CN105424778A - Novel PVC film pH electrode optimization method based on tri-n-dodecylamine - Google Patents
Novel PVC film pH electrode optimization method based on tri-n-dodecylamine Download PDFInfo
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- CN105424778A CN105424778A CN201510744172.4A CN201510744172A CN105424778A CN 105424778 A CN105424778 A CN 105424778A CN 201510744172 A CN201510744172 A CN 201510744172A CN 105424778 A CN105424778 A CN 105424778A
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- pvc film
- dodecylamine
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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
Abstract
The invention discloses a novel PVC film pH electrode optimization method based on tri-n-dodecylamine. A novel pH electrode comprises solid electrolyte PEDOT serving as a transitional layer and an ion-sensitive PVC film. The film thickness of solid electrolyte PEDOT and electropolymerization potential are optimized, and the formula and the film thickness of the ion-sensitive PVC film are optimized. Compared with existing pH electrodes based on tri-n-dodecylamine, the novel pH electrode is greatly improved in the aspects of response time, stability and the like and is applicable to continuous detection.
Description
Technical field
The present invention relates to pH electrode, specifically a kind of PVC film based on three n-dodecylamines novel pH electrode optimization method.
Background technology
PH value detects with the field such as industry, agricultural, medical science, environment, scientific research closely related, and the research of novel pH sensor has also become the focus of current research.
Based on the hydrogen ion carrier all solid-state electrode of Polyvinylchloride (PVC) matrix, owing to preparing easily, being easy to microminiaturization, the life-span is long, compared with the glass electrode not feature such as cracky and resistance to HF erosion, its research enjoys domestic and international concern.
Various based on PVC film all-solid-state pH type of electrodes, conductive substrates, solid-state electrolyte layer, pH sensitive membrane three part can be divided into from functional structure.Along with the discovery of new material apply, the synthesis of new chemical reagent, and the research of new preparation process, as screen printing technique, more enrich new-type PVC film pH electrode family, and electrode performance has also had qualitative leap more in early days, but all solid state ion selection type electrode is still incomplete, has that such as sensitivity is low, potential stability is not good, a comparatively outstanding defect such as the response time is long, still be difficult to the critical conditions requirement adapting to on-line checkingi, clinical analysis, thus apply limited.
Summary of the invention
In order to solve the above-mentioned technical matters that prior art exists, the invention provides a kind of novel pH electrode optimization method based on three n-dodecylamine PVC film, described novel pH electrode comprises solid electrolyte PEDOT as transition bed and ion-sensitive PVC film, comprise and the thickness of solid electrolyte PEDOT and electropolymerization current potential are optimized, and ion-sensitive PVC film formula and thickness are optimized.
Further, the thickness of described solid electrolyte PEDOT adopts formula (1) to estimate:
（1）
In formula: L is thickness (cm), the electricity (C/cm2) that q consumes for unit area, x is anion doped coefficient, M
eDOT, M
abe respectively EDOT and Doped anions weight-average molecular weight (g/mol), F is Faraday constant (C/mol), d is density polymer (g/cm3).
Further, adopt 1.0V to be polymerized current potential, 2.400e-002 ~ 2.600e-002C is polymerized electricity electropolymerization.
Further, described ion-sensitive PVC film formula is 1.0% 3 n-dodecylamine, 0.5%KTpClPB, 65.5%DOS, 33.0%PVC.
Further, get 5mg purity be 99.7% KTPclPB powder dissolution be in the tetrahydrofuran solution of 97% to 1ml massfraction, be configured to the KTpClPB solution of 5mg/ml; The DOS dissolution homogeneity that the above-mentioned KTpClPB solution getting 100uL and the massfraction of 72uL are 99.7% mixes; Get 33mg purity be 99.7% PVC powder be directly dissolved into above-mentioned mixed solution, then to add 500ul massfraction be in the tetrahydrofuran solution of 97%, vibration; The most backward mixed solution adds the Tridodecylamine solution that 1ul massfraction is 98%, leave standstill 3 hours after using magnetic stirring apparatus fully to be vibrated by mixed solution, make it to mix, stable after for subsequent use as mother liquor; A certain amount of PVC film liquid of spot printing on solid electrolyte PEDOT, forms the film that one deck is about 3mm*3mm area, pole effect time and stabilizing effect the best when mother liquor consumption is 3uL ~ 4uL.
PH electrode optimization method based on neutral grain carrier three n-dodecane amine (tridodecylamine) of the present invention, take screen-printed carbon electrodes as substrate, electropolymerization method is adopted to prepare solid-state conductive polymer P EDOT (PSS) layer as solid electrolyte, inquire into polymerization current potential, electricity to the affecting laws of response time, stability, optimized fabrication has the technological parameter of the PEDOT film of either high redox electric capacity; Manually drip and be coated with containing neutral grain hydrogen ion carrier, using Polyvinylchloride as the sensitive membrane of supporter, prepare all solid state plate pH electrode, and by lot of experiments responsive thickness, electrode performance is affected, experimental study shows, the pH electrode of electrode of the present invention more in the past based on three n-dodecylamines in response time and stability etc. has larger improvement, is adapted to the application of continuous detecting.
