CN109406603A - A kind of highly selective cadmium ion selection electrode and preparation method thereof - Google Patents
A kind of highly selective cadmium ion selection electrode and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of highly selective cadmium ion selection electrodes and preparation method thereof, it is the lower end that pvc pipe is sticked at by cadmium ion selection electrode sensitive film, is filled with 10 in pvc pipe‑3 mol·L‑1Cadmium standard solution, insertion Ag/AgCl electrode cover electrode cap as internal reference electrode, draw lead, and highly selective cadmium ion selection electrode is made.Cadmium ion imprinted polymer micro-nano ball and polyvinyl chloride, dibutyl phthalate, tetraphenylboron sodium, are dissolved in appropriate tetrahydrofuran, and above-mentioned solution is poured into naturally dry on sheet glass, obtain cadmium ion selective sensitivity film.Core-shell type cadmium ion imprinted polymer micro-nano ball is applied in the analytical technology of ion-selective electrode (ISE) by the present invention for the first time, the function of ion-selective electrode is further enhanced and perfect, performance further increases, it is sensitiveer, reliable, the ion-selective electrode of preparation has that highly selective, long service life, probe response be fast, high sensitivity, can quick and precisely detect the cadmium ion in solution.
Description
Technical field
The invention belongs to analyze a kind of electrode used in measurement field, it is related to a kind of detection cadmium ion electrode used therein, specifically
Be related to it is a kind of for detect cadmium ion with highly selective cadmium ion selection electrode and preparation method thereof.
Technical background
Cadmium is exceeded to generate injury to human body, and cadmium can pollute the environment, therefore have to the quantitative detection of cadmium ion
Significance.Copper diethlydithiocarbamate is the major class in chemical sensor, also known as ionophore type sensor, as ion selects
Electrode.Ion selective electrode is the electrochemical sensing for changing according to ion-selective membrane current potential with effects of ion concentration and establishing
Device.The framework material of Copper diethlydithiocarbamate sensing membrane is PVC, and the selectivity of sensing membrane relies on active constituent therein such as ion
The selective enumeration method to object ion is realized in the interaction of carrier or sensibility molecular receptor and object.Selectivity is electrode
One important indicator of performance.Ionic imprinting technique is a kind of for having the work of specific recognition and combination to object ion
With, and the technology of preparing of the polymer with particular space structure hole, ion imprinted polymer have very template ion
Strong specificity uses ion imprinted polymer that will greatly improve the selectivity of electrode as carrier.Surface ion engram technology
A kind of novel ionic imprinting technique, it by by the design of ion identification site in carrier surface or close to the place on surface,
To improve the effect of mass transmitting between recognition site and object ion, be conducive to the elution of template ion and in conjunction with effectively
Ground avoids various drawbacks that conventional method prepares ion imprinted polymer.The measurement of electric potential type ion blotting sensor be with from
Sub- imprinted polymer is detected one kind electricity of electrode potential variation after test analyte by sensitive membrane as sensitive membrane made from carrier
The characteristics of chemical sensor, this kind of sensor, is that the template molecule being added when preparing molecular engram film does not need to remove, while to
The size that survey analyte does not need to spread and pass through molecular engram film therefore test analyte yet is unrestricted.Murray G M etc.
Realize the development of electric potential type molecular engram sensor at first, Murray G M, Jenkins A L, Bzhel yonsk Y A,
et al.Molecularly imprinted polymers for the selective sequestering and
Sensing of [J] .JHopkins APL Tech D, 1997,1:464-472., they are prepared for a series of trace polymerization
Object, and it is prepared for corresponding ion selective electrode, using Potentiometric Determination lead ion, which has very lead ion
The logarithm of strong selective potential response and activity has good linear relationship.Murray G M etc. prepares imprinted polymer
For method using bulk polymerization, obtained in this way is bulk polymer, is polymerize after ground, screening process
Composition granule.Although this preparation method is simple, there are the deficiencies such as product shape is irregular, imprinting efficiency is low.
Summary of the invention
The purpose of the present invention is to solve existing bulk polymerizations, and blocky imprinted polymer, product shape is prepared
Shape is irregular, polymer obtained, just obtain polymer beads after ground, screening process, and imprinting efficiency is low etc. asks
Topic, a kind of highly selective cadmium ion selection electrode provided and preparation method thereof.
The technical solution adopted by the invention is as follows:
1, a kind of highly selective cadmium ion selects electrode, comprising:
Cadmium ion selects electrode sensitive film, it sticks at the lower end of pvc pipe, is filled with 10 in pvc pipe-3 mol·L-1Cadmium standard solution,
Be inserted into Ag/AgCl electrode and be used as internal reference electrode, cover electrode cap, draw lead, be made described in a kind of highly selective cadmium from
Son selection electrode.
