CN106018506B - A method of detecting lead ion using electrochemical sensor - Google Patents
A method of detecting lead ion using electrochemical sensor Download PDFInfo
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Abstract
The present invention relates to a kind of methods detecting lead ion using electrochemical sensor, electrochemical sensor involved in this method is formed by working electrode, to electrode, reference electrode, electrolytic cell and electrochemical workstation, working electrode is by glass-carbon electrode substrate, Nafion membrane and orderly tubulose mesoporous carbon/amino pyrene compound composition, wherein working electrode is using glass-carbon electrode as basal electrode, in the orderly tubulose mesoporous carbons of its surface modification Nafion//amino pyrene complexes membrane.Electrochemical sensor in this method combines the characteristics of tubulose mesoporous carbon Large ratio surface, Nafion and amino castor can effectively adsorb heavy metal ion, and lead ion can be detected in tremendous range, and detection, which is reached the standard grade, reaches 500 μ g/L.This method favorable reproducibility, strong antijamming capability and stability are high, can be used for lead ion field assay.
Description
Technical field
The present invention relates to heavy metal ion electrochemical sensor fields, specifically electrochemical sensor are utilized to detect lead ion
Method.
Background technology
In recent years, as industrial or agricultural and economy are grown rapidly, there is heavy metal (ρ > in air, soil, water body;5g/
cm3) pollution, heavy metal pollution, which has become, endangers one of maximum problem of environmental pollution.Heavy metal contaminants are difficult in the environment
With degradation, and can in animal and plant body extended stationary periods with accumulation, be gradually enriched with by food chain, into human body after concentration
Thousands of times of ground increase, and greatly damage the health of resident.By taking land pollutant as an example, Xinjiang Coal and mineral resources are rich
Richness inevitably brings the pollution of lead during exploitation and use.Related investigation display：Xinjiang crow Shandong wood at present
Neat city and Shihezi etc. ground have been subjected to the pollution of lead ion.Therefore, the detection pair of heavy metal especially lead ion is realized
The safety for ensuring the full boundary people, has great importance.
Some ripe methods such as spectrum, chromatography, inductively coupled plasma mass spectrometry etc. have been used for detecting lead gold
Belong to ion.But in these methods, some there are instrument price costliness, operating cost is high, it is not portable the shortcomings of, some
Then need complicated pre-treatment.Therefore, it is not easy to realize online, real-time, continuous heavy metal analysis.Electrochemical method is (i.e. electrochemical
Learn sensor) easy to automate, portability, it is expected to realize online, real-time, continuous pollutant monitoring.It has been demonstrated,
In terms of heavy metal lead ion detection, this method has high accuracy and low detection limit.In addition, coming for actual sample detection
It says, electrochemical sensor also gives satisfactory result.Core component of the working electrode as electrochemical sensor determines
The sensing capabilities for sensor such as detect limit, stability, sensitivity and linear measurement range.Therefore, obtaining, there is high electro-catalysis to live
Property, good dispersibility and long-time stability working electrode materials be stablized, the weight of efficient lead ion electrochemical sensor
In it is weight.
Invention content
Present invention aims at provide a kind of method detecting lead ion using electrochemical sensor, involved in this method
Electrochemical sensor formed by working electrode, to electrode, reference electrode, electrolytic cell and electrochemical workstation, working electrode
It is by glass-carbon electrode substrate, Nafion membrane and orderly tubulose mesoporous carbon/amino pyrene composition, wherein working electrode is with glass-carbon electrode
Basal electrode, in the orderly tubulose mesoporous carbons of its surface modification Nafion//amino pyrene complexes membrane.Electrochemistry in this method passes
Sensor combines the characteristics of tubulose mesoporous carbon Large ratio surface, Nafion and amino castor can effectively adsorb heavy metal ion, can be in pole
Lead ion is detected in a wide range of, detection, which is reached the standard grade, reaches 500 μ g/L.This method favorable reproducibility, strong antijamming capability and stability are high,
It can be used for lead ion field assay.
