CN106018506A - Method for detecting lead ions by utilizing electrochemical sensor - Google Patents
Method for detecting lead ions by utilizing electrochemical sensor Download PDFInfo
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- CN106018506A CN106018506A CN201610307740.9A CN201610307740A CN106018506A CN 106018506 A CN106018506 A CN 106018506A CN 201610307740 A CN201610307740 A CN 201610307740A CN 106018506 A CN106018506 A CN 106018506A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention relates to a method for detecting lead ions by utilizing an electrochemical sensor. The electrochemical sensor related in the method consists of a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrochemical workstation, wherein the working electrode consists of a glassy carbon electrode substrate, a Nafion membrane and an orderly tubular mesoporous carbon/amino pyrene compound, the working electrode uses the glassy carbon electrode as a substrate electrode, and the surface of the substrate electrode is modified with a Nafion/orderly tubular mesoporous carbon/amino pyrene compound membrane. The electrochemical sensor in the method integrates the characteristics of the large specific surface of tubular mesoporous carbon and effective heavy metal ion adsorption of Nafion and amino pyrene and can detect the lead ions within a great range, and the upper detection limit reaches 500 micrograms per liter. The method has good reproducibility, strong anti-interference capability and high stability and can be used for lead ion field analysis.
Description
Technical field
The present invention relates to heavy metal ion electrochemical sensor field, specifically utilize the side of electrochemical sensor detection lead ion
Method.
Background technology
In recent years, along with industrial or agricultural and economic fast development, air, soil, water body all exist heavy metal (ρ > 5g/cm3)
Polluting, heavy metal pollution has become as one of maximum problem of environmental pollution of harm.Heavy metal contaminants is difficult to degrade in the environment,
And can extended stationary periods and accumulation in animal and plant body, be progressively enriched with by food chain, enter concentration after human body thousands of
Increase again, greatly damage the health of resident.As a example by land pollutant, Xinjiang Coal and rich in mineral resources, in exploitation
And during using, inevitably bring the pollution of lead.Relevant investigation display: Xinjiang Urumqi city and stone at present
The ground such as He Zi city have been subjected to the pollution of lead ion.Therefore, it is achieved the detection of heavy metal particularly lead ion is to guaranteeing the full boundary people
Safety, have great importance.
The method of some maturations such as spectrum, chromatograph, inductively coupled plasma mass spectrometry etc. have been used for detecting lead metal ion.
But, in these methods, the shortcomings such as it is expensive that some exists instrument price, and operating cost is high, the most portable, some then needs
Complicated pre-treatment.Therefore, it is difficult to realize online, real-time, continuous print heavy metal analysis.(i.e. electrochemistry passes electrochemical method
Sensor) easily be automated, portability, be expected to realize online, in real time, continuous print pollutant monitoring.Have been demonstrated,
Heavy metal lead ion detection aspect, the method has high accuracy and low detection limit.Additionally, for actual sample detects,
Electrochemical sensor give also gratifying result.Working electrode, as the core component of electrochemical sensor, decides biography
The sensing capabilities of sensor such as detects limit, stability, sensitivity and linear measurement range etc..Therefore, it is thus achieved that have high electrocatalytic active,
The working electrode material of good dispersibility and long-time stability be in the weight obtaining stable, efficient lead ion electrochemical sensor it
Weight.
Summary of the invention
Present invention aim at, it is provided that a kind of method utilizing electrochemical sensor detection lead ion, the electrification related in the method
Learning sensor by working electrode, form electrode, reference electrode, electrolyzer and electrochemical workstation, working electrode is by glass
Carbon electrode substrate, Nafion membrane and orderly tubulose mesoporous carbon/amino pyrene composition, wherein working electrode is with glass-carbon electrode for substrate electricity
Pole, modifies Nafion/ orderly tubulose mesoporous carbon/amino pyrene complexes membrane on its surface.Electrochemical sensor knot in the method
Closed tubulose mesoporous carbon Large ratio surface, Nafion and amino castor can the feature of active adsorption heavy metal ion, can be at tremendous range
Interior detection lead ion, detection is reached the standard grade and is reached 500 μ g/L.The method favorable reproducibility, capacity of resisting disturbance is strong and stability is high, can
For lead ion field assay.
