CN102243209A - Portable heavy metal chrome sensor, preparation process and detection method thereof - Google Patents
Portable heavy metal chrome sensor, preparation process and detection method thereof Download PDFInfo
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- CN102243209A CN102243209A CN2010101722401A CN201010172240A CN102243209A CN 102243209 A CN102243209 A CN 102243209A CN 2010101722401 A CN2010101722401 A CN 2010101722401A CN 201010172240 A CN201010172240 A CN 201010172240A CN 102243209 A CN102243209 A CN 102243209A
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Abstract
The invention relates to a portable heavy metal chrome sensor, a preparation process and a detection method thereof. The portable heavy metal chrome sensor is characterized in that: three electrodes are arranged on a polyester film substrate through silk-screen printing, wherein the three electrodes comprise a functional graphite work electrode, a carbon auxiliary electrode and a silver and silver chloride reference electrode; carbon lead wires of the three electrodes are arranged on the polyester film substrate through the silk-screen printing, wherein a insulated layer printed through insulating slurry is covered on front ends of the three carbon lead wires and the area on the substrate except the three electrodes. With the present invention, the portable heavy metal chrome sensor has characteristics of fastness, one man operation, easy carrying, low cost and simple operation, single use; introduction of the mercury film electrode is avoided, such that pollution is not generated; the detection method has high sensitivity and good reproducibility. Therefore, the portable heavy metal chrome sensor is an environmental-protection product for assurance of water environment ecological security, and the detection method is an environmental-protection monitoring method for the assurance of the water environment ecological security.
Description
Technical field
But the present invention relates to the sensor of content of beary metal in a kind of fast detecting water, be specifically related to a kind of portable heavy metal chromium sensor and preparation technology and detection method, belong to technical field of analytical instruments.
Background technology
Chromium exists with sexavalence, trivalent or divalence in environment, wherein sexavalent chrome is important environmental contaminants, can cause that liver, ephrosis become, because its oxidisability and to the high osmosis of skin, can make skin ulcer, respiratory tract, alimentary canal there are stimulation, carcinogenic, mutagenesis, are considered to carcinogen.Chromium content will make the people vomit when 0.1mg/L is above in the potable water, infringement enteron aisle and kidney; In addition, sexavalent chrome can kill the animals and plants that swim in the water body, and the self purification process of water is produced harmful effect.Its pollution source are mainly from industry such as chrome ore exploitation processing, plating, process hides, textile and papers.The early stage promulgation of China " industry " three wastes " emission standard " (GBJ4-73) pointed out, sexavalent chrome be 5 kinds to one of bigger first kind objectionable impurities of human body infringement, therefore require to carry out strictness and monitor to hexavalent chromium polluted in the environment.Therefore, need a kind of method of operating simple, cost is low, quick, portable chromic detecting instrument.The main method of measuring content of 6-valence Cr ions in the waste water at present has atomic absorption spectrography (AAS), plasma mass spectroscopy, fluorescence method, spectrophotometric method, chemoluminescence method, yet said method sample preparation complexity, consuming time, simultaneously can not be at the pollution source scene to the sexavalent chrome The real time measure in the waste water.
Summary of the invention:
Technical matters to be solved by this invention is: solve the problem that above-mentioned prior art exists, be nonferrous metallurgy, electronics, the discharge of wastewater on-line monitoring of industries such as plating, machinery provides a kind of and part operate fast, single, is easy to carry, low-cost and simple to operate, the disposable portable heavy metal chromium sensor of use and preparation technology and detection method, reach the control quantity of wastewater effluent and stop contamination accident and take place, also can be used for surface water such as cross section of river and detect automatically, guarantee the water environment ecological safety.
The technical solution used in the present invention is: this portable heavy metal chromium sensor, and three electrodes of serigraphy on the mylar substrate: one is functionalization graphite working electrode, and one is the carbon auxiliary electrode, one is silver and silver chloride contrast electrode; And on the mylar substrate carbon extension line of above-mentioned three electrodes of serigraphy.
In the technique scheme, on the forward part and three electrodes substrate in addition of three electrode carbon extension lines, also being coated with the insulation course that the insulation slurry is printed.
In the technique scheme, the slurry that described functionalization graphite working electrode is made by functionalization dag, carbon dust and printing ink is printed onto to dry on the surface of polyester and forms.