A kind of method detecting lead ion using electrochemical sensor of the present invention, the electrochemistry involved in this method
Sensor is formed by working electrode, to electrode, reference electrode, electrolytic cell and electrochemical workstation, and working electrode (2) is by glass
Carbon electrode substrate (6), Nafion membrane (7) and orderly tubulose mesoporous carbon/amino pyrene (8) composition, working electrode (2), to electrode (3)
Be connected on electrochemical workstation (1) with one end of reference electrode (4), working electrode (2), to electrode (3) and reference electricity
The other end of pole (4) is individually positioned in the electrolyte in electrolytic cell (5), and the electrolyte in electrolytic cell (5) is containing waiting for sounding lead
Acetic acid-sodium acetate buffer solution of ion, reference electrode (4) are silver or silver chloride electrode, are platinum filament to electrode (3), specific to grasp
It follows these steps to carry out：
The preparation of tubulose ordered mesopore carbon/amino pyrene compound：
A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15,
It is heated 24 hours through temperature 50 C and 90 DEG C are each, gained yellow powder is put into porcelain boat, and porcelain boat is put into tube furnace, in temperature 850
DEG C annealing 4 hours, obtain black powder, then impregnated with hydrofluoric acid solution, stir 24 hours, filtering leave and take black powder, spend
Ion water washing is put into 60 DEG C of dryings of oven temperature to get order mesoporous to tubulose ordered mesopore carbon, then by amino pyrene and tubulose
Carbon ULTRASONIC COMPLEX obtains tubulose ordered mesopore carbon/amino pyrene compound (8) of favorable dispersibility；
The preparation of working electrode：
B, the tubulose ordered mesopore carbon obtained step a/amino pyrene compound (8) is soluble in water, is configured to the outstanding of 1mg/L
Supernatant liquid, it is ultrasonic to evenly dispersed；
C, the progress sanding and polishing processing of glass-carbon electrode substrate (6) surface is used into liquid relief after being cleaned with ethyl alcohol and deionized water
Rifle takes the suspension in step b, in drop coating to glass-carbon electrode substrate (6), after drying 24 hours at room temperature, then is added dropwise 0.5%
Nafion solution obtains the glass-carbon electrode substrate (6) of Nafion/ tubuloses ordered mesopore carbon/amino pyrene load after 6 hours；
D, by the glass-carbon electrode substrate (6) of the tubulose ordered mesopore carbon in step c/amino pyrene load, reference electrode (4) and
One end of electrode (3) is connected respectively on electrochemical workstation (1), then the other end is immersed to containing in electrolytic cell (5) respectively
In the acetic acid-sodium acetate buffer solution of lead ion to be measured, pH 4.5, the enrichment voltage of load sedimentation potential -1.2V, the time is
120s places a magneton in the electrolytic cell (5), controls mixing speed, the lead ion in electrolyte under the action of electric field force,
Glass-carbon electrode substrate (6) surface for moving to tubulose ordered mesopore carbon/amino pyrene load, is reduced into metal simple-substance, is attached to pipe
In the glass-carbon electrode substrate (6) of shape ordered mesopore carbon/amino pyrene load, lead ion enrichment in situ is completed, work electricity has been obtained
Pole (2)；
E, anti-interference and stability test is carried out according to a conventional method to electrochemical sensor；
The detection of lead ion：
F, stop stirring, after standing 10s, a forward scan voltage, scanning range are loaded on working electrode (2)
It is -1-0V, the lead simple substance of enrichment is transformed into lead ion dissolution, by electrochemical workstation (1) record current-voltage change situation,
Current -voltage curve has been obtained, the dissolution peak point current under different plumbum ion concentrations is measured, measured ion concentration is treated with peak current
Draw sensing curve graph.