A kind of method utilizing electrochemical sensor detection lead ion of the present invention, the electrochemical sensor related in the method
By working electrode, forming electrode, reference electrode, electrolyzer and electrochemical workstation, working electrode (2) is by glass carbon
Electrode basement (6), Nafion membrane (7) and orderly tubulose mesoporous carbon/amino pyrene (8) composition, working electrode (2), to electricity
One end of pole (3) and reference electrode (4) is connected on electrochemical workstation (1), working electrode (2), to electrode
And the other end of reference electrode (4) is individually positioned in the electricity in the electrolyte in electrolyzer (5), in electrolyzer (5) (3)
Solving liquid is the acetic acid-sodium acetate buffer solution containing lead ion to be measured, and reference electrode (4) is silver or silver chloride electrode, to electrode
(3) being platinum filament, concrete operations follow these steps to carry out:
The preparation of tubulose ordered mesopore carbon/amino pyrene complex:
A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15, warp
Temperature 50 C and 90 DEG C of each heating 24 hours, gained yellow powder puts into porcelain boat, and porcelain boat is put into tube furnace, temperature 850 DEG C
Anneal 4 hours, obtain black powder, then soak with hydrofluoric acid solution, stir 24 hours, filter and leave and take black powder, use
Deionized water wash, puts into oven temperature 60 DEG C and is dried, i.e. obtain tubulose ordered mesopore carbon, then by orderly to amino pyrene and tubulose
Mesoporous carbon ULTRASONIC COMPLEX obtains tubulose ordered mesopore carbon/amino pyrene complex (8) of favorable dispersibility；
The preparation of working electrode:
B, tubulose ordered mesopore carbon step a obtained/amino pyrene complex (8) are soluble in water, are configured to the outstanding of 1mg/L
Supernatant liquid, ultrasonic to dispersed；
C, glass-carbon electrode substrate (6) surface is carried out sanding and polishing process, after cleaning with ethanol and deionized water, use liquid-transfering gun
Take the suspension in step b, in drop coating to glass-carbon electrode substrate (6), after being dried 24 hours under room temperature, then drip 0.5%
Nafion solution, after 6 hours, obtain the glass-carbon electrode substrate (6) of Nafion/ tubulose ordered mesopore carbon/amino pyrene load；
D, glass-carbon electrode substrate (6) by the load of the tubulose ordered mesopore carbon in step c/amino pyrene, reference electrode (4) and
One end of electrode (3) is connected respectively on electrochemical workstation (1), then the other end is immersed respectively in electrolyzer (5)
The acetic acid-sodium acetate buffer solution containing lead ion to be measured in, pH 4.5, load sedimentation potential-1.2V enrichment voltage, the time
For 120s, placing a magneton, control mixing speed in electrolyzer (5), the lead ion in electrolyte is at electric field force
Under effect, move to glass-carbon electrode substrate (6) surface of tubulose ordered mesopore carbon/amino pyrene load, be reduced into metal simple-substance,
It is attached in the glass-carbon electrode substrate (6) of tubulose ordered mesopore carbon/amino pyrene load, completes lead ion enrichment in situ, obtain
Working electrode (2)；
E, electrochemical sensor is carried out according to a conventional method anti-interference and stability test；
The detection of lead ion:
F, stopping stirring, after standing 10s, in working electrode (2) one forward scan voltage of upper loading, sweep limits
Being-1-0V, the lead simple substance of enrichment is transformed into lead ion dissolution, by electrochemical workstation (1) record current-change in voltage situation,
Obtain current-voltage curve, measured the dissolution peak point current under different plumbum ion concentration, treat measured ion concentration with peak current
Draw sensing curve chart.
A kind of method utilizing electrochemical sensor detection lead ion of the present invention, the tubulose obtained in the method is order mesoporous
The resistance to acids and bases that carbon electrode material has had, high specific surface area (Fig. 3 a), good order (Fig. 3 b).Pass through ammonia afterwards
The ordered mesopore carbon of base pyrene non-covalent modification/amino pyrene complex has good dispersibility (Fig. 3 c).The height of this nano-complex
Nitrogen lewis base (Fig. 3 d) in specific surface, loose structure and amino pyrene can be with active adsorption lead ion (lewis acid).Cause
This range of linearity that can improve Electrochemical Detection heavy metal and sensing speed.
