CN101975811A - Electrochemical sensor for field trace heavy metal detection - Google Patents
Electrochemical sensor for field trace heavy metal detection Download PDFInfo
- Publication number
- CN101975811A CN101975811A CN2010102682026A CN201010268202A CN101975811A CN 101975811 A CN101975811 A CN 101975811A CN 2010102682026 A CN2010102682026 A CN 2010102682026A CN 201010268202 A CN201010268202 A CN 201010268202A CN 101975811 A CN101975811 A CN 101975811A
- Authority
- CN
- China
- Prior art keywords
- electrode
- detection
- heavy metal
- liquid
- bismuth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to the field of electrochemical sensors, in particular to an electrochemical sensor for field trace heavy metal detection. In the electrochemical sensor, a working electrode, a reference electrode and an auxiliary electrode are connected to a control potentiometer through leads; the working electrode is plated with a film by using electroplate liquid before the detection of a practical sample; and before detection, the practical sample needs mixing with detection liquid. A detection method comprises the following steps of: adding a sample to be detected into the detection liquid on site, mixing uniformly and standing for later use; and putting the cleaned and ground working electrode into the electroplate liquid together with the reference electrode and the auxiliary electrode for pre-plating a bismuth film, inserting the three electrodes into the detection liquid and detecting the concentration of heavy metals in the sample to be detected by an electrochemical co-plating method. The sensor has low cost, high sensitivity and high repeatability, is easy and convenient to operate and can be widely applied to rapid on-site detection and daily monitoring of heavy metal ions in fresh water, sea water, articles for daily use and body fluid.
Description
Technical field
The present invention relates to the electrochemical sensor field, a kind of specifically electrochemical sensor that is used for on-the-spot trace heavy metal detection.
Background technology
Along with China's socio-economic development, process of industrialization is accelerated, and heavy metal pollution problem becomes increasingly conspicuous, and has become one of environment focus that the whole society shows great attention to.Heavy metal element can be accumulated in human body, can cause harm such as anaemia, nervous function imbalance or injury of kidney.In recent years, China's heavy metal pollution was situation occurred frequently.And the heavy metal pollution incident that takes place in succession recently especially to heavy metal monitoring have higher requirement, also more urgent need is proposed for the quick on-line monitoring early warning of heavy metal pollution incident simultaneously.Accurate on-site measurement trace heavy metal content has fast and effeciently become the important content in the analytical approach research in recent years.
The content of beary metal main method of measuring in the water sample is atomic absorption spectrography (AAS), atomic fluorescence spectrometry, ICP-AES and galvanochemistry stripping voltammetry at present.Atomic absorption spectrography (AAS) is to measure a kind of important method of water sample heavy metal concentration, be widely used in the environmental monitoring as standard, but this method needs large-sized analytic instrument-Atomic Absorption Spectrometer, and determination step is many, and the time is long, and cost is higher.Same atomic fluorescence spectrometry and ICP-AES also exist and need that large-scale instrument and equipment, monitoring velocity are slow, poor continuity, analysis cost is high and can't on-line monitoring etc. defective.The galvanochemistry stripping voltammetry has certain advantage than said method with advantages such as its instrument cost is cheap, easy to operate, standing charges are low, sensitivity height in the METHOD FOR CONTINUOUS DETERMINATION of heavy metal.It is the electrochemical sensor of working electrode that yet traditional galvanochemistry stripping voltammetry all is to use based on mercury electrode.Because the hypertoxicity of mercury and its special complicacy aspect transportation, operation, reservation, be subjected to very big restriction based on the electrochemical sensor of mercury electrode.Pressing for a kind of new, environment amenable electrochemical sensor now replaces mercury electrode and carries out Electrochemical Detection.
Be a kind of eco-friendly metallic element owing to bismuth at present, and have the electrochemical properties close that the existing bismuth film electrode that adopts carries out pertinent literature report and patented claim that heavy metal detects with mercury.The main preplating bismuth embrane method that adopts or plate the detection that the bismuth embrane method is carried out heavy metal altogether.It is unstable, oxidized easily that yet the bismuth film that preplating is good is exposed in the air, causes the detection signal instability, poor reproducibility.Plate the bismuth embrane method altogether again because the easy hydrolysis of bismuth ion, make this method in acid medium, to use, limited its application in detecting at the scene.
