CN103364477A - Method for detecting trace quantity of metal ions based on potential adjustment stripping voltammetry - Google Patents
Method for detecting trace quantity of metal ions based on potential adjustment stripping voltammetry Download PDFInfo
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- CN103364477A CN103364477A CN2013103314951A CN201310331495A CN103364477A CN 103364477 A CN103364477 A CN 103364477A CN 2013103314951 A CN2013103314951 A CN 2013103314951A CN 201310331495 A CN201310331495 A CN 201310331495A CN 103364477 A CN103364477 A CN 103364477A
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Abstract
The invention discloses a method for detecting trace quantity of metal ions based on potential adjustment stripping voltammetry. The method comprises the following steps of 1, carrying out enrichment deposition of metal ions in a detected solution on the surface of an inert work electrode by an electrochemical method, 2, through potential adjustment, applying an appropriate potential in short time so that interfering ions are dissolved out in advance, and 3, dissolving out the detected metal ions by voltammetry and recording a stripping voltammetry curve. Compared with the conventional stripping voltammetry, in detection of trace quantity of metal ions in the solution, the method can greatly reduce a detection limit to a 1.0*10<-9>g/L grade. In continuous determination, the method has greatly improved reappearance, stability and reliability. The method can be used for detection of content of trace quantity of metal ions in aqueous solutions such as seawater, surface water and industrial wastewater, and in digested aqueous solutions of water-insoluble substances such as foods, electronic products and organic substances.
Description
Technical field
The invention belongs to the chemical analysis technology field, be specifically related to a kind of trace metal ion detection method based on the electric potential regulating stripping voltammetry.
Background technology
Along with increase and urbanization and the social industrialized development of population, concentration of metal ions raises gradually in the nature soil environment, in the surface water and in the seawater, causes serious metallic pollution.Simultaneously, metallic ion has strong enriching, is difficult to degraded in environment, in case enrichment in humans and animals, plant will cause to environment and people's health very large harm.Therefore, set up effectively reliably detection method, all have very important significance at aspects such as food security, clinical medicine and environment measurings.
The technology that detects at present trace metal ion mainly contains atomic absorption spectrography (AAS), ultraviolet-visible spectrophotometry, atomic fluorescence spectrometry, x ray fluorescence spectrometry and coupled plasma mass spectroscopy etc.Although these instruments have higher sensitivity and selectivity, instrument involves great expense, and needs higher operation cost, and these have all limited their utilizations in reality detects greatly.By contrast, detect with electrochemical method counterweight metal, have instrument simple, easy to operate quick, highly sensitive, be easy to the advantages such as microminiaturized.Especially anodic stripping voltammetry, it is a kind of very sensitive volt-ampere (polarogram) analytical approach, can be used for the mensuration of trace metal ion.This technology is first test substance to be enriched on the working electrode by cathodic reduction, then changes the current potential of electrode, makes the again stripping of material that is enriched on this electrode, carries out quantitative test according to resulting volt-ampere curve in the Anodic Stripping process again.When using at present Anodic Voltammetry trace metal ion concentration, in the situation that electrode is not modified, detectability is mostly in the 1mg/L rank; There is simultaneously a relatively poor problem of experimental result reappearance, affected its application in reality detects greatly like this.
Therefore, be necessary to seek a kind of easy, detect the electrochemical method of trace metal ion reliably.Require working electrode not need special modification, instrument is simple, convenient to operation, automaticity is high, highly sensitive, good stability, is applicable to the detection of trace metal ion in environmental monitoring and other aqueous solution.
Summary of the invention
The object of the present invention is to provide a kind of trace metal ion detection method based on the electric potential regulating stripping voltammetry, have detection sensitivity height, good reproducibility, convenient to operation, automaticity high, be a kind of can fast detecting in the liquid to be measured the qualitative and quantitative analysis method of ultratrace metal ion.
For achieving the above object, the present invention adopts following technical scheme:
A kind of trace metal ion detection method based on the electric potential regulating stripping voltammetry deposits to the inertia working electrode surface with electrochemical method with metallic ion enrichment in the liquid to be measured first; Then by electric potential regulating, apply at short notice a suitable potential, make in advance stripping of interfering ion; Carry out again at last the stripping of metallic ion to be measured with voltammetry, and record Stripping Voltammetry curve.
