CN103278551A - 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 - Google Patents
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 Download PDFInfo
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Abstract
The invention discloses an active carbon double-electrode system-based heavy metal electrochemical sensor. The active carbon double-electrode system-based heavy metal electrochemical sensor comprises a work electrode and an auxiliary electrode. The work electrode and the auxiliary electrode are respectively connected to an electrochemical workstation by leads. The auxiliary electrode is prepared from active carbon. The active carbon double-electrode system-based heavy metal electrochemical sensor does not adopt a reference electrode adopted by the traditional three-electrode system, does not need regular maintenance, prolongs a sensor service life and reduces a maintenance cost. The invention also discloses a method for detection of heavy metals by the active carbon double-electrode system-based heavy metal electrochemical sensor. The method utilizes a square wave anodic stripping voltammetry method to determine a heavy metal concentration, has high detection sensitivity, good reappearance and high stability, realizes recycle of the electrodes only by electrocleaning, can be operated simply, has low energy consumption and can be used for on-site real-time monitoring of heavy metals.
Description
Technical field
The invention belongs to the Electrochemical Detection field, relate in particular to a kind of heavy metal electrochemical sensor and detection method thereof based on activated charcoal two electrode systems.
Background technology
In recent years, heavy metal pollution aggravates to have become undisputable fact day by day in all kinds of water environments.Along with the development of large-scale industry, heavy metal pollution has become one of maximum pollution of harm, since characteristics such as its toxicity is big, easily enrichment, difficult degradation, the human and hydrobiological existence of serious threat.For reflection water environment live telecast in time, need monitor in real time it, thereby raise the efficiency, reduce cost.Therefore, the heavy metal sensor of exploitation high sensitivity, low cost, miniaturization is realized the on-line real time monitoring water environment, and the protection of human beings'health and environment is significant.
The method that detects heavy metal element mainly contains atomic spectroscopy, mass spectrometry, spectrophotometric method and stripping voltammetry etc.Some needs complicated pretreatment such as extraction, enrichment method several analytical approachs such as atomic spectroscopy, mass spectrometry and spectrophotometric method, and detection time is long, the analysis cost height; Some can not carry out multielement analysis, and sensitivity is low, and most of instrument and equipment is expensive, and complicated operation can not be realized on-line monitoring.And simple based on the instrument and equipment of stripping voltammetry, easily be automated and portability, because highly sensitive, characteristics such as antijamming capability is strong, and detection speed is fast are the effective means that detects heavy metal element.
Stripping voltammetry adopts traditional three-electrode system at present: working electrode, auxiliary electrode, contrast electrode, wherein contrast electrode has stable electromotive force, be the benchmark of potential electrode electromotive force, its performance directly influences stability, reappearance and the accuracy that heavy metal detects.Be that the application for a patent for invention of CN 101706471 B discloses a kind of electrochemical sensor of measuring concentration of heavy metal ions in water sample as notification number.Be specially and comprise working electrode, contrast electrode and auxiliary electrode, working electrode, contrast electrode and auxiliary electrode are connected in the control potentiometer by lead respectively; Working electrode is made up of polyfluortetraethylene pipe and the carbon electrode among being sandwiched in, and the bottom of carbon electrode is connected with the lead-in wire of drawing, and the top is provided with sensitive membrane.In order to guarantee the performance of contrast electrode, need regularly it to be safeguarded, calibrate and changes, increased cost simultaneously; In addition, contrast electrode material commonly used such as silver chloride, calomel, mereurous sulfate etc., not only the life-span limited, also can be in testing process contaminated samples, can't be applicable to the online Non-Destructive Testing of water quality.
Therefore, the contrast electrode in the abandoning tradition three-electrode system, selecting suitable auxiliary electrode is that metering circuit raising electromotive force benchmark will be the research emphasis of further optimizing electrochemical sensor, reducing cost.At present existing pertinent literature and patent are mentioned large-area alloy steel and be can be used as auxiliary electrode, and replace contrast electrode, as the electromotive force benchmark of metering circuit.But, through discovering, when 100uA electric current process alloy steel, its electromotive force still can drift about, the accuracy of counterweight metal detection has certain influence, has limited it in the application of high concentration heavy metal detection range, and large tracts of land alloy steel volume is bigger, is difficult to realize miniaturization.