A kind of method detecting lead ion using electrochemical sensor of the present invention, the tubulose obtained in this method have
Resistance to acid and alkali that sequence mesoporous carbon electrode material has had, high specific surface area (Fig. 3 a), good order (Fig. 3 b).Pass through later
The ordered mesopore carbon of amino pyrene non-covalent modification/amino pyrene compound has good dispersed (Fig. 3 c).The nano-complex
High-ratio surface, the nitrogen lewis base (Fig. 3 d) in porous structure and amino pyrene can effective adsorpting lead ion (lewis acid).
Therefore the range of linearity and sensing speed of Electrochemical Detection heavy metal can be improved.
Description of the drawings
Fig. 1 is electrochemical sensor schematic diagram of the present invention, wherein 1 is electrochemical workstation, 2 be working electrode, and 3 is to electricity
Pole, 4 be reference electrode, and 5 be electrolytic cell；
Fig. 2 is the schematic diagram of the electrochemical sensor working electrode of the present invention, wherein 6 be glass-carbon electrode substrate, 7 are
Nafion membrane, 8 be tubulose mesoporous carbon/amino pyrene nano-complex；
Fig. 3 is the phenogram of tubulose ordered mesopore carbon and tubulose ordered mesopore carbon/amino pyrene compound of the invention, wherein
A is the nitrogen adsorption characterization of tubulose ordered mesopore carbon prepared by embodiment 1；B is tubulose ordered mesopore carbon prepared by embodiment 1
Transmission electron microscope characterizes；C is that tubulose ordered mesopore carbon prepared by embodiment 1 and tubulose ordered mesopore carbon/amino pyrene are compound
The scatter diagram of object in water, the wherein bottle on the left side are tubulose ordered mesopore carbon/amino pyrene compound, and the bottle on the right is independent
Tubulose ordered mesopore carbon；D is the molecular structural formula of amino pyrene, contains nitrogen lewis base；
Differential pulse anodic stripping voltammetry curves and corresponding working curve diagram of the Fig. 4 for present invention analysis lead ion, and
Its anti-interference ability and stability test figure.
Specific implementation mode
Embodiment 1
A kind of method detecting lead ion using electrochemical sensor of the present invention, the electrochemistry involved in this method
Sensor is formed by working electrode, to electrode, reference electrode, electrolytic cell and electrochemical workstation, and working electrode 2 is by glass carbon
Electrode basement 6, Nafion membrane 7 and orderly tubulose mesoporous carbon/amino pyrene compound 8 form, working electrode 2, to electrode 3 and reference
One end of electrode 4 is connected on electrochemical workstation 1, and working electrode 2 distinguishes the other end of electrode 3 and reference electrode 4
It is placed in the electrolyte in electrolytic cell 5, the electrolyte in electrolytic cell 5 is the Acetic acid-sodium acetate buffering containing lead ion to be measured
Solution, reference electrode 4 are silver or silver chloride electrode, are platinum filament to electrode 3, concrete operations follow these steps to carry out：
The preparation of tubulose ordered mesopore carbon/amino pyrene compound：
A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15,
It is heated 24 hours through temperature 50 C and 90 DEG C are each, gained yellow powder is put into porcelain boat, and porcelain boat is put into tube furnace, in temperature 850
DEG C annealing 4 hours, obtain black powder, then impregnated with hydrofluoric acid solution, stir 24 hours, filtering leave and take black powder, spend
Ion water washing is put into 60 DEG C of dryings of oven temperature to get order mesoporous to tubulose ordered mesopore carbon, then by amino pyrene and tubulose
Carbon ULTRASONIC COMPLEX obtains tubulose ordered mesopore carbon/amino pyrene compound 8 of favorable dispersibility；
The preparation of working electrode：
B, the tubulose ordered mesopore carbon/amino pyrene compound 8 obtained step a is soluble in water, is configured to the suspension of 1mg/L
Liquid, it is ultrasonic to evenly dispersed；
C, the progress sanding and polishing processing of 6 surface of glass-carbon electrode substrate is used into liquid-transfering gun after being cleaned with ethyl alcohol and deionized water
It takes the suspension in step b, in drop coating to glass-carbon electrode substrate 6, after drying 24 hours at room temperature, then is added dropwise 0.5%
Nafion solution obtains the glass-carbon electrode substrate 6 of Nafion/ tubuloses ordered mesopore carbon/amino pyrene load after 6 hours；
D, by the glass-carbon electrode substrate 6 of the tubulose ordered mesopore carbon in step c/amino pyrene load, reference electrode 4 and to electricity
One end of pole 3 is connected respectively on electrochemical workstation 1, then the other end is immersed respectively in electrolytic cell 5 and contains lead ion to be measured