Summary of the invention
The object of the present invention is to provide a kind of electrochemical sensor that on-the-spot trace heavy metal detects that is used for.
For achieving the above object, technical scheme provided by the invention is:
A kind of electrochemical sensor that is used for on-the-spot trace heavy metal detection comprises working electrode, contrast electrode, auxiliary electrode, electroplate liquid and detection liquid, and working electrode, auxiliary electrode and contrast electrode are connected in the CONTROLLED POTENTIAL instrument by lead respectively;
Described working electrode, auxiliary electrode and contrast electrode detect preceding through the electroplate liquid plated film; Described electroplate liquid is the mixed liquor that contains bismuth nitrate, and wherein the concentration of bismuth is 0.05～1.5mg/L in the mixed liquor, and the pH value is 2～5.
The heavy metal of trace detection is plumbous, cadmium, copper, arsenic, mercury, chromium, silver, zinc, cobalt or nickel.Described working electrode can be carbon, gold, platinum, aluminium, copper, iron, indium, tungsten or electroconductive ITO electrode; Contrast electrode can be saturated calomel electrode, silver/silver chloride electrode or biliquid receiving electrode; Auxiliary electrode is platinized platinum electrode, glass-carbon electrode.Described electroplate liquid is the mixed liquor that contains bismuth nitrate, and promptly bismuth nitrate and buffering solution mix, and wherein buffer solution can be acetate, phosphate or citrate buffer solution; The concentration of bismuth is 0.05～1.5mg/L in the mixed liquor, and the pH value is 2～5.Described detection liquid is that bismuth nitrate and acid solution mix, and acid solution can be hydrochloric acid, nitric acid, sulfuric acid or perchloric acid solution; The concentration of bismuth is 0.1～4.0mg/L in the mixed liquor, and the pH value is 0～4.
The detection method that is used for the electrochemical sensor that on-the-spot trace heavy metal detects: testing sample is added detection liquid by 1: 1～1: 9 volume ratio mix set aside for use; To clean, polish back working electrode and contrast electrode, auxiliary electrode put into electroplate liquid in the lump and carried out preplating bismuth film, then three electrodes inserted and detects in the liquid, adopts galvanochemistry heavy metal concentration in the electroplating method detection testing sample altogether.
During described plated film, three electrodes are inserted in the electroplate liquid ,-1.0～-0.3V, adopt potentiostatic electrodeposition 0.5～3min, at working electrode surface preplating bismuth film.
Described three electrodes are inserted detected in the liquid liquid, when adopting galvanochemistry electroplating method detecting in the testing sample heavy metal altogether,-1.6～-the 0.3V scope in, adopt constant potential codeposition bismuth and metal 0.5～5min to be measured, and between-1.4～0.3V, apply forward scan current potential oxidation stripping, and the current potential increment is 0.004V, amplitude is 0.05V, pulse width is 0.2s, and time of repose is 15s.
The advantage that the present invention had: easy and simple to handle, highly sensitive, property is good again, can use in applications such as environmental monitoring, food security and clinical detection.
Electroplate liquid of the present invention and detect liquid and be fit to on-the-spot the detection, and adopt pre-plated film and galvanochemistry to plate mode that stripping detects combination altogether and carry out on-the-spot actual sample and detect, easy and simple to handle, measure when helping carrying out various heavy.Counterweight metal detection of the present invention highly sensitive, detectability can reach 0.10ppb.In addition, the present invention requires simple, quick, with low cost, the good stability of detection to The pretreatment, can be widely used in the detection of heavy metal ion in waste water, fresh water, seawater, articles for daily use and the body fluid.
Description of drawings
The sensor that Fig. 1 adopts for the embodiment of the invention.
Fig. 2 is that the reappearance of the invention process ratio sensor counterweight metallic lead sample detection detects figure.
Fig. 3 is the working curve diagram of the invention process ratio sensor counterweight metallic lead sample detection.