Summary of the invention
Easily pollute the problem of testing sample during at the maintenance cost height of existing three-electrode system sensor and online the detection, the invention provides a kind of heavy metal electrochemical sensor of two electrode systems, this sensor need not periodic maintenance and can keep stable electromotive force, is applicable to that the heavy metal of various water environments is monitored in real time.
A kind of heavy metal electrochemical sensor based on activated charcoal two electrode systems comprises working electrode and auxiliary electrode, and described working electrode and auxiliary electrode are connected in electrochemical workstation by lead respectively; The material of described auxiliary electrode is activated charcoal.
The present invention adopts the absorbent charcoal material of non-modified as auxiliary electrode, surface area is big, and electric double layer capacitance is big, can keep stabilizing potential, can be used as the electromotive force benchmark of heavy metal in detecting, and various ions such as a large amount of sodium that exist, potassium, calcium, magnesium do not influence the performance of activated charcoal in the water environment.Use this electrochemical sensor and carry out heavy metal when detecting, electrochemical workstation produces pumping signal and puts on the working electrode, gathers the response current signal from auxiliary electrode simultaneously.
As preferably, working electrode of the present invention is glass-carbon electrode, gold electrode, platinum electrode, silver electrode, titanium electrode or tungsten electrode.According to metal target to be measured, can select different working electrodes; When the heavy metal kind in the needs detection liquid to be measured and content, can select different working electrodes for use, carry out continuous detecting.
The present invention also provides and has utilized above-mentioned heavy metal electrochemical sensor based on activated charcoal two electrode systems to detect the method for heavy metal, adopts square wave Anodic Stripping Voltammetry Determination heavy metal concentration to be measured, detection sensitivity height, favorable reproducibility.
A kind of method that detects heavy metal based on the heavy metal electrochemical sensor of activated charcoal two electrode systems of utilizing comprises the steps:
(1) will mix set aside for use in the volume ratio adding supporting electrolyte of testing sample by 1:1～3;
(2) will polish the working electrode and the auxiliary electrode that activate is fixed in the electrolytic cell in the lump; Described working electrode and contrast electrode are connected in electrochemical workstation by lead respectively;
(3) adopt square wave Anodic Stripping Voltammetry Determination heavy metal concentration to be measured.
The present invention considers the instability of coated electrode and the restriction in life-span, therefore do not adopt coating technique, but adopt the square wave anodic stripping voltammetry directly on naked working electrode with constant potential enrichment metal to be measured, after a period of time, apply the forward scan signal, make burning stripping to be measured, measure heavy metal concentration to be measured according to stripping curve.As preferably, the heavy metal described in the step (3) is lead, cadmium, mercury, zinc, copper or arsenic.
When adopting square wave Anodic Stripping Voltammetry Determination heavy metal concentration to be measured in the step (3), earlier-2V～-the 0.5V scope in, adopt constant potential enrichment metal 2～10min to be measured, apply square wave forward scan current potential then, make enriched in metals oxidation stripping.After electrochemical workstation has recorded voltammogram ,+0.5～+ the 1V current potential under cleaning electrode 30s, the heavy metal of its remained on surface is removed, and the kept dry electrode, make things convenient for recycling of sensor.
Compared with prior art, the present invention has following beneficial effect:
(1) sensor of the present invention has only used two electrodes can reach the purpose that detects heavy metal.Owing to abandoned contrast electrode in traditional three-electrode system, do not need the periodic maintenance sensor, prolonged sensor serviceable life, reduced maintenance cost.
(2) auxiliary electrode in the sensor of the present invention has been abandoned the large tracts of land alloy steel, adopts the porous activated carbon material, and its surface area can keep stable electromotive force much larger than working electrode, satisfies stripping voltammetry and detects in the heavy metal strict demand to the stabilizing potential benchmark.This activated carbon electrodes still can keep stable electromotive force under complex environment, the life-span is long, and its volume is little, is conducive to the miniaturization of sensor.
(3) sensor of the present invention can detect heavy metals such as lead, cadmium, zinc, copper, mercury, arsenic by selecting different working electrodes.
(4) sensor of the present invention is considered instability and the life-span of coated electrode, only adopts bare electrode to detect heavy metal accurately, reliably, has reduced the cost of sensor thus, improve its reliability, and this detection limit can satisfy drinking water standard.
(5) sensor of the present invention can satisfy heavy metal pollution and detects needs, and highly sensitive, favorable reproducibility, stability are high, and electrode only to need electricity to clean namely reusable, simple to operate, energy consumption is low, can be used for the on-the-spot heavy metal that detects in real time.
