CN104020213B - A kind of electrochemical sensor and preparation method who simultaneously detects cadmium and lead ion - Google Patents
A kind of electrochemical sensor and preparation method who simultaneously detects cadmium and lead ion Download PDFInfo
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Abstract
The present invention relates to a kind of electrochemical sensor and preparation method that can simultaneously detect cadmium and lead ion, this sensor is by electrochemical workstation, working electrode, to electrode, reference electrode, electrolytic cell composition, wherein, working electrode is taking glass-carbon electrode as substrate, finishing Nafion/ nitrogen doped micropore carbon composite membrane. When can realizing Determination of Trace Amount Cadmium, lead ion, this electrochemical sensor detects, does is detectability respectively 1.5? μ g/L, 0.05? μ g/L. Working electrode preparation method in the present invention is simple, environmental protection, working electrode combine hetero atom, Nafion effectively Adsorption of Heavy Metal Ions and bismuth and heavy metal to be measured can form the feature of alloy, can significantly improve the sensitivity of glass-carbon electrode sensing heavy metal ion. This electrochemical sensor favorable reproducibility, antijamming capability is strong and detectability is low, can be applicable to cadmium ion and lead ion field assay.
Description
Technical field
The present invention relates to trace heavy metal ion electrochemical sensor field, specifically for trace analysis cadmium and plumbous a kind of nitrogenThe preparation method of doped micropore carbon modified electrode material and the film modified glass-carbon electrode of Nafion/ nitrogen doped micropore carbon/bismuth.
Background technology
In recent years, hypertoxic heavy metal (as cadmium, plumbous etc.) pollution problem is day by day serious. Severe toxicity heavy metal is mainly by metal smeltingThe approach such as refining, combustion of fossil fuel, mining and sewage discharge enter the ecosystem, then in soil, water body and atmosphere, followRing, and easily by food chain move in vivo, enrichment. Cadmium is not human essential elements. By sucking by cadmium pollutionFlue dust and absorption can be caused poisoning by the food of cadmium pollution, water. The compound of cadmium and cadmium is by international cancer research institution(IARC) be classified as carcinogenic substance. Lead is that one has a highly toxic heavy metal species to the many organs of human body, defends according to the world in 2004Raw tissue is about global human health risk assessment, and global 0.6% disease is because lead contamination causes. Therefore, realize soonSpeed, accurate, Site Detection Determination of Trace Amount Cadmium and plumbous significant to ecological environment and human health.
The method of traditional detection heavy metal ion of comparative maturity mainly contains atomic absorption spectrography (AAS) (AtomicAbsorptionSpectroscopy) and various Instrument crosslinking technology, as inductively coupled plasma mass spectrometry(InductivelyCoupledPlasmaMassSpectrometry), inductively coupled plasma atomic emission spectrumAnalysis (InductivelyCoupledPlasmaAtomicEmissionSpectrometry) etc. But these traditionAll more consuming time and cost of equipment costlinesses of detection means. Some method also needs complicated pre-treatment, is therefore not suitable forLine and field assay detect. Comparatively speaking, anodic stripping voltammetry be realize online, fast detection of trace heavy metal ionThe effective means of one class. Wherein, differ from formula pulsed anode stripping voltammetry (DPASV) with its highly sensitive characteristic by wideGeneral application.
The key that realizes high sensitivity, the detection of low detectability is the decorative material of working electrode. Modified electrode material should be concreteThere are the features such as electric transmission is fast, electrochemical surface area large, acid and alkali-resistance. The material that is applied at present modification have CNT,The nano materials such as Graphene, nano metal and metal oxide. But above-mentioned decorative material or there is bad dispersibility, modify after easilyAssemble or there is the problems such as ph stability is poor, electric conductivity is not high. Therefore, be necessary to research and develop novel modified electrode material,In order to improve sensitivity and the stability of Electrochemical Detection heavy metal.
Summary of the invention
The object of the invention is to provide a kind of electrochemical sensor and preparation method who simultaneously detects cadmium and lead ion, this sensorBy electrochemical workstation, working electrode, to electrode, reference electrode, electrolytic cell composition, wherein, working electrode is with glass carbonElectrode is substrate, finishing Nafion/ nitrogen doped micropore carbon composite membrane, this electrochemical sensor can realize Determination of Trace Amount Cadmium,When lead ion, detect, detectability is respectively 1.5 μ g/L, 0.05 μ g/L. Working electrode preparation side in the present inventionMethod is simple, environmental protection. Working electrode combines effectively Adsorption of Heavy Metal Ions and bismuth and treat check weighing of hetero atom, NafionMetal can form the feature of alloy, can significantly improve the sensitivity of glass-carbon electrode sensing heavy metal ion. This electrochemical sensorFavorable reproducibility, antijamming capability is strong and detectability is low, can be applicable to cadmium ion and lead ion field assay.
