 2017,163,78-84).
Currently, all solid state ion selective electrode based on tungsten disulfide nano slices modified electrode does not have been reported that also.
Summary of the invention
The deficiencies of present invention is in order to overcome unstable existing Coating Ions electrodes selective current potential and poor repeatability, provides
A kind of all solid state ion selective electrode based on conductive tungsten disulfide nano slices modified electrode.
Specific technical solution is as follows:
A kind of all solid state ion selective electrode based on conductive tungsten disulfide nano slices modified electrode, including electrode basement
And successively it is coated on conductive tungsten disulfide nano slices decorative layer and ion selectivity polymer film in the electrode basement.
Tungsten disulfide nano slices have layer structure, and have the advantageous characteristics such as high-specific surface area and high conductivity, two sulphur
Change tungsten nanometer sheet decorative layer and the electron transport rate between electrode basement and ion selectivity polymer film is greatly improved, together
When can reduce interference of the extraneous factor to electrode performance.
The electrode basement is glass-carbon electrode, carbon paste electrode, gold electrode or screen printing electrode.
In terms of the raw material of mass percent, the ion selectivity polymer film includes:
Plasticizer can improve the plasticity of film, and lipophilicity macromolecular can exclude in real solution lipophilic anion to ion
The interference of carrier, improves the sensitivity of electrode, and reduces the impedance of film.
The ionophore is non-conductive polymer polymer；The polymer is polyvinyl chloride (PVC) and poly- first
At least one of base methyl acrylate (PMMA)；The plasticizer is dinitrobenzene Octyl Ether, dioctyl adipate and neighbour
At least one of butyl phthalate；The lipophilicity macromolecular is at least one in tetrachlorobenzene boronation potassium and tetraphenylboron sodium
Kind.
The ionophore is Calcium ionophore, potassium ion carrier or sodium ion carrier；
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, (-)-(R, R)-N, N '-two-[11- (ethoxy carbonyl
Base) undecyl]-N, N ', 4,5- tetramethyl -3,6- dioxaoctane-diamides, diethyl N, N '-[(4R, 5R) -4,5- bis-
Methyl-1,8- dioxo -3,6- dioxa octamethylene] bis- (12- methylamino laurates), N, N, N ', N '-four [cyclohexyl] two
Glycolic acid diamides, N, N, N ',-four cyclohexyl -3- oxa- glutaramide of N ', four [2- (diphenylphosphine of tert-butyl-cup [4] aromatic hydrocarbons
At least one of acyl group) ether]；
The potassium ion carrier is valinomycins, 4- tert-butyl -2,2,14,14- tetraethyl substitution -2a, 14a, dioxy
Four tert-butyl ester of bridge cup [4] aromatic hydrocarbons-tetraacethyl, bis- [(Benzo15crown5 derivatives) -4 '-ylmethyl] pimelates, 2- dodecyl -2-
Methyl-1, at least one of 3- glyceryl bis- [N- [5 '-nitros (Benzo15crown5 derivatives) -4 '-yl] carbamates]；
The sodium ion carrier is N, N ', N "-three heptyl-N, N ', N "-" (3- oxygen of-propylidyne three of trimethyl -4,4 ', 4
Miscellaneous butyramide), N, N '-dibenzyl-N, N '-two oxygroup diacetayl amide of diphenyl -1,2- benzene, N, N, N ',-four cyclohexyl -1 N ',
The bis- decahydronaphthalene naphthalene -16- crown-s 5 of two oxygroup diacetayl amide of 2- benzene, 2,3:11,12-, 4- octadecanoid acid methyl-N, N, N ', N '-four
It is two oxygroup diacetayl amide of cyclohexyl -1,2- benzene, bis- [(12- crown ether -4) methyl] -2- dodecyl -2- dimethyl malenates, double
In the bis- dodecyl malonates of [(12-crown-4) methyl] 2,2- and 4- tert-butyl p tertButylcalixarene-tetraacetic acid tetraethyl ester at least
It is a kind of.
The present invention also provides described, and all solid state ion selectivity based on conductive tungsten disulfide nano slices modified electrode is electric
The preparation method of pole, comprising the following steps:
(1) using conductive tungsten disulfide nano slices modified electrode substrate；
(2) under atmosphere of inert gases, in the electrode basement surface Coating Ions choosing of conductive tungsten disulfide nano slices modification
Selecting property polymer film solution, after drying to obtain the final product.
The conductive tungsten disulfide nano slices can be used the prior art and are prepared.
Preferably, the conductive tungsten disulfide nano slices are inserted method using chemical lithium and are prepared.Specifically it can refer to document:
CarmenCMayorga-Martinez, AdrianoAmbrosi, Alex Yong ShengEng, Zden ě kSofer,
MartinPumera, Electrochemistry Communications, 2015,56,24-28.