Accompanying drawing explanation
Fig. 1 is electrochemical sensor schematic diagram of the present invention, and wherein 1 is electrochemical workstation, and 2 is working electrode, and 3 is to electricity
Pole, 4 is reference electrode, and 5 is electrolyzer；
Fig. 2 is the schematic diagram of the electrochemical sensor working electrode of the present invention, and wherein 6 is glass-carbon electrode substrate, and 7 is Nafion
Film, 8 is tubulose mesoporous carbon/amino pyrene nano-complex；
Fig. 3 is tubulose ordered mesopore carbon and the phenogram of tubulose ordered mesopore carbon/amino pyrene complex of the present invention, and wherein a is
The nitrogen adsorption of the tubulose ordered mesopore carbon of embodiment 1 preparation characterizes；B is the saturating of the tubulose ordered mesopore carbon of embodiment 1 preparation
Penetrate ultramicroscope to characterize；C is tubulose ordered mesopore carbon and the tubulose ordered mesopore carbon/amino pyrene complex of embodiment 1 preparation
Scatter diagram in water, wherein the bottle on the left side is tubulose ordered mesopore carbon/amino pyrene complex, and the bottle on the right is single
Tubulose ordered mesopore carbon；D is the molecular structural formula of amino pyrene, containing nitrogen lewis base；
Fig. 4 is differential pulse anodic stripping voltammetry curve and the working curve diagram of correspondence that the present invention analyzes lead ion, and its is anti-
Interference performance and stability test figure.
Detailed description of the invention
Embodiment 1
A kind of method utilizing electrochemical sensor detection lead ion of the present invention, the electrochemical sensor related in the method
By working electrode, forming electrode, reference electrode, electrolyzer and electrochemical workstation, working electrode 2 is by glass-carbon electrode
Substrate 6, Nafion membrane 7 and orderly tubulose mesoporous carbon/amino pyrene complex 8 form, working electrode 2, to electrode 3 and ginseng
It is connected on electrochemical workstation 1 than one end of electrode 4, working electrode 2, to another of electrode 3 and reference electrode 4
End is individually positioned in the electrolyte in electrolyzer 5, and the electrolyte in electrolyzer 5 is the acetic acid-acetic acid containing lead ion to be measured
Sodium buffer solution, reference electrode 4 is silver or silver chloride electrode, is platinum filament to electrode 3, and concrete operations follow these steps to carry out:
The preparation of tubulose ordered mesopore carbon/amino pyrene complex:
A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15, warp
Temperature 50 C and 90 DEG C of each heating 24 hours, gained yellow powder puts into porcelain boat, and porcelain boat is put into tube furnace, temperature 850 DEG C
Anneal 4 hours, obtain black powder, then soak with hydrofluoric acid solution, stir 24 hours, filter and leave and take black powder, use
Deionized water wash, puts into oven temperature 60 DEG C and is dried, i.e. obtain tubulose ordered mesopore carbon, then by orderly to amino pyrene and tubulose
Mesoporous carbon ULTRASONIC COMPLEX obtains the tubulose ordered mesopore carbon/amino pyrene complex 8 of favorable dispersibility；
The preparation of working electrode:
B, the tubulose ordered mesopore carbon/amino pyrene complex 8 step a obtained are soluble in water, are configured to the suspension of 1mg/L,
Ultrasonic to dispersed；
C, glass-carbon electrode substrate 6 surface is carried out sanding and polishing process, after cleaning with ethanol and deionized water, take with liquid-transfering gun
Suspension in step b, in drop coating to glass-carbon electrode substrate 6, after being dried 24 hours, then drips the Nafion of 0.5% under room temperature
Solution, after 6 hours, obtains the glass-carbon electrode substrate 6 of Nafion/ tubulose ordered mesopore carbon/amino pyrene load；
D, glass-carbon electrode substrate 6 by the load of the tubulose ordered mesopore carbon in step c/amino pyrene, reference electrode 4 and to electrode
One end of 3 is connected respectively on electrochemical workstation 1, then the other end is immersed respectively in electrolyzer 5 containing lead ion to be measured
In Acetic acid-sodium acetate buffer, pH 4.5, load the enrichment voltage of sedimentation potential-1.2V, the time is 120s, in electrolysis