Accompanying drawing explanation
Fig. 1 is electrode structure schematic diagram of the present invention;
Fig. 2 is the cyclic voltammetry curve figure of carbon paste electrode in EDOT/PSS mixed aqueous solution;
Fig. 3 is the pH-Electric Potential graph of relation of 5 pH electrodes in target detection solution of spot printing 3 ~ 4uLPVC film liquid.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
As shown in Figure 1, novel pH electrode optimization method based on three n-dodecylamine PVC film of the present invention, by improving thickness and the electropolymerization current potential of solid electrolyte PEDOT, and the formula of ion-sensitive PVC film and thickness, (response time and stability are as final test rating in stability and response time to make PH electrode, both is relative relation, general stability is better, response time is longer, so by technologic innovation and improvement, make both reach optimum under experimental conditions) on promote to some extent.Experimental study shows, the pH electrode of this PH electrode more in the past based on three n-dodecylamines in response time and stability etc. has larger improvement, is adapted to the application of continuous detecting.
1. improve thickness and the electropolymerization current potential of solid electrolyte PEDOT.
PEDOT, as the transition bed between ion sensitive membrane and electrode basement, can overcome that conventional liquid Inner electrolysis matter cannot be inverted, the shortcoming of non-refractory high pressure, and to O
2and CO
2(pH) compared with the insensitive good characteristic of PPy, the stability of current potential is conducive to.In addition, suitable electric capacity is also a key factor of ion selection type electrode stability, by experiment method obtain higher redox electric capacity with reduce solid-state in fill electrolytical polarizability, overcome the heterogeneity of transfer process from sub-– – electronic conduction and the electromagnetic interference (EMI) of outside.
The thickness of PEDOT can adopt formula (1) to estimate:
（1）
(1), in formula: L is thickness (cm), the electricity (C/cm2) that q consumes for unit area, x is anion doped coefficient, M
eDOT, M
abe respectively EDOT and Doped anions weight-average molecular weight (g/mol), F is Faraday constant (C/mol), d is density polymer (g/cm3).
Can find out that PEDOT film electropolymerization affects by polymeric monomer concentration, supporting electrolyte kind, polymerization electricity from formula (1), also relevant to polymerization current potential in addition.The size of polymerization current potential determines solid electrolyte structural form, and polymerization current potential affects the surface topography of solid electrolyte film, and along with the rising of polymerization current potential, film becomes coarse gradually; Polymerization electricity decides solid electrolyte thickness, and the blocked up meeting of solid electrolyte membrane causes certain retardation to electron transmission, thus affects response time and potential stability.
The present invention adopts constant potential to be polymerized PEDOT (PSS) film, when polymerization current potential is greater than 0.78V, could at base electrode Surface Creation sky blue thin polymer film, also can according to cyclic voltammetry curve figure, as shown in Figure 2, about 0.8V starts polymerization reaction take place.
Electropolymerization process of optimization is as follows: design polymerization current potential 0.9V, 1.0V, 1.1V, 1.2V, 1.3V, and the reaction time controls as 400s, and gained film respectively label is a, b, c, d, e; After selected the best polymerization current potential, controlling electricity range intervals is 2.000e-002 ~ 2.200e-002C, 2.200e-002 ~ 2.400e-002C, 2.400e-002 ~ 2.600e-002C, 2.600e-002 ~ 2.800e-002C, 2.800e-002 ~ 3.000e-002C, prepares film and is labeled as A
i, B
i, C
i, D
i, E
i(i=1,2,3,4,5), clean in deionized water to remove residual monomer and electrolyte, are transferred to 0.1mol/LNaNO after drying in moisture-resistant cabinet
3in solution, three-electrode method is adopted to carry out electric conductivity test.
The results show: PEDOT (PSS) film that control 1.0V is polymerized current potential, prepared by 2.400e-002 ~ 2.600e-002C polymerization electricity has larger redox electric capacity, and response speed, potential stability improve.
2. improve ion-sensitive PVC film formula and optimize thickness
Ion-sensitive PVC film is the most crucial part of ion-selective electrode, and the principal element affecting the responding ability of ion-selective electrode sensitive membrane has the matrix of sensitive membrane, film formulation, the preparation technology of film and the size etc. of film.Wherein, film size especially film thickness, determine the mechanical property of film, response time and membrane impedance, and to find a suitable film thickness be also determine ion detection lower limit, the key factor of response time, also need binding film component feature and the requirement of target detection ion in addition.
New film formulation, experimental result shows: the responsive film formulation (wt%) of PVC hydrogen ion: 1.0% 3 n-dodecylamine, 0.5%KTpClPB, 65.5%DOS, 33.0%PVC, the optimal stability of this film formulation.Configuration experiment mother liquor used process: get 5mg purity be 99.7% KTPclPB powder dissolution be in the tetrahydrofuran solution of 97% to 1ml massfraction, be configured to the KTpClPB solution of 5mg/ml; The DOS dissolution homogeneity that the above-mentioned KTpClPB solution getting 100uL and the massfraction of 72uL are 99.7% mixes; Get 33mg purity be 99.7% PVC powder be directly dissolved into above-mentioned mixed solution, then to add 500ul massfraction be in the tetrahydrofuran solution of 97%, vibration; The most backward mixed solution adds the Tridodecylamine solution that 1ul massfraction is 98%, leave standstill 3 hours after using magnetic stirring apparatus fully to be vibrated by mixed solution, make it to mix, stable after for subsequent use as mother liquor.