Acetic acid-sodium acetate buffer solution in, pH 4.5, the enrichment voltage of load sedimentation potential -1.2V, time 120s, in electrolytic cell 5
One magneton of middle placement controls mixing speed, and the lead ion in electrolyte moves to tubulose and be orderly situated between under the action of electric field force
6 surface of glass-carbon electrode substrate of hole carbon/amino pyrene load, is reduced into metal simple-substance, is attached to tubulose ordered mesopore carbon/amino pyrene
In the glass-carbon electrode substrate 6 of load, lead ion enrichment in situ is completed, working electrode 2 has been obtained；
E, anti-interference and stability test is carried out according to a conventional method to electrochemical sensor；
By the glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load, to electrode 3, one end point of reference electrode 4
It is not connected on electrochemical workstation 1, then the other end is immersed to the pH=of the 5mL containing lead ion to be measured in electrolytic cell 5 respectively
In 4.5 Acetic acid-sodium acetate buffer solution, the lead ion of 300 μ g/L is then added, then the interfering ion with concentration is added simultaneously
Zn2+,Ca2+,Mg2+,Na+,K+,Al3+,Fe3+,Fe2+,Cd2+,Hg2+, the enrichment voltage of load sedimentation potential -1.2V, enrichment time
For 120s, a magneton is placed in electrolytic cell 5, controls mixing speed, after the completion of waiting electrochemical workstations enrichment procedure, quickly
Stop stirring, after standing 10s, a forward scan voltage is loaded on working electrode 2, scanning range is -1~0V, is terminated
The elementary lead of current potential 0V, amplitude 80mV, pulse width 50ms, the 4mV enrichments of current potential increment are oxidized to lead ion dissolution, by electrification
1 record current of work station-voltage change situation is learned, current -voltage curve has been obtained, test result (Fig. 4 C) is shown in numerous dry
Disturbing the differential pulsed anode Stripping Voltammetry curve peak current in the presence of ion on lead influences within 3%, it was demonstrated that is related in the invention
And electrochemical sensor have high anti-interference ability；
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load is stored 6 months in refrigerator, then will be deposited
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load after storage, to electrode 3, one end of reference electrode 4 connects respectively
It is connected on electrochemical workstation 1, then the other end is immersed to the pH=4.5 of the 5mL containing lead ion to be measured in electrolytic cell 5 respectively
In Acetic acid-sodium acetate buffer solution, the lead ion of 200 μ g/L, the enrichment voltage of load sedimentation potential -1.2V, enrichment are then added
Time is 120s, and a magneton is placed in electrolytic cell 5, controls mixing speed, after the completion of waiting electrochemical workstations enrichment procedure,
Quickly stopping stirring, after standing 10s, a forward scan voltage is loaded on working electrode 2, scanning range is -1~0V,
Current potential 0V, amplitude 80mV, pulse width 50ms are terminated, the elementary lead of current potential increment 4mV enrichments is oxidized to lead ion dissolution, by
1 record current of electrochemical workstation-voltage change situation, has obtained current -voltage curve, and data result is as shown in Figure 4 D, deposits
Lead ion Stripping Currents only decline about 11% after storage six months, show that the sensor has high stability；
The detection of lead ion：
E, stopping stirring, after standing 10s, a forward scan voltage is loaded on working electrode 2, scanning range is-
1V terminates current potential 0V, amplitude 80mV, pulse width 50ms, and current potential increment 4mV, it is molten that the lead simple substance of enrichment is oxidized to lead ion
Go out, by 1 record current of electrochemical workstation-voltage change situation, obtained current -voltage curve, by lead ion standard inventory
Solution with the Acetic acid-sodium acetate of pH=4.5 be buffer solution dilution plumbum ion concentration be 100 μ g/L, 200 μ g/L, 300 μ g/L, 400
μ g/L, 500 μ g/L, record the differential pulse anodic stripping voltammetry curve of lead ion, the lead ion pair of various concentration in prepare liquid
Its different peak point current is answered, is worked curve (Fig. 4 A, 4B) with peak current-concentration, working electrode 2 (tubulose ordered mesopore carbon/
Amino pyrene/glass-carbon electrode) it is 100-500 μ g/L, the linear relation of fitting to the responsing linear range concentration range of lead ion
It is：Y=0.69+0.05x, coefficient R=0.999, the method for the invention are extremely wide to the range of linearity of lead ion, present
The advantage of composite material.
