CN105738435B - A kind of polymer film Copper diethlydithiocarbamate of fluorine ion and its application - Google Patents
A kind of polymer film Copper diethlydithiocarbamate of fluorine ion and its application Download PDFInfo
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- CN105738435B CN105738435B CN201610071438.8A CN201610071438A CN105738435B CN 105738435 B CN105738435 B CN 105738435B CN 201610071438 A CN201610071438 A CN 201610071438A CN 105738435 B CN105738435 B CN 105738435B
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- 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
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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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Abstract
The invention belongs to analysis and testing technology fields, and in particular to a kind of polymer film Copper diethlydithiocarbamate of fluorine ion and its application.Polymer film Copper diethlydithiocarbamate is using tetraphenylphosphonibromide bromide antimony as ionophore, using cation-exchanger as ionic sites.The detection of fluorine ions in water body can be realized using inventive sensor.Inventive sensor is of simple structure and low cost, high sensitivity, has good actual application prospect.
Description
Technical field
The invention belongs to analysis and testing technology fields, and in particular to a kind of polymer film Copper diethlydithiocarbamate of fluorine ion and
It is applied.
Background technology
Fluorine ion is often added to as active ingredient in toothpaste, but excessive fluorine ion can upset the normal life of human body
Reason function causes lesion in turn.On the other hand, fluorine ion is also particular kind of in environment to detect frequently as indicant
Organophosphor poison gas.Thus, the detection of fluorine ion has important physiology and Significance for Environment.Current fluorine ion sensing device makes more
Spectroscopy instrument is used to read means as signal, these methods are easy to be interfered by turbidity and coloration, and apparatus structure is complicated, cost
It is higher, it is unsuitable for quick, Site Detection.Development structure fluorine ion sensing device that is simple, of low cost, being easy to miniaturization is still
One problem.
Polymer film ion-selective electrode is of simple structure and low cost, high sensitivity, be very suitable for it is live quickly point
Analysis.Although a variety of polymer membrane electrodes to cation sensitive have been developed and have been widely used in environmental monitoring, it is cloudy from
The development of sub-electrode is relatively slow.Since fluorine ion has very high aquation energy, fluorine ion is selected using effective ionophore
Selecting property to be extracted into polymer film mutually be the key point of this kind of technology.
Invention content
The purpose of the present invention is to provide a kind of polymer film Copper diethlydithiocarbamate of fluorine ion and its applications.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of polymer film Copper diethlydithiocarbamate of fluorine ion, polymer film Copper diethlydithiocarbamate are with tetraphenylphosphonibromide bromide antimony
For ionophore, using cation-exchanger as ionic sites.
The polymer film Copper diethlydithiocarbamate of the fluorine ion will in tetraphenylphosphonibromide bromide Sb doped to polymer film as from
Subcarrier；The dosage of tetraphenylphosphonibromide bromide antimony accounts for the 0.5%~5% of polymer film weight.
The dosage of the cation-exchanger is the 10%~50% of the amount of tetraphenylphosphonibromide bromide antimony substance.
The polymer film is film matrix, plasticizer and cation-exchanger composition；Film matrix is polyvinyl chloride, poly- ammonia
Ester, silicon rubber, acetate fiber, polyacrylamide or polymethylacrylic acid-dimethylaminoethyl methacrylate；Plasticizer is neighbour
Nitrobenzene octyl ether, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl adipate
Or dioctyl sebacate；Cation-exchanger is four (4- fluorophenyls) Boratexes, four (4- chlorphenyls) Boratexes, four (4- methyl
Phenyl) Boratex, four (4- trifluoromethyls) Boratexes, four (3,5- bis- (trifluoromethyl) phenyl) Boratexes, tetraphenyl boron
Sour sodium or the ionophore I-XI that adds lustre to.
Application of the polymer film Copper diethlydithiocarbamate in environment water detects fluorine ion.
