CN102980931B - All-solid-state selective electrode based on functional ion liquid and preparation method of all-solid-state selective electrode - Google Patents
All-solid-state selective electrode based on functional ion liquid and preparation method of all-solid-state selective electrode Download PDFInfo
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Abstract
The invention discloses an all-solid-state selective electrode based on functional ion liquid and a preparation method of the all-solid-state selective electrode. The selective electrode comprises a substrate, an internal reference electrode, a solid-state ion layer and an ion sensitive film, wherein the solid-stage ion layer consists of the functional ion liquid; cations of the functional ion liquid have oxidation-reduction groups; and anions are hydrophobic groups. Due to the hydrophobicity and the light nonsensitivity of the functional ion liquid, influence of environment factors such as a water layer and light on the all-solid-state selective electrode is reduced; and the operability and the stability of the electrode during actual application are improved further.
Description
Technical field
The present invention relates to electrochemical sensor technology field, particularly relate to a kind of all solid state ion-selective electrode based on functional ion liquid and preparation method thereof.
Background technology
Ion-selective electrode is a kind of indicator electrode measuring some particular ion concentration in solution with potential method.It has the features such as highly sensitive, selectivity good, measurement range is wide, easy to operate, cost is low, is therefore widely used in the fields such as environment, food, medicine, industry, biology.
Common ion-selective electrode is made up of ion sensitive membrane, internal reference electrode and internal-filling liquid.During measurement, internal reference electrode and outer contrast electrode are formed ion transducer, these two electrodes are inserted in solution to be measured simultaneously, and connect and compose an electrochemical cell with external measurement mechanism, measure the electromotive force of this electrochemical cell, the ion concentration in solution to be measured can be extrapolated according to Nernst equation.But the use of internal-filling liquid, make the structure of electrode become complicated, preparation process is loaded down with trivial details, makes electrode cannot be microminiaturized and integrated, thus limits ion-selective electrode and detects the application with monitored in vivo aspect at the scene simultaneously.
All solid state ion-selective electrode is removed by the internal-filling liquid layer in conventional ion electrodes selective, and adopt solid-state middle layer to substitute.During electrode fabrication, solid-state middle layer is clipped between internal reference electrode and ion sensitive membrane, plays the effect of transduction signal, is transformed into the electronic signal on electrode conductor by the ion signal in ion sensitive membrane.The preparation process of this electrode is very simple, be easy to microminiaturized, and has the potentiometric analysis performance consistent with conventional ion electrodes selective.In this kind of ion-selective electrode, the selection in solid-state middle layer is crucial.In existing bibliographical information, self assembled monolayer, conducting polymer, carbon nanomaterial and gold nano-material etc. by as solid-state middle layer for developing all solid state ion-selective electrode.
Ionic liquid is a class green reagent, and structure is made up of negative ions, and it has the feature such as higher ionic conductivity, preferably physical and chemical stability, wider electrochemical window, stable electrochemical properties, preferably bio-compatibility.Meanwhile, the performance of ionic liquid has adjustability, namely can design the composition of its zwitterion as required and change its substituting group, and then changing its performance.Functional ion liquid be for a certain performance or application design there is specific functional groups or substituent ionic liquid.Therefore, the ionic liquid that some have special nature can be designed, can as solid-state middle layer, for developing all solid state ion-selective electrode.
Document (Cecylia Wardak.A highly selective lead-sensitive electrode withsolid contact based on ionic liquid.Journal of Hazardous Materials 186 (2011) 1131-1135) reports a kind of lead ion electrodes selective based on ionic liquid, this article author adopts the potpourri of ionic liquid and polymkeric substance-Polyvinylchloride to serve as solid-state middle layer, ionic liquid used is that some are water insoluble but be dissolved in the ionic liquid of tetrahydrofuran solvent, serve as the effect of cementing agent inside, due to non-oxidation reducing activity, this solid-state middle layer cannot transport membranes electric potential signal effectively, thus the steady operation of ion-selective electrode is unfavorable for.
Patent CN101852761A discloses a kind of all-solid sodium ion selective electrode, comprise substrate, electrode basement system, solid-state electrolyte layer, sodion sensitive membrane and insulation course, electrode basement system is located on substrate, by reaction electrode, contact electrode and the conductive lead wire composition being connected these two electrodes, solid-state electrolyte layer is located on reaction electrode, solid-state electrolyte layer is covered with sodion sensitive membrane, sodion sensitive membrane is surrounded by insulation course, and be provided with the opening making sodion sensitive membrane exposed, disclosed in this patent, the solid-state electrolyte layer of electrodes selective is made up of conducting polymer, easily water layer is there is in electrode film, and be subject to the interference of dissolved oxygen DO, electrode stability is poor.