Specifically, tungsten disulfide nano slices the preparation method is as follows: tungsten disulphide powder is dispersed in n-BuLi, will
Solution stirs 72 hours under vacuum conditions to form tungsten disulfide suspension, washs gained suspension number using n-hexane later
After secondary by solvent filter remove, by obtained tungsten disulphide powder it is soluble in water and in ice-water bath ultrasound 60 minutes, acquisition
Dispersion liquid is then with 2500rpm centrifugation 15 minutes, and careful collection contains the supernatant of a small amount of tungsten disulfide nano slices, by supernatant
It is centrifuged again 20 minutes in 6500rpm, collects the precipitating containing tungsten disulfide nano slices.
Step (1) includes being dispersed in water conductive tungsten disulfide nano slices, obtains conductive tungsten disulfide nano slices dispersion
Liquid；Conductive tungsten disulfide nano slices dispersant liquid drop is added to the electrode basement surface, drying and forming-film to get.
In step (2), the ion selectivity polymer film solution is made of solute and solvent, and the solute includes
Ionophore, polymer, plasticizer and lipophilicity macromolecular.
In ion selectivity polymer film solution, the quality of solvent is 4~10 times of solute gross mass.
Preferably, the solvent is tetrahydrofuran.
Compared with prior art, the invention has the benefit that
Tungsten disulfide nano slices have layer structure, and have the advantageous characteristics such as high-specific surface area and high conductivity, two sulphur
Change tungsten nanometer sheet decorative layer and the electron transport rate between electrode basement and ion selectivity polymer film is greatly improved, together
When can reduce interference of the extraneous factor to electrode performance.Compared to traditional Coating Ions electrodes selective, of the invention is complete solid
It is more stable and reproducible that state ion selective electrode not only has many advantages, such as current potential, but also its is low in cost, and preparation is simple；Phase
Than in the ion selective electrode containing internal-filling liquid, all solid state ion selective electrode of the invention have higher sensitivity and
Selectivity.
Detailed description of the invention
Fig. 1 is the dynamic response figure of all solid state Calcium signaling prepared by embodiment 1；
Fig. 2 is the potassium ion selective screen printing electrode based on tungsten disulfide nano slices modified electrode in embodiment 8
Water layer test chart；
Fig. 3 is the sodium ion selective electrode without tungsten disulfide nano slices modification in comparative example 1 and two sulphur in embodiment 9
Change electrochemical impedance spectrogram of the sodium ion selective electrode in 0.1mol/L sodium chloride solution of tungsten nanometer sheet modification, in figure
(a) it is the response curve of the sodium ion selective electrode of tungsten disulfide nano slices modification, (b) is to be repaired without tungsten disulfide nano slices
The response curve of the sodium ion selective electrode of decorations.
Specific embodiment
Embodiment 1
A kind of all solid state Calcium signaling is by tungsten disulfide nano slices modified electrode and the calcium ion of electrode surface
Selective polymerisation object film composition, tungsten disulfide nano slices modified electrode are the glass-carbon electrode of tungsten disulfide nano slices modification.
The all solid state Calcium signaling the preparation method is as follows:
(1) 10 μ L tungsten disulfide nano slices dispersion liquids (concentration 1mg/mL) are added dropwise in glassy carbon electrode surface, at room temperature
It is dry, it is prepared into required tungsten disulfide nano slices modified electrode；
Method is inserted using chemical lithium and prepares tungsten disulfide nano slices, specifically can refer to document: Carmen C Mayorga-
Martinez, Adriano Ambrosi, Alex Yong Sheng Eng, Zden ě k Sofer, Martin Pumera,
Electrochemistry Communications, 2015,56,24-28.The specific method is as follows: tungsten disulphide powder is dispersed
In n-BuLi, solution is stirred to 72 hours to form tungsten disulfide suspension under vacuum conditions, use n-hexane later
Washing gained suspension for several times afterwards by solvent filter remove, by obtained tungsten disulphide powder it is soluble in water and in ice-water bath surpass
Sound 60 minutes, for the dispersion liquid of acquisition then with 2500rpm centrifugation 15 minutes, careful collection contained a small amount of tungsten disulfide nano slices
Supernatant is centrifuged 20 minutes by supernatant again in 6500rpm, is collected the precipitating containing tungsten disulfide nano slices, will finally be obtained
The precipitating obtained is soluble in water to be used for further purposes.
