CN104020213A - Electrochemical sensor for simultaneously detecting cadmium and lead ions and preparation method - Google Patents
Electrochemical sensor for simultaneously detecting cadmium and lead ions and preparation method Download PDFInfo
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Abstract
The invention relates to an electrochemical sensor for simultaneously detecting cadmium and lead ions and a preparation method. The sensor is composed of an electrochemical work station, a working electrode, a counter electrode, a reference electrode and an electrolytic tank, wherein the working electrode adopts a glassy carbon electrode as a base, and a Nafion/N-doped micropore carbon composite membrane is modified on the surface of the working electrode; the electrochemical sensor can realize the simultaneous detection of the trace cadmium and lead ions, and the detection limits are respectively 1.5mug/L and 0.05 mug/L. The preparation method of the working electrode provided by the invention has the advantages that simplicity and environmental protection are realized, the working electrode combines the characteristic that hetero atoms and Nafion can effectively adsorb heavy metal ions, and bismuth and to-be-detected heavy metal can form an alloy, and the sensitivity of sensing heavy metal ions of the glassy carbon electrode is remarkably improved. The electrochemical sensor provided by the invention has the advantages that the reproducibility is good, the antijamming capability is strong, the detection limits are low, and the electrochemical sensor is applied in on-site analysis of cadmium and lead ions.
Description
Technical field
The present invention relates to trace heavy metal ion electrochemical sensor field, specifically for trace analysis cadmium and a kind of nitrogen doped micropore carbon modified electrode material of lead and the preparation method of 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 mainly enter the ecosystem by approach such as metal smelt, combustion of fossil fuel, mining and sewage discharges, then in soil, water body and atmosphere, circulate, and easily by food chain move in vivo, enrichment.Cadmium is not human essential elements.Can be caused poisoning by sucking by the flue dust of cadmium pollution and taking in by the food of cadmium pollution, water.The compound of cadmium and cadmium is classified as carcinogenic substance by international cancer research institution (IARC).Lead is that one has a highly toxic heavy metal species to the many organs of human body, and according to the World Health Organization (WHO) in 2004, about global human health risk assessment, global 0.6% disease was because lead contamination causes.Therefore, realize quick, accurate, Site Detection Determination of Trace Amount Cadmium and plumbous significant to ecologic environment and human health.
The method of traditional detection heavy metal ion of comparative maturity mainly contains atomic absorption spectrography (AAS) (Atomic Absorption Spectroscopy) and various Instrument crosslinking technology, as inductively coupled plasma mass spectrometry (Inductively Coupled Plasma Mass Spectrometry), inductively coupled plasma atomic emission spectrum analysis (Inductively Coupled Plasma Atomic Emission Spectrometry) etc.But these traditional detection meanss are more consuming time and cost of equipment costliness all.Some method also needs complicated pre-treatment, is therefore not suitable for online and on-the site analysis detection.Comparatively speaking, anodic stripping voltammetry is to realize the effective means of a class online, fast detection of trace heavy metal ion.Wherein, differing from formula pulsed anode stripping voltammetry (DPASV) is widely used with its highly sensitive characteristic.
The key that realizes high sensitivity, the detection of low detectability is the decorative material of working electrode.Modified electrode material should specifically have the features such as electric transmission is fast, electrochemical surface area large, acid and alkali-resistance.The material that is applied at present modification has the nano materials such as carbon nano-tube, Graphene, nano metal and metal oxide.But above-mentioned decorative material or have bad dispersibility, easily assemble after modifying or have 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 sensor is by electrochemical workstation, working electrode, to electrode, contrast electrode, electrolytic cell composition, wherein, working electrode is taking glass-carbon electrode as substrate, finishing Nafion/ nitrogen doped micropore carbon composite membrane, when this electrochemical sensor can be realized Determination of Trace Amount Cadmium, lead ion, detect, detectability is 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 heteroatoms, 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 on-the site analysis.