Fig. 4 is the detection curve figure of the invention process ratio sensor to variable concentrations heavy metal cadmium sample.
Fig. 5 is the invention process ratio sensor to the reality detection figure of water sample lead ion from the beginning.
Embodiment
Sensor is for comprising working electrode, contrast electrode, auxiliary electrode, electroplate liquid and detection liquid, and working electrode 1, auxiliary electrode 2 and contrast electrode 3 are connected in CONTROLLED POTENTIAL instrument 4 by lead respectively; Three electrodes insert in the detection liquid 6 stand-by.The sensor synoptic diagram as shown in Figure 1.
Described working electrode 1 needs before detection through electroplate liquid 5 plated films; Described electroplate liquid is the mixed liquor that contains bismuth nitrate, and wherein the concentration of bismuth is 0.05～1.5mg/L in the mixed liquor, and the pH value is 2～5.
Working electrode can be carbon, gold, platinum, aluminium, copper, iron, indium, tungsten or electroconductive ITO electrode; Contrast electrode can be saturated calomel electrode, silver/silver chloride electrode or biliquid receiving electrode; Auxiliary electrode is platinized platinum electrode, glass-carbon electrode.
Working electrode adopts platinum electrode, and detecting liquid is the mixed liquor of bismuth nitrate and perchloric acid, and wherein bi concns is 1.2mg/L, and the pH value of solution value is 2; Electroplate liquid is the mixed liquor of bismuth nitrate and citrate buffer solution, and wherein bi concns is 0.8mg/L, and the pH value of solution value is 4.Described citrate buffer solution is the mixed liquor of citric acid and sodium dihydrogen phosphate.
Cyclic voltammetric to electrode is swept in the clean back of platinum electrode polishing reach steady state (SS) in the 0.5M sulfuric acid solution, clean with high purity water.Platinum electrode is put into electroplate liquid, preplating bismuth film 2min.In detecting liquid, add the standard lead ion solution of 1 μ mol/L concentration ,-0.9V constant potential codeposition bismuth and plumbous 3min.-0.9～-applying forward scan current potential oxidation stripping between the 0.3V, the current potential increment is 0.004V, and amplitude is 0.05V, and pulse width is 0.2s, and time of repose is 15s.Triplicate, figure are as shown in Figure 2.From this figure counterweight metal ion detection of the present invention as can be known good reappearance is arranged, standard deviation only is 4.9%.
Working electrode adopts gold electrode, and detecting liquid is the mixed liquor of bismuth nitrate and hydrochloric acid, and wherein bi concns is 0.8mg/L, and the pH value of solution value is 1.5; Electroplate liquid is the mixed liquor of bismuth nitrate and phosphate buffered solution, and wherein bi concns is 1.5mg/L, and the pH value of solution value is 3.Described phosphate buffered solution is the mixed liquor of phosphoric acid and sodium hydrogen phosphate.
Cyclic voltammetric to electrode is swept in the clean back of gold electrode polishing reach steady state (SS) in the 0.5M sulfuric acid solution, clean with high purity water.Gold electrode is put into electroplate liquid, preplating bismuth film 1.5min.In detecting liquid, add standard lead ion solution ,-1.0V constant potential codeposition bismuth and plumbous 3min.-0.9～-applying forward scan current potential oxidation stripping between the 0.3V, the current potential increment is 0.004V, and amplitude is 0.05V, and pulse width is 0.2s, and time of repose is 15s.The peak current size is linear with plumbum ion concentration, as shown in Figure 3.From this figure as can be known the present invention with this understanding the heavy metal lead ion detection is had good linear relationship in the 0.1-1000ppb scope, the linear dependence degree is 0.9992.
Working electrode adopts glass-carbon electrode, and detecting liquid is the mixed liquor of bismuth nitrate and sulfuric acid, and wherein bi concns is 0.8mg/L, and the pH value of solution value is 1; Electroplate liquid is the mixed liquor of bismuth nitrate and acetate buffer solution, and wherein bi concns is 0.5mg/L, and the pH value of solution value is 2.5.Described acetate buffer solution is the mixed solution of acetic acid and sodium acetate.
