CN103175882A - Electrochemical sensor probe for fast detecting chemical oxygen demand and preparation method thereof - Google Patents
Electrochemical sensor probe for fast detecting chemical oxygen demand and preparation method thereof Download PDFInfo
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- CN103175882A CN103175882A CN2013100815385A CN201310081538A CN103175882A CN 103175882 A CN103175882 A CN 103175882A CN 2013100815385 A CN2013100815385 A CN 2013100815385A CN 201310081538 A CN201310081538 A CN 201310081538A CN 103175882 A CN103175882 A CN 103175882A
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Abstract
The invention provides an electrochemical sensor probe for detecting chemical oxygen demand. The electrochemical sensor probe comprises a glassy carbon electrode and a chemical oxygen demand electrochemical-sensitive membrane, wherein the chemical oxygen demand electrochemical-sensitive membrane is positioned on the exposed surface of the glassy carbon electrode head (1) of the glassy carbon electrode. A method for forming the chemical oxygen demand electrochemical-sensitive membrane comprises the following steps of: immersing the glassy carbon electrode into a disodium hydrogen phosphate (Na2HPO4) solution being 0.1 mol per liter (mol L-1); and applying constant potential to a glassy carbon working electrode for a period of time by adopting a common three-electrode system so as to obtain the COD (Chemical Oxygen Demand) electrochemical-sensitive membrane. The electrochemical sensor probe provided by the invention has the characteristics of high sensitivity, fast analyses, easiness in operation, environmental friendliness, good reproducibility, high sensitivity and accuracy, high practicability, convenience in large-range popularization and use, and the like and can overcome the defects of complex operation, time consumption, certain environmental pollution, and the like of the traditional potassium dichromate national standard method.
Description
Technical field
The invention belongs to electrochemical sensor and Water Environmental Pollution Control field, be specifically related to fast detecting COD electrochemical sensor probe and preparation method thereof.
Background technology
Chemical oxygen demand (COD) (COD) is to weigh an important indicator of water pollution degree, refers under certain condition, and the reducing substances in water body is by the corresponding oxygen concentration of the oxygenant of strong oxidizer oxidation consumption.China's surface water quality falls into 5 types (GB3838-2002), comprises source water, Drinking Water, fishery water, process water, agricultural water etc.I class and II class water chemistry oxygen demand (COD)≤15mg L
-1, III class water chemistry oxygen demand (COD)≤20mg L
-1, IV class water chemistry oxygen demand (COD)≤30mg L
-1, V class water chemistry oxygen demand (COD)≤40mg L
-1The numerical value of chemical oxygen demand (COD) (COD) shows that more greatly the pollution condition of water body is more serious.Therefore monitor water body COD concentration to environmental improvement and guarantee that water safety is most important.Chemical oxygen demand (COD) (COD) assay method often comprises potassium dichromate method (GB 11914-89), spectrophotometric method, rapid-digestion method and electrochemical method at present.The potassium dichromate method oxidation efficiency is high, favorable reproducibility.Spectrophotometric method and rapid-digestion method also grow up on traditional potassium dichromate method basis, but these methods all can be used the strong oxidizer potassium dichromate, catalyst sulfuric acid silver and chlorion screening agent mercuric sulfate.Too much the use of reagent not only can cause certain contaminative to environment, and testing cost is high, complicated operation, analysis time long (at least 15 minutes rapid-digestion time).Electrochemical method determining chemical oxygen demand (COD) (COD), as measured signal, analysis time is short with the electric current of the electric weight that consumes in reducing substances oxidizing process in water body or generation, and operation is simple, highly sensitive fast.Although electrochemical method determining chemical oxygen demand (COD) (COD) has relevant report, the structure majority of its sensing material is based on the nanometer sensitive membrane, and preparation process is relatively loaded down with trivial details, and inconvenience is generally promoted the use of.Therefore, the research high sensitivity, fast, environmental friendliness, chemical oxygen demand (COD) (COD) electrochemical sensor that simple to operate, accuracy is high, practical still be full of challenge and novelty.
Summary of the invention
Task of the present invention is to provide a kind of chemical oxygen demand (COD) fast detecting electrochemical sensor probe, makes it have the characteristics such as highly sensitive, that analysis speed is fast, simple to operate, environmental friendliness, favorable reproducibility accuracy are high and practical.
Another task of the present invention is to provide the preparation method of this chemical oxygen demand (COD) fast detecting electrochemical sensor probe.