Embodiment 2
The electrochemical sensor being related to is same as Example 1；
Concrete operations follow these steps to carry out：
The preparation of tubulose ordered mesopore carbon/amino pyrene compound：
A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15,
It is heated 24 hours through temperature 50 C and 90 DEG C are each, gained yellow powder is put into porcelain boat, and porcelain boat is put into tube furnace, in temperature 850
DEG C annealing 4 hours, obtain black powder, then impregnated with hydrofluoric acid solution, stir 24 hours, filtering leave and take black powder, spend
Ion water washing is put into 60 DEG C of dryings of oven temperature to get order mesoporous to tubulose ordered mesopore carbon, then by amino pyrene and tubulose
Carbon ULTRASONIC COMPLEX obtains tubulose ordered mesopore carbon/amino pyrene compound 8 of favorable dispersibility；
The preparation of working electrode：
B, the tubulose ordered mesopore carbon/amino pyrene compound 8 obtained step a is soluble in water, is configured to the suspension of 1mg/L
Liquid, it is ultrasonic to evenly dispersed；
C, the progress sanding and polishing processing of 6 surface of glass-carbon electrode substrate is used into liquid-transfering gun after being cleaned with ethyl alcohol and deionized water
It takes the suspension in step b, in drop coating to glass-carbon electrode substrate 6, after drying 24 hours at room temperature, then is added dropwise 0.5%
Nafion solution obtains the glass-carbon electrode substrate 6 of Nafion/ tubuloses ordered mesopore carbon/amino pyrene load after 6 hours；
D, by the glass-carbon electrode substrate 6 of the tubulose ordered mesopore carbon in step c/amino pyrene load, reference electrode 4 and to electricity
One end of pole 3 is connected respectively on electrochemical workstation 1, then the other end is immersed respectively in electrolytic cell 5 and contains lead ion to be measured
Acetic acid-sodium acetate buffer solution in, pH 4.5, the enrichment voltage of load sedimentation potential -1.2V, time 120s, in electrolytic cell 5
One magneton of middle placement controls mixing speed, and the lead ion in electrolyte moves to tubulose and be orderly situated between under the action of electric field force
6 surface of glass-carbon electrode substrate of hole carbon/amino pyrene load, is reduced into metal simple-substance, is attached to tubulose ordered mesopore carbon/amino pyrene
In the glass-carbon electrode substrate 6 of load, lead ion enrichment in situ is completed, working electrode 2 has been obtained；
E, anti-interference and stability test is carried out according to a conventional method to electrochemical sensor；
By the glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load, to electrode 3, one end point of reference electrode 4
It is not connected on electrochemical workstation 1, then the other end is immersed to the pH=of the 5mL containing lead ion to be measured in electrolytic cell 5 respectively
In 4.5 Acetic acid-sodium acetate buffer solution, the lead ion of 300 μ g/L is then added, then the interfering ion with concentration is added simultaneously
Zn2+,Ca2+,Mg2+,Na+,K+,Al3+,Fe3+,Fe2+,Cd2+,Hg2+, the enrichment voltage of load sedimentation potential -1.2V, enrichment time
For 120s, a magneton is placed in electrolytic cell 5, controls mixing speed, after the completion of waiting electrochemical workstations enrichment procedure, quickly
Stop stirring, after standing 10s, a forward scan voltage is loaded on working electrode 2, scanning range is -1~0V, is terminated
The elementary lead of current potential 0V, amplitude 80mV, pulse width 50ms, the 4mV enrichments of current potential increment are oxidized to lead ion dissolution, by electrification
