CN101377473B - Fast quantitative electroanalysis method - Google Patents
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- CN101377473B CN101377473B CN2007101212252A CN200710121225A CN101377473B CN 101377473 B CN101377473 B CN 101377473B CN 2007101212252 A CN2007101212252 A CN 2007101212252A CN 200710121225 A CN200710121225 A CN 200710121225A CN 101377473 B CN101377473 B CN 101377473B
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- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000126 substance Substances 0.000 claims abstract description 19
- 238000004458 analytical method Methods 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 9
- 238000012360 testing method Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000013459 approach Methods 0.000 claims description 8
- 230000005611 electricity Effects 0.000 claims description 7
- 238000011002 quantification Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 claims 1
- 230000005477 standard model Effects 0.000 claims 1
- 238000000840 electrochemical analysis Methods 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000003869 coulometry Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001567 chrono-coulometry Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000011263 electroactive material Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012113 quantitative test Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004082 amperometric method Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012742 biochemical analysis Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- NAOLGLVUSGCEPZ-UHFFFAOYSA-N nitrobenzene;hydrate Chemical compound O.[O-][N+](=O)C1=CC=CC=C1 NAOLGLVUSGCEPZ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a quantitive electrochemical analysis method for fast analyzing substance concentration, which utilizes different electrode systems aiming at different substances. The method determines potential interval between reduction (or oxidization) peaks of the to-be-tested substance by the means of cyclic voltammetry; and based on the interval, the method determines the potential step intervals for three times of potential steps; current-time data is recorded during the three times of potential steps; electric quantity is obtained by integral upon the time with the current peak corresponding to the second potential step interval; the electric quantity is in linear relationship with the concentration of the to-be-detected substance, which can prove the quantitive characteristic. The invention has fast analysis speed and simple operation.
Description
Invention field
The present invention relates to a kind of method of electrochemical quantitative analysis fast, particularly relate to a kind of method of confirming measured object concentration through quick change current potential and with the electron transfer amount in this process.
Background technology
Electrochemical methods is to utilize the electricity of material and the method that electrochemical properties is analyzed.It normally makes sample solution to be analyzed constitute a chemical cell; Measure according to the inner link between some physical quantity and its chemistry amount of battery composition then, can be divided into amperometry, potentiometry, method of coulometric analysis and volt-ampere analysis etc.At present, the method for electrochemical analysis widespread use is a cyclic voltammetry.This method control electrode electromotive force is with different speed; Scan repeatedly with the triangular waveform one or many in time; Potential range is to make different and reduction and oxidation reaction can alternately take place on the electrode, and record current-potential curve, can carry out quantitative test through redox peak current on the curve.Use cyclic voltammetry, because the restriction of circulating path and sweep velocity helps little for improving analysis speed.
Method of coulometric analysis is the general name of carrying out the analytical approach of coulometry, also claims coulometry, is a kind ofly to be consumed in the method that the required electric weight of test substance in the solution measures quantitatively this content of material through mensuration.Through coming the method that system is analyzed is called chronocoulometry through the electric charge that flows through in the electrolytic cell circuit in metering a period of time; Also claim the timing coulometry; Often be used to study the electrode surface adsorption phenomena, and measure electroactive material or surface reactive material electrochemical methods quantitatively in the electrode surface adsorbance.And the selectivity of this method is not good, should not be as the quantitative test in the complicated solution.
Potential step method is to measure corresponding current value with the potential step signal simultaneously as control signal, can draw out electric current-time curve.This method is usually used in the drafting of polarization curve.
Present pollutant analysis method mainly is analysis by titration, gravimetry, ultraviolet/visible/infrared spectrophotometer, gas phase or liquid phase chromatography, gas phase or liquid phase mass spectrometry method, atomic fluorescence/atomic absorption/atomic emission spectrometry etc.These conventional method ubiquity analysis speeds are slow, are difficult to realize shortcomings such as on-line monitoring.And present rapid electrochemical analysis method focuses mostly on aspect biochemical analysis (like Chinese patent CN1975403, CN1325490), and the environmental protection aspect generally is confined to electrochemical analysis (like Chinese patent CN1645127) and gas sensor aspect (like Chinese patent CN2754096) of COD in the water etc.These method specific aims are stronger, and versatility is not enough, and the material that can detect is more limited.
Summary of the invention
The objective of the invention is in order to solve the slower problem of analytical approach detection speed of existing water pollutant; Develop a kind of electrochemical method of high speed detection water pollutant; Promptly use the detection selectivity of the continuous step method raising of narrow current potential potential step chronocoulometry, keep the method for express-analysis characteristic simultaneously.
The principle of rapid electrochemical analysis method provided by the invention is following:
Electrolytic tank uses three-electrode system, and its working electrode reply measured object has high selectivity, and contrast electrode is saturated calomel electrode (SCE), and auxiliary electrode is the platinized platinum electrode, and the auxiliary electrode area should be more than or equal to working electrode.
