CN104267086B - Chemically modified carbon paste electrode as well as preparation method and application thereof - Google Patents
Chemically modified carbon paste electrode as well as preparation method and application thereof Download PDFInfo
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- CN104267086B CN104267086B CN201410541908.3A CN201410541908A CN104267086B CN 104267086 B CN104267086 B CN 104267086B CN 201410541908 A CN201410541908 A CN 201410541908A CN 104267086 B CN104267086 B CN 104267086B
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Abstract
The invention discloses a chemically modified carbon paste electrode which comprises an electrode tube, carbon paste filled in the electrode tube as well as an electrode lead contacted with the carbon paste and lead out from the electrode tube, wherein the carbon paste comprises a conductive carbon material, a bonding agent and a composite modifier; the composite modifier comprises bismuth-contained solid powder and a chelating agent; the bismuth-contained solid powder adopts solid bismuth substances which are insoluble with water; and the chelating agent is a hydrophobic organic reagent and can form a chelate with at least one of lead ions, cadmium ions and zinc ions. The detection limit of the chemically modified carbon paste electrode to lead ions, cadmium ions and zinc ions reaches 1.0*10<-12> M; and compared with the detection limit of a conventional chemically modified carbon paste electrode, the detection limit is reduced by 1-3 orders of magnitude, and the detection performance is remarkably improved on the basis of the conventional chemically modified carbon paste electrode.
Description
Technical field
The present invention relates to electro chemical analysis field, particularly relate to a kind of chemically modified carbon paste electrode and preparation side thereof
Method and application.
Background technology
In everyday environments, lead ion, cadmium ion and zinc ion are main heavy metal contaminants, tool
There is obvious bio-toxicity, and also can not degrade.As long as environment has the heavy metal ion such as lead, cadmium and zinc
Poisonous effect can be produced, not only cause environmental pollution, and after entering biological chain, meeting harmful to human is just
It is frequently grown growth, becomes the important pollutant in environment with potential hazard, therefore to the heavy metal such as lead, cadmium
The detection tool of ion is of great significance.
The traditional analysis of detection lead ion, cadmium ion and zinc ion mainly has atomic absorption spectrography (AAS), X-
Ray fluorescence spectrometry, UV-vis spectroscopy spectrographic method, atomic emission spectrometry etc..But with traditional analysis side
Method compares, and electrochemical method equipment automatization relatively easy, easy, is easy to carry, have both simultaneously highly sensitive,
Accuracy is high, good selective, is therefore widely used in the analysis of lead ion, cadmium ion and zinc ion,
And the stripping voltammetry of chemically modified carbon paste electrode therein is the most conventional method.Carbon magma electricity
The stripping voltammetry of pole is because having the advantages such as environmental toxicity little, excellent electrochemical performance, good stability, and gets over
More receive publicity and pay attention to, but the stripping voltammetry of most chemically modified carbon paste electrode detection lead from
The detection limit of son, cadmium ion and zinc ion is the lowest, it is impossible to meet the requirement of surface water water quality monitoring,
Hinder the commercialized development of heavy metal ion carbon paste electrode.It is published in such as Samo B.Hocevar etc.
The paper of Electrochimica Acta 2005,51,706 710 has reported a kind of carbon paste electrode cried containing bismuth meal,
The detection limit of cadmium, lead ion is respectively 1.2 and 0.9ppb (i.e. 1 × 10-8M and 6 × 10-9M)；Permitted
Gorgeous rosy clouds etc. are published in " Food technology is with economical ", and the paper of 2014,39,39-42 has reported a kind of ethylenediamine tetrem
Acid (EDTA) decorating carbon paste electrode the detection for cadmium ion, under optimal detection condition, the detection of cadmium ion
It is limited to 1 × 10-8Mol/L (signal to noise ratio is 3).Wu Hua etc. are at " application chemical industry ", and what 2012,41,880-883 delivered combines
State multiple detection heavy metal ion reported in article " New research progress of a chemically modified carbon paste electrode " literary composition
Chemically modified carbon paste electrode, its detection limit is also many 10-8M to 10-10Between M.Therefore, chemical modification
Carbon paste electrode can't be used for the monitoring of surface water quality heavy metal, and its detection performance further improves to become
For researcher in this field's urgent problem.