Specific detection process includes the following steps：
(1) it is that reference electrode carries out potentiometric detection using polymer membrane electrode as working electrode, saturated calomel electrode；
(2) potential value (glycine buffer that pH is 3.0) of the fluorine ion of record various concentration on the working electrode (s；
(3) for the electric potential signal generated using various concentration fluorine ion as ordinate, it is bent that a concentration of abscissa draws standard work
Line；
(4) actual sample is tested according to the step of (1)-(3), according to standard working curve calculate sample in fluorine from
The concentration value of son.
Advantage for present invention：
The present invention is ionophore using tetraphenylphosphonibromide bromide antimony and addition cation-exchanger can be real in polymer film
The selective enumeration method of existing fluorine ion；It is simple as the sensor structure of carrier using tetraphenylphosphonibromide bromide antimony of the present invention, it can give birth on a large scale
Production；The sensor selectivity is good, other ions not Interference Detection；And then it is used in environment water to fluorine using inventive sensor
Quick, the highly sensitive detection of ion.Fluoride ion electrode of the present invention needs not rely on complicated instrument and equipment, while electrode fabrication letter
It is single, of low cost, be easy to minimize, be very suitable for field quick detection.
Description of the drawings
Fig. 1 is the potential response figure of fluorine ion provided in an embodiment of the present invention (wherein illustration is calibration curve).
Specific implementation mode
Below in conjunction with embodiment and attached drawing, the invention will be further elaborated.
The present invention is using tetraphenylphosphonibromide bromide antimony as ionophore, using cation-exchanger as ionic sites, can build Gao Xuan
The electric potential type fluorine ion sensing device of selecting property, it can be achieved that fluorine ions in water body highly selective detection.
Embodiment 1
By taking the detection to fluorine ion as an example.Its operating procedure is as follows：
Polymer film Copper diethlydithiocarbamate is electrode basement adherency doping using tetraphenylphosphonibromide bromide antimony as the polymerization of ionophore
Object film；It is using tetraphenylphosphonibromide bromide antimony as ionophore, specific to prepare using cation-exchanger as ionic sites：
Weigh 196mg polyvinyl chloride, 196mg ortho-nitrophenyls octyl ether, 4.0mg tetraphenylphosphonibromide bromides antimony and the (3,5- bis- of 2.5mg tetra-
(trifluoromethyl) phenyl) Boratex is dissolved in 3.0mL tetrahydrofurans, and fixed internal diameter on a glass is poured into after stirring evenly is
In the glass ring of 3.5cm.Wait for tetrahydrofuran volatilization after, using card punch by film be cut into internal diameter be 3mm sequin simultaneously
Bottom is pasted to be cased in the liquid-transfering gun pipette tips of pvc pipe.Using the glycine buffer of pH=3.0 (containing 10mM's in pvc pipe
NaCl it) is used as internal-filling liquid and activating solution activated electrode, for use.
Or doping is adhered to electrode basement by the polymer film of ionophore of tetraphenylphosphonibromide bromide antimony.
The potentiometric detection of fluorine ion：
(1) using it is above-mentioned prepare polymer film Copper diethlydithiocarbamate as working electrode, saturated calomel electrode be reference electricity
Potentiometric detection extremely is carried out to fluorine ion；
(2) potential value (glycine buffer that pH is 3.0) of the fluorine ion of record various concentration on the working electrode (s；
Using the fluorine ion storing solution of sodium fluoride configuration 1M, fluorine ion is added in the glycine buffer for being 3.0 to pH
Storing solution, it is 10 to make the ultimate density of fluorine (including fluorine ion and hydrofluoric acid)-1、10-2、10-3、10-4、10-5、10-6M, record is not
Potential value is generated with concentration fluorine ion.After being corrected to the concentration of fluorine ion, experimental result is shown in Fig. 1, (wherein illustration is correction
Curve).As seen from Figure 1, the electrode response speed is fast, high sensitivity, it can be achieved that fluorine ion quick, highly sensitive detection.