Placing a magneton in pond 5, control mixing speed, the lead ion in electrolyte is under the effect of electric field force, and moving to tubulose has
Glass-carbon electrode substrate 6 surface of sequence mesoporous carbon/amino pyrene load, is reduced into metal simple-substance, be attached to tubulose ordered mesopore carbon/
In the glass-carbon electrode substrate 6 of amino pyrene load, complete lead ion enrichment in situ, obtained working electrode 2；
E, electrochemical sensor is carried out according to a conventional method anti-interference and stability test；
By the glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load, to electrode 3, one end of reference electrode 4 connects respectively
Receive on electrochemical workstation 1, then the other end is immersed respectively the pH=4.5 of the 5mL containing lead ion to be measured in electrolyzer 5
Acetic acid-sodium acetate buffer in, then add the lead ion of 300 μ g/L, then be simultaneously introduced the interfering ion Zn of same concentration2+,
Ca2+,Mg2+,Na+,K+,Al3+,Fe3+,Fe2+,Cd2+,Hg2+, loading the enrichment voltage of sedimentation potential-1.2V, enrichment time is 120s,
In electrolyzer 5, place a magneton, control mixing speed, after waiting electrochemical workstation enrichment procedure to complete, quickly stop stirring
Mixing, after standing 10s, load a forward scan voltage on working electrode 2, sweep limits is-1～0V, terminates
Current potential 0V, amplitude 80mV, pulse width 50ms, the simple substance lead of current potential increment 4mV enrichment is oxidized to lead ion dissolution,
By electrochemical workstation 1 record current-change in voltage situation, having obtained current-voltage curve, test result (Fig. 4 C) shows
Show and in the presence of numerous interfering ions, the differential pulsed anode Stripping Voltammetry curve peak electric current of lead is affected within 3%, it was demonstrated that should
The electrochemical sensor related in invention has high capacity of resisting disturbance；
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load is stored 6 months in refrigerator, after then storing
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load, to electrode 3, one end of reference electrode 4 is connected respectively to
On electrochemical workstation 1, then the other end is immersed respectively the vinegar of the pH=4.5 of the 5mL containing lead ion to be measured in electrolyzer 5
In acid-sodium-acetate buffer, then add the lead ion of 200 μ g/L, load the enrichment voltage of sedimentation potential-1.2V, rich
Integrate the time as 120s, electrolyzer 5 is placed a magneton, controls mixing speed, wait electrochemical workstation enrichment procedure complete
Cheng Hou, quickly stops stirring, after standing 10s, loads a forward scan voltage, sweep limits on working electrode 2
It is-1～0V, terminates current potential 0V, amplitude 80mV, pulse width 50ms, the simple substance lead quilt of current potential increment 4mV enrichment
It is oxidized to lead ion dissolution, by electrochemical workstation 1 record current-change in voltage situation, obtains current-voltage curve, number
According to result as shown in Figure 4 D, after storing six months, lead ion Stripping Currents only declines about 11%, shows that this sensor has high
Stability；
The detection of lead ion:
E, stopping stirring, after standing 10s, load a forward scan voltage on working electrode 2, and sweep limits is-1
V, terminates current potential 0V, amplitude 80mV, and pulse width 50ms, current potential increment 4mV, the lead simple substance of enrichment is oxidized to
Lead ion dissolution, by electrochemical workstation 1 record current-change in voltage situation, has obtained current-voltage curve, by lead ion
The Acetic acid-sodium acetate of Standard Stock solutions pH=4.5 be buffer 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, the differential pulse anodic stripping voltammetry curve of record lead ion, different in liquid to be measured
The lead ion of concentration its different peak point current corresponding, works curve (Fig. 4 A, 4B) with peak current-concentration, working electrode 2
(tubulose ordered mesopore carbon/amino pyrene/glass-carbon electrode) is 100-500 μ g/L to the responsing linear range concentration range of lead ion,
The linear relation of matching is: y=0.69+0.05x, coefficient R=0.999, linear to lead ion of the method for the invention
Scope is the widest, presents the advantage of composite.