Summary of the invention
The invention provides a kind of all solid state ion-selective electrode based on functional ion liquid, solve existing electrodes selective stability and the poor problem of repeatability.
A kind of all solid state ion-selective electrode based on functional ion liquid, comprise substrate, internal reference electrode, solid ionic layer and ion sensitive membrane, described solid ionic layer is made up of functional ion liquid, the cationic-charge of functional ion liquid has oxidation-reduction quality group, and negative ion is hydrophobic group.
Functional ion liquid negative ion of the present invention has strong-hydrophobicity, cationic-charge has oxidizing reducing group, functional ion liquid is made to have hydrophobic nature and light insensitivity, the impact on all solid state ion-selective electrode such as water layer, light can be reduced, improve electrode operability in actual applications and stability.
Preferably, described kation is trimethylaniline ion, N-methyl thiophane ion or 1-ethyl dicyclopentadienyl iron base-3 methylimidazole ion; Described negative ion is hexafluorophosphoricacid acid ions, two fluoroform sulfimide ion.
Described functional ion liquid is water insoluble, is solid-state under room temperature, most preferably is trimethylaniline hexafluorophosphate, the two fluoroform sulfimide salt of N-methyl thiophane or 1-ethyl dicyclopentadienyl iron base-3 methylimidazole hexafluorophosphate.
In order to ensure that solid ionic layer plays good signal transformation among electrode, the thickness of preferred described solid ionic layer is 1 ~ 5 μm, most preferably is 3 μm.
The all solid state ion-selective electrode of the present invention can detect kation and negative ion, as potassium ion, sodion, calcium ion, chlorion, nitrate ion, sulfate ion etc., correspondingly ion sensitive membrane is potassium ion sensitive membrane, sodion sensitive membrane, calcium ion sensitive membrane, chlorion sensitive membrane, nitrate ion sensitive membrane, sulfate ion sensitive membrane etc.
Described internal reference electrode is located on substrate, solid ionic layer is arranged on above internal reference electrode, ion sensitive membrane is overlying on solid ionic layer, generally, described all solid state ion-selective electrode also comprises the contact conductor be connected with internal reference electrode, during use, contact conductor movable end is connected with outer contrast electrode.Described contact conductor is generally copper conductor.
Preferably, described contrast electrode is gold electrode, platinum electrode or carbon electrode, and above-mentioned electrode is conventional electrode.
Described substrate is made up of high-molecular organic material, as PE, PVC etc.
Present invention also offers the described preparation method based on all solid state ion-selective electrode of functional ion liquid, comprise the following steps:
Substrate arranges internal reference electrode; Dripped by functional ion liquid dissolution homogeneity and be coated in internal reference electrode surface, drying volatilizes solvent, obtained solid ionic layer; Ion-sensitive coating solution is dripped and is coated in solid ionic layer surface, dry obtained ion sensitive membrane; Functional ion liquid is room temperature solid ionic liquid, and cationic-charge has oxidation-reduction quality group, and negative ion is hydrophobic group.
Before contrast electrode is set, with absolute ethyl alcohol, internal reference electrode, substrate surface can be carried out pre-service, remove the floating dust on its surface, make its clean surface, state consistency, and fully dry.
The solvent that described functional ionic liquid liquid solution is selected is organic solvent, as acetone etc.
Described ion-sensitive coating solution is obtained by conventional method, is generally and ionophore, polymkeric substance (PVC etc.), plastifier, the large molecule of lipophilicity and solvent is mixed.
Compared with prior art, beneficial effect of the present invention is:
The ionic liquid with specific function is incorporated in all solid state ion-selective electrode and serves as signal transduction layer by the present invention, utilize high ion conductivity and the electron conduction of functional ion liquid, ion signal in ion sensitive membrane is transformed into electronic signal, and electronic signal is passed to electrode basement, to realize the transmission of electrode response signal, eliminate the problem such as the signal transmission barrier layer existed in traditional all solid state ion-selective electrode and then the potential response caused instability.
The present invention utilizes hydrophobic nature and the light insensitivity of functional ion liquid, reduces environmental factor if water layer, light etc. are on the impact of all solid state ion-selective electrode, and then improves this electrode operability in actual applications and stability.
Accompanying drawing explanation
Fig. 1 is the structural representation of electrode of the present invention;
Fig. 2 is the potential response calibration curve based on the full-solid potassium ion electrodes selective of trimethylaniline hexafluorophosphate in the embodiment of the present invention 1;
Fig. 3 is the response slope relation curve over time based on the full-solid potassium ion electrodes selective of trimethylaniline hexafluorophosphate in the embodiment of the present invention 1;
Fig. 4 is the potential response calibration curve based on all solid state Calcium signaling of the two fluoroform sulfimide salt of N-methyl thiophane in the embodiment of the present invention 2;
The potential response calibration curve that Fig. 5 obtains when being and detecting calcium ion in milk based on all solid state Calcium signaling of the two fluoroform sulfimide salt of N-methyl thiophane in the embodiment of the present invention 2.