Cyclic voltammetric to electrode is swept in the clean back of glass-carbon electrode polishing reach steady state (SS) in the 0.5M sulfuric acid solution, clean with high purity water.Glass-carbon electrode is put into electroplate liquid, preplating bismuth film 1.5min.In detecting liquid, add variable concentrations standard cadmium-ion solution ,-1.0V constant potential codeposition bismuth and cadmium 3min.-1.0～-applying forward scan current potential oxidation stripping between the 0.6V, the current potential increment is 0.004V, and amplitude is 0.05V, and pulse width is 0.2s, and time of repose is 15s.The peak current size is linear with plumbum ion concentration, as shown in Figure 4.From this figure as can be known the present invention heavy metal cadmium is had good response.
Working electrode adopts glass-carbon electrode, and detecting liquid is the mixed liquor of bismuth nitrate and high pure nitric acid (content 68%), and wherein bi concns is 1.5mg/L, and the pH value of solution value is 2; Electroplate liquid is the mixed liquor of bismuth nitrate and acetate buffer solution, and wherein bi concns is 1.5mg/L, and the pH value of solution value is 4.5.Described acetate buffer solution is the mixed solution of acetic acid and sodium acetate.
Adopt standard addition method to measure.Concrete steps are as follows: be to add to be measured tap water sample at 1: 1 according to volume ratio in detecting liquid at first, leave standstill after mixing.The glass-carbon electrode that will clean up and carry out activating after (being the clean back of polishing sweep cyclic voltammetric to electrode in the 0.5M sulfuric acid solution reach steady state (SS)) is put into electroplate liquid, preplating bismuth film 2.5min.Then working electrode, contrast electrode and auxiliary electrode three electrodes are added and detect in the liquid ,-1.1V constant potential codeposition 3min.-0.9～-applying forward scan current potential oxidation stripping between the 0.3V, the current potential increment is 0.004V, and amplitude is 0.05V, and pulse width is 0.2s, and time of repose is 15s, promptly obtains the peak current signal.Simultaneously get the liquid to be measured of amount same as described above in addition, in liquid to be measured, add the plumbous standard solution of a series of variable concentrations (be respectively 5,10,15ppb), detect the plumbous peak current signal that obtains corresponding a series of plumbous standard solution by above-mentioned same assay method.With lead concentration current signal is mapped, extrapolated curve promptly obtains containing in the actual detected liquid concentration of lead ion.
Because dilution in 1: 1, so actual tap water sample concentration is for detecting the twice that obtains sample concentration.Peak current size and plumbum ion concentration relation as shown in Figure 5.From this figure as can be known the present invention can realize the scene of trace heavy metal ion the actual water sample is detected.
In addition, because during the actual detected sample, sample such as clean seawater, lake water, tap water etc., since the heavy metal in the different test sample be with test sample in organism exist with the form of complexing, therefore before actual detected, can according to the actual conditions of testing sample in good time when detecting liquid and mix, testing sample is 1 with detection liquid by volume: the ratio of 1-9 is mixed, promptly testing sample is carried out certain pre-treatment, make heavy metal ion dissociate out.
Claims (8)
1. one kind is used for the electrochemical sensor that on-the-spot trace heavy metal detects, comprise working electrode, contrast electrode, auxiliary electrode, electroplate liquid and detection liquid, it is characterized in that: working electrode (1), auxiliary electrode (2) and contrast electrode (3) are connected in CONTROLLED POTENTIAL instrument (4) by lead respectively;
Described working electrode (1), auxiliary electrode (2) and contrast electrode (3) detect preceding through the electroplate liquid plated film; Described electroplate liquid is the mixed liquor that contains bismuth nitrate, and wherein the concentration of bismuth is 0.05～1.5mg/L in the mixed liquor, and the pH value is 2～5.
2. by the described electrochemical sensor that is used for on-the-spot trace heavy metal detection of claim 1, it is characterized in that: the heavy metal of trace detection is lead, cadmium, copper, arsenic, mercury, chromium, silver, zinc, cobalt or nickel.