(2) it by the pure water rinse of tungsten disulfide nano slices modified electrode obtained surface, is dripped after drying under nitrogen atmosphere
Upper 100 μ L calcium ion polymer film solution, at room temperature dry 24 hours to get；
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 1.0%；
Polymer is polyvinyl chloride, and on the basis of the gross mass of solute, the mass percent concentration of polymer is 33.0%；
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 5 times of Solute mass.
All solid state ion selective electrode made from embodiment 1 is put into 0.01mol/L calcium chloride solution and is impregnated at least
24 hours, it is subsequently placed in 10-9In the calcium chloride solution of mol/L, calcium ion concentration is incrementally increased, observes its potential response, such as Fig. 1
It is shown.Potential response is successively increased with the increase of calcium ion concentration, at the same the response time within 10s, illustrate with curing
Tungsten nanometer sheet is that the Calcium signaling of decorative layer has high electronic conduction ability.
Embodiment 2~7
Compared with Example 1, 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
One of ether], other parameters are the same as embodiment 1.
After tested, all solid state ion selective electrode made from embodiment 2~7 and all solid state ion made from embodiment 1
The performance of electrodes selective is similar.
Embodiment 8
A kind of full-solid potassium ion electrodes selective is by tungsten disulfide nano slices modified electrode and the potassium ion of electrode surface
Selective polymerisation object film composition, tungsten disulfide nano slices modified electrode are the screen printing electrode of tungsten disulfide nano slices modification.
The full-solid potassium ion electrodes selective the preparation method is as follows:
(1) 10 μ L tungsten disulfide nano slices dispersion liquids (concentration 1mg/mL) are added dropwise in screen printing electrode surface, room
The lower drying of temperature, is prepared into required tungsten disulfide nano slices modified electrode；
(2) it by the pure water rinse of tungsten disulfide nano slices modified electrode obtained surface, is dripped after drying under nitrogen atmosphere
Upper 100 μ L potassium ion polymer film solution, at room temperature dry 24 hours to get；
Potassium ion polymer film solution is by potassium ion carrier, polymer, plasticizer, lipophilicity macromolecular and solvent group
At；
Potassium ion carrier is valinomycins, on the basis of the gross mass of solute, the mass percent concentration of potassium ion carrier
It is 1.0%；
Polymer is polyvinyl chloride, and on the basis of the gross mass of solute, the mass percent concentration of polymer 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 5 times of Solute mass.
All solid state ion selective electrode made from embodiment 8 is put into 0.01mol/L Klorvess Liquid and is impregnated at least
24 hours, then full-solid potassium ion electrodes selective is placed in the Klorvess Liquid of 0.1mol/L, observes its response, then
Electrode is placed in the sodium chloride solution of 0.1mol/L again, observes its potential response, finally places it in the chlorine of 0.1mol/L again
Change in potassium solution, observes potential response.As a result it as shown in Fig. 2, electrode is after these steps, is modified based on tungsten sulfide nanometer sheet
Screen printing electrode be able to maintain and its stable potential response and repeatability.
Embodiment 9
A kind of all-solid sodium ion selective electrode is by tungsten disulfide nano slices modified electrode and the sodium ion of electrode surface
Selective polymerisation object film composition, tungsten disulfide nano slices modified electrode are the glass-carbon electrode of tungsten disulfide nano slices modification.
The all-solid sodium ion selective electrode the preparation method is as follows:
(1) 10 μ L tungsten disulfide nano slices dispersion liquids (concentration 1mg/mL) are added dropwise in glassy carbon electrode surface, at room temperature
It is dry, it is prepared into required tungsten disulfide nano slices modified electrode；
(2) it by the pure water rinse of tungsten disulfide nano slices modified electrode obtained surface, is dripped after drying under nitrogen atmosphere
Upper 100 μ L sodium ion polymer film solution, at room temperature dry 24 hours to get；
Sodium ion polymer film solution is by sodium ion carrier, polymer, plasticizer, lipophilicity macromolecular and solvent group
At；
Sodium ion carrier be 4- tert-butyl p tertButylcalixarene-tetraacetic acid tetraethyl ester, on the basis of the gross mass of solute, calcium from
The mass percent concentration of subcarrier is 1.0%；
Polymer is polyvinyl chloride, and on the basis of the gross mass of solute, the mass percent concentration of polymer 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 5 times of Solute mass.
Comparative example 1
Tungsten disulfide nano slices modified electrode in embodiment 9 is substituted for the glass carbon without tungsten disulfide nano slices modification
Electrode, other are the same as embodiment 9.
All solid state ion selective electrode made from embodiment 9 and comparative example 1 is put into 0.01mol/L sodium chloride solution
It impregnates at least 24 hours, is then respectively placed in the sodium chloride solution of 0.1mol/L and observes the response of its electrochemical impedance, see Fig. 3.