When the current potential that applies on the electrode met or exceeded reduction (or oxidation) current potential of test substance, test substance can obtain (or losing) electronics from electrode, and redox reaction takes place on electrode surface.Because testing concentration difference in the sample, the amount of enrichment is also inequality on electrode surface, and therefore when applying certain voltage, the amount of substance that electrochemical reaction takes place is different, and this just causes electron transfer amount difference in the path.Through detecting the electric weight that shifts in this process, find that testing concentration is linear dependence in itself and the sample, this is the quantitative basis of this method.
The characteristics of this method are to confirm the potential region at reduction (or oxidation) peak of test substance through cyclic voltammetry; This spike potential interval is narrow as far as possible; Be called narrow current potential, serve as that foundation is carried out the continuous step test of narrow current potential with this potential region, thereby have only test substance can be reduced (or oxidation).This method that Here it is is got rid of chaff interference, is improved optionally foundation.
Fast quantification electricity analytical method provided by the invention, its step is following:
1) battery system in the analytical approach uses three-electrode system; In electrolytic tank, add water sample to be measured; Carry out cyclic voltammetry scan in the electrolytic tank of band Luggin capillary, narrow potential step scope (V is confirmed in reduction (or oxidation) peak position according to test substance on cyclic voltammetry curve
1, V
2).
2) potential control method is improved three potential step methods in the analytical approach, record current-time data (Fig. 1).The potential step scope is 0 → V for the first time
1, current potential arrives V
1The back kept 1～5 second, and in this process, every reduction (oxidation) current potential is higher than (being lower than) V
1Electroactive material can reduce (oxidation) reaction, thereby remove near the chaff interference the electrode; The potential step scope is V for the second time
1→ V
2, current potential arrives V
1The back kept 1～5 second, in this process, and test substance generation electrochemical reduction (or oxidation) reaction, the recorded electronic transfer amount is that electric weight is as quantitative basis; The potential step scope is V for the third time
2→ 0, stablized after the step 1～5 second, make the group of electrode surface revert to original state, be convenient to detect next time.The method T.T. is no more than 15 seconds, and speed is very fast.
3) the sample determination method in the analytical approach is: the normal concentration solution series of preparation test substance, adopt 2) described in method measure respectively and record current-time data.According to electric current-time data, in second time potential step time range, to time integral, obtain charge value with electric current.Charge value-test substance concentration with normal concentration solution series is the straight line that coordinate system adopts least square fitting, is typical curve; According to 2) said method measures the electric current-time data of unknown sample, and calculating electrical quantity value is also tried to achieve unknown sample concentration according to typical curve.
Compared with prior art, advantage of the present invention is:
Compare with gas chromatography/makings logotype method, this method does not need large-scale instrument, and cost is low; Sample need not extract and separate, and pre-treatment is simple; Sample is without chromatographic resolution, and analysis speed is fast.Compare with AAS, this method need not developer, and is simple to operate; Compare with atomic absorption/emission spectrometry, this method equipment is simple, and is easy to operate, and range of linearity broad can detect enriched sample.
Description of drawings
Electric current-time data that three potential step methods of Fig. 1 are gathered
Embodiment
Embodiment 1:
Use the nitroreduction enzyme modified electrode to be working electrode, the platinized platinum electrode is an auxiliary electrode, and saturated calomel electrode is a reference; Get narrow potential region (0.60V ,-0.80V), begin the negative sense potential step from 0V; Snap time is 3 seconds for the first time, and snap time is 3 seconds for the second time, and snap time is 2 seconds for the third time.PH value of solution 7.5 to be measured, reduction peak is quantitative, and solution is without deoxygenation, and the method can be used for detecting water nitrobenzene, the error that the deoxygenation of avoiding ventilating causes, and oxygen reduction has been accomplished during step more for the first time, can not cause interference.
Embodiment 2:
Use glass-carbon electrode to be working electrode, the platinized platinum electrode is an auxiliary electrode, and saturated calomel electrode is a reference; (0.51V 0.60V), begins the forward potential step from 0V to get narrow potential region; Snap time is 2 seconds for the first time, and snap time is 2 seconds for the second time, and snap time is 2 seconds for the third time.PH value of solution 5.6 to be measured, oxidation peak is quantitative, and the method can be used to detect forulic acid concentration.
Embodiment 3:
Use glass-carbon electrode to be working electrode, after 2.0V polarized 2 minutes in advance,, immerse lead nitrate solution then again-1.0V polarization 1 minute; Activation was used after 10 minutes under stirring condition, and platinum electrode is an auxiliary electrode, and silver/silver chloride electrode is a reference; Get narrow potential region (0.40V ,-0.55V), begin the negative sense potential step from 0V; Snap time is 2 seconds for the first time, and snap time is 3 seconds for the second time, and snap time is 2 seconds for the third time.PH value of solution 5.0 to be measured, reduction peak is quantitative, and the method can be used for detecting WS lead ion (Pb
2+) concentration.