Of the present invention a kind of for detect the electrochemical sensor of cadmium, lead ion simultaneously, this sensor is by electrochemistryWork station, working electrode, to electrode, reference electrode, electrolytic cell composition, using silver/silver chloride electrode and platinum filament as referenceElectrode (4) and to electrode (3), working electrode (2) is by glass-carbon electrode substrate (6), original position is electroplated bismuth film (7), nitrogenDoped micropore carbon (8) composition, the electrolyte in electrolytic cell (5) is for containing bismuth ion (Bi3+) and cadmium ion (Cd to be measured2+)、Lead ion (Pb2+) acetic acid-sodium acetate buffer solution, working electrode (2), to electrode (3) and reference electrode (4) oneIt is upper that end is connected to electrochemical workstation (1), working electrode (2), to electrode (3) and reference electrode (4) separatelyOne end is placed on respectively in the electrolyte in electrolytic cell (5).
Described time, detect the preparation method of the electrochemical sensor of cadmium, lead ion, follow these steps to carry out:
A, at room temperature, is dissolved in zinc nitrate and methylimidazole respectively in methyl alcohol, then by molten the methyl alcohol of methylimidazoleLiquid is poured in the methanol solution of zinc nitrate, leaves standstill 24 hours, and centrifugation is washed with methyl alcohol and DMFWash, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, then by zeolite imidazoles metallic framework chemical combinationPorcelain boat is put in thing-8, and porcelain boat is put into tube furnace, rises to 600 DEG C with 5 DEG C/min of temperature, calcine 5 hours, then with5 DEG C/min of temperature rate of temperature fall is down to room temperature, obtains black powder, then uses the salt acid soak of 35wt.%, and stirring 24 is littleTime, filter and leave and take black powder, with deionized water washing, put into 60 DEG C of oven temperatures dry, obtain nitrogen doped microporeCarbon (8);
B, nitrogen doped micropore carbon (8) is dissolved in DMF, then drips Nafion liquid, be mixed with 1-3DMF-Nafion suspension of mg/L, ultrasonic to dispersed;
C, sanding and polishing processing is carried out in glass-carbon electrode substrate (6) surface, with after ethanol and washed with de-ionized water, with moving liquidRifle is got suspension, drips and is coated onto glass-carbon electrode substrate (6) above, and under room temperature, the dry Nafion/ nitrogen that obtains after 24 hours adulterates micro-The glass-carbon electrode substrate (6) of hole carbon load;
D, by the glass-carbon electrode substrate (6) of nitrogen doped micropore carbon (8) load, reference electrode (4), to electrode (3)One end is immersed respectively containing 0-600 μ g/L bismuth ion and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, and pH3.0-6.0, is connected respectively to electrochemical workstation (1) by the other end upper, loads the richness of sedimentation potential-0.9--1.2VCollecting voltage, the time is 30-210s, places a magneton in electrolytic cell (5), controls mixing speed, in electrolyteBismuth ion, cadmium ion and lead ion, under the effect of electric field force, move to the glass-carbon electrode of nitrogen doped micropore carbon (8) loadSubstrate (6) surface, is reduced into metal simple-substance, is attached to the glass-carbon electrode substrate (6) of nitrogen doped micropore carbon (8) loadUpper, complete the load that original position is electroplated bismuth film (7), obtain working electrode (2);
E, stop stirring, leave standstill after 10s, at a upper forward scan voltage, the scanning model of loading of working electrode (2)Enclose is-1-0V that the bismuth of enrichment, cadmium, plumbous simple substance are oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemistry work(1) record current-voltage change of standing situation, has obtained current-voltage curve, measures different cadmium ions and lead ion denseAnodic Stripping peak point current under degree, treats measured ion concentration drawing curve map, cadmium ion and lead ion with peak currentDifference between the value of peak voltage exceedes 100mV, illustrates that the present invention can distinguish cadmium ion and lead ion, realizes inspection simultaneouslySurvey cadmium ion and lead ion.