Summary of the invention
For solving the problems referred to above, the invention provides a kind of chemically modified carbon paste electrode, this carbon magma
The carbon paste of electrode is by adding bismuth-containing pressed powder and chelating agen, and both combine, and repair as this chemistry
Composite modified dose of decorations carbon paste electrode, so that this chemically modified carbon paste electrode detection lead ion, cadmium ion
Significantly reduce with the detection limit of zinc ion, the inspection of the chemically modified carbon paste electrode of dressing agent single with existing use
Rising limit is compared, and reduces 1～3 order of magnitude, on the basis of existing chemically modified carbon paste electrode, and its inspection
Survey performance to be substantially improved；Present invention also offers a kind of chemically modified carbon paste electrode preparation method and
Application in terms of lead ion, cadmium ion and zinc ion in detection environment.
First aspect, the invention provides a kind of chemically modified carbon paste electrode, including electrode shell, is filled in
Carbon paste in described electrode shell, and contact with described carbon paste and by the electrode drawn in described electrode shell
Lead-in wire, described carbon paste includes conductive carbon material, binding agent and composite modified dose, and described composite modified dose includes
Bismuth-containing pressed powder and chelating agen；Described bismuth-containing pressed powder is water-fast solid bi-containing substance；Described
Chelating agen is hydrophobic, can form chelating with at least one ion in lead ion, cadmium ion and zinc ion
The reagent of thing.
Chelating agen of the present invention be hydrophobic, in lead ion, cadmium ion and zinc ion at least
A kind of ion has the indissoluble organic micromolecule compound of chelation or insoluble macromolecular compound；Use
Binding agent be methyl-silicone oil, paraffin oil, mineral oil, vaseline, nitric acid dibutyl ester, silicone rubber or epoxy
The hydrophobic stickum such as resin；The conductive carbon material used is graphite powder, mesoporous carbon, fullerene or carbon
The conductive carbon material often used in the prior aries such as nanotube；The bismuth-containing pressed powder used is various granularity
Powder, such as micron order, nanometer grade powder, and the powder of various microscopic appearance, as bar-shaped, needle-like,
Graininess, flower-shaped etc..
Preferably, described carbon paste includes the described conductive carbon material of mix homogeneously, described binding agent and described multiple
Close dressing agent.
Preferably, the described composite modified dose of described chelating agen including mix homogeneously and described bismuth-containing pressed powder.
Preferably, described bismuth-containing pressed powder is bismuth meal, bismuth oxide powder or Bismuth hydrate. powder.
Wherein, bismuth meal is the powder of bismuth metal.
Preferably, described chelating agen is 8-hydroxyquinoline, benzoin oxime, diacetyldioxime or dithizone.
Preferably, conductive carbon material described in described carbon paste, described bismuth-containing pressed powder, described chelating agen with
The mass ratio of described binding agent is (20～90): (0.5～50): (0.5～30): (10～50).
Preferably, conductive carbon material described in described carbon paste, described bismuth-containing pressed powder, described chelating agen with
The mass ratio of described binding agent is (60～80): (0.5～10): (0.5～5): (10～30).
Preferably, conductive carbon material described in described carbon paste, described bismuth-containing pressed powder, described chelating agen with
The mass ratio of described binding agent is 70:2:2:30.
Second aspect, the invention provides the preparation method of a kind of chemically modified carbon paste electrode, including walking as follows
Rapid:
(1) by conductive carbon material, binding agent and composite modified dose of mixing, described composite modified dose includes bismuth-containing
Pressed powder and chelating agen, obtain carbon paste；Described bismuth-containing pressed powder is water-fast solid bi-containing substance；
Described chelating agen is hydrophobic, can be formed with at least one ion in lead ion, cadmium ion and zinc ion
The reagent of chelate；
(2) described carbon paste is filled in electrode shell；
(3) one end of contact conductor is loaded on described electrode shell inside and is connected with described carbon paste, by described
The other end of contact conductor, from the internal extraction of described electrode shell, obtains described chemically modified carbon paste electrode.
Use chemically modified carbon paste electrode prepared by the present invention, user only need a high grade sand paper or
Polishing cloth, polishing paper, take out polishing old electrode and can reuse, it is not necessary to the operations such as other plating bismuth, makes
With very convenient, for automatization's lead, cadmium and zinc detecting instrument user, electrode updates very
Convenient, the operation sequence of further self-reacting device can also simplify, and its class of liquids carried also will significantly
Reduce, thus reduce volume, reduce cost.