Embodiment 2
The electrochemical sensor related to is same as in Example 1；
Concrete operations follow these steps to carry out:
The preparation of tubulose ordered mesopore carbon/amino pyrene complex:
A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15, warp
Temperature 50 C and 90 DEG C of each heating 24 hours, gained yellow powder puts into porcelain boat, and porcelain boat is put into tube furnace, temperature 850 DEG C
Anneal 4 hours, obtain black powder, then soak with hydrofluoric acid solution, stir 24 hours, filter and leave and take black powder, use
Deionized water wash, puts into oven temperature 60 DEG C and is dried, i.e. obtain tubulose ordered mesopore carbon, then by orderly to amino pyrene and tubulose
Mesoporous carbon ULTRASONIC COMPLEX obtains the tubulose ordered mesopore carbon/amino pyrene complex 8 of favorable dispersibility；
The preparation of working electrode:
B, the tubulose ordered mesopore carbon/amino pyrene complex 8 step a obtained are soluble in water, are configured to the suspension of 1mg/L,
Ultrasonic to dispersed；
C, glass-carbon electrode substrate 6 surface is carried out sanding and polishing process, after cleaning with ethanol and deionized water, take with liquid-transfering gun
Suspension in step b, in drop coating to glass-carbon electrode substrate 6, after being dried 24 hours, then drips the Nafion of 0.5% under room temperature
Solution, after 6 hours, obtains the glass-carbon electrode substrate 6 of Nafion/ tubulose ordered mesopore carbon/amino pyrene load；
D, glass-carbon electrode substrate 6 by the load of the tubulose ordered mesopore carbon in step c/amino pyrene, reference electrode 4 and to electrode
One end of 3 is connected respectively on electrochemical workstation 1, then the other end is immersed respectively in electrolyzer 5 containing lead ion to be measured
In Acetic acid-sodium acetate buffer, pH 4.5, load the enrichment voltage of sedimentation potential-1.2V, the time is 120s, in electrolysis
Placing a magneton in pond 5, control mixing speed, the lead ion in electrolyte is under the effect of electric field force, and moving to tubulose has
Glass-carbon electrode substrate 6 surface of sequence mesoporous carbon/amino pyrene load, is reduced into metal simple-substance, be attached to tubulose ordered mesopore carbon/
In the glass-carbon electrode substrate 6 of amino pyrene load, complete lead ion enrichment in situ, obtained working electrode 2；
E, electrochemical sensor is carried out according to a conventional method anti-interference and stability test；
By the glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load, to electrode 3, one end of reference electrode 4 connects respectively
Receive on electrochemical workstation 1, then the other end is immersed respectively the pH=4.5 of the 5mL containing lead ion to be measured in electrolyzer 5
Acetic acid-sodium acetate buffer in, then add the lead ion of 300 μ g/L, then be simultaneously introduced the interfering ion Zn of same concentration2+,
Ca2+,Mg2+,Na+,K+,Al3+,Fe3+,Fe2+,Cd2+,Hg2+, loading the enrichment voltage of sedimentation potential-1.2V, enrichment time is 120s,
In electrolyzer 5, place a magneton, control mixing speed, after waiting electrochemical workstation enrichment procedure to complete, quickly stop stirring
Mixing, after standing 10s, load a forward scan voltage on working electrode 2, sweep limits is-1～0V, terminates
Current potential 0V, amplitude 80mV, pulse width 50ms, the simple substance lead of current potential increment 4mV enrichment is oxidized to lead ion dissolution,
By electrochemical workstation 1 record current-change in voltage situation, having obtained current-voltage curve, test result (Fig. 4 C) shows
Show and in the presence of numerous interfering ions, the differential pulsed anode Stripping Voltammetry curve peak electric current of lead is affected within 3%, it was demonstrated that should
The electrochemical sensor related in invention has high capacity of resisting disturbance；
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load is stored 6 months in refrigerator, after then storing
The glass-carbon electrode substrate 6 of tubulose ordered mesopore carbon/amino pyrene load, to electrode 3, one end of reference electrode 4 is connected respectively to
On electrochemical workstation 1, then the other end is immersed respectively the vinegar of the pH=4.5 of the 5mL containing lead ion to be measured in electrolyzer 5
In acid-sodium-acetate buffer, then add the lead ion of 200 μ g/L, load the enrichment voltage of sedimentation potential-1.2V, rich
Integrate the time as 120s, electrolyzer 5 is placed a magneton, controls mixing speed, wait electrochemical workstation enrichment procedure complete