Of the present invention a kind of for detect the electrochemical sensor of cadmium, lead ion simultaneously, this sensor is by electrochemical workstation, working electrode, to electrode, contrast electrode, electrolytic cell composition, using silver/silver chloride electrode and platinum filament as contrast 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, the electrolytic solution in electrolytic cell (5) is for containing bismuth ion (Bi
3+) and cadmium ion (Cd to be measured
2+), lead ion (Pb
2+) acetic acid-sodium acetate buffer solution, working electrode (2), that one end of electrode (3) and contrast electrode (4) is connected to electrochemical workstation (1) is upper, working electrode (2), the other end of electrode (3) and contrast electrode (4) is placed on respectively in the electrolytic solution 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, 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, centrifuging, 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 tubular 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 with 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 suspending liquid 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 suspending liquid 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, contrast electrode (4), one end of electrode (3) 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, 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 stirring rate, bismuth ion in electrolytic solution, 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 stirring, after leaving standstill 10s, at a forward scan voltage of the upper loading of working electrode (2), sweep limit is-1-0V, the bismuth of enrichment, cadmium, plumbous simple substance is oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation (1) record current-change in voltage situation, obtain 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, difference between the value of the peak voltage of cadmium ion and lead ion exceedes 100mV, illustrate that the present invention can distinguish cadmium ion and lead ion, realize and detect cadmium ion and lead ion simultaneously.
One of the present invention is for detect cadmium simultaneously, the electrochemical sensor of lead ion, carbon in the nitrogen doped micropore carbon 8 obtaining in this sensor, the content of nitrogen is respectively 68at.%, (Fig. 4 a) for 25at.%, wherein nitrogen is mainly with pyridine nitrogen (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, nitrogen in nitrogen doped micropore carbon 8 can adsorb the cadmium ion detecting in liquid, lead ion, studies have reported that the pyridine nitrogen in the material with carbon element of nitrogen atom doping, pyrroles's nitrogen has electrochemical activity, can effectively improve the electric transmission of electrochemical process, therefore improve the doping amount of nitrogen and the nitrogen content of high electrochemical activity and be conducive to improve the sensitivity of Electrochemical Detection heavy metal and sensing speed.The nitrogen content of the nitrogen-doped carbon that in nitrogen doped micropore carbon 8 of the present invention, the content of nitrogen obtains than general post-decoration method 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, and 4 is contrast electrode, and 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 electroplate bismuth film for original position, and 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 that the X-ray diffraction of the embodiment of the present invention 1 zeolite imidazoles metallic framework compound-8 of preparing characterizes; B is that zeolite imidazoles metallic framework compound-8 scanning electron microscope prepared by embodiment 1 characterizes, and the illustration in the upper right corner is enlarged drawing; C is the nitrogen adsorption desorption curve of the nitrogen doped micropore carbon prepared of embodiment 1, and open circles curve is adsorption curve, filled circles curve desorption curve; D is that the scanning electron microscope 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 the full spectrogram of nitrogen doped micropore 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 pyrroles's nitrogen;
Fig. 5 is DPASV curve and the corresponding working curve diagram that the present invention analyzes cadmium ion, lead ion.
Embodiment
Embodiment 1
The preparation of nitrogen doped micropore carbon
Under room temperature, by 1.032g Zn (NO
3)
25H
