CN103134839A - Method for rapidly detecting trace heavy metal ions - Google Patents
Method for rapidly detecting trace heavy metal ions Download PDFInfo
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- CN103134839A CN103134839A CN2013100521108A CN201310052110A CN103134839A CN 103134839 A CN103134839 A CN 103134839A CN 2013100521108 A CN2013100521108 A CN 2013100521108A CN 201310052110 A CN201310052110 A CN 201310052110A CN 103134839 A CN103134839 A CN 103134839A
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Abstract
The invention relates to a method for rapidly detecting trace heavy metal ions. A related device in the method is composed of an electrolytic cell, working electrode signal channels, bismuth electrode arrays, a composite structure working electrode, a reference electrode and a counter electrode. An electrochemical stripping voltmeter-ammeter method is adopted to carry out detection. Through three bismuth electrode arrays with different structures, namely, a three-dimensional flower-shaped array, a nanowire array and a nanometer needle tip array, planar integration and three-dimensional integration are respectively achieved by the method, and an electrochemical transducer of the composite structure working electrode is constructed. The electrochemical transducer of the composite structure working electrode has the advantages of being low in manufacturing cost, high in performance, capable of achieving large-area preparation and the like. Through the electrochemical transducer, trace heavy metal in water can be detected rapidly, and the electrochemical transducer is low in cost, environment-friendly, and capable of being portable for carrying out detection. The defects that due to the fact that when the stripping voltmeter-ammeter method in the prior art is used for detecting the trace heavy metal ions, only working electrodes of one structure is used so that detection sensitivity is not high and limit of detection is not high are overcome.
Description
Technical field
The invention belongs to the electrochemical sensor technical field, be specifically related to a kind of method of fast detection of trace heavy metal ion.
Background technology
The prerequisite of Heavy Metal Pollution is can the heavy metal in pollutant be detected fast and accurately.In numerous detection methods, the Electrochemical Stripping voltammetry has easy to detect, economic advantage, is one of prefered method of Heavy Metals in Waters ion fast detecting.
Heavy metal toxicity is large, be difficult in environment by metabolism, easily by the biosome enrichment and biological amplification is arranged, and is a kind of pollutant of serious harm ecologic environment.The prerequisite of Heavy Metal Pollution is to detect fast and accurately it.The Electrochemical Stripping voltammetry is the quickest, the sensitiveest and detection means the most easily at present.
It is all that working electrode with single structure detects that present trace heavy metal ion detects electrochemical sensor, the working electrode of this single structure is low in the current potential resolution characteristic, the shortcomings such as detectability is not high are so carry out will being difficult to realize when simultaneous quantitative detects to simultaneous contents of many kinds of heavy metal ion.
The present invention constructs respectively the electrod-array of three kinds of different structures with the bismuth material, concrete three-dimensional flower shape array, nano-wire array and the nanometer pinpoint array of comprising, again that the electrod-array of three kinds of different structures is integrated, construct high performance composite structure working electrode electrochemical sensor.
In reality detects, take full advantage of the detection characteristic of the electrode of three kinds of different structures, can quantitatively detect fast and accurately trace heavy metal ion in water body simultaneously.This pick-up unit and application have low cost, high-performance, eco-friendly advantage, can obtain applications well in the heavy metal contaminants context of detection.
Summary of the invention
The object of the invention is, a kind of method of fast detection of trace heavy metal ion is provided, in the method, related device is by electrolytic tank, working electrode signalling channel, bismuth pole array, composite structure working electrode, contrast electrode with electrode is formed, adopt the Electrochemical Stripping voltammetry to detect, the method is passed through the bismuth pole array of three kinds of different structures: three-dimensional flower shape array, nano-wire array and nanometer pinpoint array, realize respectively Planar integration and three-dimensional integrated, the electrochemical sensor of structure composite structure working electrode.The electrochemical sensor of this composite structure working electrode have low cost of manufacture, performance high, can realize the outstanding advantages such as large tracts of land preparation.For trace heavy metal in water body can fast detecting low cost, high-performance, environmental friendliness, electrochemical sensor that can portable detection.Solve the working electrode of only using a kind of structure when prior art utilizes stripping voltammetry to detect trace heavy metal ion, detection sensitivity is hanged down and the not high shortcoming of detectability.
