CN108508076A - The method that ion liquid abstraction differential pulse voltammetry measures copper ion concentration - Google Patents
The method that ion liquid abstraction differential pulse voltammetry measures copper ion concentration Download PDFInfo
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- CN108508076A CN108508076A CN201810280010.3A CN201810280010A CN108508076A CN 108508076 A CN108508076 A CN 108508076A CN 201810280010 A CN201810280010 A CN 201810280010A CN 108508076 A CN108508076 A CN 108508076A
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Abstract
The invention discloses a kind of methods that ion liquid abstraction differential pulse voltammetry measures copper ion concentration.First by the NH of copper ion solution and PAN ethanol solutions, pH=8.03‑NH4It is stood after 15 s of Cl buffer solutions concussion reaction, adds 1 butyl, 3 methylimidazole hexafluorophosphate concussion reaction, 6 min, centrifugation obtains ionic liquid phase.It takes 30 μ L ionic liquids mutually to drip to glassy carbon electrode surface, three-electrode system is formed with filamentary silver, platinum filament, realize that ion liquid abstraction differential pulse voltammetry measures copper ion concentration with differential pulse voltammetry.The range of linearity that this method detects copper ion is 2.0 × 10‑6Mol/L to 1.0 × 10‑4Mol/L, calibration curve coefficient correlation R2=0.9964, detection limit is 2.41 × 10‑7 mol/L.The method of the present invention has good stability and reproducibility, and ionic liquid is environmentally protective extractant, has good foreground to detection Cu (II).
Description
Technical field
The invention belongs to electrochemical analysis detection technique field, more particularly to a kind of ion liquid abstraction differential pulse voltammetry
The method that method measures copper ion concentration.
Background technology
Ionic liquid is developed from traditional high-temperature molten salt, and the main distinction of it and conventional liquid substance is ionic liquid
Body composition is entirely ion, and it is that the height of fusing point is different from the main distinction of fused salt.Ionic liquid is to many organic
Object and inorganic salts have good dissolubility, and environmentally safe, are referred to as " green solvent ".Not volatile excellent of ionic liquid
Promise extraction process constancy of volume；The advantages that stability height, good conductivity, keeps fine during electrochemical measurement
Electroactive and chemical property stabilization.
Sample detection (such as spectroscopic methodology) is carried out using conventional method and has such as that consumption of organic solvent is big, operating procedure is numerous
The shortcomings of miscellaneous and operating time is long.Using Single-drop microextraction technique device is simple, solvent dosage is few, at low cost etc. in the present invention
Remarkable advantage establishes one kind in conjunction with the outstanding advantages such as electrochemical detection method is highly sensitive, equipment is simple, testing cost is low
The method of mono- drop Electrochemical Detection PAN-Cu (II) complex compound of ion liquid abstraction-.
Invention content
The present invention provides a kind of methods that ion liquid abstraction differential pulse voltammetry measures copper ion concentration.
The specific steps are：
（1）0.0938 g copper nitrate solids are weighed, add deionized water dissolving complete, 50 mL capacity are transferred to glass bar drainage
In bottle, it is settled to graduation mark with deionized water, is shaken up, the copper nitrate solution of a concentration of 0.01 mol/L is obtained, by 0.01 mol/
The copper nitrate solution of L dilutes step by step obtains a concentration of 6 × 10-4 mol/L、3.6×10-4 mol/L、1.8×10-4 mol/L、6
×10-5 mol/L、4.8×10-5 mol/L、2.4×10-5 Mol/L and 1.2 × 10-5 The serial low concentration copper ion of mol/L is molten
Liquid.
（2）150 μ L steps are pipetted respectively（1）Low concentration copper ion solution obtained in seven 1.5 mL centrifuge tubes, then
Move into the NH of 600 pH=8.0 μ L successively respectively3-NH4Cl buffer solutions and 150 μ L a concentration of 6 × 10-3The PAN- second of mol/L
Alcoholic solution is stood after shaking 15 s of centrifuge tube.
（3）It pipettes 50 μ L ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphates respectively with liquid-transfering gun and step is added
（2）Stand seven centrifuge tubes in, then with microoscillator shake 6min, by the centrifuge tube after concussion be put into centrifuge with
The rotating speed of 4000 r/min centrifuges 6 min, takes out centrifuge tube, removes supernatant with liquid-transfering gun, preserves bottom ionic liquid phase.