Of the present invention a kind of for detect the electrochemical sensor of cadmium, lead ion simultaneously, the nitrogen obtaining in this sensor is mixedIn assorted microporous carbon 8, the content of carbon, nitrogen is respectively 68at.%, and (a), wherein nitrogen is mainly with pyridine nitrogen to Fig. 4 to 25at.%(N1 in Fig. 4 b), the existence of pyrroles's nitrogen (N2 in Fig. 4 b) form, nitrogen-atoms is lewis base, and cadmium ion,Lead ion is lewis acid, and the nitrogen in nitrogen doped micropore carbon 8 can adsorb the cadmium ion, the lead ion that detect in liquid, has research reportPyridine nitrogen in the material with carbon element of road nitrogen atom doping, pyrroles's nitrogen has electro-chemical activity, can effectively improve electrochemistry mistakeThe electric transmission of journey, therefore improves the doping amount of nitrogen and the nitrogen content of high electrochemical activity and is conducive to improve an Electrochemical Detection huge sum of moneyBelong to sensitivity and sensing speed. The nitrogen that in nitrogen doped micropore carbon 8 of the present invention, the content of nitrogen obtains than general post-decoration method is mixedThe nitrogen content of assorted carbon is high, and nitrogen content is mainly to exist with the pyridine nitrogen of high electrochemical activity and the form of pyrroles's nitrogen.
Brief description of the drawings
Fig. 1 is sensor schematic diagram of the present invention, and wherein 1 is electrochemical workstation, and 2 is working electrode, and 3 is to electrode, 4For reference electrode, 5 is electrolytic cell;
Fig. 2 is the schematic diagram of working sensor electrode of the present invention, and wherein 6 is glass-carbon electrode substrates, and 7 is original position plating bismuthFilm, 8 is nitrogen doped micropore carbon;
Fig. 3 is the phenogram of zeolite imidazoles metallic framework compound-8 of the present invention and nitrogen doped micropore carbon, and wherein a is thisThe X-ray diffraction of zeolite imidazoles metallic framework compound-8 prepared by inventive embodiments 1 characterizes; B is that embodiment 1 makesStandby zeolite imidazoles metallic framework compound-8 SEM characterizes, and the illustration in the upper right corner is enlarged drawing; C is realThe nitrogen adsorption desorption curve of executing nitrogen doped micropore carbon prepared by example 1, open circles curve is adsorption curve, filled circles curve is de-Attached curve; D is that the SEM of nitrogen doped micropore carbon characterizes, the illustration enlarged drawing in the upper right corner;
Fig. 4 is that the x-ray photoelectron spectroscopy of the nitrogen doped micropore carbon prepared of the embodiment of the present invention 1 characterizes, and wherein a is nitrogen dopingThe full spectrogram of microporous carbon X-ray electronic energy; B is the meticulous spectrogram of nitrogen element in nitrogen doped micropore carbon, and N1 is pyridine nitrogen, and N2 is pyrroleCough up nitrogen;
Fig. 5 is DPASV curve and the corresponding working curve diagram that the present invention analyzes cadmium ion, lead ion.
Detailed description of the invention
Embodiment 1
The preparation of nitrogen doped micropore carbon
Under room temperature, by 1.032gZn (NO3)2·5H2O and 1.052g methylimidazole are dissolved in respectively in 80mL methyl alcohol, quietPut 24 hours, then the methanol solution of methylimidazole is poured in the methanol solution of zinc nitrate, centrifugation, uses firstAlcohol and DMF washing, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, shouldZeolite imidazoles metallic framework compound-8 present granatohedron, and (Fig. 3 b) for the general 80nm of average grain diameter; Again willPorcelain boat is put in zeolite imidazoles metallic framework compound-8, and porcelain boat is put into tube furnace (GSL-1500X, Hefei section crystalline substance),Rise to 600 DEG C with 5 DEG C/min of temperature, calcine 5 hours, be then down to room temperature with 5 DEG C/min of temperature rate of temperature fall,Arrive black powder, then use the salt acid soak of 35wt.%, stir 24 hours, filter and leave and take black powder, use deionized waterWashing, puts into 60 DEG C of oven temperatures dry, obtains nitrogen doped micropore carbon 8; The nitrogen doped micropore carbon 8 obtaining has kept boilingThe crystalline form of stone imidazoles metallic framework compound-8, has some collapses a little, and average grain diameter is 40nm, disperses more even(d), nitrogen doped micropore carbon 8 pore-size distributions are 0.8 for Fig. 3The poromerics of-1.0nm, specific area is 941m2/ g (figure3c), in nitrogen doped micropore carbon 8, the content of carbon, nitrogen is respectively 68at.%, and (a), wherein nitrogen is mainly Fig. 4 25at.%With pyridine nitrogen (N1 in Fig. 4 b), the existence of pyrroles's nitrogen (N2 in Fig. 4 b) form;