2o and 1.052g methylimidazole are dissolved in respectively in 80mL methyl alcohol, leave standstill 24 hours, then the methanol solution of methylimidazole is poured in the methanol solution of zinc nitrate, centrifuging, with methyl alcohol and DMF washing, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, these zeolite imidazoles metallic framework compound-8 present granatohedron, and (Fig. 3 b) for the general 80nm of mean grain size; Again porcelain boat is put into in zeolite imidazoles metallic framework compound-8, porcelain boat is put into tubular 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, obtain black powder, use again the salt acid soak of 35wt.%, stir 24 hours, filter and leave and take black powder, wash with deionized water, put into 60 DEG C of oven temperatures dry, obtain nitrogen doped micropore carbon 8; The nitrogen doped micropore carbon 8 obtaining has kept the crystalline form of zeolite imidazoles metallic framework compound-8, has a little some collapses, and mean grain size is 40nm, and relatively evenly (d), nitrogen doped micropore carbon 8 pore diameter distributions are 0.8 for Fig. 3 in dispersion
the poromerics of-1.0nm, specific surface area is 941m
2(Fig. 3 c) for/g, in nitrogen doped micropore carbon 8, the content of carbon, nitrogen is respectively 68at.%, (a), wherein nitrogen is mainly with pyridine nitrogen (N1 in Fig. 4 b) to Fig. 4 to 25at.%, 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.%Nafion liquid, be mixed with DMF-Nafion suspending liquid 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 5 μ L suspending liquid with liquid-transfering gun, drip and be coated onto in glass-carbon electrode substrate 6, the dry glass-carbon electrode substrate 6 that obtains the load of Nafion/ nitrogen doped micropore carbon after 24 hours under room temperature;
By the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, contrast electrode 4, one end of electrode 3 is immersed respectively containing 300 μ g/L bismuth ions and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, pH4.5, the other end is connected respectively on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-0.9V, time is 150s, in electrolytic cell 5, place a magneton, control stirring rate, bismuth ion in electrolytic solution, cadmium ion and lead ion are 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, complete the load that original position is electroplated bismuth film 7, obtain working electrode 2,
The detection of cadmium and lead ion
Stop stirring, after leaving standstill 10s, on working electrode 2, load a forward scan voltage, sweep limit is-1V, stop current potential 0V, sweep amplitude 50mV, pulse width 50ms, current potential increment 4mV, the bismuth of enrichment, cadmium, plumbous simple substance is oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-change in voltage situation, obtain current-voltage curve, difference between the value of the peak voltage of cadmium ion and lead ion exceedes 100mV, illustrate that the present invention can distinguish cadmium ion and lead ion, realize and detect cadmium ion and lead ion simultaneously.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, the spike potential of cadmium is at-0.84V, and plumbous spike potential is at-0.60V;
By cadmium ion, lead ion standard inventory solution is that damping fluid dilution concentration of cadmium ions is 2 μ g/L, 4 μ g/L, 6 μ g/L, 8 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L with acetic acid-sodium acetate of pH=4.5; Plumbum ion concentration is 0.5 μ g/L, 4 μ g/L, 6 μ g/L, 8 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L.Record the poor formula pulsed anode Stripping Voltammetry curve of cadmium ion, lead ion, the cadmium ion of variable concentrations, corresponding its different peak point current of lead ion in liquid to be measured, with peak current-concentration curve (Fig. 5 b that works, 5d), working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) is divided into small concentration and large two scopes of concentration to the responsing linear range of cadmium ion, small concentration scope is 2-10 μ g/L, the linear relation of matching is: y=0.01943x-0.0237, coefficient R=0.9778; The large concentration range of linearity is 10-100 μ g/L, and the linear relation of matching is: y=0.02477x-0.1092, and coefficient R=0.9930, the detectability (based on 3 times noises) of sensor of the present invention to cadmium ion is 1.5 μ g/L; Working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) is divided into small concentration and large two scopes of concentration to the responsing linear range of lead ion, wherein small concentration scope is 0.5-10 μ g/L, the linear relation of matching is: y=0.00906x+0.0655, coefficient R=0.9870; The large concentration range of linearity is 10-100 μ g/L, the linear relation of matching is: y=0.02424x-0.1148, 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 electroplate bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to the detectability of cadmium ion, lead ion all lower than the drinking water standard (cadmium ion: 3 μ g/L, lead ion: 10 μ g/L) of the World Health Organization (WHO).