It can be seen from the figure that compared to the sodium ion selective electrode modified without tungsten disulfide nano slices, tungsten disulfide nano slices
The sodium ion selective electrode of modification has faster electron transport rate.
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 all solid state ion selective electrode based on conductive tungsten disulfide nano slices modified electrode, which is characterized in that packet
Conductive tungsten disulfide nano slices decorative layer and the ion selectivity for including electrode basement and being successively coated in the electrode basement
Polymer film.
2. all solid state ion selectivity electricity according to claim 1 based on conductive tungsten disulfide nano slices modified electrode
Pole, which is characterized in that the electrode basement is glass-carbon electrode, carbon paste electrode, gold electrode or screen printing electrode.
3. all solid state ion selectivity electricity according to claim 1 based on conductive tungsten disulfide nano slices modified electrode
Pole, which is characterized in that in terms of the raw material of mass percent, the ion selectivity polymer film includes:
4. all solid state ion selectivity electricity according to claim 3 based on conductive tungsten disulfide nano slices modified electrode
Pole, which is characterized in that the ionophore is non-conductive polymer polymer.
5. all solid state ion selectivity electricity according to claim 4 based on conductive tungsten disulfide nano slices modified electrode
Pole, which is characterized in that the ionophore is Calcium ionophore, potassium ion carrier or sodium 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
At least 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
At least one of base -1,3- glyceryl bis- [N- [5 '-nitros (Benzo15crown5 derivatives) -4 '-yl] carbamates]；
The sodium ion carrier is N, N ', N "-three heptyl-N, N ', N "-" (3- oxa- fourth of-propylidyne three of trimethyl -4,4 ', 4
Amide), N, N '-dibenzyl-N, N '-two oxygroup diacetayl amide of diphenyl -1,2- benzene, N, N, N ',-four cyclohexyl -1,2- benzene of N '
The bis- decahydronaphthalene naphthalene -16- crown-s 5 of two oxygroup diacetayl amides, 2,3: 11,12-, 4- octadecanoid acid methyl-N, N, N ',-four hexamethylene of N '
Two oxygroup diacetayl amide of base -1,2- benzene, bis- [(12- crown ether -4) methyl] -2- dodecyl -2- dimethyl malenates, bis- [(12-
Crown- 4) methyl] at least one of the bis- dodecyl malonates of 2,2- and 4- tert-butyl p tertButylcalixarene-tetraacetic acid tetraethyl ester.
6. all solid state ion selectivity electricity according to claim 3 based on conductive tungsten disulfide nano slices modified electrode
Pole, which is characterized in that the polymer is at least one of polyvinyl chloride and polymethyl methacrylate.
7. all solid state ion selectivity electricity according to claim 3 based on conductive tungsten disulfide nano slices modified electrode
Pole, which is characterized in that the lipophilicity macromolecular is at least one of tetrachlorobenzene boronation potassium and tetraphenylboron sodium.
8. a kind of according to any one of claims 1 to 7 complete solid based on conductive tungsten disulfide nano slices modified electrode
The preparation method of state ion selective electrode, which comprises the following steps:
(1) using conductive tungsten disulfide nano slices modified electrode substrate；
(2) under atmosphere of inert gases, in the electrode basement surface Coating Ions selectivity of conductive tungsten disulfide nano slices modification
Polymer film solution, after drying to obtain the final product.
9. all solid state ion selective electrode according to claim 8 based on conductive tungsten disulfide nano slices modified electrode
Preparation method, which is characterized in that the conductive tungsten disulfide nano slices are inserted method using chemical lithium and are prepared.
10. all solid state ion selectivity electricity according to claim 8 based on conductive tungsten disulfide nano slices modified electrode
The preparation method of pole, which is characterized in that in ion selectivity polymer film solution, the quality of solvent be solute gross mass 4~
10 times.
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| CN104833767A (en) * | 2015-06-02 | 2015-08-12 | 青岛大学 | Preparation method and application of GR/WS2-AuNPs-WS2 compound molecular imprinting sensor |
| CN105293580A (en) * | 2015-10-15 | 2016-02-03 | 南京大学 | Method for preparing dispersion liquid of two-dimensional nano-sheet layer of transition metal sulfide |
| WO2017201081A1 (en) * | 2016-05-16 | 2017-11-23 | Agilome, Inc. | Graphene fet devices, systems, and methods of using the same for sequencing nucleic acids |
| CN106315678A (en) * | 2016-08-22 | 2017-01-11 | 河南师范大学 | Method for preparing 1T-phase monolayer tungsten disulfide nanoflakes |
| CN106335927A (en) * | 2016-08-22 | 2017-01-18 | 河南师范大学 | Method for preparing 2H phase single layer tungsten disulfide nano sheet |
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