Various chelating agen of the present invention, bismuth-containing pressed powder, conductive carbon material and binding agent all can be from
Directly buy on market or directly prepared by prior art.Electrode shell of the present invention is poly-
The insulation tube often used in the prior aries such as tetrafluoroethene pipe, glass tubing or plastic tube；The contact conductor used
For the conductor wire often used in the prior aries such as copper conductor or silver wire.
Preferably, in step (1), by described conductive carbon material, described binding agent and described composite modified dose
Uniformly mixing.
Preferably, in step (1), the described composite modified dose of bismuth-containing pressed powder including mix homogeneously and chela
Mixture.
Preferably, in step (1), described bismuth-containing pressed powder is bismuth meal, bismuth oxide powder or Bismuth hydrate.
Powder.
Preferably, in step (1), described chelating agen be 8-hydroxyquinoline, benzoin oxime, diacetyldioxime or
Dithizone.
Preferably, conductive carbon material described in carbon paste, described bismuth-containing pressed powder, institute described in step (1)
The mass ratio stating chelating agen and described binding agent is (20～90): (0.5～50): (0.5～30): (10
～50).
Preferably, conductive carbon material described in carbon paste, described bismuth-containing pressed powder, institute described in step (1)
The mass ratio stating chelating agen and described binding agent is (60～80): (0.5～10): (0.5～5): (10
～30).
Preferably, conductive carbon material described in carbon paste, described bismuth-containing pressed powder, institute described in step (1)
The mass ratio stating chelating agen and described binding agent is 70:2:2:30.
The third aspect, present invention also offers the chemically modified carbon paste electrode described in first aspect at detection environment
Application in terms of middle lead ion, cadmium ion and zinc ion, comprises the steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte is first added,
Form system to be measured, then the pH value of described system to be measured is set；
(2) using the above chemically modified carbon paste electrode is the three-electrode system that working electrode is constituted, and is suitable for
Stripping voltammetry detects lead ion, cadmium ion and the zinc ion in system to be measured.
In the carbon paste of the chemically modified carbon paste electrode of present invention offer, bismuth-containing pressed powder and chelate combinations
Together, as composite modified dose of this chemically modified carbon paste electrode.When conductive carbon material, binding agent and multiple
When this chemically modified carbon paste electrode detection lead ion, cadmium ion and the zinc ion that obtain after closing dressing agent mixing,
First the chelating agen on carbon paste surface chelates the lead ion in system solution to be measured, cadmium ion and zinc ion so that it is
Being enriched in the bismuth-containing solid powder particle near surface on carbon paste surface, this allows for bismuth-containing solid powder particle table
Lead ion that lead ion, cadmium ion and zinc ion concentration near face is significantly larger than in bulk solution, cadmium ion
And zinc ion concentration.Ensuing stripping voltammetry, identical with the carbon paste electrode of conventional bismuth-containing pressed powder,
But due to bismuth-containing solid powder particle surface of the present invention via chelating agen be enriched higher concentration lead ion,
Cadmium ion and zinc ion, thus its detection electric current significantly increases.It is to say, for same lead ion,
Cadmium ion and zinc ion concentration, the current signal of the chemically modified carbon paste electrode that the present invention provides is big；Same
Current signal, lead ion, cadmium ion and zinc ion that the chemically modified carbon paste electrode of present invention offer is corresponding are dense
Spending lower, its detection performance is substantially improved.
Reagent used in the present invention is analytical pure, and water is redistilled water.
Preferably, described chemically modified carbon paste electrode is lead ion, cadmium ion and zinc ion in detection environment
The application of aspect, comprises the steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte second is first added
Acid-sodium acetate, phosphate, acetate or citrate, form system to be measured, propping up in described system to be measured
The concentration holding electrolyte phosphate, acetate or citrate is 0.001mol/L～0.5mol/L, then by institute
The pH value stating system to be measured is set to 2～7；
(2) using the above chemically modified carbon paste electrode is the three-electrode system that working electrode is constituted, and is suitable for
DPASV differential pulse anodic stripping voltammetry detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most described three-electrode system is inserted described system to be measured, then at the enrichment electricity of-1.4V～-1.2V
The lower stirring in position enrichment 0.5min～20min, static after, potential range is set for-1.3V～-0.45V, current potential increment
For 1mV～20mV, pulse amplitude is 1mV～100mV, and pulse width is 0.001s～1s, and the pulse period is
0.002s～2s, does Anodization scan, records anodic stripping voltammetry curve.