May further comprise the steps:
(1) electrochemical deposition process of trace metal ion
Inertia working electrode and contrast electrode, auxiliary electrode (to electrode) after cleaning, polishing are put in the liquid to be measured in the lump.Use first one or more combined methods in potentiostatic method, linear scanning method, the cyclic voltammetry, trace metal ion enrichment in the solution is deposited on the inertia working electrode surface.
(2) pre-process in leaching
By electric potential regulating, use at short notice one or more combined methods in potentiostatic method, linear scanning method, the cyclic voltammetry, apply a suitable potential to working electrode, make in advance stripping of interfering ion.The scanning current potential upper limit that the stripping current potential that potentiostatic method sets in this process and linear scanning method or cyclic voltammetry set is less than the stripping current potential of metallic ion to be measured.
(3) the Electrochemical Stripping process of trace ion
Utilize one or more combined methods in potentiostatic method, linear scanning method, the cyclic voltammetry, working electrode is applied predetermined voltage, make enrichment be deposited on the working electrode surface metallic ion to be measured again stripping in solution, and record Stripping Voltammetry curve.
Remarkable advantage of the present invention is:
(1) electric potential regulating voltammetry of the present invention is compared with the stripping voltammetry of routine, can realize the highly sensitive detection to trace metal ion, and detectability is minimum can decrease to 1.0 * 10
-9The g/L rank has solved most of detection methods effectively for the detection sensitivity of trace metal ion in actual sample problem on the low side.
(2) the present invention requires simply, detects and change fast and automatically degree height, the reappearance in the time of can improving METHOD FOR CONTINUOUS DETERMINATION, stability and reliability sample pretreatment.
(3) instrument cost of the present invention is cheap, simple to operate, can be widely used in the fields such as environmental monitoring and food security.
Description of drawings
Fig. 1 is electric potential regulating voltammetry and conventional square wave voltammetry electrode potential variation waveform synoptic diagram in experimentation in the embodiment of the invention 1.
(A) electrode potential changes synoptic diagram in the electric potential regulating voltammetry experimentation
I: the potentiostatic method deposition process of trace metal ion;
II: the pre-process in leaching that disturbs metallic ion;
III: the current potential initialization process before the square wave voltammetry stripping of trace metal ion;
IV: the square wave volt-ampere process in leaching of trace metal ion; E
1 : sedimentation potential; E
2 : pre-stripping current potential; t
1 : sedimentation time; t
2 : pre-dissolution time; t
3 : the current potential preset time before the square wave voltammetry stripping.
(B) potential change synoptic diagram in the conventional square wave voltammetry experimentation
I: the potentiostatic electrodeposition enrichment process of trace metal ion;
II: the square wave volt-ampere process in leaching of trace metal ion; E
1 : sedimentation potential; t
1 : sedimentation time.
Fig. 2 is trace Hg in the embodiment of the invention 1
2+The square wave volt-ampere stripping curve that detects.
Fig. 3 is trace Hg in the embodiment of the invention 2
2+The square wave volt-ampere stripping curve that detects.
Fig. 4 is trace Hg in the embodiment of the invention 3
2+The square wave volt-ampere stripping curve that detects.
Fig. 5 is trace Cu in the embodiment of the invention 4
2+The differentiated pulse volt-ampere stripping curve that detects.
Fig. 6 is trace Ag in the embodiment of the invention 5
+The linear sweep stripping curve that detects.