2, a kind of preparation method of highly selective cadmium ion selection electrode, comprising the following steps:
1) cadmium ion selection electrode sensitive film is prepared:
A, prepared by carrier
Synthetic polystyrene micro-nano ball first is as bulb, then synthesizes poly- using polystyrene micro-nano ball as core ion, trace
The cadmium ion imprinted polymer micro-nano ball that object is shell mechanism is closed, as carrier；
The synthesis of polystyrene micro-nano ball: 10 mL of styrene monomer and 90 mL of distilled water is measured, detergent alkylate sulphur is weighed
Sour sodium 0.35g is mixed with the former to be added in 250mL flask, then mixed liquor ultrasonic disperse 0.5h at room temperature will be dissolved into
90 g ammonium persulfates in 40mL distilled water are added in flask, are passed through nitrogen 30min sealing, protect in a nitrogen environment, open
Electromagnetic agitation, 70 DEG C of water bath with thermostatic control are reacted 24 hours, are obtained white polystyrene micro-nano ball lotion, will be gathered with filter
The filtering cleaning of styrene micro-nano ball, then cleaned with ethyl alcohol, washed polystyrene micro-nano ball is put into vacuum oven room temperature
Dry 48h；
The synthesis of cadmium ion imprinted polymer micro-nano ball: the selection of function monomer, oxime are the compounds containing C=NOH, as
Metal ion chelation agent is widely used in experimental study and industrial production, selects to be easy the benzoin oxime of purchase to be function list
Body, by 0.5 mmol cadmium nitrate, 6 mmol methacrylic acids, 1 mmol benzoin oxime is dissolved in 5 mL methanol, is added one
Quantitative crosslinking agent methacrylate, suitable initiator azodiisobutyronitrile and enter 0.98 g phthalic acid, two fourth
50 mL of 0.1% lauryl sodium sulfate and 1.0% polyvinyl alcohol liquid is added after dissolving under the conditions of magnetic agitation in ester,
0.125 g polystyrene micro-nano ball is added after magnetic agitation dissolution, it is molten with constant rate of speed magnetic agitation at room temperature
Swollen 24 h is sealed after then passing to 30 min of nitrogen, is placed in heat collecting type constant-temperature heating magnetic stirring apparatus under nitrogen protection,
It is stirred in 65 DEG C of constant temperature constant speed, product is centrifugated by 24 h of thermal-initiated polymerization, and the core-shell type cadmium ion for obtaining white is poly-
Close object micro-nano ball；Obtained core-shell type cadmium ion polymer micro-nanometer ball is placed in Soxhlet extractor with methanol/acetic acid
The solution of (V/V=9:1) extracts, eluted template molecule, is up to can't detect Cd (II) with ultraviolet spectra in reflux solution
Only, then again with methanol repeated washing for several times, to remove remaining acetic acid, is finally putting into drying in vacuum oven, obtains
Cadmium ion imprinted polymer micro-nano ball；
B, by the obtained carrier cadmium ion imprinted polymer micro-nano ball of step a and polyvinyl chloride, dibutyl phthalate,
Tetraphenylboron sodium is in mass ratio 1:(30~60): (40~80): after (1~5) mixing, it is dissolved in appropriate tetrahydrofuran, interval
Ultrasonic disperse, above-mentioned solution, which is poured into viscous diameter on the glass sheet, is in the glass ring of 80mm, at room temperature naturally dry for 24 hours,
Obtain cadmium ion selective sensitivity film.
2) a kind of, preparation of highly selective cadmium ion selection electrode
Using mass percent is the THF(tetrahydrofuran of 5% PVC powder) solution is as adhesive, by cadmium ion selective sensitivity film
The lower end for sticking at pvc pipe, after drying, insertion Ag/AgCl electrode is molten with the cadmium nitrate of certain molar concentration as internal reference electrode
Liquid is made as internal-filling liquid, the upper end cover top electrode end cap of pvc pipe, extraction wire and selects electricity with highly selective cadmium ion
Pole.Electrode performance is tested so as to lower electrochemical cell.
Hg-Hg2Cl2/ KCl (satd.) ︱ test fluid ︱ PVC film ︱ 0.001molL-1Cd2+0.01lmolL-1KCl/AgCl-Ag
Electrode is using preceding in the 1.0 × 10 of pH=7.O-3mol·L-1Cd2+It is impregnated 24 hours in solution.