Compared with prior art, there is advantages that
1, the carbon paste of a kind of chemically modified carbon paste electrode that the present invention provides is by adding bismuth-containing pressed powder and chela
Mixture, makes both combine, as composite modified dose of this chemically modified carbon paste electrode, so that
The detection limit of this chemically modified carbon paste electrode detection lead ion, cadmium ion and zinc ion has reached 1.0 × 10-12M,
Use this chemically modified electrode of composite modified dose, compared with the chemically modified electrode only using single dressing agent,
Detection limit reduces by 1～3 order of magnitude, and on the basis of existing chemically modified carbon paste electrode, it detects performance
Substantially it is improved.
2, a kind of chemically modified carbon paste electrode that the present invention provides is easy to update, and the most only needs by grinding operation more
This electrode surface new, just can put back into, further simplify the operation sequence of self-reacting device, greatly
Decrease greatly its class of liquids carried, thus reduce the volume of self-reacting device, reduce cost.
3, a kind of chemically modified carbon paste electrode that the present invention provides can realize easily and fast, delicately to certainly
Lead, cadmium and the electrochemical gaging of zinc in the samples such as water, lake water, snow water；Its electrochemical window is wider, operation letter
Single, there is high detection sensitivity, be conducive to lead, cadmium and zinc are measured simultaneously；Further,
Chelating agen by design choice Adsorption of Lead, cadmium and zinc, it is also possible to for specific lead ion, cadmium ion
Selective enumeration method is carried out with zinc ion.
Accompanying drawing explanation
Fig. 1 be Application Example 1 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion, wherein in illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.
Fig. 2 be Application Example 2 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion, wherein in illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.
Fig. 3 be Application Example 3 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion, wherein in illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.
Fig. 4 be Application Example 4 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion, wherein in illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.
Fig. 5 be the lead ion of same concentrations in comparative example 1 of the present invention～comparative example 4, cadmium ion and
Anodic stripping voltammetry figure in zinc ion solution.
Detailed description of the invention
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, under
Face combines accompanying drawing and preferred embodiment, is described in further detail the present invention.Should be appreciated that this place is retouched
The specific embodiment stated, only in order to explain the present invention, is not used in the restriction present invention.
The Preparation equipment used is ultrasonic wave concussion instrument and mortar.
Embodiment 1:
The preparation method of a kind of chemically modified carbon paste electrode, comprises the steps:
(1) first, take the mortar of a 100mL, in this mortar, then add the bismuth oxide of 10.0mg
Powder；
(2) measure 1mL ethanol and add this mortar, wherein containing 5mg diacetyldioxime in this 1mL ethanol,
Bismuth oxide powder in stirring grinding body becomes pastel with diacetyldioxime, prepares composite modified dose；
(3) after ethanol is evaporated completely completely, mortar adds the graphite powder of 60mg, stirs；Again
Adding the methyl-silicone oil of 10mg, stirring prepares required carbon paste；
(4) taking internal diameter is 2mm, and external diameter is 5mm, and the polyfluortetraethylene pipe of a length of 40mm is as electricity
Pole shell, two ends are polished smooth on sand paper, clean by ultrasonic cleaning, dry, standby；
(5) carbon paste that step (3) prepares closely is inserted in the polytetrafluoroethylene electrode shell cleaned,
Insert a diameter of 2mm, the copper conductor of a length of 50mm in one end of the electrode mouth of pipe, make 20mm copper conductor
It is exposed to electrode shell outer as lead-in wire, obtains required chemically modified carbon paste electrode.