Embodiment 2
The preparation of nitrogen doped micropore carbon
Under room temperature, by 1.032g Zn (NO
3)
25H
2o and 1.052g methylimidazole are dissolved in respectively in 80mL methyl alcohol, leave standstill 24 hours, then the methanol solution of methylimidazole is poured in the methanol solution of zinc nitrate, centrifuging, with methyl alcohol and DMF washing, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, these zeolite imidazoles metallic framework compound-8 present granatohedron, and (Fig. 3 b) for the general 80nm of mean grain size; Again porcelain boat is put into in zeolite imidazoles metallic framework compound-8, porcelain boat is put into tubular 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, obtain black powder, use again the salt acid soak of 35wt.%, stir 24 hours, filter and leave and take black powder, wash with deionized water, put into 60 DEG C of oven temperatures dry, obtain nitrogen doped micropore carbon 8; The nitrogen doped micropore carbon 8 obtaining has kept the crystalline form of zeolite imidazoles metallic framework compound-8, has a little some collapses, and mean grain size is 40nm, and relatively evenly (d), nitrogen doped micropore carbon 8 pore diameter distributions are 0.8 for Fig. 3 in dispersion
the poromerics of-1.0nm, specific surface area is that (Fig. 3 c) for 941m2/g, in nitrogen doped micropore carbon 8, the content of carbon, nitrogen is respectively 68at.%, (Fig. 4 a) for 25at.%, wherein nitrogen is mainly 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.%Nafion liquid, be mixed with DMF-Nafion suspending liquid 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 5 μ L suspending liquid with liquid-transfering gun, drip and be coated onto in glass-carbon electrode substrate 6, the dry glass-carbon electrode substrate 6 that obtains the load of Nafion/ nitrogen doped micropore carbon after 24 hours under room temperature;
By the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, contrast electrode 4, one end of electrode 3 is immersed respectively containing 100 μ g/L bismuth ions and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, pH3, the other end is connected respectively on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-1.2V, time is 120s, in electrolytic cell 5, place a magneton, control stirring rate, bismuth ion in electrolytic solution, cadmium ion and lead ion are 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, complete the load that original position is electroplated bismuth film 7, obtain working electrode 2,
The detection of cadmium and lead ion
Stop stirring, after leaving standstill 10s, on working electrode 2, load a forward scan voltage, sweep limit is-1V, stop current potential 0V, sweep amplitude 50mV, pulse width 50ms, current potential increment 4mV, the bismuth of enrichment, cadmium, plumbous simple substance is oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-change in voltage situation, obtain current-voltage curve, difference between the value of the peak voltage of cadmium ion and lead ion exceedes 100mV, explanation can be distinguished cadmium ion and lead ion, realize and detect cadmium ion and lead ion simultaneously, 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, 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 damping fluid dilution concentration of cadmium ions is 2 μ g/L, 4 μ g/L, 6 μ g/L, 8 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L with acetic acid-sodium acetate of pH=4.5; Plumbum ion concentration is 0.5 μ g/L, 4 μ g/L, 6 μ g/L, 8 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L; Record the poor formula pulsed anode Stripping Voltammetry curve of cadmium ion, lead ion, the cadmium ion of variable concentrations, corresponding its different peak point current of lead ion in liquid to be measured, with peak current-concentration curve (Fig. 5 b that works, 5d), working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) is divided into small concentration and large two scopes of concentration to the responsing linear range of cadmium ion, small concentration scope is 2-10 μ g/L, the linear relation of matching is: y=0.01943x-0.0237, coefficient R=0.9778; The large concentration range of linearity is 10-100 μ g/L, and the linear relation of matching is: y=0.02477x-0.1092, and coefficient R=0.9930, the detectability (based on 3 times noises) of sensor of the present invention to cadmium ion is 1.5 μ g/L; Working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) is divided into small concentration and large two scopes of concentration to the responsing linear range of lead ion, wherein small concentration scope is 0.5-10 μ g/L, the linear relation of matching is: y=0.00906x+0.0655, coefficient R=0.9870; The large concentration range of linearity is 10-100 μ g/L, the linear relation of matching is: y=0.02424x-0.1148, 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 electroplate bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to the detectability of cadmium ion, lead ion all lower than the drinking water standard (cadmium ion: 3 μ g/L, lead ion: 10 μ g/L) of the World Health Organization (WHO).