Description of drawings
Fig. 1 detects the structural representation of heavy metal for adopting electrochemical sensor of the present invention;
Fig. 2 investigates figure for the electromotive force of auxiliary electrode among the present invention;
Fig. 3 is the reappearance detection figure of the present invention to the heavy metal lead cadmium;
Fig. 4 investigates figure for the present invention to the linearity of the plumbous cadmium sample of 10～500ug/L concentration;
Fig. 5 investigates figure for the present invention to the linearity of the plumbous cadmium sample of 2～10ug/L concentration;
Fig. 6 investigates figure for the present invention to the linearity of the mercury sample of 5～100ug/L concentration;
Fig. 7 is that the present invention is to the actual plumbous cadmium ion detection figure that drinks water sample.
Embodiment
Below in conjunction with embodiment and accompanying drawing, describe the present invention.
Figure 1 shows that and use the structural representation that electrochemical sensor of the present invention detects heavy metal, wherein, working electrode 1 and auxiliary electrode 2 are connected in the small electrical chem workstation 7 of development voluntarily by lead, and wherein, the material of auxiliary electrode adopts activated charcoal.Measuring cell is formed by electrolytic cell 5, stepper motor 3 and stirring rod 4 integrated designs, be the stability that guarantees to install during the stirring, also be provided with electrode mounting hole and holder 6, wherein, stepper motor 3 links to each other with electrochemical workstation 7, stirring rate and time by the programmed control enrichment stage, do not need artificial control.Electrolytic cell 5 in the measuring cell and the material of stirring rod 4 are teflon, and stirring rod length can guarantee that the position of electrolytic cell and electrode is unaffected under the bigger situation of rotating speed to liquid to be measured bottom.When the content of beary metal in the detection water body, electrochemical workstation 7 produces pumping signals and puts on the working electrode 1, gathers the response current signals from auxiliary electrode 2 simultaneously.
1, the electromotive force of activated carbon electrodes is investigated
When heavy metal concentration was the ppm magnitude, the stripping peak current can if activated carbon electrodes still can keep stable electromotive force when so high electric current passes through, prove that then it can be used as the auxiliary electrode in the two electrode heavy metal sensors up to 100uA.Investigate activated carbon electrodes, glass-carbon electrode, gold electrode, platinum electrode, the potential change situation of graphite electrode when electric current passes through by traditional three-electrode system, wherein, the electrode of investigating is working electrode, platinum electrode is auxiliary electrode, silver/silver chloride is contrast electrode, is connected to electrochemical workstation, adopts the chronoptentiometry record when electric current is scanned up to 100uA gradually by 0uA, the potential change situation of electrode is seen Fig. 2.When electric current surpasses 20uA, platinum, gold, glass carbon, four kinds of electrodes of graphite all taken place great electrode polarization (＞500mV), and the activated carbon electrodes with electric double layer capacitance still can keep stable current potential up to the electric current of 100uA the time.Prove that thus two electrode heavy metal sensors of the present invention meet the stable requirement of auxiliary electrode electromotive force.
2, the reappearance of counterweight metal detection of the present invention is investigated
Use the alumina powder polishing electrode of 0.3～0.05um, be minute surface until electrode surface, do not have till the cut, use ethanol, the ultrasonic 5min of distilled water then respectively.The electrode that pre-service is good places the standard solution that contains 50ug/L lead, cadmium, selects glass-carbon electrode as working electrode.At first under-1.9V enrichment voltage, stir enrichment 120s, leave standstill 15s after, adopt square wave scanning voltammetry, from-1.9V forward scan is to 0V, sweep speed is 0.5v/s, square-wave cycle 10ms, square wave amplitude 20mV, stepped voltage 5mv.Record stripping curve, calculate the stripping peak current of plumbous cadmium.Each measure finish after, electrode is placed acetic acid-sodium acetate buffer solution, under+0.5V, clean 30s, remain in the heavy metal ion of electrode surface with stripping.To 50ug/L lead, the replicate determination of cadmium standard solution 6 times, as shown in Figure 3.From this figure as can be known sensor of the present invention have good reappearance in order to detect heavy metal ion, relative standard deviation plumbous, cadmium only is 0.85% and 1.55%.