3. by the described electrochemical sensor that is used for on-the-spot trace heavy metal detection of claim 1, it is characterized in that: described working electrode can be carbon, gold, platinum, aluminium, copper, iron, indium, tungsten or electroconductive ITO electrode; Contrast electrode can be saturated calomel electrode, silver/silver chloride electrode or biliquid receiving electrode; Auxiliary electrode is platinized platinum electrode, glass-carbon electrode.
4. by the described electrochemical sensor that is used for on-the-spot trace heavy metal detection of claim 1, it is characterized in that: described electroplate liquid is the mixed liquor that contains bismuth nitrate, be that bismuth nitrate and buffering solution mix, wherein buffer solution can be acetate, phosphate or citrate buffer solution; The concentration of bismuth is 0.05～1.5mg/L in the mixed liquor, and the pH value is 2～5.
5. by the described electrochemical sensor that is used for on-the-spot trace heavy metal detection of claim 1, it is characterized in that: described detection liquid is that bismuth nitrate and acid solution mix, and acid solution can be acetic acid, hydrochloric acid, nitric acid, sulfuric acid or perchloric acid solution; Wherein the concentration of bismuth is 0.1～4.0mg/L in the mixed liquor, and the pH value is 0～4.
6. one kind by the described detection method that is used for the electrochemical sensor that on-the-spot trace heavy metal detects of claim 1, it is characterized in that: testing sample is added in the detection liquid by 1: 1～1: 9 volume ratio mix set aside for use; To clean, polish back working electrode and contrast electrode, auxiliary electrode put into electroplate liquid in the lump and carried out preplating bismuth film, then three electrodes inserted and detects in the liquid, adopts galvanochemistry heavy metal concentration in the electroplating method detection testing sample altogether.
7. by the described detection method that is used for the electrochemical sensor of on-the-spot trace heavy metal detection of claim 6, it is characterized in that: during described plated film, three electrodes are inserted in the electroplate liquid ,-1.0～-0.3V, adopt potentiostatic electrodeposition 0.5～3min, at working electrode surface preplating bismuth film.
8. by the described detection method that is used for the electrochemical sensor of on-the-spot trace heavy metal detection of claim 6, it is characterized in that: described three electrodes are inserted detected in the liquid liquid, when adopting galvanochemistry electroplating method detecting in the testing sample heavy metal altogether,-1.6～-the 0.3V scope in, adopt constant potential codeposition bismuth and metal 0.5～5min to be measured, and between-1.4～0.3V, apply forward scan current potential oxidation stripping, the current potential increment is 0.004V, amplitude is 0.05V, pulse width is 0.2s, and time of repose is 15s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102682026A CN101975811A (en) | 2010-08-27 | 2010-08-27 | Electrochemical sensor for field trace heavy metal detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102682026A CN101975811A (en) | 2010-08-27 | 2010-08-27 | Electrochemical sensor for field trace heavy metal detection |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101975811A true CN101975811A (en) | 2011-02-16 |
Family
ID=43575714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102682026A Pending CN101975811A (en) | 2010-08-27 | 2010-08-27 | Electrochemical sensor for field trace heavy metal detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101975811A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103018302A (en) * | 2012-12-04 | 2013-04-03 | 南京化工职业技术学院 | Method for modifying and detecting trace heavy metal by glassy carbon electrode |
| CN106198698A (en) * | 2016-07-04 | 2016-12-07 | 大连大学 | A kind of measure the method for micro cyanide content in complex sample |
| CN107402250A (en) * | 2016-05-20 | 2017-11-28 | 无锡创晨科技有限公司 | A kind of multi-parameter water quality heavy metal automatic on-line detector and detection method |