Claims (4)
1. fast quantification electricity analytical method, its step is following:
1) battery system in the analytical approach uses three-electrode system, in the electrolytic tank of band Luggin capillary, adds water sample to be measured, carries out cyclic voltammetry scan, and the reduction of the test substance on the cyclic voltammetry curve or oxidation peak scope are narrow potential step scope (V
1, V
2);
2) control of Electric potentials adopts three potential step methods, record current-time data in the analytical approach.The potential step scope is 0 → V for the first time
1, current potential arrives V
1The back keeps a period of time; The potential step scope is V for the second time
1→ V
2, current potential arrives V
1The back keeps a period of time; The potential step scope is V for the third time
2→ 0, keep a period of time after the step;
3) the sample determination method in the analytical approach is: the normal concentration solution series of preparation test substance, adopt 2) described in method measure respectively and record current-time data.According to electric current-time data, in second time potential step time range, to time integral, obtain charge value with electric current.Charge value-test substance concentration with normal concentration solution series is the straight line that coordinate system adopts least square fitting, is typical curve; According to 2) said method measures the electric current-time data of unknown sample, and calculating electrical quantity value is also tried to achieve unknown sample concentration according to typical curve.
2. fast quantification electricity analytical method according to claim 1, wherein: three-electrode system described in the step 1) is meant the system that is made up of working electrode, contrast electrode, auxiliary electrode; The sweep velocity of said cyclic voltammetry scan is 10～500mV/s; Said oxidation/reduction peak potential region refers to that oxidation/reduction peak has just occured to the potential region of end, and its scope is at 0.01～0.30V.
3. fast quantification electricity analytical method according to claim 1; Three potential step methods wherein: step 2) are meant the method for the continuous step of CONTROLLED POTENTIAL three times; Each step begins to accomplish the used time less than 0.5 second to potential change from potential change, and three potential change time adds the retention time and is no more than 15 seconds; Said a period of time is meant 1～5 second.
4. fast quantification electricity analytical method according to claim 1, wherein: the normal concentration solution series of test substance described in the step 3) is meant the concentration known standard model of 2～20 variable concentrations, its pH should be identical with the actual analysis sample; Said second time the potential step time range be meant since the second time step to a period of time step begins for the third time; Said typical curve, its linearly dependent coefficient needs greater than 0.9.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101212252A CN101377473B (en) | 2007-08-31 | 2007-08-31 | Fast quantitative electroanalysis method |
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| CN2007101212252A CN101377473B (en) | 2007-08-31 | 2007-08-31 | Fast quantitative electroanalysis method |
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| CN101377473A CN101377473A (en) | 2009-03-04 |
| CN101377473B true CN101377473B (en) | 2012-04-25 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101782545A (en) * | 2010-03-09 | 2010-07-21 | 中国科学院过程工程研究所 | Method for purifying ionic liquid concentration |
| CN104062339B (en) * | 2014-07-09 | 2016-08-31 | 华南师范大学 | [Ru (tatp) 3] 2+ modified electrode and the method being used for detecting glucose in blood, uric acid and ascorbic acid thereof |
| CN110186981A (en) * | 2019-04-19 | 2019-08-30 | 九江德福科技股份有限公司 | A kind of Quantitative Monitoring method of chloride ion |
| CN113418824B (en) * | 2021-05-07 | 2023-02-10 | 华东理工大学 | Method for testing gas adsorption capacity |
| CN113219025B (en) * | 2021-05-07 | 2023-07-25 | 安徽大学 | Method for quantitatively detecting potassium bromate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5562815A (en) * | 1994-02-09 | 1996-10-08 | Pacesetter Ab | Apparatus and method for the electrochemical determination of the oxygen concentration of a liquid medium |
| CN1278063A (en) * | 1999-05-28 | 2000-12-27 | 株式会社明电舍 | Electrochemical analysis using electrode coated with conductive diamond, and electrochemical analysis system therewith |
| EP1236995A1 (en) * | 1995-11-16 | 2002-09-04 | USF Filtration and Separations Group Inc. | Repetitive potential step method for amperometric detection |
| CN1715899A (en) * | 2004-07-02 | 2006-01-04 | 中国科学院福建物质结构研究所 | A kind of preparation method of novel residual chlorine detecting electrode |
-
2007
- 2007-08-31 CN CN2007101212252A patent/CN101377473B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5562815A (en) * | 1994-02-09 | 1996-10-08 | Pacesetter Ab | Apparatus and method for the electrochemical determination of the oxygen concentration of a liquid medium |
| EP1236995A1 (en) * | 1995-11-16 | 2002-09-04 | USF Filtration and Separations Group Inc. | Repetitive potential step method for amperometric detection |
| CN1278063A (en) * | 1999-05-28 | 2000-12-27 | 株式会社明电舍 | Electrochemical analysis using electrode coated with conductive diamond, and electrochemical analysis system therewith |
| CN1715899A (en) * | 2004-07-02 | 2006-01-04 | 中国科学院福建物质结构研究所 | A kind of preparation method of novel residual chlorine detecting electrode |
Non-Patent Citations (1)
| Title |
|---|
| 褚道葆等.邻硝基苯酚在纳米TiO2膜修饰电极上的异相电催化还原.《应用化学》.2004,第21卷(第10期), * |
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