Realize that concrete scheme of the present invention is:
the electrochemical sensor probe of detection chemical oxygen demand (COD) provided by the invention, COD electrochemical sensitive membrane by glass-carbon electrode and glass-carbon electrode head (1) exposed surface that is positioned at glass-carbon electrode consists of, described glass-carbon electrode is by glass-carbon electrode head (1), electrode jacket (2) and copper rod shape wire (3) consist of, glass-carbon electrode head (1) is packaged in the centre of electrode jacket (2) one ends, one end of glass-carbon electrode head (1) is exposed to the exposed surface of the end face formation glass-carbon electrode head (1) of electrode jacket (2), one end of copper rod shape wire (3) in electrode jacket (2) be packaged in electrode jacket (2) in glass-carbon electrode head (1) be connected, the other end of copper rod shape wire (3) extends to outside electrode jacket (2).Described electrode jacket (2) is made of teflon, polychlorotrifluoroethylene or polyetheretherketone (PEEK).The COD electrochemical sensitive membrane that is positioned at glass-carbon electrode head (1) surface of glass-carbon electrode is to prepare by the following method formation: will polish and immerse 0.1 mole every liter (mol L to the exposed surface position of the glass-carbon electrode head (1) of minute surface
-1) sodium hydrogen phosphate (Na
2HPO
4) in solution, adopt usual three-electrode system, with 1.0～2.5 volts (V), be preferably 1.0～2.5 volts, more preferably the current potential of 1.8 volts carries out electrochemical activation, and the potential activation time is 10～500 seconds (s), is preferably 10～500 seconds, more preferably 300 seconds, namely form the COD electrochemical sensitive membrane on the surface of glass-carbon electrode head (1).
The preparation method of the electrochemical sensor of detection chemical oxygen demand (COD) provided by the invention probe comprises the following steps: will polish and immerse 0.1 mole every liter (mol L to the exposed surface position of the glass-carbon electrode head (1) of minute surface
-1) sodium hydrogen phosphate (Na
2HPO
4) in solution, adopt usual three-electrode system, current potential with 1.0～2.5 volts (V) carries out the constant potential electrochemical activation, and the potential activation time is 10～500 seconds (s), forms the COD electrochemical sensitive membrane on the surface of glass-carbon electrode head (1).
In said method, preferably carrying out constant potential electrochemical activation current potential is 1.5～2 volts, more preferably 1.8 volts; The preferred potential activation time is 100～400 seconds, more preferably 300 seconds.
This sensor only need activate 5 minutes with common glass-carbon electrode in the phosphate electrolyte, namely obtain chemical oxygen demand (COD) (COD) sensitive membrane, do not relate to the modification of other nano material, sensitive membrane construction method Simple fast, practical, be convenient to promote the use of on a large scale.
The glass-carbon electrode head is generally cylindrical shape, and diameter does not wait at 1～6 millimeter, 1～5 millimeter of length, and overcoat is generally by teflon, and polychlorotrifluoroethylene or polyetheretherketone (PEEK) are made.Glass-carbon electrode in the embodiment of the present invention is available from the farsighted Science and Technology Ltd. of Wuhan Grolsch, and its glass-carbon electrode head diameter is 3 millimeters, and length is 4 millimeters, and lagging material is teflon, and copper rod shape diameter of wire is 1 millimeter.Glass-carbon electrode is dipped in 0.1 mole every liter (mol L
-1) sodium hydrogen phosphate (Na
2HPO
4) in solution, adopt common three-electrode system, apply constant potential a period of time to glass carbon working electrode, namely obtain chemical oxygen demand (COD) (COD) galvanochemistry sensitive membrane.Apply the current potential size and apply potential time length by change, having realized the catalytic activity regulation and control of glass-carbon electrode to COD.Electrochemistry experiment shows, puts on glass carbon working electrode with 1.8 volts of (V) current potentials, and after 300 seconds duration (s), formed sensitive membrane has the highest COD catalytic response electric current.The COD electrochemical sensor that this method is prepared detects and is limited to 0.33 milligram every liter (mg L
-1), testing result is consistent with National Standard Method.
That the electrochemical sensor of detection chemical oxygen demand (COD) provided by the invention probe has is highly sensitive, analysis speed is fast, simple to operate, environmental friendliness, favorable reproducibility, sensitivity and accuracy high, practical, the characteristics such as be convenient to promote the use of on a large scale.Can overcome complicated operation that existing potassium dichromate National Standard Method has, consuming time and have deficiencies such as certain environment contaminative.