The present invention and traditional ion selective electrode rely on ionophore realization and examine to the selective enumeration method of object ion
Survey is compared, and ion imprinted polymer has very strong specificity to template ion identification, uses ion imprinted polymer as load
Body will greatly improve the selectivity of electrode.It is obtained poly- that blocky imprinted polymer this method is prepared in bulk polymerization
Closing object can generate that accessibility is poor, dynamics identification is slow, template ion is not easy the disadvantages of thoroughly removing, and surface imprinted due to printing
Mark site on the surface of the material, can solve these problems to a certain extent.The polymer micro-nanometer of nucleocapsid structure or shell mechanism
Ball is established binding site is unified in shell structurre, the binding site of polymer surfaces be conducive to template molecule elution and
Diffusion.Core-shell type cadmium ion polymer micro-nanometer ball good dispersion, particle diameter distribution made from seeds swelling suspension polymerization are equal
It is even.It will be core ion imprinted polymer as the cadmium ion imprinted polymer micro-nano ball of shell mechanism using polystyrene micro-nano ball
It is applied to cadmium ion selection electrode preparation for the first time.The electrode is used to detect cadmium ion, and measurement quickly, accurately, can be used for Industry Waste
The fields such as water, biomedicine and food carry out qualitative and quantitative detection.
Detailed description of the invention:
Fig. 1 is cadmium ion selective sensitivity film composed structure and electrode operation principle schematic diagram of the invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the imprinted polymer micro-nano ball in the present invention；
Fig. 3 is the infrared spectrogram of different polymer, in which: imprinted polymer (b) is washed after blank imprinted polymer (a) elution
Imprinted polymer (c) before de-；
The infrared spectroscopy of imprinted polymer (b), the preceding imprinted polymer (c) of elution after giving blank imprinted polymer (a), eluting
Figure.As seen from the figure, in 1455 cm-1With 1385 cm-1The absorption peak being formed about is-C in benzoin oxime=N stretching vibration
Absorption peak; 1160 cm-1It is nearby the N-O stretching vibration absworption peak of benzoin oxime.Curve a, b are in 1385 cm-1Nearby have
It absorbs, and absorption intensity is similar;Curve c is in 1385 cm-1Nearby also there is absorption, but absorption intensity obviously becomes larger, because not
The presence of cadmium ion changes the dipole moment of benzoin oxime in imprinted polymer through eluting, and dipole moment is made to become larger, absorption peak
Intensity becomes larger.This variation illustrates Cd2+Interaction is produced between ion and benzoin oxime, in addition, by curve a and b
Known to, the infrared spectroscopy feature of imprinted polymer and blank imprinted polymer after elution is almost the same, after illustrating elution
Template Cd in imprinted polymer2+Ion is eluted, and leaves the void structure to match with its functional group；
Fig. 4 is electrode to this special response curve of the energy of cadmium ion；
Fig. 5 is influence diagram of the pH value of solution to electrode.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples
Agents useful for same of the present invention is that analysis is pure, and configuration solution is all made of secondary distilled water；Polyvinyl chloride (PVC), average polymerization
Degree 700 ± 50, Dajie Chemical Co., Ltd., Tianjin；Dibutyl phthalate, styrene, the limited public affairs of Aladdin share
Department；Neopelex, ammonium persulfate, benzoin oxime, lauryl sodium sulfate, methacrylate, two isobutyl of azo
Nitrile, methacrylic acid, Sinopharm Chemical Reagent Co., Ltd.；Tetraphenylboron sodium, Brassica rapa L analyse Chemical Industry Science Co., Ltd；Tetrahydro
Furans, Wuxi City Ya Sheng chemical industry Chemical Co., Ltd.；Cadmium nitrate, chemical reagent work, HeFei University of Technology；Acetone, HeFei University of Technology's examination
Agent factory；PHS -2C digital ph, Hangzhou Dong Xing Instrument Ltd.；218 type Ag/AgCl electrodes, Shanghai precision scientific instrument
Co., Ltd；217 type biliquids meet saturated calomel electrode calomel electrode, Shanghai Lei Ci instrument plant；Mechanical stopwatch, upper starfish bore stopwatch
Co., Ltd；JB-EA type blender, Shanghai Precision Scientific Apparatus Co., Ltd；FA1604N type electronic balance, Shanghai precision section
Learn Instrument Ltd..
The preparation of cadmium nitrate standard solution:
It weighs 2.364g cadmium nitrate to be placed in a beaker, spends secondary distilled water dissolution, be transferred in 100mL volumetric flask, add secondary
Distilled water constant volume matches to obtain 0.100molL-1Cadmium nitrate standard solution.The preparation of remaining concentration is prepared using dilution method step by step.