1 record current of work station-voltage change situation is learned, current -voltage curve has been obtained, test result (Fig. 4 C) is shown in numerous dry
Disturbing the differential pulsed anode Stripping Voltammetry curve peak current in the presence of ion on lead influences within 3%, it was demonstrated that is related in the invention
And electrochemical sensor have high anti-interference ability；
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load is stored 6 months in refrigerator, then will be deposited
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load after storage, to electrode 3, one end of reference electrode 4 connects respectively
It is connected on electrochemical workstation 1, then the other end is immersed to the pH=4.5 of the 5mL containing lead ion to be measured in electrolytic cell 5 respectively
In Acetic acid-sodium acetate buffer solution, the lead ion of 200 μ g/L, the enrichment voltage of load sedimentation potential -1.2V, enrichment are then added
Time is 120s, and a magneton is placed in electrolytic cell 5, controls mixing speed, after the completion of waiting electrochemical workstations enrichment procedure,
Quickly stopping stirring, after standing 10s, a forward scan voltage is loaded on working electrode 2, scanning range is -1~0V,
Current potential 0V, amplitude 80mV, pulse width 50ms are terminated, the elementary lead of current potential increment 4mV enrichments is oxidized to lead ion dissolution, by
1 record current of electrochemical workstation-voltage change situation, has obtained current -voltage curve, and data result is as shown in Figure 4 D, deposits
Lead ion Stripping Currents only decline about 11% after storage six months, show that the sensor has high stability；
Lead ion in testing laboratory's tap water：
Water sample is derived from the tap water in laboratory, takes the 5mL NaAc_HAc buffer solutions containing tap water water sample, is put into
In 10mL electrolytic cells, then lead ion is added as detection liquid, by tubulose ordered mesopore carbon/amino pyrene compound 8 into electrolytic cell
The glass-carbon electrode substrate 6 of load, reference electrode 4 immerse electrolytic cell to one end of electrode 3, the other end are connected respectively to respectively
On electrochemical workstation 1, the enrichment voltage of load sedimentation potential -1.2V, time 120s places a magnetic in electrolytic cell 5
Son controls mixing speed, and the lead ion in electrolyte moves to tubulose ordered mesopore carbon/amino pyrene under the action of electric field force
6 surface of glass-carbon electrode substrate that compound 8 loads, is reduced into lead simple substance, is attached to tubulose ordered mesopore carbon/amino pyrene compound
In the glass-carbon electrode substrate 6 of 8 loads；
Stop stirring, after standing 10s, a forward scan voltage is loaded on working electrode 2, scanning range is -1-
0V terminates current potential 0V, sweep amplitude：50mV；Pulse width：50ms, current potential increment：The elementary lead of 4mV, enrichment are oxidized to lead
Ion release has obtained current -voltage curve by 1 record current of electrochemical workstation-voltage change situation, measures tap water
The Anodic Stripping peak point current of middle lead calculates lead ion content using working curve.
Utilize a concentration of 105.56 μ g for the lead ion that the electrochemical sensor involved in the method for the invention detects
L-1,303.99μgL-1, 531 μ gL-1, the rate of recovery of lead ion is respectively 105.56%, 101.33% and 106.2% (table 1)：
Table 1
As can be seen from Table 1：Working electrode 2 (Nafion/ tubuloses of the present invention using in electrochemical sensor
Ordered mesopore carbon/amino pyrene/glass-carbon electrode) it can be applied to the detection of lead ion in tap water.