The preparation of working electrode
Nitrogen doped micropore carbon 8 is dissolved in the DMF of 5mL, then drips 15 μ L0.5wt.%NafionLiquid, is mixed with DMF-Nafion suspension of 1mg/L, ultrasonic to dispersed;
Sanding and polishing processing is carried out in glass-carbon electrode substrate 6 surfaces, with after ethanol and washed with de-ionized water, pipette with liquid-transfering gun5 μ L suspension, drip and are coated onto in glass-carbon electrode substrate 6, under room temperature, are dried and obtain Nafion/ nitrogen doped micropore after 24 hoursThe glass-carbon electrode substrate 6 of carbon load;
By the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, reference electrode 4, immerses and contains respectively one end of electrode 3300 μ g/L bismuth ions and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, pH4.5, divides the other endBe not connected on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-0.9V, the time is 150s, at electrolytic cellIn 5, place a magneton, control mixing speed, bismuth ion, cadmium ion and the lead ion in electrolyte is in the effect of electric field forceUnder, move to glass-carbon electrode substrate 6 surfaces of nitrogen doped micropore carbon 8 loads, be reduced into metal simple-substance, be attached to nitrogen dopingIn the glass-carbon electrode substrate 6 of microporous carbon 8 loads, complete the load that original position is electroplated bismuth film 7, obtained working electrode 2;
The detection of cadmium and lead ion
Stop stirring, leave standstill after 10s, load a forward scan voltage on working electrode 2, sweep limits is-1V,Stop current potential 0V, sweep amplitude 50mV, pulse width 50ms, current potential increment 4mV, the bismuth of enrichment, cadmium, plumbous singleMatter is oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-voltage change situation,Obtained current-voltage curve, the difference between the value of the peak voltage of cadmium ion and lead ion exceedes 100mV, and this is describedBrightly can distinguish cadmium ion and lead ion, realize and detect cadmium ion and lead ion simultaneously. Measure different cadmium ions and lead ion denseAnodic Stripping peak point current under degree, treats measured ion concentration drawing curve map with peak current, and the spike potential of cadmium is-0.84V, plumbous spike potential is at-0.60V;
By cadmium ion, lead ion standard inventory solution is that buffer solution dilution concentration of cadmium ions is with acetic acid-sodium acetate of pH=4.52μg/L、4μg/L、6μg/L、8μg/L、10μg/L、20μg/L、30μg/L、40μg/L、50μg/L、60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L; Plumbum ion concentration be 0.5 μ g/L, 4 μ g/L,6μg/L、8μg/L、10μg/L、20μg/L、30μg/L、40μg/L、50μg/L、60μg/L、70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L. Record the poor formula pulsed anode stripping of cadmium ion, lead ionVolt-ampere curve, the cadmium ion of variable concentrations, corresponding its different peak point current of lead ion in liquid to be measured, with peak current-concentrationThe curve (Fig. 5 b, 5d) of working, working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to cadmium fromThe responsing linear range of son is divided into small concentration and large two scopes of concentration, and small concentration scope is 2-10 μ g/L, the line of matchingSexual intercourse formula is: y=0.01943x-0.0237, coefficient R=0.9778; The large concentration range of linearity is 10-100 μ g/L,The linear relation of matching is: y=0.02477x-0.1092, coefficient R=0.9930, sensor of the present invention to cadmium fromThe detectability (based on 3 times of noises) of son is 1.5 μ g/L; Working electrode 2 (original position plating bismuth film/nitrogen doped micropore carbon/Glass-carbon electrode) responsing linear range of lead ion is divided into small concentration and large two scopes of concentration, wherein small concentration scope is0.5-10 μ g/L, the linear relation of matching is: y=0.00906x+0.0655, coefficient R=0.9870; Large concentrationThe range of linearity is 10-100 μ g/L, and the linear relation of matching is: y=0.02424x-0.1148, and coefficient R=0.9948,The detectability (based on 3 times noises) of sensor of the present invention to lead ion is 0.05 μ g/L, working electrode 2 (original position electricityPlating bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to all drinking lower than the World Health Organization of the detectability of cadmium ion, lead ionWater quality standard (cadmium ion: 3 μ g/L, lead ion: 10 μ g/L).