A certain amount of PVC film liquid of spot printing on solid electrolyte film, form the film that one deck is about 3mm*3mm area, for probing into sensitive membrane thickness, electrode performance is affected, controlling PVC film liquid consumption is respectively 3uL, 4uL, 5uL, 6uL, at room temperature 25 DEG C, in self-control variable concentrations standard pH buffer solutions, measure the electromotive force of all-solid-state pH electrode relative to standard A g/AgCl contrast electrode.Experimental study shows, as shown in Figure 3: pole effect time and stabilizing effect the best when control PVC film liquid consumption is 3uL ~ 4uL.
Claims (5)
1. the novel pH electrode optimization method based on three n-dodecylamine PVC film, described novel pH electrode comprises solid electrolyte PEDOT as transition bed and ion-sensitive PVC film, it is characterized in that: comprise and the thickness of solid electrolyte PEDOT and electropolymerization current potential are optimized, and ion-sensitive PVC film formula and thickness are optimized.
2. as claimed in claim 1 based on the novel pH electrode optimization method of three n-dodecylamine PVC film, it is characterized in that: the thickness of described solid electrolyte PEDOT adopts formula (1) to estimate:
（1）
In formula: L is thickness (cm), the electricity (C/cm2) that q consumes for unit area, x is anion doped coefficient, M
eDOT, M
abe respectively EDOT and Doped anions weight-average molecular weight (g/mol), F is Faraday constant (C/mol), d is density polymer (g/cm3).
3. as claimed in claim 2 based on the novel pH electrode optimization method of three n-dodecylamine PVC film, it is characterized in that: adopt 1.0V to be polymerized current potential, 2.400e-002 ~ 2.600e-002C is polymerized electricity electropolymerization.
4., as claimed in claim 1 based on the novel pH electrode optimization method of three n-dodecylamine PVC film, it is characterized in that: described ion-sensitive PVC film formula is 1.0% 3 n-dodecylamine, 0.5%KTpClPB, 65.5%DOS, 33.0%PVC.
5. as claimed in claim 4 based on the novel pH electrode optimization method of three n-dodecylamine PVC film, it is characterized in that: get 5mg purity be 99.7% KTPclPB powder dissolution be in the tetrahydrofuran solution of 97% to 1ml massfraction, be configured to the KTpClPB solution of 5mg/ml; The DOS dissolution homogeneity that the above-mentioned KTpClPB solution getting 100uL and the massfraction of 72uL are 99.7% mixes; Get 33mg purity be 99.7% PVC powder be directly dissolved into above-mentioned mixed solution, then to add 500ul massfraction be in the tetrahydrofuran solution of 97%, vibration; The most backward mixed solution adds the Tridodecylamine solution that 1ul massfraction is 98%, leave standstill 3 hours after using magnetic stirring apparatus fully to be vibrated by mixed solution, make it to mix, stable after for subsequent use as mother liquor; A certain amount of PVC film liquid of spot printing on solid electrolyte PEDOT, forms the film that one deck is about 3mm*3mm area, pole effect time and stabilizing effect the best when mother liquor consumption is 3uL ~ 4uL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109991293A (en) * | 2019-04-17 | 2019-07-09 | 中国科学院海洋研究所 | A kind of high flexible all-solid-state pH electrodes selective and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102914582A (en) * | 2012-10-11 | 2013-02-06 | 山东大学 | Voltammetric sensor plated with conductive polymer nanometer film and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102914582A (en) * | 2012-10-11 | 2013-02-06 | 山东大学 | Voltammetric sensor plated with conductive polymer nanometer film and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| HUI XU 等: "An all-solid-state screen-printed carbon paste reference electrode based on poly(3,4-ethylenedioxythiophene) as solid contact transducer", 《MEASUREMENT SCIENCE AND TECHNOLOGY》 * |
| N. ZINE 等: "All-solid-state hydrogen sensing microelectrodes based on novel PPy[3,3’-Co(1,2-C2B9H11)2] as a solid internal contact", 《MATERIALS SCIENCE & ENGINEERING C》 * |
| S. PATRA 等: "Scanning electron microscopy studies of PEDOT prepared by various electrochemical routes", 《SYNTHETIC METALS》 * |
| X.DU 等: "Effects of polymerization potential on the properties of electrosynthesized PEDOT films", 《ELECTROCHIMICA ACTA》 * |
| 陶益杰 等: "电致变色导电聚合物PEDOT的研究进展", 《材料导报：综述篇》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109991293A (en) * | 2019-04-17 | 2019-07-09 | 中国科学院海洋研究所 | A kind of high flexible all-solid-state pH electrodes selective and preparation method thereof |
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