| CN107991365A (en) * | 2017-11-27 | 2018-05-04 | 宇星科技发展(深圳)有限公司 | A kind of on-line cleaning method for the heavy metal on-line computing model working electrode based on anodic stripping voltammetry |
| CN108627565A (en) * | 2018-05-14 | 2018-10-09 | 桂林理工大学 | Bismuth, copper the admixture plates the film strip and the preparation method and application thereof |
| CN110333276A (en) * | 2019-06-28 | 2019-10-15 | 广州钰芯传感科技有限公司 | A kind of highly integrated electrode of bismuth film and the preparation method and application thereof for fast detection of trace cadmium |
| CN110426430A (en) * | 2019-09-02 | 2019-11-08 | 西安热工研究院有限公司 | A kind of big pipeline material field electrochemical test device of power plant and method |
| CN110927236A (en) * | 2019-12-09 | 2020-03-27 | 新疆天业（集团）有限公司 | Method for detecting lead ion content of industrial wastewater based on electrochemical sensor |
| CN112946047A (en) * | 2021-01-28 | 2021-06-11 | 中国科学院烟台海岸带研究所 | Electrochemical method for rapidly detecting inorganic phosphorus in water body dissolved state |
| CN113092564A (en) * | 2019-12-23 | 2021-07-09 | 上海雄图生物科技有限公司 | Method for rapidly detecting heavy metals in water |
| CN113820370A (en) * | 2021-09-30 | 2021-12-21 | 中国科学院合肥物质科学研究院 | Method for detecting heavy metal As (III) in natural water body |
| CN114002279A (en) * | 2021-10-12 | 2022-02-01 | 华中科技大学 | Method for efficiently detecting content of germanium ions in trace amount and application of method in germanium ore metallurgy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6682647B1 (en) * | 2000-05-10 | 2004-01-27 | New Mexico State University Technology Transfer Corporation | Bismuth-based electrochemical stripping analysis |
| CN101706468A (en) * | 2008-12-12 | 2010-05-12 | 烟台海岸带可持续发展研究所 | Preparation of bismuth membrane electrode |
-
2010
- 2010-08-27 CN CN2010102682026A patent/CN101975811A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6682647B1 (en) * | 2000-05-10 | 2004-01-27 | New Mexico State University Technology Transfer Corporation | Bismuth-based electrochemical stripping analysis |
| CN101706468A (en) * | 2008-12-12 | 2010-05-12 | 烟台海岸带可持续发展研究所 | Preparation of bismuth membrane electrode |
Non-Patent Citations (4)
| Title |
|---|
| 《Electroanalysis》 20061231 Agnieszka Krolicka等 Effects of Electroplating Variables on the Voltammetric Properties of Bismuth Deposits Plated Potentiostatically 第1649-1657页 5-8 第18卷, 第17期 * |
| 《分析化学（FENXI HUAXUE）研究简报》 20020930 李建平等 铋膜电极电位溶出法测定痕量铅、镉、锌 第1092-1095页 1-8 第30卷, 第9期 * |
| 董良飞等: "铋膜电极微分电位溶出法测定酒中铅和锌", 《酿酒科技》 * |
| 黄华伟等: "铋膜电极微分脉冲溶出伏安法测定食用明胶中的铅", 《应用化工》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103018302A (en) * | 2012-12-04 | 2013-04-03 | 南京化工职业技术学院 | Method for modifying and detecting trace heavy metal by glassy carbon electrode |
| CN107402250A (en) * | 2016-05-20 | 2017-11-28 | 无锡创晨科技有限公司 | A kind of multi-parameter water quality heavy metal automatic on-line detector and detection method |
| CN106198698A (en) * | 2016-07-04 | 2016-12-07 | 大连大学 | A kind of measure the method for micro cyanide content in complex sample |
| CN107991365A (en) * | 2017-11-27 | 2018-05-04 | 宇星科技发展(深圳)有限公司 | A kind of on-line cleaning method for the heavy metal on-line computing model working electrode based on anodic stripping voltammetry |
| CN108627565A (en) * | 2018-05-14 | 2018-10-09 | 桂林理工大学 | Bismuth, copper the admixture plates the film strip and the preparation method and application thereof |
| CN110333276A (en) * | 2019-06-28 | 2019-10-15 | 广州钰芯传感科技有限公司 | A kind of highly integrated electrode of bismuth film and the preparation method and application thereof for fast detection of trace cadmium |
| CN110426430A (en) * | 2019-09-02 | 2019-11-08 | 西安热工研究院有限公司 | A kind of big pipeline material field electrochemical test device of power plant and method |
| CN110927236A (en) * | 2019-12-09 | 2020-03-27 | 新疆天业（集团）有限公司 | Method for detecting lead ion content of industrial wastewater based on electrochemical sensor |