Embodiment 2
The preparation of nitrogen doped micropore carbon
Under room temperature, by 1.032gZn (NO3)2·5H2O and 1.052g methylimidazole are dissolved in respectively in 80mL methyl alcohol, quietPut 24 hours, then the methanol solution of methylimidazole is poured in the methanol solution of zinc nitrate, centrifugation, uses firstAlcohol and DMF washing, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, shouldZeolite imidazoles metallic framework compound-8 present granatohedron, and (Fig. 3 b) for the general 80nm of average grain diameter; Again willPorcelain boat is put in zeolite imidazoles metallic framework compound-8, and porcelain boat is put into tube furnace (GSL-1500X, Hefei section crystalline substance),Rise to 600 DEG C with 5 DEG C/min of temperature, calcine 5 hours, be then down to room temperature with 5 DEG C/min of temperature rate of temperature fall,Arrive black powder, then use the salt acid soak of 35wt.%, stir 24 hours, filter and leave and take black powder, use deionized waterWashing, puts into 60 DEG C of oven temperatures dry, obtains nitrogen doped micropore carbon 8; The nitrogen doped micropore carbon 8 obtaining has kept boilingThe crystalline form of stone imidazoles metallic framework compound-8, has some collapses a little, and average grain diameter is 40nm, disperses more even(d), nitrogen doped micropore carbon 8 pore-size distributions are 0.8 for Fig. 3The poromerics of-1.0nm, specific area is 941m2/g (figure3c), in nitrogen doped micropore carbon 8, the content of carbon, nitrogen is respectively 68at.%, and (a), wherein nitrogen is mainly Fig. 4 25at.%With pyridine nitrogen (N1 in Fig. 4 b), the existence of pyrroles's nitrogen (N2 in Fig. 4 b) form;
The preparation of working electrode
Nitrogen doped micropore carbon 8 is dissolved in the DMF of 5mL, then drips 15 μ L0.5wt.%NafionLiquid, is mixed with DMF-Nafion suspension of 1mg/L, ultrasonic to dispersed;
Sanding and polishing processing is carried out in glass-carbon electrode substrate 6 surfaces, with after ethanol and washed with de-ionized water, pipette with liquid-transfering gun5 μ L suspension, drip and are coated onto in glass-carbon electrode substrate 6, under room temperature, are dried and obtain Nafion/ nitrogen doped micropore after 24 hoursThe glass-carbon electrode substrate 6 of carbon load;
By the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, reference electrode 4, immerses and contains respectively one end of electrode 3100 μ g/L bismuth ions and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, pH3, by the other end respectivelyBe connected on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-1.2V, the time is 120s, at electrolytic cell 5Magneton of middle placement, control mixing speed, bismuth ion, cadmium ion and lead ion in electrolyte under the effect of electric field force,Glass-carbon electrode substrate 6 surfaces that move to 8 loads of nitrogen doped micropore carbon, are reduced into metal simple-substance, are attached to nitrogen doped microporeIn the glass-carbon electrode substrate 6 of carbon 8 loads, complete the load that original position is electroplated bismuth film 7, obtained working electrode 2;
The detection of cadmium and lead ion
Stop stirring, leave standstill after 10s, load a forward scan voltage on working electrode 2, sweep limits is-1V,Stop current potential 0V, sweep amplitude 50mV, pulse width 50ms, current potential increment 4mV, the bismuth of enrichment, cadmium, plumbous singleMatter is oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-voltage change situation,Obtained current-voltage curve, the difference between the value of the peak voltage of cadmium ion and lead ion exceedes 100mV, and explanation canDistinguish cadmium ion and lead ion, realize and detect cadmium ion and lead ion simultaneously, measure under different cadmium ions and plumbum ion concentrationAnodic Stripping peak point current, treats measured ion concentration drawing curve map with peak current, and the spike potential of cadmium is at-0.84V,Plumbous spike potential is at-0.60V;
By cadmium ion, lead ion standard inventory solution is that buffer solution dilution concentration of cadmium ions is with acetic acid-sodium acetate of pH=4.52μg/L、4μg/L、6μg/L、8μg/L、10μg/L、20μg/L、30μg/L、40μg/L、50μg/L、60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L; Plumbum ion concentration be 0.5 μ g/L, 4 μ g/L,6μg/L、8μg/L、10μg/L、20μg/L、30μg/L、40μg/L、50μg/L、60μg/L、70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L; Record the poor formula pulsed anode stripping of cadmium ion, lead ionVolt-ampere curve, the cadmium ion of variable concentrations, corresponding its different peak point current of lead ion in liquid to be measured, with peak current-concentrationThe curve (Fig. 5 b, 5d) of working, working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to cadmium fromThe responsing linear range of son is divided into small concentration and large two scopes of concentration, and small concentration scope is 2-10 μ g/L, the line of matchingSexual intercourse formula is: y=0.01943x-0.0237, coefficient R=0.9778; The large concentration range of linearity is 10-100 μ g/L,The linear relation of matching is: y=0.02477x-0.1092, coefficient R=0.9930, sensor of the present invention to cadmium fromThe detectability (based on 3 times of noises) of son is 1.5 μ g/L; Working electrode 2 (original position plating bismuth film/nitrogen doped micropore carbon/Glass-carbon electrode) responsing linear range of lead ion is divided into small concentration and large two scopes of concentration, wherein small concentration scope is0.5-10 μ g/L, the linear relation of matching is: y=0.00906x+0.0655, coefficient R=0.9870; Large concentrationThe range of linearity is 10-100 μ g/L, and the linear relation of matching is: y=0.02424x-0.1148, and coefficient R=0.9948,The detectability (based on 3 times noises) of sensor of the present invention to lead ion is 0.05 μ g/L, working electrode 2 (original position electricityPlating bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to all drinking lower than the World Health Organization of the detectability of cadmium ion, lead ionWater quality standard (cadmium ion: 3 μ g/L, lead ion: 10 μ g/L).