Description of drawings
Fig. 1 chemical oxygen demand (COD) fast detecting provided by the invention electrochemical sensor is visited the structural representation of first embodiment;
The surface topography map of the COD electrochemical sensitive membrane (or being called the electrode sensitive film) of Fig. 2 chemical oxygen demand (COD) fast detecting provided by the invention electrochemical sensor probe; Figure A in Fig. 2 is the atomic force microscope figure of naked glass-carbon electrode sensor probe sensitive membrane; Figure B in Fig. 2 is the atomic force microscope figure (B) of glass-carbon electrode sensor probe sensitive membrane after pre-service.The atomic force microscope model is SPA400 (NSK Electronics Co., Ltd.).Figure A in Fig. 2 is that soak time is the atomic force microscope figure of the naked glass-carbon electrode sensor probe A of 0 second; B figure in Fig. 2 is the atomic force microscope figure of the activation glass-carbon electrode sensor probe B of 300 seconds under 1.8 volts of current potentials.
(sensor probe B) glass-carbon electrode surface atom force microscope figure after Fig. 2 has showed unprocessed (sensor probe A) and noble potential activation process, glass-carbon electrode activates the rear surface tactical rule as we can clearly see from the figure, and roughness is higher.
Its electrode sensitive film preparation parameter is as shown in the table:
The impact of the different soak times of Fig. 3 on chemical oxygen demand (COD) (COD) response current, Fig. 3 is that the actual lake water water sample of 40.7mg L-1 chemical oxygen demand (COD) (COD) is at the i-t response curve on different soak time glass-carbon electrodes surface.The mensuration medium is sodium hydrogen phosphate (Na2HPO4) solution of 0.1 mole every liter, and 1.8 volts of activation potentials are measured 1.5 volts of current potentials.Can see, water sample is less at undressed glass-carbon electrode surface respond electric current, illustrates that this anodizing activity is relatively poor.After noble potential pre-service after a while, a significantly current step has upwards appearred in identical chemical oxygen demand (COD) (COD) water sample on the activated glassy carbon electrode surface, response current significantly increases, and illustrates that activated glassy carbon electrode has stronger enhancement effect to chemical oxygen demand (COD) (COD) mensuration.In addition, demonstrated the strongest catalytic activity through 300 seconds pre-service glass-carbon electrodes, therefore 300 seconds is sensor probe sensitive membrane optimum activating time.
Embodiment
The preparation of the electrochemical sensor probe of embodiment 1 detection chemical oxygen demand (COD) provided by the invention
Fig. 1 is the structural representation of the electrochemical sensor probe embodiments of detection chemical oxygen demand (COD) provided by the invention, the electrochemical sensor probe of this detection chemical oxygen demand (COD) is made of the COD electrochemical sensitive membrane of glass-carbon electrode and glass-carbon electrode head (1) exposed surface that is positioned at glass-carbon electrode, described glass-carbon electrode is by glass-carbon electrode head (1), electrode jacket (2) and copper rod shape wire (3) consist of, glass-carbon electrode head (1) is packaged in the centre of electrode jacket (2) one ends, one end of glass-carbon electrode head (1) is exposed to the exposed surface of the end face formation glass-carbon electrode head (1) of electrode jacket (2), one end of copper rod shape wire (3) in electrode jacket (2) be packaged in electrode jacket (2) in glass-carbon electrode head (1) be connected, the other end of copper rod shape wire (3) extends to outside electrode jacket (2).Glass-carbon electrode is available from the farsighted Science and Technology Ltd. of Wuhan Grolsch, and the diameter of its glass-carbon electrode head (1) is 3 millimeters, and length is 4 millimeters, and its electrode jacket (2) is made by teflon, and the diameter of copper rod shape wire (3) is 1 millimeter.
0.1 mole every liter (mol L is immersed at the exposed surface position of polishing to the glass-carbon electrode head (1) of minute surface
-1) sodium hydrogen phosphate (Na
2HPO
4) in solution, adopt the three-electrode system of usual (being usually practical in prior art), apply 1.8 volts of constant potentials to working electrode, continue 300 seconds, namely form chemical oxygen demand (COD) (COD) galvanochemistry sensitive membrane on the surface of glass-carbon electrode head (1).
(1) chemical oxygen demand (COD) (COD) galvanochemistry sensitive membrane surface topography map (seeing Fig. 2)
Chemical oxygen demand (COD) (COD) the galvanochemistry sensitive membrane surface topography map of the electrochemical sensor probe of the detection chemical oxygen demand (COD) of above-described embodiment 1 preparation is seen Fig. 2.In Fig. 2, figure A is the atomic force microscope figure of naked glass-carbon electrode sensor probe sensitive membrane, and in Fig. 2, figure B is the atomic force microscope figure of glass-carbon electrode sensor probe sensitive membrane after pre-service.Atomic force microscope model used is SPA400 (NSK Electronics Co., Ltd.).Figure A in Fig. 2 is that soak time is the atomic force microscope figure of the naked glass-carbon electrode sensor probe A of 0 second; B figure in Fig. 2 is the atomic force microscope figure of the activation glass-carbon electrode sensor probe B of 300 seconds under 1.8 volts of current potentials, and its electrode sensitive film preparation parameter is as shown in the table:
(sensor probe B) glass-carbon electrode surface atom force microscope figure after Fig. 2 has showed unprocessed (sensor probe A) and noble potential activation process, glass-carbon electrode activates the rear surface tactical rule as we can clearly see from the figure, and roughness is higher.