Embodiment
As shown in Figure 1, a kind of all solid state ion-selective electrode based on functional ion liquid, comprises internal reference electrode 3, substrate 4, solid ionic layer 2, ion-sensitive mould 1 and contact conductor 5;
Internal reference electrode 3 is located on substrate 4, and contact conductor 5 is connected with internal reference electrode 3, internal reference electrode 3 is covered with solid ionic layer 2, solid ionic layer 2 is covered with ion-sensitive mould 1, and contact conductor 5 is through substrate 4.Below that the present invention provides two kinds of all solid state ion-selective electrode according to the material difference of solid ionic layer 2:
Embodiment 1
(1) internal reference electrode is set on substrate, internal reference electrode is connected with contact conductor;
(2) with absolute ethyl alcohol, internal reference electrode, substrate surface are carried out pre-service, remove the floating dust on its surface, make its clean surface, state consistency, and fully dry;
(3) take 40mg trimethylaniline hexafluorophosphate, be dissolved in 1mL organic solvent-acetone, obtain ionic liquid solution;
(4) 33mg Polyvinylchloride (polymkeric substance), 0.4mg tetrachlorobenzene boronation potassium (the large molecule of lipophilicity) and 1.6mg valinomycins (potassium ion carrier) is taken, be dissolved in 1.5mL organic solvent tetrahydrofuran, then 65 μ L dinitro benzenes Octyl Ether (plastifier) are instilled, abundant mixing, obtains the responsive mould solution of potassium ion;
(5) get appropriate functional ionic liquid liquid solution, drop in clean electrode basement surface, afterwards electrode is placed on room temperature and is evaporated completely down to solvent acetone, obtained solid ionic layer;
(6) get appropriate potassium ion sensitive membrane solution, drop in functional ion liquid layer surface, afterwards electrode is placed on room temperature down to organic solvent tetrahydrofuran volatilization completely, obtained ion sensitive membrane.
The full-solid potassium ion electrodes selective of preparation is placed in the solution to be measured containing finite concentration potassium ion, and insert outer contrast electrode (Ag/AgCl, 3.3mol/L KCl solution), measure the electrode potential of ion-selective electrode relative to outer contrast electrode by external equipment.
Fig. 2 is the potential response calibration curve of the full-solid potassium ion electrodes selective prepared in the present embodiment, its correction equation is EMF (mV)=59.2Ln (C)+482.6, wherein EMF is potential value (mV), C is potassium concentration (mol/L), and related coefficient is 0.9918.
The full-solid potassium ion electrodes selective prepared in the present embodiment is preserved 30 days continuously under normal temperature normality, within every two days, detect its response characteristic, if Fig. 3 is the situation of change of its response slope with the holding time, as can be seen from Figure 3, response slope based on the full-solid potassium ion electrodes selective of functional ion liquid maintains 59.2mv/decade substantially, illustrates that ion-selective electrode of the present invention has good job stability.
Embodiment 2
(1) internal reference electrode is set on substrate, internal reference electrode is connected with contact conductor;
(2) with absolute ethyl alcohol, internal reference electrode, substrate surface are carried out pre-service, remove the floating dust on its surface, make its clean surface, state consistency, and fully dry;
(3) take the two fluoroform sulfimide salt of 40mg N-methyl thiophane, be dissolved in 1mL organic solvent-acetone, obtain ionic liquid solution;
(4) 33mg Polyvinylchloride (polymkeric substance), 0.2mg tetraphenylboron sodium (the large molecule of lipophilicity) and 1.8mg 10 is taken, two [(octadecylamino formoxyl) Methoxyacetyl]-1 of 19-, 4,7,13,16-five oxa--10,19-diazacyclo heneicosane (Calcium ionophore), be dissolved in 1.2mL organic solvent tetrahydrofuran, then instill 65 μ L dioctyl adipates (plastifier), fully mix;
(5) get appropriate functional ionic liquid liquid solution, drop in clean electrode basement surface, afterwards electrode is placed on room temperature and is evaporated completely down to solvent acetone, obtained solid ionic layer;
(6) get appropriate calcium ion sensitive membrane solution, drop in functional ion liquid layer surface, afterwards electrode is placed on room temperature and is evaporated completely down to solvents tetrahydrofurane, obtained ion sensitive membrane.
The all solid state Calcium signaling of preparation is placed in the solution to be measured containing finite concentration calcium ion, and insert outer contrast electrode (Ag/AgCl, 3.3mol/L KCl solution), measure the electrode potential of ion-selective electrode relative to outer contrast electrode by external equipment.