The method of a kind of fast detection of trace heavy metal ion of the present invention, in the method, related device is by electrolytic tank, working electrode signalling channel, bismuth pole array, composite structure working electrode, contrast electrode with electrode is formed, adopt the Electrochemical Stripping voltammetry to detect, concrete operations follow these steps to carry out:
A, in electrolytic tank (1) fixedly composite structure working electrode (4), contrast electrode (5) and to electrode (6) respectively, be provided with bismuth pole array (3) on composite structure working electrode (4), be provided with working electrode signalling channel (2) on bismuth pole array (3), wherein bismuth pole array (3) is that bismuth nano-wire array and bismuth nanometer pinpoint array consist of by the three-dimensional flower shape of bismuth array;
b, to contain copper, plumbous, zinc, mercury, the aqueous solution of one or more in cadmium and arsenic is put into electrolytic tank (1), each electrode of composite structure working electrode (4) connects respectively a working electrode signalling channel (2), working electrode signalling channel (2) accesses respectively on existing electrochemical analyser according to a conventional method, carrying out scanning quantitation detects, each voltammetric signal after detection, all by independent record, by volt-ampere analysis software, three voltammetric signals are carried out analysis-by-synthesis and typical curve comparison at last, can obtain kind and the concentration of heavy metal ion.
In step a, composite structure working electrode (4) is configured to Planar Compound structure or three-dimensional composite structure.
The three-dimensional flower shape of bismuth in step a bismuth pole array (3) array, each three-dimensional flower shape bismuth structure is all that the nanometer bismuth thin slice by two dimension consists of, the thickness of nanometer bismuth thin slice is 20-150nm.
The bottom of the bismuth nano-wire array in step a bismuth nano-wire array (3) is fixed by the template of growing nano linear array, and the height that exposes the bismuth nano-wire array of template is 10-200 μ m.
The top of the bismuth nanometer pinpoint array in step a bismuth nano-wire array (3) is the tip-like structure, from the long-pending maximum in array bottom section, diminishes gradually toward the top sectional area.
Three-dimensional flower shape array in step a bismuth nano-wire array (3), the bismuth material on bismuth nano-wire array and bismuth nanometer pinpoint array is monocrystalline.
The method of a kind of fast detection of trace heavy metal ion of the present invention, the three-dimensional flower shape array in the method in bismuth nano-wire array (3), being prepared as of bismuth nano-wire array and bismuth nanometer pinpoint array:
3 D stereo flower shape array in bismuth nano-wire array (3) is constructed by electrochemical deposition method, and elder generation is dissolved in bismuth salt in the middle of aqueous solution, obtains containing the solution of bismuth ion; As working electrode, will contain the solution of bismuth ion as electrolytic solution with the substrate of conduction, the current density when controlling electrochemical deposition, the method by electrochemical deposition prepares the bismuth micro-nano structure array;
The preparation of the nano-wire array in bismuth nano-wire array (3) realizes by template limiting growth method, have in the middle of first preparing and receive the anodic oxidation aluminium formwork of even rice hole, then in the hole of template the inside by the grow nano wire of bismuth of the method for electro-deposition, remove at last the first half of template, obtain the bismuth nano-wire array, and the lower end of these nano wire formation links by template and is integrated;
The preparation of the nanometer pinpoint array in bismuth nano-wire array (3) realizes by plated film on base material, first prepare the tip-like aluminum oxide nano-wire array, then the method by plated film coats the last layer bismuth thin film in its outside, obtains at last the tip-like nano-wire array that the surface coats bismuth thin film.
Prepare the electrod-array of three kinds of structures, after being three-dimensional flower shape array, nano-wire array and nanometer pinpoint array, take them as working electrode, make contrast electrode with Ag/AgCl, make electrode of platinum filament, form the electrochemical reaction pick-up unit of three-electrode system.
In the electrochemical reaction pick-up unit, the position of three composite structure working electrodes (4) can be positioned at same plane, can be also three-dimensional the placement.
When multiple trace heavy metal ion detects in to water body, each working electrode is connected with an independent working electrode signalling channel (2), at last ion and kind and concentration is determined that signal by three signalling channels of software compare of analysis obtains.
Description of drawings
Fig. 1 is the pick-up unit schematic diagram of fast detection of trace heavy metal ion of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but the present invention is not only limited to the embodiment that provides.