(2) enhancement effect of activated glassy carbon electrode (seeing Fig. 3)
Fig. 3 shows that different soak times are on the impact of chemical oxygen demand (COD) (COD) response current.Fig. 3 is that the actual lake water water sample of 40.7mg L-1 chemical oxygen demand (COD) (COD) is at the i-t response curve on different soak time glass-carbon electrodes surface.The mensuration medium is sodium hydrogen phosphate (Na2HPO4) solution of 0.1 mole every liter, and 1.8 volts of activation potentials are measured 1.5 volts of current potentials.Can see, water sample is less at undressed glass-carbon electrode surface respond electric current, illustrates that this anodizing activity is relatively poor.After noble potential pre-service after a while, a significantly current step has upwards appearred in identical chemical oxygen demand (COD) (COD) water sample on the activated glassy carbon electrode surface, response current significantly increases, and illustrates that activated glassy carbon electrode has stronger enhancement effect to chemical oxygen demand (COD) (COD) mensuration.In addition, demonstrated the strongest catalytic activity through 300 seconds pre-service glass-carbon electrodes, therefore 300 seconds is sensor probe sensitive membrane optimum activating time.
(3) practical application
In well-beaten situation, study chemical oxygen demand (COD) (COD) response signal of actual water sample with Amperometric.Above-mentioned top condition activated glassy carbon electrode is dipped in 9.00 milliliters, the sodium hydrogen phosphate (Na of 0.1 mole every liter
2HPO
4) in solution, the ampere test experience time is 100 seconds, detecting current potential is 1.5 volts.After i-t curve background current was stable, experiment moved to 50 seconds when locating, and added rapidly the water sample of 1.00 milliliters, measured the added value of electric current as the current responsing signal of water sample chemical oxygen demand (COD) (COD).
The electrochemical sensor probe of the detection chemical oxygen demand (COD) of embodiment 1 preparation is used for the detection of 8 parts of actual lake water of separate sources or river water sample, the water sample sequence number is denoted as respectively 1,2,3,4,5,6,7,8, calculates gained in the typical curve of the mensuration of actual water sample chemical oxygen demand (COD) (COD) by response current substitution formulation in advance.Each water sample replicate determination three times, RSD illustrates this sensor probe favorable reproducibility lower than 5%.For the accuracy of inspection, contrast with potassium dichromate National Standard Method (GB11914-89) mensuration, the results are shown in Table 1.The electrochemical sensor probe measurement result of the detection chemical oxygen demand (COD) of National Standard Method (GB11914-89) measurement result and embodiment 1 preparation is coincide very much, and (relative error is lower than 7%, this deviation is generally in tolerance interval), illustrate that the electrochemical sensor probe accuracy of detection chemical oxygen demand (COD) provided by the invention is good.
Table 1 actual water sample chemical oxygen demand (COD) (COD) is measured
Comprehensive above experimental data, we can obtain as drawing a conclusion: the electrochemical sensor probe of detection chemical oxygen demand (COD) provided by the invention (COD) has following characteristics: (1) is highly sensitive: (COD) sensitive thin film take activated glassy carbon electrode as chemical oxygen demand (COD), by the high catalytic activity of activation glass carbon, significantly improve chemical oxygen demand (COD) (COD) electrochemical oxidation signal, finally realized chemical oxygen demand (COD) (COD) high sensitivity measuring.Detectability can reach 0.33mg L
-1(2) analysis speed is fast: pretreatment of glassy carbon electrode 5 minutes, preparation chemical oxygen demand (COD) (COD) electrochemical sensing film.Minute lower than 7 minutes, satisfies the fast detecting requirement altogether lower than 2 minutes analysis time.(3) simple to operate: during mensuration, based on the electrochemical oxidation signal of reducing substances in water body on the activated glassy carbon electrode surface, 0.02 mole of every liter of chlorion does not disturb its signal, thereby can directly measure, and operates very simple.(4) environmental friendliness: this sensor probe mainly is made of the glass-carbon electrode material, and noble potential activated glassy carbon electrode in common phosphate electrolyte is minimum to environment and human body danger property, is a kind of environmentally friendly sensor.(5) the favorable reproducibility accuracy is high: it is that the RSD of 8.7%, 11 sensor probe measurement result is 5.6% that 1 continuous 11 measurement result of sensor probe get relative standard deviation.The mensuration that sensor probe provided by the invention is used for a large amount of actual water sample, measurement result and potassium dichromate method measurement result is identical (relative error is lower than 7%) very.(6) practical: this sensor probe only need activate 5 minutes with common glass-carbon electrode in the phosphate electrolyte, namely obtain chemical oxygen demand (COD) (COD) sensitive membrane, do not relate to the modification of other nano material, sensitive membrane construction method Simple fast, practical, be convenient to promote the use of on a large scale.Therefore, than consuming time, complicated operation, have the potassium dichromate National Standard Method of certain environment contaminative, chemical oxygen demand (COD) (COD) the electrochemical sensor probe that strengthens based on the activated glassy carbon electrode signal provided by the invention have advantages of high sensitivity, fast, environmental friendliness, simple to operate, accuracy is high, practical.