Embodiment 3
The preparation of nitrogen doped micropore carbon
Under room temperature, by 1.032gZn (NO3)2·5H2O and 1.052g methylimidazole are dissolved in respectively in 80mL methyl alcohol, quietPut 24 hours, then the methanol solution of methylimidazole is poured in the methanol solution of zinc nitrate, centrifugation, uses firstAlcohol and DMF washing, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, shouldZeolite imidazoles metallic framework compound-8 present granatohedron, and (Fig. 3 b) for the general 80nm of average grain diameter; Again willPorcelain boat is put in zeolite imidazoles metallic framework compound-8, and porcelain boat is put into tube furnace (GSL-1500X, Hefei section crystalline substance),Rise to 600 DEG C with 5 DEG C/min of temperature, calcine 5 hours, be then down to room temperature with 5 DEG C/min of temperature rate of temperature fall,Arrive black powder, then use the salt acid soak of 35wt.%, stir 24 hours, filter and leave and take black powder, use deionized waterWashing, puts into 60 DEG C of oven temperatures dry, obtains nitrogen doped micropore carbon 8; The nitrogen doped micropore carbon 8 obtaining has kept boilingThe crystalline form of stone imidazoles metallic framework compound-8, has some collapses a little, and average grain diameter is 40nm, disperses more even(d), nitrogen doped micropore carbon 8 pore-size distributions are 0.8 for Fig. 3The poromerics of-1.0nm, specific area is 941m2/g (figure3c), in nitrogen doped micropore carbon 8, the content of carbon, nitrogen is respectively 68at.%, and (a), wherein nitrogen is mainly Fig. 4 25at.%With pyridine nitrogen (N1 in Fig. 4 b), the existence of pyrroles's nitrogen (N2 in Fig. 4 b) form;
The preparation of working electrode
Nitrogen doped micropore carbon 8 is dissolved in the DMF of 5mL, then drips 15 μ L0.5wt.%NafionLiquid, is mixed with DMF-Nafion suspension of 1mg/L, ultrasonic to dispersed;
Sanding and polishing processing is carried out in glass-carbon electrode substrate 6 surfaces, with after ethanol and washed with de-ionized water, pipette with liquid-transfering gun5 μ L suspension, drip and are coated onto in glass-carbon electrode substrate 6, under room temperature, are dried and obtain Nafion/ nitrogen doped micropore after 24 hoursThe glass-carbon electrode substrate 6 of carbon load;
By the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, reference electrode 4, immerses and contains respectively one end of electrode 3600 μ g/L bismuth ions and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, pH6, by the other end respectivelyBe connected on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-1V, the time is 210s, at electrolytic cell 5Magneton of middle placement, control mixing speed, bismuth ion, cadmium ion and lead ion in electrolyte under the effect of electric field force,Glass-carbon electrode substrate 6 surfaces that move to 8 loads of nitrogen doped micropore carbon, are reduced into metal simple-substance, are attached to nitrogen doped microporeIn the glass-carbon electrode substrate 6 of carbon 8 loads, complete the load that original position is electroplated bismuth film 7, obtained working electrode 2;
The detection of cadmium and lead ion
Stop stirring, leave standstill after 10s, load a forward scan voltage on working electrode 2, sweep limits is-1V,Stop current potential 0V, sweep amplitude 50mV, pulse width 50ms, current potential increment 4mV, the bismuth of enrichment, cadmium, plumbous singleMatter is oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-voltage change situation,Obtained current-voltage curve, the difference between the value of the peak voltage of cadmium ion and lead ion exceedes 100mV, and this is describedBrightly can distinguish cadmium ion and lead ion, realize and detect cadmium ion and lead ion simultaneously. Measure different cadmium ions and lead ion denseAnodic Stripping peak point current under degree, treats measured ion concentration drawing curve map with peak current, and the spike potential of cadmium is-0.84V, plumbous spike potential is at-0.60V;