Cheng Hou, quickly stops stirring, after standing 10s, loads a forward scan voltage, sweep limits on working electrode 2
It is-1～0V, terminates current potential 0V, amplitude 80mV, pulse width 50ms, the simple substance lead quilt of current potential increment 4mV enrichment
It is oxidized to lead ion dissolution, by electrochemical workstation 1 record current-change in voltage situation, obtains current-voltage curve, number
According to result as shown in Figure 4 D, after storing six months, lead ion Stripping Currents only declines about 11%, shows that this sensor has high
Stability；
Lead ion in testing laboratory's tap water:
Water sample takes from the tap water of laboratory, takes the 5mL NaAc_HAc buffer solution containing tap water water sample, puts into 10mL
In electrolyzer, then tubulose ordered mesopore carbon/amino pyrene complex 8, as detection liquid, is loaded by interpolation lead ion in electrolyzer
Glass-carbon electrode substrate 6, reference electrode 4, one end of electrode 3 is immersed electrolyzer respectively, the other end is connected respectively to electricity
On chem workstation 1, loading the enrichment voltage of sedimentation potential-1.2V, the time is 120s, places one in electrolyzer 5
Individual magneton, controls mixing speed, and the lead ion in electrolyte, under the effect of electric field force, moves to tubulose ordered mesopore carbon/ammonia
Glass-carbon electrode substrate 6 surface of base pyrene complex 8 load, is reduced into lead simple substance, is attached to tubulose ordered mesopore carbon/amino pyrene
In the glass-carbon electrode substrate 6 of complex 8 load；
Stopping stirring, after standing 10s, load a forward scan voltage on working electrode 2, sweep limits is-1-0
V, terminates current potential 0V, sweep amplitude: 50mV；Pulse width: 50ms, current potential increment: 4mV, the simple substance lead of enrichment
It is oxidized to lead ion dissolution, by electrochemical workstation 1 record current-change in voltage situation, obtains current-voltage curve,
Measure the anodic stripping peak point current of lead in tap water, utilize working curve to calculate lead ion content.
The concentration utilizing the lead ion that the electrochemical sensor related in the method for the invention detects is 105.56 μ g L-1,
303.99μgL-1, 531 μ gL-1, the response rate of lead ion is respectively 105.56%, 101.33% and 106.2% (table 1):
Table 1
As can be seen from Table 1: (Nafion/ tubulose is situated between the working electrode 2 utilized in electrochemical sensor of the present invention in order
Hole carbon/amino pyrene/glass-carbon electrode) can apply to the detection of lead ion in tap water.
Claims (1)
- null1. the method utilizing electrochemical sensor detection lead ion，It is characterized in that the electrochemical sensor related in the method is by working electrode、To electrode、Reference electrode、Electrolyzer and electrochemical workstation composition，Working electrode (2) is by glass-carbon electrode substrate (6)，Nafion membrane (7) and orderly tubulose mesoporous carbon/amino pyrene complex (8) composition，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 individually positioned in the electrolyte in electrolyzer (5)，Electrolyte in electrolyzer (5) is the acetic acid-sodium acetate buffer solution containing lead ion to be measured，Reference electrode (4) is silver or silver chloride electrode，It is platinum filament to electrode (3)，Concrete operations follow these steps to carry out:The preparation of tubulose ordered mesopore carbon/amino pyrene complex:A, by furfuryl alcohol, trimethylbenzene, oxalic acid the pregnant note of mixed solution in the duct of ordered mesoporous silica dioxide SBA-15, through each heating of temperature 50 C and 90 DEG C 24 hours, gained yellow powder puts into porcelain boat, and porcelain boat is put into tube furnace, anneals 4 hours temperature 850 DEG C, obtain black powder, soak with hydrofluoric acid solution again, stir 24 hours, filter and leave and take black powder, it is washed with deionized, puts into oven temperature 60 DEG C and be dried；I.e. obtain tubulose ordered mesopore carbon；At tubulose ordered mesopore carbon/amino pyrene complex (8) that amino pyrene and tubulose ordered mesopore carbon ULTRASONIC COMPLEX are obtained favorable dispersibility；The preparation of working electrode:B, tubulose ordered mesopore carbon step a obtained/amino pyrene complex (8) are soluble in water, are configured to the suspension of 1mg/L, ultrasonic to dispersed；C, glass-carbon electrode substrate (6) surface is carried out sanding and polishing process, after cleaning with ethanol and deionized water, the suspension in step