In the technique scheme, described functionalization dag is that graphite has adopted pre-oxidation treatment, has increased the enrichment adsorption function of graphite film, the sensitivity that has improved sensor.
The preparation technology of portable heavy metal chromium sensor of the present invention is: at first functionalization dag, carbon dust and printing ink are made working electrode printing slurry, by the screen printing technique preparation and to be printed onto thickness separately be on 250 microns the mylar, place baking oven to dry then, make working electrode, and the carbon electrode lead-in wire of printing carbon auxiliary electrode, silver and silver chloride contrast electrode and three electrodes; The carbon extension line upper surface that then reaches three electrodes again on the substrate beyond above-mentioned working electrode, contrast electrode and the auxiliary electrode applies one deck insulation slurry, form insulation course, insulation course covers the carbon extension line forward part of three electrodes, and insulation course is stretched out in the carbon extension line rear section of each electrode.
The detection method of portable heavy metal chromium sensor of the present invention is: sensor of the present invention is connected with electrochemical workstation; Be used to detect the heavy metal content of 6-valence Cr ions, at 0.1MH
2SO
4Add sample to be tested in the solution, solution is immersed in the sensor lower end of printing electrode, adopt the linear sweep volt-ampere analysis, according to reduction peak current that obtains and the linear relationship between the chromic concentration, the concentration of mensuration heavy metal hexavalent chromium.
Serigraphy prepares the sensor electrode technology not only provides the possibility of suitability for industrialized production for the electrochemical sensing of heavy metal ion, and make simple, cheap, be easy to carry, be easy to microminiaturized and integrated.The serigraphy ultimate principle of prior art is: utilize the saturating printing ink of screen printing forme picture and text part mesh, the non-graphic part mesh not ultimate principle of strike through prints.On screen printing forme one end, pour printing ink into during printing, apply certain pressure, move towards the screen printing forme other end simultaneously with scraping the printing ink position of scraper plate on screen printing forme.Printing ink is expressed on the stock from the mesh of picture and text part by scraper plate in moving.Owing to the viscous effect of printing ink makes the trace set within limits, the printing process middle scraper is line with screen printing forme and stock all the time and contacts, osculatory moves with scraper plate and moves, extruding by scraper plate during printing, printing ink is transferred on the stock by the mesh of picture and text part, formed the picture and text the same with original copy.
The measuring-signal of the heavy metal electrochemical analysis of prior art is electric signal such as electricity is led, current potential, electric current, electric weight, the conversion that does not need analytic signal is direct record just, so the apparatus of electrochemical analysis is simple much small-sized, be easy to robotization and analysis continuously.In the check and analysis of sample, electrochemical analysis method is a kind of generally acknowledged quick, sensitive, trace analysis method accurately, and instrument is simple, cheap, can realize water quality is carried out scene monitoring in real time.Development is also developed high sensitivity, can be become the focus of current research simultaneously to the electrochemical sensor of heavy metal lead, cadmium and the online detection of zinc ion.
In the practical application of electrochemical sensor, because the complicacy of full pattern and the easy amalgamation of existing metal electrode cause the measurement result sensitivity of sensor lower.Disposable sensor of the present invention is used and is made the hexavalent chromium detection avoid traditional mercury electrode, make the portability of instrument strengthen greatly, can carry out the scene out of doors and detect, and realize heavy metal hexavalent chromium fast detecting in the waste water, make detection dirigibility on opportunity strengthen greatly.
The present invention compared with prior art has the screen printing electrode preparation simply, and is easy to process, cost is low, has avoided the introducing of mercury film electrode simultaneously, and is pollution-free, the sensor detecting method made from this screen printing electrode is simple, and characteristics such as highly sensitive, favorable reproducibility.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Label declaration: 1. mylar, 2. carbon electrode lead-in wire, 3. working electrode, 4. auxiliary electrode, 5. contrast electrode, 6. carbon electrode lead-in wire end.
Fig. 2 is the scanning electron microscope diagram of working electrode of the present invention.
Fig. 3 electrochemical analyser that to be sensor of the present invention collocation detect full pattern is figure as a result.
Fig. 4 says described Fig. 3 electrochemical analyser result's linear graph on being.
Embodiment
Below in conjunction with accompanying drawing and example the present invention is further described:
Embodiment 1: product structure of the present invention.