3, the present invention detects the linearity investigation of heavy metal lead cadmium simultaneously
At first with lead, the cadmium standard solution stepwise dilution of redistilled water with 100mg/L, and with 0.1mol/L acetic acid-acetic acid salt solution mix, be mixed with the plumbous cadmium standard solution that concentration is respectively 10ug/L, 20ug/L, 30ug/L, 50ug/L, 70ug/L, 90ug/L, 110ug/L, 130ug/L, 150ug/L, 200ug/L, 300ug/L, 400ug/L, 500ug/L.After the electrode pre-service, insert in the liquid to be measured, select glass-carbon electrode as working electrode, under-1.9V enrichment voltage, stir enrichment 120s, leave standstill 15s after, adopt square wave scanning voltammetry, from-1.9V forward scan is to 0V, and sweep speed is 0.5v/s, square-wave cycle 10ms, square wave amplitude 20mV, stepped voltage 5mv.Measure the series of standards solution for preparing successively, the record current response can obtain its calibration curve, sees Fig. 4.In 10ug/L～500ug/L concentration range, related coefficient plumbous and cadmium is respectively 0.9989 and 0.9992.Use the same method detect low concentration lead, cadmium solution (＜10ug/L), the results are shown in Figure 5, its related coefficient still can reach more than 0.998, be that 3 detection limits that can obtain plumbous and cadmium are respectively 0.5ug/L and 1ug/L according to signal to noise ratio (S/N ratio), proved when sensor of the present invention is applicable to various heavy metal ion and measured, and highly sensitive, linear good, under the situation of bare electrode, detection limit can reach below the 1ug/L.
4, the present invention detects the linearity investigation of heavy metal Hg
Mix at first with the mercury standard solution stepwise dilution of redistilled water with 100mg/L, and with 0.1mol/L buffer solution, be mixed with the mercury standard solution that concentration is respectively 5ug/L, 10ug/L, 15ug/L, 20ug/L, 30ug/L, 50ug/L, 100ug/L.Use the alumina powder polishing electrode of 0.3～0.05um, be minute surface until electrode surface, do not have till the cut, use ethanol, the ultrasonic 5min of distilled water then respectively.The electrode that pre-service is good inserts in the liquid to be measured, select gold electrode as working electrode, under-0.6V enrichment voltage, stir enrichment 300s, after leaving standstill 15s, adopt square wave scanning voltammetry, from-0.6V forward scan to 1V, sweep speed is 0.5v/s, square-wave cycle 10ms, square wave amplitude 20mV, stepped voltage 5mv.Measure the series of standards solution for preparing successively, the record current response can obtain its calibration curve, sees Fig. 6.In 5ug/L～100ug/L concentration range, the related coefficient of mercury is 0.9985, and reappearance is good, and relative standard deviation is in 3%.Be that 3 detection limits that can obtain mercury are respectively 1ug/L according to signal to noise ratio (S/N ratio), proved when sensor of the present invention is applicable to various heavy metal ion and measured, and highly sensitive, linear good.
5, the present invention measures lead, the cadmium content of actual potable water
Get the part potable water, mix as liquid to be measured with acetic acid-acetate solution of 0.1mol/L volume ratio with 1:1.The selection working electrode is glass-carbon electrode, adopts standard addition method to measure, and finds not contain lead, cadmium in the potable water; Detect this liquid to be measured with atomic absorption method, do not detect heavy metal lead, cadmium equally.Therefore get the liquid to be measured of same amount, add lead, the cadmium standard solution of 50ug/L, 100ug/L, 150ug/L, 200ug/L, 300ug/L respectively, detect the response current signal that obtains a series of plumbous cadmium standard solution by above-mentioned similar detection method, see Fig. 7.Can obtain plumbous cadmium content in the actual detected liquid according to standard addition method.This shows that the present invention can realize the online detection of the heavy metal of actual water sample.
The present invention has utilized the electromotive force of activated charcoal stable, has made up the heavy metal sensor of galvanochemistry two electrode detection systems as auxiliary electrode with activated charcoal.The contrast electrode in traditional three-electrode system has been abandoned in this invention, simplify the structure, and cost is low, safe and reliable, the detection heavy metal is highly sensitive, reappearance is good, can realize robotization, the convenient online detection that is used for various actual water environments has the excellent popularization using value.
Claims (5)
1. the heavy metal electrochemical sensor based on activated charcoal two electrode systems is characterized in that, comprise working electrode and auxiliary electrode, described working electrode and auxiliary electrode are connected in electrochemical workstation by lead respectively; The material of described auxiliary electrode is activated charcoal.