（4）Take 30 μ L steps（3）Obtained ionic liquid mutually drips to glassy carbon electrode surface, and by filamentary silver, platinum filament and drop
Contact ensures that filamentary silver, platinum filament are not touched mutually with glass-carbon electrode, carries out differential pulse voltammetry scanning after stablizing, is linearly returned
The equation is returned to be：y=0.1211x+1.086E-7, wherein x is copper ion concentration, and y is current strength, R2=0.9956, the range of linearity is
2.0×10-6Mol/L to 1.0 × 10-4Mol/L, detection are limited to 3 σ/k=2.41 × 10-7Mol/L realizes ionic liquid
It extracts differential pulse voltammetry and measures copper ion concentration.
The glass-carbon electrode is polished into minute surface with alumina powder, uses HNO successively3, ethyl alcohol and distilled water carries out ultrasound and washes
It washs, is finally cleaned up with deionized water.
Complex compound is extracted into ionic liquid by the method for the present invention using the property of complexing agent PAN and copper ion complexing, is solved
Glyoxaline ion liquid itself to the copper ion in water phase without extracting power the shortcomings that, the method for the present invention high sensitivity, detection
It limits low, greatly reduces the pollution to environment.
Description of the drawings
Fig. 1 is Cu (II)-PAN- [Bmim] PF in the embodiment of the present invention6Extraction system measures copper ion response diagram.
Fig. 2 is Cu (II)-DDTC- [Bmim] PF in the embodiment of the present invention6Extraction system measures copper ion response diagram.
Fig. 3 is Cu (II)-dithizone-[Bmim] PF in the embodiment of the present invention6Extraction system measures copper ion response diagram.
Fig. 4 is Cu (II)-PAN- [Bmim] PF in the embodiment of the present invention6The pH value of extraction system optimizes.
Fig. 5 is Cu (II)-PAN- [Bmim] PF in the embodiment of the present invention6The ionic liquid of extraction system mutually example compared with water
Optimization.
Fig. 6 is Cu (II)-PAN- [Bmim] PF in the embodiment of the present invention6The PAN concentration optimizations of extraction system.
Fig. 7 is various concentration Cu in the embodiment of the present invention（II）Differential pulse voltammetry linear response figure.
Fig. 8 is Cu (II)-PAN- [Bmim] PF in the embodiment of the present invention6Extraction system differential pulse voltammetry survey copper from
The linearity curve of son.
Specific implementation mode
It elaborates to the present invention below with reference to Figure of description and specific embodiment.
Embodiment：
（1）0.0938 g copper nitrate solids are weighed, add deionized water dissolving complete, 50 mL capacity are transferred to glass bar drainage
In bottle, it is settled to graduation mark with deionized water, is shaken up, the copper nitrate solution of a concentration of 0.01 mol/L is obtained, by 0.01 mol/
The copper nitrate solution of L dilutes step by step obtains a concentration of 6 × 10-4 mol/L、3.6×10-4 mol/L、1.8×10-4 mol/L、6
×10-5 mol/L、4.8×10-5 mol/L、2.4×10-5 Mol/L and 1.2 × 10-5 The serial low concentration copper ion of mol/L is molten
Liquid.
（2）150 μ L steps are pipetted respectively（1）Low concentration copper ion solution obtained in seven 1.5 mL centrifuge tubes, then
Move into the NH of 600 pH=8.0 μ L successively respectively3-NH4Cl buffer solutions and 150 μ L a concentration of 6 × 10-3The PAN- second of mol/L
Alcoholic solution is stood after shaking 15 s of centrifuge tube.
（3）It pipettes 50 μ L ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphates respectively with liquid-transfering gun and step is added
（2）Stand seven centrifuge tubes in, then with microoscillator shake 6min, by the centrifuge tube after concussion be put into centrifuge with
The rotating speed of 4000 r/min centrifuges 6 min, takes out centrifuge tube, removes supernatant with liquid-transfering gun, preserves bottom ionic liquid phase.
（4）Take 30 μ L steps（3）Obtained ionic liquid mutually drips to glassy carbon electrode surface, and by filamentary silver, platinum filament and drop
Contact ensures that filamentary silver, platinum filament are not touched mutually with glass-carbon electrode, and differential pulse voltammetry scanning is carried out after stablizing.