(3) for the electric potential signal generated using various concentration fluorine ion as ordinate, it is bent that a concentration of abscissa draws standard work
Line；
(4) measurement of selectivity factor
It is respectively configured 10 using the pH glycine buffers for being 3.0-1The fluorine ion of M, iodide ion, perchlorate,
Thiocyanate ion, bromide ion, nitrate ion, nitrite ion and Chloride Solution utilize step using separate solution method
Suddenly (1) electrode is measured selectivity factor, and what is measured the results are shown in Table 1.As can be seen from Table 1, inventive sensor selects
Property is good, other ions not Interference Detection.
The selectivity factor table of 1 fluoride ion electrode of table
| Ion | I- | ClO4 - | SCN- | Br- | NO3 - | NO2 - | Cl- |
| Selectivity factor | 0.5 | 0.4 | -0.2 | -1.7 | -2.0 | -2.2 | -2.2 |
Embodiment 2
By taking the detection to fluorine ion as an example.Its operating procedure is as follows：
Polymer film Copper diethlydithiocarbamate is electrode basement adherency doping using tetraphenylphosphonibromide bromide antimony as the polymerization of ionophore
Object film；It is using tetraphenylphosphonibromide bromide antimony as ionophore, specific to prepare using cation-exchanger as ionic sites：
196mg polyvinyl chloride, 196mg dioctyl phthalates, 4.0mg tetraphenylphosphonibromide bromides antimony and 4.0mg is weighed to add lustre to
Ionophore IV is dissolved in 3.0mL tetrahydrofurans, and the glass that fixed internal diameter on a glass is 3.5cm is poured into after stirring evenly
In ring.After waiting for tetrahydrofuran volatilization, film is cut into internal diameter as the sequin of 3mm using card punch and pastes bottom set
Have in the liquid-transfering gun pipette tips of pvc pipe.It is used in pvc pipe in glycine buffer (NaCl containing the 10mM) conduct of pH=3.0
Filling liquid and activating solution activated electrode, for use.
The potentiometric detection of fluorine ion：
(1) using it is above-mentioned prepare polymer film Copper diethlydithiocarbamate as working electrode, saturated calomel electrode be reference electricity
Potentiometric detection extremely is carried out to fluorine ion；
(2) potential value (glycine buffer that pH is 3.0) of the fluorine ion of record various concentration on the working electrode (s；
The fluorine ion storing solution that 1M is configured using sodium fluoride is the fluorine of addition 1M in 3.0 glycine buffer to pH
Ion stock liquid, it is 10 to make the ultimate density of fluorine (including fluorine ion and hydrofluoric acid)-1、10-2、10-3、10-4、10-5、10-6M, note
Record potential value.After being corrected to the concentration of fluorine ion, experimental result is shown in Fig. 1 (wherein illustration is calibration curve).It can be with by Fig. 1
Find out, the electrode response speed is fast, high sensitivity, it can be achieved that fluorine ion quick, highly sensitive detection.
(3) for the electric potential signal generated using various concentration fluorine ion as ordinate, it is bent that a concentration of abscissa draws standard work
Line；
(4) fluorine ion in tap water is tested according to the step of (1)-(3), sample is calculated according to standard working curve
The concentration value of middle fluorine ion.Commodity in use lanthanum fluoride crystal membrane electrode is detected above-mentioned sample simultaneously, two kinds of electrode institutes
2 must be the results are shown in Table.Result as can be seen from Table 2 obtained by the two is consistent, illustrates that the accuracy of the invention is higher.