b is taken with liquid-transfering gun, drop coating is in glass-carbon electrode substrate (6), after being dried 24 hours under room temperature, drip the Nafion solution of 0.5% again, after 6 hours, obtain the glass-carbon electrode substrate (6) of Nafion/ tubulose ordered mesopore carbon/amino pyrene load；nulld、Glass-carbon electrode substrate (6) by the tubulose ordered mesopore carbon in step c/amino pyrene load、Reference electrode (4) and the one end to electrode (3) are connected respectively on electrochemical workstation (1)，Again the other end is immersed respectively in the acetic acid-sodium acetate buffer solution containing lead ion to be measured in electrolyzer (5)，pH 4.5，Load the enrichment voltage of sedimentation potential-1.2 V，Time is 120 s，A magneton is placed in electrolyzer (5)，Control mixing speed，Lead ion in electrolyte is under the effect of electric field force，Move to glass-carbon electrode substrate (6) surface of tubulose ordered mesopore carbon/amino pyrene load，It is reduced into metal simple-substance，It is attached in the glass-carbon electrode substrate (6) of tubulose ordered mesopore carbon/amino pyrene load，Complete lead ion enrichment in situ，Obtain working electrode (2)；E, electrochemical sensor is carried out according to a conventional method anti-interference and stability test；The detection of lead ion:F, stopping stirring, after standing 10 s, at working electrode (2) one forward scan voltage of upper loading, sweep limits is-1-0 V, the lead simple substance of enrichment is transformed into lead ion dissolution, by electrochemical workstation (1) record current-change in voltage situation, has obtained current-voltage curve, measure the dissolution peak point current under different plumbum ion concentration, treat measured ion concentration with peak current and draw sensing curve chart.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090288962A1 (en) * | 2008-05-21 | 2009-11-26 | Battelle Memorial Institute | Electrochemical Sensor and Methods for Making and Using Same |
| CN102891300A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for manufacturing mesoporous carbon composite material of lithium battery |
| CN103983681A (en) * | 2014-05-23 | 2014-08-13 | 湖南大学 | Electrochemical sensor for detecting heavy metals and preparation method and application thereof |
| CN104483366A (en) * | 2014-12-05 | 2015-04-01 | 湖南大学 | Biosensor for detecting lead, as well as preparation method and application of biosensor for detecting lead |
| CN105092683A (en) * | 2015-08-31 | 2015-11-25 | 湖南大学 | Electrochemical sensor for detecting lead and preparation method and application of electrochemical sensor |
-
2016
- 2016-05-11 CN CN201610307740.9A patent/CN106018506B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090288962A1 (en) * | 2008-05-21 | 2009-11-26 | Battelle Memorial Institute | Electrochemical Sensor and Methods for Making and Using Same |
| CN102891300A (en) * | 2012-09-24 | 2013-01-23 | 上海锦众信息科技有限公司 | Method for manufacturing mesoporous carbon composite material of lithium battery |
| CN103983681A (en) * | 2014-05-23 | 2014-08-13 | 湖南大学 | Electrochemical sensor for detecting heavy metals and preparation method and application thereof |
| CN104483366A (en) * | 2014-12-05 | 2015-04-01 | 湖南大学 | Biosensor for detecting lead, as well as preparation method and application of biosensor for detecting lead |
| CN105092683A (en) * | 2015-08-31 | 2015-11-25 | 湖南大学 | Electrochemical sensor for detecting lead and preparation method and application of electrochemical sensor |
Non-Patent Citations (2)
| Title |
|---|
| AN-HUI LU, ET AL.: "Easy synthesis of an ordered mesoporous carbon with a hexagonally packed tubular structure", 《CARBON》 * |
| 郭卓, 等.: "介孔碳/聚苯胺修饰电极的制备及其对Cu<sup>2+</sup>的响应研究", 《无机化学学报》 * |
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| CN106770540B (en) * | 2016-11-23 | 2019-02-19 | 中国科学院新疆理化技术研究所 | A kind of cadmium lead electrochemical sensor and preparation method thereof of N doping mesoporous carbon modification |
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| CN113336208A (en) * | 2021-05-20 | 2021-09-03 | 武汉大学 | Ultra-small nickel phosphide @ mesoporous carbon composite material and preparation method and application thereof |
| CN114199977A (en) * | 2021-11-23 | 2022-03-18 | 江苏大学 | Electrochemical heavy metal rapid detection method based on electric drive pre-enrichment |
| CN114199977B (en) * | 2021-11-23 | 2023-08-22 | 江苏大学 | Electrochemical heavy metal rapid detection method based on electric drive pre-enrichment |
| CN115047055A (en) * | 2022-05-27 | 2022-09-13 | 长垣烹饪职业技术学院 | Method and system for detecting lead ions by sensor |
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