The extraction system that different complexing agents are formed is detected Cu (II) by differential pulse voltammetry, such as Fig. 1, figure
2 and Fig. 3.There is larger potential error when making complexing agent with dithizone, but as it with DDTC makees complexing agent, can not rationally judge
The current potential and background peaks of copper quasi-molecular ions are larger.It is verified through many experiments, makees the method for complexing agent complex copper ion not only with PAN
Efficiently, preferable reproducibility, the present invention also finally choose Cu (II)-PAN- [Bmim] PF in difference Voltammetric detection6Extraction
System carries out Copper Ion.
Cu (II) is detected under different pH condition by differential pulse voltammetry, such as Fig. 4.The result shows that
PH is in 4.0 ~ 8.0 ranges, and peak current increases with the increase of pH, and when pH is more than 8, peak current subtracts with the increase of pH
Small, the present invention is final as a result, chooses NH3-NH4Optimal pH of pH of buffer=8.0 Cl as the extraction system.
By differential pulse voltammetry in the case where difference compares extraction conditions to 1 × 10-4 Mol/L Cu (II) be detected as
Fig. 5.The result shows that when ionic liquid phase dosage is less than 50 μ L, compared to less than 1:When 18, peak point current declines rapidly, the phenomenon
It is to cause extraction incomplete since ionic liquid phase volume is too small, ionic liquid is mutually embezzled and/or the complex ion of nearly saturated mode is in quilt
By the dual obstruction of excessive PAN and high viscosity small size ionic liquid phase when reduction, the sensitive point on electrode is reduced and is surveyed
It is without mixing to determine process so that Cu (II) successfully cannot be reduced out.And work as ionic liquid dosage and be less than 50 μ L, compared to big
In 1:When 18, peak current is equally gradually reduced, because concentration of Cu (the II)-PAN complex compounds in ionic liquid phase is gradually dilute
It releases.The experimental results showed that the optimum amount of extraction system extractant is 50 μ L, it is most preferably comparably 1:18.
By differential pulse voltammetry to 1 × 10 under different PAN concentration extraction conditions-4 Mol/L Cu (II) are examined
It surveys, such as Fig. 6.As seen from the figure, when amount of complex is relatively low, peak current rises with the increase of amount of complex obviously, in PAN concentration
For 0.0012 mol/L when, peak current is maximum, then shows downward trend, therefore select a concentration of 0.0012 mol/L's
Optium concentration condition of the PAN- ethanol solutions as experiment complexing agent.
Use is detected to the Cu (II) of various concentration by differential pulse voltammetry, such as Fig. 7 and Fig. 8.By Cu2+ Deposit
Solution (1 × 10-2 Mol/L it) is diluted to a concentration of 6 × 10 step by step-4Mol/L, 3.6 × 10-4Mol/L, 1.8 × 10-4 mol/
L, 6 × 10-5 Mol/L, 4.8 × 10-5 Mol/L, 2.4 × 10-5 Mol/L, 1.2 × 10-5 The series concentration of mol/L, pipettes this
The Cu of series concentration2+Each 150 μ L of solution (blank sample is to move into 150 μ L deionized waters) in seven 1.5 ml centrifuge tubes, then
The NH of pH=8.0 is moved into successively3-NH4It is stood after 600 μ L, PAN- ethanol solution of Cl buffer solutions, 150 μ L, 15 s of concussion centrifuge tube；
Pipette ionic liquid [Bmim] PF6 In 50 μ L to centrifuge tube, 6 min are centrifuged with 4000 r/min of rotating speed after concussion, take out centrifugation
Pipe, removes supernatant with liquid-transfering gun, and single drop differential pulse voltammetry analysis is mutually carried out to ionic liquid, obtains equation of linear regression
For：y=0.1211x+1.086E-7 (R2=0.9956), the range of linearity is 2.0 × 10-6Mol/L to 1.0 × 10-4Mol/L, inspection
Rising limit is 3 σ/k=2.41 × 10-7 mol/L。
The above is only the preferred embodiments of the invention, protection scope of the present invention is not limited merely to above-described embodiment,
It is within the scope of the invention with various process programs of the present inventive concept without substantial differences.