Such as pipette 0.100 molL of 10mL-1Cadmium nitrate standard solution adds secondary distilled water constant volume, shakes up in 100mL volumetric flask,
With 0.01 molL-1Cadmium nitrate standard solution.Step by step dilution can with solution to 10-7mol·L-1。
Specific embodiments of the present invention are as follows:
One, the preparation of electrode selective sensitivity film:
Sequentially add 0.007g tetraphenylboron sodium, 0.06g cadmium ion imprinted polymer micro-nano ball, 5mL tetrahydrofuran, 0.2mL neighbour
Above-mentioned solution is poured into viscous diameter on the glass sheet by dibatyl phithalate, 0.2g polyvinyl chloride powder, interval ultrasound 10min
For in the glass ring of 80mm, naturally dry for 24 hours, obtains flexible and flexible cadmium ion selective sensitivity film at room temperature.
Two, the assembly of electrode
Use the polyvinyl chloride powder tetrahydrofuran solution that mass percent is 5% as adhesive, by film obtained, sticking at diameter is
The lower end of the pvc pipe of 16mm, is firmly bonded and dries, and is filled with 10-3 mol·L-1Cadmium standard liquid is inserted into Ag/AgCl electrode as internal reference
Than electrode, electrode cap is covered, draws lead, electrode is made.10 are used before electrode use-3 mol·L-1Cadmium standard liquid activation for 24 hours it
Afterwards, until being washed to potential value stabilization with second distillation.
Three, the performance test with highly selective cadmium ion selection electrode
Measuring has the electricity such as highly selective response curve, response time, the PH scope of application, the selectivity of cadmium ion selection electrode
Pole performance parameter.
The measurement of 1 electrode potential of test case
The measurement of current potential uses PHS -2C type pH meter.Outer reference electrode is that 217 type biliquids connect saturated calomel electrode.
Electrode performance is tested so as to lower electrochemical cell.
Hg-Hg2Cl2/ KCl (satd.) ︱ test fluid ︱ PVC film ︱ 0.01molL-1Cd2+0.01lmolL-1KCl/AgCl-Ag
Specific measuring method: solution to be measured uses concentration for 10-1~10-7Cadmium standard solution.Measure the certain density cadmium of 30mL
Standard solution is connected in 50mL beaker, by membrane electrode and outer reference electrode with pH meter, and pH meter is adjusted to mV grades, by concentration from low
To high assay.Constant agitation speed when measurement.
Fig. 4 provides electrode to this special response curve of the energy of cadmium ion, the range of linearity 10 of electrode work-1~10-5. mol·
L-1, y=- 25.9x+182.3, R2=0.9998。
The range of linearity, slope, detection limit, response time, the service life parameter of 1 electrode of table
Influence of 2 pH value of solution of test case to electrode
When investigating the influence of pH value of solution, HNO is used3PH value of solution is adjusted with NaoH.Fig. 5 give electrode response current potential and 1.0 ×
10-3mol·L-1Cadmium-ion solution pH relational graph.As seen from Figure 5, within the scope of the pH of investigation, different PH test is molten
Influence of the liquid to cadmium ion selection electrode performance, when the pH value of test solution is in 3.5~8 ranges, the response of electrode is basic
It remains unchanged, the electrode pH scope of application 3.5~8.
The test of 3 interference coefficient of test case
Fixation interfering ion concentration method in the mixed solution method being recommended to use using IUPAC selects coefficient to measure electrode, Gu
Determining interfering ion concentration is 10-2 mol·L-1Change concentration of cadmium ions, measures the interference coefficient of part ion, the results are shown in Table 2.
The selection coefficient of the various interfering ions of table 2
| Interfering ion | Na+ | Ca2+ | Cu2+ | Fe3+ | Hg2+ | Ag+ | Ni2+ |
| Select coefficient | 4.61×10-3 | 5.21×10-4 | 7.32×10-3 | 7.19×10-3 | 3.18×10-2 | 2.49×10-3 | 2.34×10-2 |
Table 2 the result shows that, the selection coefficient of all interfering ions is much smaller than 1 in table, illustrate the cadmium ion selection electrode to cadmium
Ion has very high selectivity.
4 reproducibility of test case
Electrode, under room temperature (25 DEG C), continuous 20 duplicate measurements 1.0 × 10 are selected with same branch cadmium ion-3mol·L-1
Cadmium-ion solution potential value, every time measurement after use secondary distilled water cleaning electrode, as a result standard deviation be 0.3V.