Embodiment 3
The preparation of nitrogen doped micropore carbon
Under room temperature, by 1.032g Zn (NO
3)
25H
2o and 1.052g methylimidazole are dissolved in respectively in 80mL methyl alcohol, leave standstill 24 hours, then the methanol solution of methylimidazole is poured in the methanol solution of zinc nitrate, centrifuging, with methyl alcohol and DMF washing, drying at room temperature obtains white powder zeolite imidazoles metallic framework compound-8, these zeolite imidazoles metallic framework compound-8 present granatohedron, and (Fig. 3 b) for the general 80nm of mean grain size; Again porcelain boat is put into in zeolite imidazoles metallic framework compound-8, porcelain boat is put into tubular 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, obtain black powder, use again the salt acid soak of 35wt.%, stir 24 hours, filter and leave and take black powder, wash with deionized water, put into 60 DEG C of oven temperatures dry, obtain nitrogen doped micropore carbon 8; The nitrogen doped micropore carbon 8 obtaining has kept the crystalline form of zeolite imidazoles metallic framework compound-8, has a little some collapses, and mean grain size is 40nm, and relatively evenly (d), nitrogen doped micropore carbon 8 pore diameter distributions are 0.8 for Fig. 3 in dispersion
the poromerics of-1.0nm, specific surface area is that (Fig. 3 c) for 941m2/g, in nitrogen doped micropore carbon 8, the content of carbon, nitrogen is respectively 68at.%, (Fig. 4 a) for 25at.%, wherein nitrogen is mainly 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.%Nafion liquid, be mixed with DMF-Nafion suspending liquid 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 5 μ L suspending liquid with liquid-transfering gun, drip and be coated onto in glass-carbon electrode substrate 6, the dry glass-carbon electrode substrate 6 that obtains the load of Nafion/ nitrogen doped micropore carbon after 24 hours under room temperature;
By the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, contrast electrode 4, one end of electrode 3 is immersed respectively containing 600 μ g/L bismuth ions and cadmium ion to be measured, in the acetic acid-sodium acetate buffer of lead ion, pH6, the other end is connected respectively on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-1V, time is 210s, in electrolytic cell 5, place a magneton, control stirring rate, bismuth ion in electrolytic solution, cadmium ion and lead ion are 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, complete the load that original position is electroplated bismuth film 7, obtain working electrode 2,
The detection of cadmium and lead ion
Stop stirring, after leaving standstill 10s, on working electrode 2, load a forward scan voltage, sweep limit is-1V, stop current potential 0V, sweep amplitude 50mV, pulse width 50ms, current potential increment 4mV, the bismuth of enrichment, cadmium, plumbous simple substance is oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-change in voltage situation, obtain current-voltage curve, difference between the value of the peak voltage of cadmium ion and lead ion exceedes 100mV, illustrate that the present invention can distinguish cadmium ion and lead ion, realize and detect cadmium ion and lead ion simultaneously.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, the spike potential of cadmium is at-0.84V, and plumbous spike potential is at-0.60V;
By cadmium ion, lead ion standard inventory solution is that damping fluid dilution concentration of cadmium ions is 2 μ g/L, 4 μ g/L, 6 μ g/L, 8 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L with acetic acid-sodium acetate of pH=4.5; Plumbum ion concentration is 0.5 μ g/L, 4 μ g/L, 6 μ g/L, 8 μ g/L, 10 μ g/L, 20 μ g/L, 30 μ g/L, 40 μ g/L, 50 μ g/L, 60 μ g/L, 70 μ g/L, 80 μ g/L, 90 μ g/L, 100 μ g/L.Record the poor formula pulsed anode Stripping Voltammetry curve of cadmium ion, lead ion, the cadmium ion of variable concentrations, corresponding its different peak point current of lead ion in liquid to be measured, with peak current-concentration curve (Fig. 5 b that works, 5d), working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) is divided into small concentration and large two scopes of concentration to the responsing linear range of cadmium ion, small concentration scope is 2-10 μ g/L, the linear relation of matching is: y=0.01943x-0.0237, coefficient R=0.9778; The large concentration range of linearity is 10-100 μ g/L, and the linear relation of matching is: y=0.02477x-0.1092, and coefficient R=0.9930, the detectability (based on 3 times noises) of sensor of the present invention to cadmium ion is 1.5 μ g/L; Working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) is divided into small concentration and large two scopes of concentration to the responsing linear range of lead ion, wherein small concentration scope is 0.5-10 μ g/L, the linear relation of matching is: y=0.00906x+0.0655, coefficient R=0.9870; The large concentration range of linearity is 10-100 μ g/L, the linear relation of matching is: y=0.02424x-0.1148, 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 electroplate bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) to the detectability of cadmium ion, lead ion all lower than the drinking water standard (cadmium ion: 3 μ g/L, lead ion: 10 μ g/L) of the World Health Organization (WHO).