Referring to Fig. 1, portable heavy metal chromium sensor of the present invention, three electrodes of serigraphy on mylar substrate 1: one is that 3, one of functionalization graphite working electrodes are that 4, one of carbon auxiliary electrodes are silver and silver chloride contrast electrode 5; And on mylar substrate 1 the carbon extension line 2 of above-mentioned three electrodes of serigraphy; On the substrate beyond the forward part of the carbon extension line 2 of three electrodes and three electrodes, also being coated with the insulation course that the insulation slurry is printed.
Above-mentioned functionalization graphite working electrode is that slurry that functionalization dag, carbon dust and printing ink are made is printed onto that oven dry forms on the mylar.
The functionalization of above-mentioned graphite working electrode, be because working electrode material graphite has been adopted pre-oxidation treatment, become the functionalization dag, concrete pre-oxidation treatment technology is: 60 milliliters in the sulfuric acid that the 5g dag is added 3M/L, stirred 12 hours, washed then 0.5-1 hour, at last oven dry, stand-by, become the functionalization dag.
Above-mentioned functions fossil China ink working electrode is made slurry by functionalization dag, carbon dust and printing ink and is printed onto that its proportioning is on the mylar substrate: the ratio of functionalization dag, carbon dust, printing ink is 1: 2: 13 or 1: 1.5: 12.
The present invention is owing to adopted pre-oxidation treatment to working electrode material graphite, what increase graphite surface contains the oxygen functional group, make sexavalent chrome be enhanced like this in the enrichment adsorptive power of electrode surface, improved the sensitivity of described sensor, simultaneously, the disposable sensor use need not to add mercury ion in sample liquid, effectively reduced the pollution of mercury to environment.
Embodiment 2: detect the sexavalent chrome in the mark-on sample in the river
When integrating electro chemical sensor of the present invention uses, can be connected as three electrode tie-in lines, add solution, use voltammetry to measure its electrochemical signals with the multifunction electric chemical analyzer with the μ-various station of AutolabIII galvanochemistry galvanochemistry worktable.Sensor of the present invention screen printing electrode as described in Figure 1 is used to detect the method for heavy metal content of 6-valence Cr ions.Adopt the linear sweep analytic approach, at first, described sensor is connected with electrochemical workstation; Secondly, get the river water sample, will treat that with sulfuric acid the test sample pH value of solution is adjusted to 1, preparation 0-1000 μ gL
-1A series of mark-on solution of hexavalent chromium.At last, solution is invaded in the sensor electrode lower end begin linear scanning-analysis method, according to the method for the invention, carry out test experiments, can obtain as the linear sweep curve among Fig. 3, the operating potential window exists: 0.8～-0.4V, hexavalent chromium concentration calibration, the peak current when reading the 0.075V current potential.As shown in Figure 4, reduction peak current and hexavalent chromium concentration 0-1000 μ gL
-1Present good linear relationship in the scope, relevant is 0.999, detects and is limited to 21 μ gL
-1
The electrode that the present invention uses is an Integrated electrode, constitutes three-electrode system.Characteristics are that method is simple, fast.Adopt disposable electrochemical sensor of the present invention, can reduce greatly, but simultaneously because silk-screen printing technique has determined prepared in batches, cost is extremely low because traditional electrode is used the analytical error of bringing repeatedly.
Claims (6)
1. portable heavy metal chromium sensor, it is characterized in that: three electrodes of serigraphy on the mylar substrate: one is functionalization graphite working electrode, and one is the carbon auxiliary electrode, one is silver and silver chloride contrast electrode; And on the mylar substrate carbon extension line of above-mentioned three electrodes of serigraphy.
2. portable heavy metal chromium sensor according to claim 1 is characterized in that: on the forward part and three electrodes substrate in addition of three electrode carbon extension lines, also being coated with the insulation course that the insulation slurry is printed.
3. portable heavy metal chromium sensor according to claim 1 is characterized in that: described functionalization graphite working electrode is that slurry that functionalization dag, carbon dust and printing ink are made is printed onto that oven dry forms on the mylar.
4. portable heavy metal chromium sensor according to claim 3 is characterized in that: described functionalization dag is that graphite has adopted pre-oxidation treatment.