Only the present invention will be described for above-mentioned test case, and is not construed as limiting the scope of claims limitation, art technology
Personnel can other conceivable substantial equivalence means, within the scope of the invention as claimed.
Claims (2)
1. a kind of highly selective cadmium ion selects electrode, characterized by comprising:
Cadmium ion selects electrode sensitive film, it sticks at the lower end of pvc pipe, is filled with 10 in pvc pipe-3 mol·L-1Cadmium standard solution,
Be inserted into Ag/AgCl electrode and be used as internal reference electrode, cover electrode cap, draw lead, be made described in a kind of highly selective cadmium from
Son selection electrode.
2. a kind of preparation method of highly selective cadmium ion selection electrode as claimed in claim 1, comprising the following steps:
1) cadmium ion selection electrode sensitive film is prepared:
A, prepared by carrier
Synthetic polystyrene micro-nano ball first is as bulb, then synthesizes poly- using polystyrene micro-nano ball as core ion, trace
The cadmium ion imprinted polymer micro-nano ball that object is shell mechanism is closed, as carrier；
The synthesis of polystyrene micro-nano ball: 10 mL of styrene monomer and 90 mL of distilled water is measured, detergent alkylate sulphur is weighed
Sour sodium 0.35g is mixed with the former to be added in 250mL flask, then mixed liquor ultrasonic disperse 0.5h at room temperature will be dissolved into
90 g ammonium persulfates in 40mL distilled water are added in flask, are passed through nitrogen 30min sealing, protect in a nitrogen environment, open
Electromagnetic agitation, 70 DEG C of water bath with thermostatic control are reacted 24 hours, are obtained white polystyrene micro-nano ball lotion, will be gathered with filter
The filtering cleaning of styrene micro-nano ball, then cleaned with ethyl alcohol, washed polystyrene micro-nano ball is put into vacuum oven room temperature
Dry 48h；
The synthesis of cadmium ion imprinted polymer micro-nano ball: by 0.5 mmol cadmium nitrate, 6 mmol methacrylic acids, 1 mmol
Benzoin oxime is dissolved in 5 mL methanol, and it is different that a certain amount of crosslinking agent methacrylate, suitable initiator azo two is added
Butyronitrile and enter 0.98 g dibutyl phthalate, 0.1% dodecyl sulphur is added after dissolving under the conditions of magnetic agitation
50 mL of sour sodium and 1.0% polyvinyl alcohol liquid, to add 0.125 g polystyrene micro-nano after magnetic agitation dissolution
Ball is swollen 24 h at room temperature with constant rate of speed magnetic agitation, seals after then passing to 30 min of nitrogen, in nitrogen protection
Under be placed in heat collecting type constant-temperature heating magnetic stirring apparatus, stirred in 65 DEG C of constant temperature constant speed, 24 h of thermal-initiated polymerization, by product
Centrifuge separation obtains the core-shell type cadmium ion polymer micro-nanometer ball of white；Obtained core-shell type cadmium ion polymer is micro-
Nanosphere is placed in Soxhlet extractor with methanol/acetic acid=9:1 solution extracting, eluted template molecule, until in reflux solution
Until can't detect Cd II with ultraviolet spectra, then again with methanol repeated washing for several times, to remove remaining acetic acid, is finally put
Enter drying in vacuum oven, obtains cadmium ion imprinted polymer micro-nano ball；
B, by the obtained carrier cadmium ion imprinted polymer micro-nano ball of step a and polyvinyl chloride, dibutyl phthalate,
Tetraphenylboron sodium is dissolved in appropriate tetrahydrofuran after mixing in mass ratio for 1:30~60:40~80:1~5, interval ultrasound point
It dissipates, above-mentioned solution, which is poured into viscous diameter on the glass sheet, is in the glass ring of 80mm, at room temperature naturally dry for 24 hours, obtains
Cadmium ion selective sensitivity film；
2) a kind of, preparation of highly selective cadmium ion selection electrode
It uses the THF solution that mass percent is 5% PVC powder as adhesive, cadmium ion selective sensitivity film is sticked at into pvc pipe
Lower end after drying, is inserted into Ag/AgCl electrode as internal reference electrode, is filled using the nitric acid cadmium solution of certain molar concentration in
Liquid, the upper end cover top electrode end cap of pvc pipe, extraction wire are made and select electrode with highly selective cadmium ion.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112326759A (en) * | 2020-10-30 | 2021-02-05 | 宁波大学 | Preparation method and application of cadmium ion selective electrode based on MOF material |
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