2. the heavy metal electrochemical sensor based on activated charcoal two electrode systems according to claim 1 is characterized in that, described working electrode is glass-carbon electrode, gold electrode, platinum electrode, silver electrode, titanium electrode or tungsten electrode.
3. a utilization detects the method for heavy metal based on the heavy metal electrochemical sensor of activated charcoal two electrode systems, it is characterized in that, comprises the steps:
(1) testing sample is added in the supporting electrolyte by 1:1～3 volume ratios mixes set aside for use;
(2) mixed solution that step (1) is obtained adds in the electrolytic cell, will be fixed in the electrolytic cell in the lump through working electrode and the auxiliary electrode of polishing; Described working electrode and contrast electrode are connected in electrochemical workstation by lead respectively;
(3) adopt square wave Anodic Stripping Voltammetry Determination heavy metal concentration to be measured.
4. utilization according to claim 3 is characterized in that based on the method for the heavy metal electrochemical sensor detection heavy metal of activated charcoal two electrode systems the heavy metal described in the step (3) is lead, cadmium, mercury, zinc, copper or arsenic.
5. utilization according to claim 3 detects the method for heavy metal based on the heavy metal electrochemical sensor of activated charcoal two electrode systems, it is characterized in that, when adopting square wave Anodic Stripping Voltammetry Determination heavy metal concentration to be measured in the step (3), earlier-2V～-the 0.5V scope in, adopt constant potential enrichment metal 2～10min to be measured, apply square wave forward scan current potential then, make enriched in metals oxidation stripping.
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| CN104568731A (en) * | 2014-12-31 | 2015-04-29 | 天津大学 | Electrochemical noise experimental method at high temperature and high pressure |
| CN106706732A (en) * | 2016-12-26 | 2017-05-24 | 安徽省碧水电子技术有限公司 | Water quality detection system based on bi-polar system |
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| CN109813759A (en) * | 2017-11-20 | 2019-05-28 | 上海观流智能科技有限公司 | A kind of detection system of specific ion |
| CN110333280A (en) * | 2019-06-05 | 2019-10-15 | 北京师范大学 | A kind of antimony form electrochemical detection method and its application based on photooxidation |
| CN111624243A (en) * | 2020-06-09 | 2020-09-04 | 中国科学院生态环境研究中心 | Core-shell structure electrode material for arsenic-antimony electrochemical detection |
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| CN103558207A (en) * | 2013-10-28 | 2014-02-05 | 青岛佳明测控科技股份有限公司 | Small portable heavy metal detection device and detection method |
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| CN104568731A (en) * | 2014-12-31 | 2015-04-29 | 天津大学 | Electrochemical noise experimental method at high temperature and high pressure |
| CN106770593A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with purging system based on the two poles of the earth system water quality detection system |
| CN106770533A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with voice broadcast based on the two poles of the earth system water quality detection system |
| CN106770534A (en) * | 2016-12-26 | 2017-05-31 | 安徽省碧水电子技术有限公司 | It is a kind of with temperature sensor based on the two poles of the earth system water quality detection system |
| CN106706732A (en) * | 2016-12-26 | 2017-05-24 | 安徽省碧水电子技术有限公司 | Water quality detection system based on bi-polar system |
| CN106841359A (en) * | 2016-12-26 | 2017-06-13 | 安徽省碧水电子技术有限公司 | It is a kind of with standard value contrast based on the two poles of the earth system water quality detection system |
| CN107576716A (en) * | 2017-09-18 | 2018-01-12 | 中国科学院烟台海岸带研究所 | A kind of acupuncture needle base working electrode electrochemical sensor for detecting trace heavy metal |
| CN109813759A (en) * | 2017-11-20 | 2019-05-28 | 上海观流智能科技有限公司 | A kind of detection system of specific ion |
| CN109813759B (en) * | 2017-11-20 | 2022-03-22 | 上海柏中观澈智能科技有限公司 | Specific ion detection system |
| CN110333280A (en) * | 2019-06-05 | 2019-10-15 | 北京师范大学 | A kind of antimony form electrochemical detection method and its application based on photooxidation |
| CN111624243A (en) * | 2020-06-09 | 2020-09-04 | 中国科学院生态环境研究中心 | Core-shell structure electrode material for arsenic-antimony electrochemical detection |
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Application publication date: 20130904 |