Embodiment 1
Bismuth 3 D stereo flower shape array in preparation bismuth nano-wire array 3:
Be 99.999% BiCl with purity
3With the electrolytic solution of the three-dimensional flower shape of deionized water preparation electro-deposition bismuth nano structure electrode array, finally consisting of of the molten electrolytic solution for preparing: BiCl
3Concentration 15 mmol/L, NaCl concentration 0.3mol/L, H
3BO
3Concentration 0.25mol/L, HCl concentration 0.45mol/L, make the working electrode of deposition use of Copper Foil, the three-dimensional flower shape nano structure electrode array of deposition in the three-electrode system electrolytic tank, deposition process is controlled by electrochemical workstation AUTOLAB, the model of instrument is PGS-TAT30, the current potential of electro-deposition is-1.3V (relative saturation saturated calomel electrode), sedimentation time is 8 minutes, the temperature of electrolytic solution keeps room temperature, by above-mentioned deposition, prepare three-dimensional flower shape nano structure electrode array, wherein the surface density of three-dimensional flower shape nanostructured reaches 2 * 10
3mm
-2, the diameter average out to 15 μ m of flower, the thickness of two-dimentional petal is 65nm, is the monocrystalline bismuth;
Nano-wire array in preparation bismuth nano-wire array 3:
Be anodised aluminium (AAO) template of 100 μ m with thickness, deposition bismuth nano-wire array electrode, on anodic oxidation aluminium formwork, the diameter of nano aperture is 30nm, the consisting of of electrolytic solution: 15g/L BiCl
3, 30g/L tartrate, the NaCl of 20g/L, 45g/L glycerine is adjusted to 0.7 with hydrochloric acid with the pH of electrolytic solution at last, deposits the nano wire of bismuth in the nano aperture of anodic oxidation aluminium formwork by pulsed deposition, sedimentation potential is-1.0V (relative saturation saturated calomel electrode) that the burst length is T
on=25 s, T
off=45 s, through after the deposition of 1000s, obtained the bismuth nano-wire array in the hole of template, corrode by 2% dilute phosphoric acid solution (volume ratio) antianode alumina formwork again, etching time is 18 minutes, obtains at last the exposed bismuth nano-wire array in the template outside in top, the total length average out to 80 μ m of bismuth nano-wire, wherein exposed length outside template is 25 μ m, and bismuth nano-wire is the monocrystalline bismuth;
Nanometer pinpoint array in preparation bismuth nano-wire array 3:
carry out reaming by the antianode alumina formwork, and reaming in control temperature and stir and obtain the aluminium oxide nano pinpoint array, plate again one deck bismuth film on array, obtain bismuth nanometer pinpoint electrod-array, the thickness of anodic oxidation aluminium formwork used is 150 μ m, hole mean diameter in template is 80nm, first with adhesive tape, one end of template is pasted before processing, protect this not contact with corrosive liquid on one side, under 25 ℃ of constant temperatures of temperature, be that 2.5% dilute phosphoric acid solution (volume ratio) carries out reaming and processes with concentration, with magnetic stirring apparatus, solution is stirred when carrying out the reaming processing, the speed that stirs is controlled to be 60 rev/mins, process through the reamings of 15 minutes, do not have one side of adhesive tape protection the array of tip-like to occur at anodic oxidation aluminium formwork, the height of needle point is 10 μ m, afterwards, with clean stream of nitrogen gas, that array is dry, dried anodised aluminium nanometer pinpoint array is put into vacuum film coating chamber, be that 99.99% bismuth is target with purity, deposition a layer thickness is the monocrystalline bismuth thin film of 12nm,
again with the three-dimensional flower shape of the bismuth in the bismuth pole array 3 for preparing array, bismuth nano-wire array and bismuth nanometer pinpoint array are fixed on Planar integration on the silicon chip that thickness is 400 μ m, then as the working electrode of three electrode inspectors, make contrast electrode 5 with Ag/AgCl, do electrode 6 with platinum guaze, to contain copper (Cu), plumbous (Pb), zinc (Zn), mercury (Hg), the aqueous solution of one or more in cadmium (Cd) and arsenic (As) is put into electrolytic tank 1, each electrode of composite structure working electrode 4 connects respectively a working electrode signalling channel 2, working electrode signalling channel 2 accesses respectively on existing electrochemical analyser according to a conventional method, carrying out scanning quantitation detects, each voltammetric signal after detection, all by independent record, by volt-ampere analysis software, three voltammetric signals are carried out analysis-by-synthesis and typical curve comparison at last, can obtain kind and the concentration of heavy metal ion.