By cadmium ion, lead ion standard inventory solution is that buffer solution dilution concentration of cadmium ions is with acetic acid-sodium acetate of pH=4.52μg/L、4μg/L、6μg/L、8μg/L、10μg/L、20μg/L、30μg/L、40μg/L、50μg/L、60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L; Plumbum ion concentration be 0.5 μ g/L, 4 μ g/L,6μg/L、8μg/L、10μg/L、20μg/L、30μg/L、40μg/L、50μg/L、60μg/L、70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L. Record the poor formula pulsed anode stripping of cadmium ion, lead ionVolt-ampere curve, the cadmium ion of variable concentrations, corresponding its different peak point current of lead ion in liquid to be measured, with peak current-concentrationThe curve (Fig. 5 b, 5d) of working, working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to cadmium fromThe responsing linear range of son is divided into small concentration and large two scopes of concentration, and small concentration scope is 2-10 μ g/L, the line of matchingSexual intercourse formula is: y=0.01943x-0.0237, coefficient R=0.9778; The large concentration range of linearity is 10-100 μ g/L,The linear relation of matching is: y=0.02477x-0.1092, coefficient R=0.9930, sensor of the present invention to cadmium fromThe detectability (based on 3 times of noises) of son is 1.5 μ g/L; Working electrode 2 (original position plating bismuth film/nitrogen doped micropore carbon/Glass-carbon electrode) responsing linear range of lead ion is divided into small concentration and large two scopes of concentration, wherein small concentration scope is0.5-10 μ g/L, the linear relation of matching is: y=0.00906x+0.0655, coefficient R=0.9870; Large concentrationThe range of linearity is 10-100 μ g/L, and the linear relation of matching is: y=0.02424x-0.1148, and coefficient R=0.9948,The detectability (based on 3 times noises) of sensor of the present invention to lead ion is 0.05 μ g/L, working electrode 2 (original position electricityPlating bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to all drinking lower than the World Health Organization of the detectability of cadmium ion, lead ionWater quality standard (cadmium ion: 3 μ g/L, lead ion: 10 μ g/L).
Embodiment 4
The anti-interference test of working electrode (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode)
By the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, reference electrode 4, immerses respectively 8mL to one end of electrode 3The buffer solution of acetic acid-sodium acetate pH4.5 in, then add 50 μ g/L cadmium ion and lead ions, 300 μ g/L'sBismuth ion, 10 times to cadmium ion, the interfering ion Ca of lead ion2+,Mg2+,Al3+,Fe2+,Fe3+,Zn2+,Co2+,Ni2+, Mn2+,Cr3+Cu2+, the other end is connected respectively on electrochemical workstation 1, load the enrichment electricity of sedimentation potential-1.2VPress, the time is 150s, places a magneton in electrolytic cell 5, controls mixing speed. This is complete by electrochemical workstationBecome enrichment process in, in the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads also with regard on original position appendix one deck bismuth film,Obtained working electrode 2, after waiting electrochemical workstation enrichment to operate, stopped stirring, after leaving standstill 10s,On working electrode 2, load a forward scan voltage, sweep limits is-1-0V to stop current potential 0V, sweep amplitude:50mV; Pulse width: 50ms; Current potential increment: 4mV, the bismuth of enrichment, cadmium, plumbous simple substance are oxidized to bismuth ion, cadmiumIon, lead ion stripping, by electrochemical workstation 1 record current-voltage change situation, obtained current-voltage curve,Test under the existence of 10 times of interfering ions, the variation of cadmium and plumbous poor formula pulsed anode Stripping Voltammetry curve peak current, 11Plant interfering ion cadmium and plumbous poor formula pulsed anode Stripping Voltammetry curve peak current affected to all in 7% (table 1):
Table 1
Working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) has well as can be seen from Table 1Antijamming capability.