Claims (9)
1. an electrochemical sensor that detects chemical oxygen demand (COD) is popped one's head in, by the COD electrochemical sensitive membrane formation of glass-carbon electrode and glass-carbon electrode head (1) exposed surface that is positioned at glass-carbon electrode.
2. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 1 is popped one's head in, it is characterized in that, described glass-carbon electrode is by glass-carbon electrode head (1), electrode jacket (2) and copper rod shape wire (3) consist of, glass-carbon electrode head (1) is packaged in the centre of electrode jacket (2) one ends, one end of glass-carbon electrode head (1) is exposed to the exposed surface of the end face formation glass-carbon electrode head (1) of electrode jacket (2), one end of copper rod shape wire (3) in electrode jacket (2) be packaged in electrode jacket (2) in glass-carbon electrode head (1) be connected, the other end of copper rod shape wire (3) extends to outside electrode jacket (2).
3. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 2 probe, is characterized in that, described electrode jacket (2) is made of teflon, polychlorotrifluoroethylene or polyetheretherketone (PEEK).
4. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 1 is popped one's head in, it is characterized in that, the COD electrochemical sensitive membrane that is positioned at glass-carbon electrode head (1) surface of glass-carbon electrode is to prepare by the following method formation: will polish and immerse 0.1 mole every liter (mol L to the exposed surface position of the glass-carbon electrode head (1) of minute surface
-1) sodium hydrogen phosphate (Na
2HP0
4) in solution, adopt usual three-electrode system, carry out electrochemical activation with the current potential of 1.0～2.5 volts (V), the potential activation time is 10～500 seconds (s), namely forms the COD electrochemical sensitive membrane on the surface of glass-carbon electrode head (1).
5. the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 3 probe, is characterized in that, the constant potential activation potential is 1.0～2.5 volts, and the potential activation time is 10～500 seconds.
6. the electrochemical sensor of according to claim 4 or 5 described detection chemical oxygen demand (COD) probe, is characterized in that, the constant potential activation potential is 1.8 volts, and the potential activation time is 300 seconds.
7. the preparation method of an electrochemical sensor probe that detects chemical oxygen demand (COD) comprises the following steps: will polish and immerse 0.1 mole every liter (mol L to the exposed surface position of the glass-carbon electrode head (1) of minute surface
-1) sodium hydrogen phosphate (Na
2HPO
4) in solution, adopt usual three-electrode system, current potential with 1.0～2.5 volts (V) carries out the constant potential electrochemical activation, and the potential activation time is 10～500 seconds (s), forms the COD electrochemical sensitive membrane on the surface of glass-carbon electrode head (1).
8. the method for the electrochemical sensor of detection chemical oxygen demand (COD) according to claim 6 probe, is characterized in that, carrying out constant potential electrochemical activation current potential is 1.5～2 volts, and the potential activation time is 100～400 seconds.
9. the method for the electrochemical sensor of according to claim 6 or 7 described detection chemical oxygen demand (COD) probe, is characterized in that, carrying out constant potential electrochemical activation current potential is 1.8 volts, and the potential activation time is 300 seconds.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108287188A (en) * | 2017-12-27 | 2018-07-17 | 华中科技大学 | A kind of bionical electrochemical probe of electrochemical polymerization molecular engram, it is prepared and application |
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2013
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Patent Citations (3)
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| CN101105472A (en) * | 2007-06-11 | 2008-01-16 | 大连理工大学 | Water body chemical oxygen demand electrochemical measuring method |
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Application publication date: 20130626 |