Bismuth 3 D stereo flower shape array in preparation bismuth nano-wire array 3:
Be 99.999% BiCl with purity
3With the electrolytic solution of the three-dimensional flower shape of deionized water preparation electro-deposition bismuth nano structure electrode array, finally consisting of of the molten electrolytic solution for preparing: BiCl
3Concentration 10mmol/L, NaCl concentration 0.3mol/L, H
3BO
3Concentration 0.25mol/L, HCl concentration 0.45mol/L, make the working electrode of deposition use of Copper Foil, the three-dimensional flower shape nano structure electrode array of deposition in the three-electrode system electrolytic tank, deposition process is controlled by electrochemical workstation AUTOLAB, the model of instrument is PGS-TAT30, the current potential of electro-deposition is-1.2V (relative saturation saturated calomel electrode), sedimentation time is 15 minutes, the temperature of electrolytic solution keeps room temperature, by above-mentioned deposition, prepare three-dimensional flower shape nano structure electrode array, wherein the surface density of three-dimensional flower shape nanostructured reaches 2 * 10
3mm
-2, the diameter average out to 12 μ m of flower, the thickness of two-dimentional petal is 40nm, is the monocrystalline bismuth;
Nano-wire array in preparation bismuth nano-wire array 3:
Be anodised aluminium (AAO) template of 100 μ m with thickness, deposition bismuth nano-wire array electrode anode, on alumina formwork, the diameter of nano aperture is 30nm, the consisting of of electrolytic solution: 20 g/L BiCl
3, 30 g/L tartrate, the NaCl of 20g/L, 45g/L glycerine is adjusted to 0.7 with hydrochloric acid with the pH of electrolytic solution at last, deposits the nano wire of bismuth in the nano aperture of anodic oxidation aluminium formwork by pulsed deposition, sedimentation potential is-1.0V (relative saturation saturated calomel electrode) that the burst length is T
on=15 s, T
off=30 s, after deposition through 900 s, obtained the bismuth nano-wire array in the hole of template, corrode by 2% dilute phosphoric acid solution (volume ratio) antianode alumina formwork again, etching time is 12 minutes, obtains at last the exposed bismuth nano-wire array in the template outside in top, the total length average out to 60 μ m of bismuth nano-wire, wherein exposed length outside template is 20 μ m, and bismuth nano-wire is the monocrystalline bismuth;
Nanometer pinpoint array in preparation bismuth nano-wire array 3:
carry out reaming by the antianode alumina formwork, and reaming in control temperature and stir and obtain the aluminium oxide nano pinpoint array, plate again one deck bismuth film on array, obtain bismuth nanometer pinpoint electrod-array, the thickness of anodic oxidation aluminium formwork used is 100 μ m, hole mean diameter in template is 40nm, first with adhesive tape, one end of template is pasted before processing, protect this not contact with corrosive liquid on one side, under 25 ℃ of constant temperatures of temperature, be that 2.5% dilute phosphoric acid solution (volume ratio) carries out reaming and processes with concentration, with magnetic stirring apparatus, solution is stirred when carrying out the reaming processing, the speed that stirs is controlled to be 80 rev/mins, process through the reamings of 20 minutes, do not have one side of adhesive tape protection the array of tip-like to occur at anodic oxidation aluminium formwork, the height of needle point is 15 μ m, use again clean stream of nitrogen gas that array is dry, dried anodised aluminium nanometer pinpoint array is put into vacuum film coating chamber, be that 99.99% bismuth is target with purity, deposition a layer thickness is the monocrystalline bismuth thin film of 20nm,
again with the three-dimensional flower shape of the bismuth in the bismuth pole array 3 for preparing array, bismuth nano-wire array and bismuth nanometer pinpoint array are fixed on the quartz ampoule inside that diameter is 20mm, the length of quartz ampoule is 60 mm, distance between the working electrode of three kinds of different structures is 10mm, then with quartz ampoule as electrolytic cell, allow aqueous solution to be detected from wherein flowing through, platinum filament on the Inserting Tube central axis is done electrode 6, make contrast electrode 5 with Ag/AgCl, to contain copper (Cu), plumbous (Pb), zinc (Zn), mercury (Hg), the aqueous solution of one or more in cadmium (Cd) and arsenic (As) is put into electrolytic tank 1, each electrode of composite structure working electrode 4 connects respectively a working electrode signalling channel 2, working electrode signalling channel 2 accesses respectively on existing electrochemical analyser according to a conventional method, carrying out scanning quantitation detects, each voltammetric signal after detection, all by independent record, by volt-ampere analysis software, three voltammetric signals are carried out analysis-by-synthesis and typical curve comparison at last, can obtain kind and the concentration of heavy metal ion.