The testing result of the originally water sample of table 2
| Result is measured using the invention | Commercialization fluoride ion electrode measures result | |
| Water sample 1 | 5.0±0.3×10-6M | 5.1±0.3×10-6M |
| Water sample 2 | 4.5±0.4×10-6M | 4.4±0.3×10-6M |
| Water sample 3 | 5.2±0.2×10-6M | 2.1±0.3×10-6M |
Claims (3)
1. a kind of polymer film Copper diethlydithiocarbamate of fluorine ion, it is characterised in that：Polymer film Copper diethlydithiocarbamate is with four
Phenyl bromination antimony is ionophore, using cation-exchanger as ionic sites；
The polymer film Copper diethlydithiocarbamate of fluorine ion will be used as ionophore in tetraphenylphosphonibromide bromide Sb doped to polymer film；Four
The dosage of phenyl bromination antimony accounts for the 0.5%~5% of polymer film weight；
The dosage of the cation-exchanger is the 10%~50% of the amount of tetraphenylphosphonibromide bromide antimony substance.
2. the polymer film Copper diethlydithiocarbamate of fluorine ion as described in claim 1, it is characterised in that：The polymer film is
Film matrix, plasticizer and cation-exchanger composition；Film matrix is polyvinyl chloride, polyurethane, silicon rubber, acetate fiber, poly- third
Acrylamide or polymethylacrylic acid-dimethylaminoethyl methacrylate；Plasticizer is ortho-nitrophenyl octyl ether, phthalic acid two
Monooctyl ester, dibutyl phthalate, diisobutyl phthalate, dioctyl adipate or dioctyl sebacate；Cation is handed over
It is four (4- fluorophenyls) Boratexes, four (4- chlorphenyls) Boratexes, four (4- aminomethyl phenyls) Boratexes, four (4- fluoroforms to change agent
Base phenyl) Boratex, four (3,5- bis- (trifluoromethyl) phenyl) Boratex, sodium tetraphenylborates or the ionophore I-XI that adds lustre to.
3. the application of the polymer film Copper diethlydithiocarbamate of fluorine ion as described in claim 1, it is characterised in that：The polymerization
Application of the object film potential type sensor in environment water detects fluorine ion.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610071438.8A CN105738435B (en) | 2016-02-01 | 2016-02-01 | A kind of polymer film Copper diethlydithiocarbamate of fluorine ion and its application |
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| CN201610071438.8A CN105738435B (en) | 2016-02-01 | 2016-02-01 | A kind of polymer film Copper diethlydithiocarbamate of fluorine ion and its application |
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| CN105738435B true CN105738435B (en) | 2018-10-23 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0186210A2 (en) * | 1984-12-28 | 1986-07-02 | TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION | Ion sensor |
| CN102539500A (en) * | 2010-12-31 | 2012-07-04 | 中国科学院烟台海岸带研究所 | Sensor based on asymmetric polymer film as well as detection method and applications thereof |
| CN104569103A (en) * | 2014-04-10 | 2015-04-29 | 中国科学院烟台海岸带研究所 | Solid-contact-type polymer film lead ion selective electrode and application thereof |
-
2016
- 2016-02-01 CN CN201610071438.8A patent/CN105738435B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0186210A2 (en) * | 1984-12-28 | 1986-07-02 | TERUMO KABUSHIKI KAISHA trading as TERUMO CORPORATION | Ion sensor |
| CN102539500A (en) * | 2010-12-31 | 2012-07-04 | 中国科学院烟台海岸带研究所 | Sensor based on asymmetric polymer film as well as detection method and applications thereof |
| CN104569103A (en) * | 2014-04-10 | 2015-04-29 | 中国科学院烟台海岸带研究所 | Solid-contact-type polymer film lead ion selective electrode and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Organoantimony compounds. 11. Studies on tetraphenylantimony(V) derivatives;R. G. GOEL;《CANADIAN JOURNAL OF CHEMISTRY》;19691231;第47卷;第4607-4612页 * |
| Voltammetric Study of the Transfer of Fluoride Ion at the Nitrobenzene Water Interface Assisted by Tetraphenylantimony;Hajime Katano等;《ANALYTICAL SCIENCES》;20040331;第20卷;第553-556页 * |
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