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, contrast electrode 4, immerses respectively one end of electrode 3 in the damping fluid of acetic acid-sodium acetate pH4.5 of 8mL, then add 50 μ g/L cadmium ion and lead ions, the bismuth ion of 300 μ g/L, 10 times to cadmium ion, the interfering ion Ca of lead ion
2+, Mg
2+, Al
3+, Fe
2+, Fe
3+, Zn
2+, Co
2+, Ni
2+, Mn
2+, Cr
3+cu
2+, the other end is connected respectively on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-1.2V, the time is 150s, places a magneton in electrolytic cell 5, controls stirring rate.In this enrichment process being completed by electrochemical workstation, 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 electrochemical workstation enrichment operated, stop stirring, after leaving standstill 10s, on working electrode 2, load a forward scan voltage, sweep limit 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, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-change in voltage situation, obtain current-voltage curve, test is under the existence of 10 times of interfering ions, the variation of cadmium and plumbous poor formula pulsed anode Stripping Voltammetry curve peak current, 11 kinds of interfering ions are on cadmium and plumbous all in 7% (table 1) of poor formula pulsed anode Stripping Voltammetry curve peak current impact:
Table 1
Working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) has good antijamming capability as can be seen from Table 1.
Embodiment 5
Detect cadmium ion, lead ion in tap water
Water sample is taken from the tap water in laboratory, dilution proportion water sample with acetic acid-sodium acetate buffer of pH=4.5 taking volume ratio as 1:1, pipette dilution water sample 8mL and put into 10mL electrolytic cell, in electrolytic cell, add 300 μ g/L bismuth ions as detecting liquid again, by the glass-carbon electrode substrate 6 of nitrogen doped micropore carbon 8 loads, contrast electrode 4, one end of electrode 3 is immersed respectively in electrolytic cell 5, the other end is connected respectively on electrochemical workstation 1, load the enrichment voltage of sedimentation potential-1.2V, time is 150s, in electrolytic cell 5, place a magneton, control stirring rate, bismuth ion in electrolytic solution, cadmium ion and lead ion are 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, complete the load that original position is electroplated bismuth film 7, obtain working electrode 2,
Stop stirring, after leaving standstill 10s, load a forward scan voltage on working electrode 2, sweep limit 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, cadmium ion, lead ion stripping, by electrochemical workstation 1 record current-change in voltage situation, obtain current-voltage curve, measure cadmium and plumbous Anodic Stripping peak point current in tap water, utilize working curve to calculate the content of cadmium ion and lead ion; The present invention can detect the lead ion of 3.2 μ g/L, do not detect cadmium ion, so add cadmium ion, the lead ion of 10 μ g/L in the water sample of dilution, utilizing the concentration of the cadmium ion that sensor of the present invention detects is 10.6 μ g/L, the concentration of lead ion is 13.7 μ g/L, calculate its recovery by working curve, the recovery of cadmium ion is 106%, and the recovery of lead ion is 105% (table 2):
Table 2
As can be seen from Table 2: the working electrode 2 (original position is electroplated bismuth film/nitrogen doped micropore carbon/glass-carbon electrode) in sensor of the present invention can be applied to the detection of cadmium ion in tap water, lead ion.
Claims (2)
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, contrast electrode, electrolytic cell composition, using silver/silver chloride electrode and platinum filament as contrast 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, electrolytic solution 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 contrast electrode (4) is connected on electrochemical workstation (1), working electrode (2), the other end to electrode (3) and contrast electrode (4) is placed on respectively in the electrolytic solution in electrolytic cell (5).
2. the preparation method of the electrochemical sensor that simultaneously detects cadmium, lead ion according to claim 1, is characterized in that following these steps to carrying 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, centrifuging, 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 tubular 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 35 wt.%, stir 24 hours, black powder is left and taken in filtration, wash with 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 suspending liquid of 1-3 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, get suspending liquid 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, contrast 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, pH 3.0-6.0, the other end is connected respectively on electrochemical workstation (1), load the enrichment voltage of sedimentation potential-0.9--1.2 V, time is 30-210 s, in electrolytic cell (5), place a magneton, control stirring rate, bismuth ion in electrolytic solution, 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 10 s, at a forward scan voltage of the upper loading of working electrode (2), sweep limit is-1-0 V, the bismuth of enrichment, cadmium, plumbous simple substance are oxidized to bismuth ion, cadmium ion, lead ion stripping, by electrochemical workstation (1) record current-change in voltage 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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