Claims (1)
1. a kind of method detecting lead ion using electrochemical sensor, it is characterised in that the electrochemical sensing involved in this method
Device is formed by working electrode, to electrode, reference electrode, electrolytic cell and electrochemical workstation, working electrode（2）It is by glass carbon electricity
Pole substrate（6）, Nafion membrane（7）With orderly tubulose mesoporous carbon/amino pyrene compound（8）Composition, working electrode（2）, to electrode
（3）And reference electrode（4）One end be connected to electrochemical workstation（1）On, working electrode（2）, to electrode（3）And reference
Electrode（4）The other end be individually positioned in electrolytic cell（5）In electrolyte in, electrolytic cell（5）In electrolyte be containing to be measured
Acetic acid-sodium acetate buffer solution of lead ion, reference electrode（4）For Ag/AgCl electrodes, to electrode（3）For platinum filament, concrete operations
It follows these steps to carry out：
The preparation of tubulose ordered mesopore carbon/amino pyrene compound：
A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15, through temperature
Each heating 24 hours of 50 DEG C and 90 DEG C of degree, gained yellow powder is put into porcelain boat, and porcelain boat is put into tube furnace, is moved back for 850 DEG C in temperature
Fire 4 hours, obtains black powder, then impregnated with hydrofluoric acid solution, stirs 24 hours, and black powder is left and taken in filtering, uses deionization
Water washing is put into 60 DEG C of dryings of oven temperature；Obtain tubulose ordered mesopore carbon；Amino pyrene and tubulose ordered mesopore carbon are surpassed again
The compound tubulose ordered mesopore carbon for the obtaining favorable dispersibility/amino pyrene compound of sound（8）；
The preparation of working electrode：
B, the tubulose ordered mesopore carbon obtained step a/amino pyrene compound（8）It is soluble in water, it is configured to the suspension of 1mg/L
Liquid, it is ultrasonic to evenly dispersed；
C, by glass-carbon electrode substrate（6）Surface carries out sanding and polishing processing and is taken with liquid-transfering gun after being cleaned with ethyl alcohol and deionized water
Suspension in step b, drop coating to glass-carbon electrode substrate（6）On, at room temperature dry 24 hours after, then be added dropwise 0.5% Nafion
Solution obtains the glass-carbon electrode substrate of Nafion/ tubuloses ordered mesopore carbon/amino pyrene load after 6 hours；
D, by the Nafion/ tubuloses ordered mesopore carbon in step c/glass-carbon electrode substrate of amino pyrene load, reference electrode（4）With
To electrode（3）One end be connected respectively to electrochemical workstation（1）On, then the other end immersed into electrolytic cell respectively（5）In contain
In the acetic acid-sodium acetate buffer solution of lead ion to be measured, pH 4.5, the enrichment voltage of -1.2 V of load sedimentation potential, the time 120
S, in electrolytic cell（5）One magneton of middle placement controls mixing speed, and the lead ion in electrolyte moves under the action of electric field force
The glass-carbon electrode substrate surface for moving on to Nafion/ tubuloses ordered mesopore carbon/amino pyrene load, is reduced into metal simple-substance, is attached to
In the glass-carbon electrode substrate of Nafion/ tubuloses ordered mesopore carbon/amino pyrene load, lead ion enrichment in situ is completed, is obtained
Working electrode（2）；
E, anti-interference and stability test is carried out according to a conventional method to electrochemical sensor；
The detection of lead ion：
F, stop stirring, after standing 10s, in working electrode（2）One forward scan voltage of upper load, scanning range is -1-0
The lead simple substance of V, enrichment are transformed into lead ion dissolution, by electrochemical workstation（1）Record current-voltage change situation, obtains
Current -voltage curve measures the dissolution peak point current under different plumbum ion concentrations, treats measured ion concentration with peak current and draws biography
Feel curve graph.
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| CN109632901B (en) * | 2019-01-30 | 2020-09-29 | 济南大学 | Electrochemical sensor for detecting lead ions and preparation method thereof |
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