Embodiment 5
Detect cadmium ion, lead ion in running water
Water sample is taken from the running water in laboratory, and the ratio with acetic acid-sodium acetate buffer of pH=4.5 taking volume ratio as 1:1 is rareRelease water sample, pipette dilution water sample 8mL and put into 10mL electrolytic cell, then add 300 μ g/L bismuth ions in electrolytic cellAs detecting liquid, by the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, reference electrode 4, divides one end of electrode 3Do not immerse in electrolytic cell 5, the other end is connected respectively on electrochemical workstation 1, load the richness of sedimentation potential-1.2VCollecting voltage, the time is 150s, places a magneton in electrolytic cell 5, controls mixing speed, bismuth ion in electrolyte,Cadmium ion and lead ion, under the effect of electric field force, move to glass-carbon electrode substrate 6 surfaces of nitrogen doped micropore carbon 8 loads,Be reduced into metal simple-substance, be attached in the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, completed original position and electroplated bismuth film7 load, has obtained working electrode 2;
Stop stirring, after leaving standstill 10s, load a forward scan voltage on working electrode 2, sweep limits is-1-0V, stops current potential 0V, sweep amplitude: 50mV; Pulse width: 50ms; Current potential increment: 4mV, the bismuth of enrichment,Cadmium, plumbous simple substance are oxidized to bismuth ion, cadmium ion, lead ion stripping, are become by electrochemical workstation 1 record current-voltageChange situation, has obtained current-voltage curve, measures cadmium and plumbous Anodic Stripping peak point current in running water, utilizes work songThe content of line computation cadmium ion and lead ion; The present invention can detect the lead ion of 3.2 μ g/L, does not detect cadmium ion,So add cadmium ion, the lead ion of 10 μ g/L, the cadmium that utilizes sensor of the present invention to detect in the water sample of dilutionThe concentration of ion is 10.6 μ g/L, and the concentration of lead ion is 13.7 μ g/L, calculates its rate of recovery by working curve,The rate of recovery of cadmium ion is 106%, and the rate of recovery of lead ion is 105% (table 2):
Table 2
As can be seen from Table 2: (it is micro-that original position is electroplated bismuth film/nitrogen doping to the working electrode 2 in sensor of the present inventionHole carbon/glass-carbon electrode) can be applied to the detection of cadmium ion in running water, lead ion.
Claims (1)
1. one kind for detect cadmium simultaneously, the electrochemical sensor of lead ion, it is characterized in that this sensor is by electrochemical workstation, working electrode, to electrode, reference electrode, electrolytic cell composition, using silver/silver chloride electrode and platinum filament as reference electrode (4) with to electrode (3), working electrode (2) is by glass-carbon electrode substrate (6), original position is electroplated bismuth film (7), nitrogen doped micropore carbon (8) composition, electrolyte in electrolytic cell (5) is for containing bismuth ion and cadmium ion to be measured, acetic acid-the sodium acetate buffer solution of lead ion, working electrode (2), one end of electrode (3) and reference electrode (4) is connected on electrochemical workstation (1), working electrode (2), the other end of electrode (3) and reference electrode (4) is placed on respectively in the electrolyte in electrolytic cell (5), concrete operations follow these steps to carry out:
A, at room temperature, zinc nitrate and methylimidazole are dissolved in respectively in methyl alcohol, then the methanol solution of methylimidazole is poured in the methanol solution of zinc nitrate, leave standstill 24 hours, centrifugation, with methyl alcohol and N, dinethylformamide washing, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, again porcelain boat is put into in zeolite imidazoles metallic framework compound-8, porcelain boat is put into tube furnace, rise to 600 DEG C with 5 DEG C/min of temperature, calcine 5 hours, then be down to room temperature with 5 DEG C/min of temperature rate of temperature fall, obtain black powder, use again the salt acid soak of 35wt.%, stir 24 hours, black powder is left and taken in filtration, wash by deionized water, put into 60 DEG C of oven temperatures dry, obtain nitrogen doped micropore carbon (8),
B, nitrogen doped micropore carbon (8) is dissolved in DMF, then drips Nafion liquid, be mixed with DMF-Nafion suspension of 1-3mg/L, ultrasonic to dispersed;
C, sanding and polishing processing is carried out in glass-carbon electrode substrate (6) surface, with after ethanol and washed with de-ionized water, get suspension with liquid-transfering gun, drip and be coated onto glass-carbon electrode substrate (6) above, the dry glass-carbon electrode substrate (6) that obtains the load of Nafion/ nitrogen doped micropore carbon after 24 hours under room temperature;
D, by the glass-carbon electrode substrate (6) of nitrogen doped micropore carbon (8) load, reference electrode (4), one end of electrode (3) is immersed respectively containing 100-600 μ g/L bismuth ion and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, pH3.0-6.0, the other end is connected respectively on electrochemical workstation (1), load the enrichment voltage of sedimentation potential-0.9--1.2V, time is 30-210s, in electrolytic cell (5), place a magneton, control mixing speed, bismuth ion in electrolyte, cadmium ion and lead ion are under the effect of electric field force, move to glass-carbon electrode substrate (6) surface of nitrogen doped micropore carbon (8) load, be reduced into metal simple-substance, be attached in the glass-carbon electrode substrate (6) of nitrogen doped micropore carbon (8) load, complete the load that original position is electroplated bismuth film (7), obtain working electrode (2),
E, stop stir, after leaving standstill 10s, at a forward scan voltage of the upper loading of working electrode (2), sweep limits is-1-0V, the bismuth of enrichment, cadmium, plumbous simple substance are oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation (1) record current-voltage change situation, have obtained current-voltage curve, measure the Anodic Stripping peak point current under different cadmium ions and plumbum ion concentration, treat measured ion concentration drawing curve map with peak current.
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