Embodiment
As working electrode, the Ag/AgCl electrode is as contrast electrode with the glass-carbon electrode after cleaning, polishing (diameter 3mm, lower same), and platinum electrode places as auxiliary electrode and contains Bi
3+Concentration is 500 μ g/L, Hg
2+Concentration is 1 ng/L, and KCl concentration is (the pH value is 4.7) in 0.2 M acetic acid-sodium-acetate buffer of 0.14 M.Be-1.2 V with potentiostatic method control sedimentation potential first, and under this current potential potentiostatic electrodeposition 300 s, make Hg to be measured in the liquid to be measured
2+Reduce enrichment at the inertia working electrode surface; Then carry out electric potential regulating by potentiostatic method, the constant potential in that 2 s apply-0.2 V to working electrode in the time makes in advance stripping of interfering ion; Carry out stripping with square wave voltammetry more at last, and record Stripping Voltammetry curve.In the situation of change of working electrode top electrode electromotive force in the experimentation shown in accompanying drawing 1 (A), by the situation of change of working electrode electromotive force in the conventional square wave voltammetry of contrast accompanying drawing 1 (B), can find that electric potential regulating voltammetry and conventional square wave method working electrode potential change in experimentation exist obvious difference.Corresponding experimental result as shown in Figure 2, from this figure as can be known, the inventive method is to the Hg of trace in the aqueous solution
2+Has good response.
As working electrode, the Ag/AgCl electrode is as contrast electrode with the glass-carbon electrode after cleaning, polishing, and platinum electrode places as auxiliary electrode and contains Bi
3+Concentration is 500 μ g/L, Hg
2+Concentration is 5 ng/L, and KCl concentration is (the pH value is 4.7) in 0.2 M acetic acid-sodium-acetate buffer of 0.14 M.Be-1.2 V～-1.0 V with linear scanning method control current potential first, and at this potential range interscan 300 s, make Hg to be measured in the liquid to be measured
2+Reduce enrichment at the inertia working electrode surface; And then be-1.2 V～-0.2 V by linear scanning method control current potential, and carry out pre-stripping in this potential range, make in advance stripping of interfering ion; Carry out stripping with square wave voltammetry at last, and record Stripping Voltammetry curve, corresponding experimental result as shown in Figure 3, from this figure as can be known, the inventive method is to the Hg of trace in the aqueous solution
2+Has good response.
As working electrode, the Ag/AgCl electrode is as contrast electrode with the glass-carbon electrode after cleaning, polishing, and platinum electrode places as auxiliary electrode and contains Bi
3+Concentration is 500 μ g/L, Hg
2+Concentration is 10 ng/L, and KCl concentration is (the pH value is 4.7) in 0.2 M acetic acid-sodium-acetate buffer of 0.14 M.Be-1.2 V～-1.0 V with cyclic voltammetry control current potential first, and at this potential range interscan 300 s, make Hg to be measured in the liquid to be measured
2+Reduce enrichment at the inertia working electrode surface; And then be-1.2 V～-0.2 V by cyclic voltammetry control current potential, and carry out pre-stripping in this potential range, make in advance stripping of interfering ion; Carry out stripping with square wave voltammetry at last, and record Stripping Voltammetry curve, corresponding experimental result as shown in Figure 4, from this figure as can be known, the inventive method is to the Hg of trace in the aqueous solution
2+Has good response.
Embodiment 4
As working electrode, the Ag/AgCl electrode is as contrast electrode with the glass-carbon electrode after cleaning, polishing, and platinum electrode places as auxiliary electrode and contains Bi
3+Concentration is 500 μ g/L, Cu
2+Concentration is (the pH value is 4.7) in 0.2 M acetic acid-sodium-acetate buffer of 30 ng/L.Be-1.2 V with potentiostatic method control sedimentation potential first, and under this current potential potentiostatic electrodeposition 300 s, make Cu to be measured in the liquid to be measured
2+Reduce enrichment at the inertia working electrode surface; Then carry out electric potential regulating by potentiostatic method, the constant potential in that 2 s apply-0.2 V to working electrode in the time makes in advance stripping of interfering ion; Carry out stripping with Differential Pulse Voltammetry more at last, and record Stripping Voltammetry curve, its experimental result is as shown in Figure 5.From this figure as can be known, the inventive method is to the Cu of trace in the aqueous solution
2+Has good response.