| CN113092564A (en) * | 2019-12-23 | 2021-07-09 | 上海雄图生物科技有限公司 | Method for rapidly detecting heavy metals in water |
| CN112946047A (en) * | 2021-01-28 | 2021-06-11 | 中国科学院烟台海岸带研究所 | Electrochemical method for rapidly detecting inorganic phosphorus in water body dissolved state |
| CN112946047B (en) * | 2021-01-28 | 2023-03-21 | 中国科学院烟台海岸带研究所 | Electrochemical method for rapidly detecting inorganic phosphorus in water body dissolved state |
| CN113820370A (en) * | 2021-09-30 | 2021-12-21 | 中国科学院合肥物质科学研究院 | Method for detecting heavy metal As (III) in natural water body |
| CN113820370B (en) * | 2021-09-30 | 2023-07-18 | 中国科学院合肥物质科学研究院 | Method for detecting heavy metal As (III) in natural water body |
| CN114002279A (en) * | 2021-10-12 | 2022-02-01 | 华中科技大学 | Method for efficiently detecting content of germanium ions in trace amount and application of method in germanium ore metallurgy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101975811A (en) | Electrochemical sensor for field trace heavy metal detection | |
| Zhang et al. | Electrochemical sensor based on carbon-supported NiCoO2 nanoparticles for selective detection of ascorbic acid | |
| CN102798657B (en) | Site fast detection method for copper, zinc, lead and cadmium as heavy metals in seawater | |
| Liao et al. | Wireless water quality monitoring and spatial mapping with disposable whole-copper electrochemical sensors and a smartphone | |
| CN101839851B (en) | Field fast detection method for heavy metal ions in water | |
| CN103592356A (en) | Method for quickly detecting lead and cadmium by adopting scanning anodic stripping voltammetry | |
| Bodini et al. | Voltammetric determination of nitrate ion at parts-per-billion levels | |
| CN103278551A (en) | Active carbon double-electrode system-based heavy metal electrochemical sensor and method for detection of heavy metals by the active carbon double-electrode system-based heavy metal electrochemical sensor | |
| Kokkinos et al. | Determination of Pb (II) by sequential injection/stripping analysis at all-plastic electrochemical fluidic cells with integrated composite electrodes | |
| CN108344792B (en) | Method for rapidly detecting total arsenic in water body | |
| Rutyna et al. | Determination of ultratrace thallium (I) by anodic stripping voltammetry at bismuth film electrodes following double deposition and stripping steps | |
| CN203535000U (en) | Portable detector for detection of heavy metal in water environment | |
| CN207557166U (en) | A kind of graphene test paper electrode and its heavy metal detector based on electrochemistry of foundation | |
| Thiruppathi et al. | Electrochemical detection of fluoride ions using 4-aminophenyl boronic acid dimer modified electrode | |
| CN101377473B (en) | Fast quantitative electroanalysis method | |
| Pan et al. | New application of tin–bismuth alloy for electrochemical determination of cadmium | |
| Sattayasamitsathit et al. | Bismuth film electrode for analysis of tetracycline in flow injection system | |
| CN111289596A (en) | Three-electrode system, electrochemical sensor and preparation method thereof, electrochemical workstation and application thereof | |
| El‐Maali et al. | Square‐Wave Stripping Voltammetry of Uranium (VI) at the Glassy Carbon Electrode. Application to Some Industrial Samples | |
| Eskilsson et al. | Reductive stripping chronopotentiometry for selenium in biological materials with a flow system | |
| Miranda et al. | On-chip optical anodic stripping with closed bipolar cells and cathodic electrochemiluminescence reporting | |
| CN101957336A (en) | Method for improving detection accuracy of electrochemical active metal ions | |
| De Souza et al. | Determination of dissolved Zn (II) and Cd (II) in estuarine water by using a bismuth film microelectrode | |
| CN106093149B (en) | For detecting electrochemica biological sensor, the preparation method and applications of α-ketoglutaric acid | |
| CN103940988A (en) | Rapid heavy metal detector based on enzyme and immune sensors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110216 |