Claims (6)
1. the method for a fast detection of trace heavy metal ion, it is characterized in that device related in the method by electrolytic tank, working electrode signalling channel, bismuth pole array, composite structure working electrode, contrast electrode and electrode is formed, adopt the Electrochemical Stripping voltammetry to detect, concrete operations follow these steps to carry out:
A, in electrolytic tank (1) fixedly composite structure working electrode (4), contrast electrode (5) and to electrode (6) respectively, be provided with bismuth pole array (3) on composite structure working electrode (4), be provided with working electrode signalling channel (2) on bismuth pole array (3), wherein bismuth pole array (3) is that bismuth nano-wire array and bismuth nanometer pinpoint array consist of by the three-dimensional flower shape of bismuth array;
b, to contain copper, plumbous, zinc, mercury, the aqueous solution of one or more in cadmium and arsenic is put into electrolytic tank (1), each electrode of composite structure working electrode (4) connects respectively a working electrode signalling channel (2), working electrode signalling channel (2) accesses respectively on existing electrochemical analyser according to a conventional method, carrying out scanning quantitation detects, each voltammetric signal after detection, all by independent record, by volt-ampere analysis software, three voltammetric signals are carried out analysis-by-synthesis and typical curve comparison at last, can obtain kind and the concentration of heavy metal ion.
2. method according to claim 1, what it is characterized in that composite structure working electrode (4) in step a is configured to Planar Compound structure or three-dimensional composite structure.
3. method according to claim 1 is characterized in that the three-dimensional flower shape of the bismuth array in step a bismuth pole array (3), and each three-dimensional flower shape bismuth structure is all that the nanometer bismuth thin slice by two dimension consists of, and the thickness of nanometer bismuth thin slice is 20-150nm.
4. method according to claim 1, is characterized in that the bottom of the bismuth nano-wire array in step a bismuth nano-wire array (3) is fixed by the template of growing nano linear array, and the height that exposes the bismuth nano-wire array of template is 10-200 μ m.
5. method according to claim 1, is characterized in that the top of the bismuth nanometer pinpoint array in step a bismuth nano-wire array (3) is the tip-like structure, from the long-pending maximum in array bottom section, diminishes gradually toward the top sectional area.
6. method according to claim 1, is characterized in that the three-dimensional flower shape array in step a bismuth nano-wire array (3), and the bismuth material on bismuth nano-wire array and bismuth nanometer pinpoint array is monocrystalline.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103402327A (en) * | 2013-08-07 | 2013-11-20 | 苏州扬清芯片科技有限公司 | Manufacturing method of printing electrode for portable heavy metal detection |
| CN108845013A (en) * | 2018-04-27 | 2018-11-20 | 桂林理工大学 | Bismuth serous coat strip and the preparation method and application thereof |
| CN112345604A (en) * | 2020-10-30 | 2021-02-09 | 广州钰芯智能科技研究院有限公司 | Nano bismuth-polypyrrole composite electrode, preparation method thereof and application of nano bismuth-polypyrrole composite electrode in heavy metal ion detection |
| CN112362712A (en) * | 2020-11-13 | 2021-02-12 | 福州大学 | Electrochemical sensor electrode capable of simultaneously detecting heavy metal lead and cadmium ions in grains |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103402327A (en) * | 2013-08-07 | 2013-11-20 | 苏州扬清芯片科技有限公司 | Manufacturing method of printing electrode for portable heavy metal detection |
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| CN108845013A (en) * | 2018-04-27 | 2018-11-20 | 桂林理工大学 | Bismuth serous coat strip and the preparation method and application thereof |
| CN112345604A (en) * | 2020-10-30 | 2021-02-09 | 广州钰芯智能科技研究院有限公司 | Nano bismuth-polypyrrole composite electrode, preparation method thereof and application of nano bismuth-polypyrrole composite electrode in heavy metal ion detection |
| CN112362712A (en) * | 2020-11-13 | 2021-02-12 | 福州大学 | Electrochemical sensor electrode capable of simultaneously detecting heavy metal lead and cadmium ions in grains |
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Application publication date: 20130605 |