As working electrode, the Ag/AgCl electrode is as contrast electrode with the glass-carbon electrode after cleaning, polishing, and platinum electrode places as auxiliary electrode and contains Bi
3+Concentration is 500 μ g/L, Ag
+Concentration is (the pH value is 4.7) in 0.2 M acetic acid-sodium-acetate buffer of 20 ng/L.Be-1.2 V with potentiostatic method control sedimentation potential first, and under this current potential potentiostatic electrodeposition 300 s, make Ag to be measured in the liquid to be measured
+Reduce enrichment at the inertia working electrode surface; Then carry out electric potential regulating by potentiostatic method, the constant potential in that 2 s apply-0.3 V to working electrode in the time makes in advance stripping of interfering ion; Carry out stripping with linear scanning method more at last, and record Stripping Voltammetry curve, its experimental result is as shown in Figure 6.From this figure as can be known, the inventive method is to the Ag of trace in the aqueous solution
+Has good response.
The above only is some embodiments of the present invention, and all equalizations of doing according to the present patent application claim change and modify, and all should belong to covering scope of the present invention.
Claims (4)
1. the trace metal ion detection method based on the electric potential regulating stripping voltammetry is characterized in that: with electrochemical method metallic ion enrichment in the liquid to be measured is deposited to the inertia working electrode surface first; Then by electric potential regulating, apply at short notice a suitable potential, make in advance stripping of interfering ion; Carry out again at last the stripping of metallic ion to be measured with voltammetry, and record Stripping Voltammetry curve.
2. the trace metal ion detection method based on the electric potential regulating stripping voltammetry according to claim 1, it is characterized in that: the electrode system of inertia working electrode, contrast electrode and auxiliary electrode is placed liquid to be measured, and it is one or more combinations in potentiostatic method, linear scanning method, the cyclic voltammetry that trace metal ion enrichment in the solution is deposited to electrochemical method on the inertia working electrode.
3. the trace metal ion detection method based on the electric potential regulating stripping voltammetry according to claim 1, it is characterized in that: the electrochemical method that makes in advance stripping of interfering ion is one or more combinations in potentiostatic method, linear scanning method, the cyclic voltammetry; In the pre-process in leaching, the upper limit of the scanning current potential that stripping current potential, linear scanning method or the cyclic voltammetry that potentiostatic method sets sets is less than the stripping current potential of metallic ion to be measured.
4. the trace metal ion detection method based on the electric potential regulating stripping voltammetry according to claim 1 is characterized in that: the volt-ampere dissolving-out method of described trace metal ion is square wave voltammetry, Differential Pulse Voltammetry
,One or more combinations in linear scanning method, the cyclic voltammetry.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558207A (en) * | 2013-10-28 | 2014-02-05 | 青岛佳明测控科技股份有限公司 | Small portable heavy metal detection device and detection method |
| CN105891294A (en) * | 2016-06-23 | 2016-08-24 | 中国科学院长春应用化学研究所 | Method for detecting heavy metal ions by electrochemical analysis |
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| CN101178380A (en) * | 2007-12-05 | 2008-05-14 | 浙江工商大学 | Method for detecting lead content in tea-leaf |
| JP2013024776A (en) * | 2011-07-22 | 2013-02-04 | Keio Gijuku | Electrochemical analysis method and device for cadmium |
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| CN101178380A (en) * | 2007-12-05 | 2008-05-14 | 浙江工商大学 | Method for detecting lead content in tea-leaf |
| JP2013024776A (en) * | 2011-07-22 | 2013-02-04 | Keio Gijuku | Electrochemical analysis method and device for cadmium |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103558207A (en) * | 2013-10-28 | 2014-02-05 | 青岛佳明测控科技股份有限公司 | Small portable heavy metal detection device and detection method |
| CN103558207B (en) * | 2013-10-28 | 2016-03-30 | 青岛佳明测控科技股份有限公司 | Small-sized can be portable heavy metal analysis device and detection method |
| CN105891294A (en) * | 2016-06-23 | 2016-08-24 | 中国科学院长春应用化学研究所 | Method for detecting heavy metal ions by electrochemical analysis |
| CN105891294B (en) * | 2016-06-23 | 2019-07-23 | 中国科学院长春应用化学研究所 | A kind of method of Applied Electrochemistry analytic approach detection heavy metal ion |
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Application publication date: 20131023 |