Fig. 4 is the potential response calibration curve of all solid state Calcium signaling prepared in the present embodiment, its correction equation is EMF (mV)=29.4Ln (C)+397.7, wherein EMF is potential value (mV), C is calcium ion concentration (mol/L), and related coefficient is 0.9927.
The all solid state Calcium signaling prepared in the present embodiment is used for the detection of calcium ion in milk.The calibration curve that Fig. 5 obtains when being calcium ion in all solid state Calcium signaling detection milk, its correction equation is EMF (mV)=29.1Ln (C)+394.5, wherein EMF (mV) is potential value, C is calcium ion concentration (mol/L), and related coefficient is 0.9908.
Above-described embodiment is used for explaining and the present invention is described, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (8)
1. all solid state ion-selective electrode based on functional ion liquid, comprise substrate (4), internal reference electrode (3), solid ionic layer (2) and ion sensitive membrane (1), it is characterized in that: described solid ionic layer (2) is made up of functional ion liquid, the cationic-charge of functional ion liquid has oxidation-reduction quality group, and negative ion is hydrophobic group; Described kation is trimethylaniline ion, N-methyl thiophane ion or 1-ethyl dicyclopentadienyl iron base-3 methylimidazole ion; Described negative ion is hexafluorophosphoricacid acid ions or two fluoroform sulfimide ion.
2. all solid state ion-selective electrode according to claim 1, is characterized in that: described functional ion liquid is room temperature solid ionic liquid.
3. all solid state ion-selective electrode according to claim 1, is characterized in that: described functional ion liquid is trimethylaniline hexafluorophosphate, the two fluoroform sulfimide salt of N-methyl thiophane or 1-ethyl dicyclopentadienyl iron base-3 methylimidazole hexafluorophosphate.
4. all solid state ion-selective electrode according to claim 1, is characterized in that: the thickness of described solid ionic layer (2) is 1 ~ 5 μm.
5. all solid state ion-selective electrode according to claim 4, is characterized in that: the thickness of described solid ionic layer (2) is 3 μm.
6. all solid state ion-selective electrode according to claim 1, is characterized in that: described internal reference electrode is gold electrode, platinum electrode or carbon electrode.
7. all solid state ion-selective electrode according to claim 1, is characterized in that: comprise the contact conductor (5) be connected with internal reference electrode (3).
8. a preparation method for all solid state ion-selective electrode based on functional ion liquid according to claim 1, comprises the following steps:
Substrate arranges internal reference electrode; Dripped by functional ion liquid dissolution homogeneity and be coated in internal reference electrode surface, drying volatilizes solvent, obtained solid ionic layer; Ion-sensitive coating solution is dripped and is coated in solid ionic layer surface, dry obtained ion sensitive membrane; Functional ion liquid is room temperature solid ionic liquid, and cationic-charge has oxidation-reduction quality group, and negative ion is hydrophobic group; Described kation is trimethylaniline ion, N-methyl thiophane ion or 1-ethyl dicyclopentadienyl iron base-3 methylimidazole ion; Described negative ion is hexafluorophosphoricacid acid ions or two fluoroform sulfimide ion.
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| JP6312396B2 (en) * | 2013-09-30 | 2018-04-18 | 株式会社日立ハイテクノロジーズ | Ion selective electrode |
| CN106198664B (en) * | 2015-05-06 | 2019-06-25 | 中国科学院烟台海岸带研究所 | A kind of solid polymer membrane ion selective electrode based on alkane functionalized nano material |
| CN104849335A (en) * | 2015-05-29 | 2015-08-19 | 李宏奎 | Method for detecting ionic calcium content of blood sample |
| CN105784805B (en) * | 2016-03-03 | 2018-10-26 | 苏州意维思自动化科技有限公司 | Chlorion selectivity solid state electrode based on graphene and preparation method and application |
| CN107449816B (en) * | 2016-05-30 | 2019-09-13 | 中国科学院化学研究所 | All solid state ion selective electrode, preparation method and biosensor |
| CN110865111A (en) * | 2019-12-25 | 2020-03-06 | 广州商辉仪业智能科技股份有限公司 | Ion selective electrode |
| CN111349047B (en) * | 2020-03-03 | 2022-06-14 | 扬州大学 | Carbon paste ion selective electrode and preparation method and application thereof |
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| CN101013766A (en) * | 2007-02-26 | 2007-08-08 | 清华大学 | Quasi solid state electrolyte and its preparing process and use |
| CN101852761A (en) * | 2010-05-18 | 2010-10-06 | 浙江大学 | All-solid sodium ion selective electrode and preparation method thereof |
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| CN101013766A (en) * | 2007-02-26 | 2007-08-08 | 清华大学 | Quasi solid state electrolyte and its preparing process and use |
| CN101852761A (en) * | 2010-05-18 | 2010-10-06 | 浙江大学 | All-solid sodium ion selective electrode and preparation method thereof |
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