5. the preparation technology of a portable heavy metal chromium sensor, it is characterized in that: at first functionalization dag, carbon dust and printing ink are made working electrode printing slurry, by the screen printing technique preparation and to be printed onto thickness separately be on 250 microns the mylar, place baking oven to dry then, make working electrode, and the carbon electrode lead-in wire of printing carbon auxiliary electrode, silver and silver chloride contrast electrode and three electrodes; The carbon extension line upper surface that then reaches three electrodes again on the substrate beyond above-mentioned working electrode, contrast electrode and the auxiliary electrode applies one deck insulation slurry, form insulation course, insulation course covers the carbon extension line forward part of three electrodes, and insulation course is stretched out in the carbon extension line rear section of each electrode.
6. the detection method of a portable heavy metal chromium sensor is characterized in that: sensor of the present invention is connected with electrochemical workstation; Be used to detect the heavy metal content of 6-valence Cr ions, at 0.1MH
2SO
4Add sample to be tested in the solution, solution is immersed in the sensor lower end of printing electrode, adopt the linear sweep volt-ampere analysis, according to reduction peak current that obtains and the linear relationship between the chromic concentration, the concentration of mensuration heavy metal hexavalent chromium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2010101722401A CN102243209A (en) | 2010-05-14 | 2010-05-14 | Portable heavy metal chrome sensor, preparation process and detection method thereof |
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| CN2010101722401A CN102243209A (en) | 2010-05-14 | 2010-05-14 | Portable heavy metal chrome sensor, preparation process and detection method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103217350A (en) * | 2013-03-28 | 2013-07-24 | 温州市质量技术监督检测院 | Portable fast chromium-contaminated water detector and detection method thereof |
| CN107941888A (en) * | 2017-11-12 | 2018-04-20 | 南京银茂铅锌矿业有限公司 | Using the method for polarography determination high-content lead zinc |
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| US5708247A (en) * | 1996-02-14 | 1998-01-13 | Selfcare, Inc. | Disposable glucose test strips, and methods and compositions for making same |
| CN2548158Y (en) * | 2002-06-20 | 2003-04-30 | 复旦大学 | Disposable electrochemical sensor for measuring blood lend concentration |
| CN1540333A (en) * | 2003-04-22 | 2004-10-27 | 英科新创(厦门)科技有限公司 | Sensng device for detecting metallic ion |
| CN101017149A (en) * | 2007-03-05 | 2007-08-15 | 浙江大学 | Disposable blood lead biosensor |
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2010
- 2010-05-14 CN CN2010101722401A patent/CN102243209A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5708247A (en) * | 1996-02-14 | 1998-01-13 | Selfcare, Inc. | Disposable glucose test strips, and methods and compositions for making same |
| CN2548158Y (en) * | 2002-06-20 | 2003-04-30 | 复旦大学 | Disposable electrochemical sensor for measuring blood lend concentration |
| CN1540333A (en) * | 2003-04-22 | 2004-10-27 | 英科新创(厦门)科技有限公司 | Sensng device for detecting metallic ion |
| CN101017149A (en) * | 2007-03-05 | 2007-08-15 | 浙江大学 | Disposable blood lead biosensor |
Non-Patent Citations (3)
| Title |
|---|
| JOSEPH WANG等: "Mercury-Free Disposable Lead Sensors Based on Potentiometric Stripping Analysis at Gold-Coated Screen-Printed Electrodes", 《ANAL. CHEM.》, vol. 65, no. 11, 1 June 1993 (1993-06-01), pages 1529 - 1532, XP002400081, DOI: 10.1021/ac00059a008 * |
| M. ENCARNACION BURGOA CALVO等: "Determination of lamotrigine by adsorptive stripping voltammetry using silver nanoparticle-modified carbon screen-printed electrodes", 《TALANTA》, vol. 74, no. 1, 24 May 2007 (2007-05-24), pages 60 - 2 * |
| OLGA DOMINGUEZ-RENEDO等: "Electrochemical determination of chromium(VI) using metallic nanoparticle-modified carbon screen-printed electrodes", 《TALANTA》, vol. 76, no. 4, 24 April 2008 (2008-04-24), pages 855 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103217350A (en) * | 2013-03-28 | 2013-07-24 | 温州市质量技术监督检测院 | Portable fast chromium-contaminated water detector and detection method thereof |
| CN107941888A (en) * | 2017-11-12 | 2018-04-20 | 南京银茂铅锌矿业有限公司 | Using the method for polarography determination high-content lead zinc |
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Application publication date: 20111116 |