Claims (1)
1. a kind of method that ion liquid abstraction differential pulse voltammetry measures copper ion concentration, it is characterised in that specific steps
For：
（1）0.0938 g copper nitrate solids are weighed, add deionized water dissolving complete, 50 mL capacity are transferred to glass bar drainage
In bottle, it is settled to graduation mark with deionized water, is shaken up, the copper nitrate solution of a concentration of 0.01 mol/L is obtained, by 0.01 mol/
The copper nitrate solution of L dilutes step by step obtains a concentration of 6 × 10-4 mol/L、3.6×10-4 mol/L、1.8×10-4 mol/L、6
×10-5 mol/L、4.8×10-5 mol/L、2.4×10-5 Mol/L and 1.2 × 10-5 The serial low concentration copper ion of mol/L is molten
Liquid；
（2）150 μ L steps are pipetted respectively（1）Low concentration copper ion solution obtained is in seven 1.5 mL centrifuge tubes, then distinguishes
The NH of 600 pH=8.0 μ L is moved into successively3-NH4Cl buffer solutions and 150 μ L a concentration of 6 × 10-3The PAN- ethyl alcohol of mol/L is molten
Liquid is stood after shaking 15 s of centrifuge tube；
（3）It pipettes 50 μ L ionic liquid 1-butyl-3-methyl imidazolium hexafluorophosphates respectively with liquid-transfering gun and step is added（2）It is quiet
In seven centrifuge tubes set, 6min then is shaken with microoscillator, the centrifuge tube after concussion is put into centrifuge with 4000
The rotating speed of r/min centrifuges 6 min, takes out centrifuge tube, removes supernatant with liquid-transfering gun, preserves bottom ionic liquid phase；
（4）Take 30 μ L steps（3）Obtained ionic liquid mutually drips to glassy carbon electrode surface, and filamentary silver, platinum filament and drop are connect
It touches, ensures that filamentary silver, platinum filament are not touched mutually with glass-carbon electrode, carry out differential pulse voltammetry scanning after stablizing, obtain linear regression
Equation is：y=0.1211x+1.086E-7, wherein x is copper ion concentration, and y is current strength, R2=0.9956, the range of linearity is
2.0×10-6Mol/L to 1.0 × 10-4Mol/L, detection are limited to 3 σ/k=2.41 × 10-7Mol/L realizes ionic liquid
It extracts differential pulse voltammetry and measures copper ion concentration；
The glass-carbon electrode is polished into minute surface with alumina powder, uses HNO successively3, ethyl alcohol and distilled water carry out supersound washing, most
It is cleaned up afterwards with deionized water.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101382514A (en) * | 2008-10-09 | 2009-03-11 | 上海交通大学 | Method for detecting oxidative metal ion in water |
| CN102798657A (en) * | 2012-09-04 | 2012-11-28 | 中国水产科学研究院黄海水产研究所 | Site fast detection method for copper, zinc, lead and cadmium as heavy metals in seawater |
| CN103336042A (en) * | 2013-06-26 | 2013-10-02 | 新余学院 | Terpyridine derivative modified electrode for electrochemically detecting copper ions and preparation method of terpyridine derivative modified electrode |
| CN103792270A (en) * | 2014-02-25 | 2014-05-14 | 浙江大学 | Parathion-methyl extraction and detection method based on N-octylpyridinium hexafluorophosphate electrode |
-
2018
- 2018-04-01 CN CN201810280010.3A patent/CN108508076A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101382514A (en) * | 2008-10-09 | 2009-03-11 | 上海交通大学 | Method for detecting oxidative metal ion in water |
| CN102798657A (en) * | 2012-09-04 | 2012-11-28 | 中国水产科学研究院黄海水产研究所 | Site fast detection method for copper, zinc, lead and cadmium as heavy metals in seawater |
| CN103336042A (en) * | 2013-06-26 | 2013-10-02 | 新余学院 | Terpyridine derivative modified electrode for electrochemically detecting copper ions and preparation method of terpyridine derivative modified electrode |
| CN103792270A (en) * | 2014-02-25 | 2014-05-14 | 浙江大学 | Parathion-methyl extraction and detection method based on N-octylpyridinium hexafluorophosphate electrode |
Non-Patent Citations (1)
| Title |
|---|
| MARIAM S. ARAIN 等: "Ultrasonic energy enhanced the efficiency of advance extraction methodology for enrichment of trace level of copper in serum samples of patients having neurological disorders", 《ULTRASONICS SONOCHEMISTRY》 * |
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