Embodiment 2:
The preparation method of a kind of chemically modified carbon paste electrode, comprises the steps:
(1) first, take the mortar of a 100mL, in this mortar, be then separately added into the oxidation of 2mg
Bismuth meal end；
(2) measure 2mL benzene and add this mortar, wherein containing 2mg dithizone, stirring in this 2mL benzene
Bismuth oxide powder in grinding body becomes pastel with dithizone, prepares composite modified dose；
(3) after benzene is evaporated completely completely, mortar adds the mesoporous carbon powder of 70mg, stirs；
Adding the paraffin oil of 30mg, stirring prepares required carbon paste；
(4) taking internal diameter is 2mm, and external diameter is 4mm, the glass tubing of a length of 40mm as electrode shell,
Two ends are polished smooth on sand paper, clean by ultrasonic cleaning, dry, standby；
(5) carbon paste that step (3) prepares closely is inserted in the glass electrode shell cleaned, at electrode
A diameter of 2mm, the copper conductor of a length of 50mm are inserted in one end of the mouth of pipe, make 20mm copper conductor be exposed to
Electrode shell is outer as lead-in wire, obtains required chemically modified carbon paste electrode.
Embodiment 3:
The preparation method of a kind of chemically modified carbon paste electrode, comprises the steps:
(1) first, take the mortar of a 25mL, in this mortar, be then separately added into the hydrogen-oxygen of 50mg
Change bismuth meal end, the benzoin oxime of 30mg and the fullerene of 20mg, stir, wherein Bismuth hydrate. powder
Composite modified dose is formed with benzoin oxime；
(2) in beaker, add the mineral oil of 50mg, stir, prepare required carbon paste；
(3) taking internal diameter is 2mm, and external diameter is 5mm, the plastic tube of a length of 40mm as electrode shell,
Two ends are polished smooth on sand paper, clean by ultrasonic cleaning, dry, standby；
(4) carbon paste that step (2) prepares closely is inserted in the plastic electrode shell cleaned, at electrode
A diameter of 2mm, the copper conductor of a length of 50mm are inserted in one end of the mouth of pipe, make 20mm copper conductor be exposed to
Electrode shell is outer as lead-in wire, obtains required chemically modified carbon paste electrode.
Embodiment 4:
The preparation method of a kind of chemically modified carbon paste electrode, comprises the steps:
(1) first, take the mortar of a 25mL, be then separately added in this beaker 0.5mg bismuth meal,
The 8-hydroxyquinoline of 0.5mg, the CNT of 80mg and the epoxy resin of 10mg, grind so that bismuth meal
It is uniformly dispersed with 8-hydroxyquinoline, CNT, prepares required carbon paste, wherein bismuth meal and 8-hydroxyquinoline
Form composite modified dose；
(2) taking internal diameter is 2mm, and external diameter is 3mm, and the polyfluortetraethylene pipe of a length of 40mm is as electrode
Shell, two ends are polished smooth on sand paper, clean by ultrasonic cleaning, dry, standby；
(3) carbon paste that step (1) prepares closely is inserted in the polytetrafluoroethylene electrode shell cleaned,
Insert a diameter of 2mm, the copper conductor of a length of 50mm in one end of the electrode mouth of pipe, make 20mm copper conductor
It is exposed to electrode shell outer as lead-in wire, obtains required chemically modified carbon paste electrode.
Embodiment 5:
The preparation method of a kind of chemically modified carbon paste electrode, comprises the steps:
(1) first, take the mortar of a 100mL, in this mortar, be then separately added into the oxidation of 2mg
Bismuth meal end；
(2) measure 2mL benzene and add this mortar, wherein containing 2mg dithizone, stirring in this 2mL benzene
Bismuth oxide powder in grinding body becomes pastel with dithizone, prepares composite modified dose；
(3) after benzene is evaporated completely completely, mortar adds the mesoporous carbon powder of 90mg, stirs；
Adding the paraffin oil of 30mg, stirring prepares required carbon paste；
(4) taking internal diameter is 2mm, and external diameter is 4mm, the glass tubing of a length of 40mm as electrode shell,
Two ends are polished smooth on sand paper, clean by ultrasonic cleaning, dry, standby；
(5) carbon paste that step (3) prepares closely is inserted in the glass electrode shell cleaned, at electrode
A diameter of 2mm, the copper conductor of a length of 50mm are inserted in one end of the mouth of pipe, make 20mm copper conductor be exposed to
Electrode shell is outer as lead-in wire, obtains required chemically modified carbon paste electrode.
For the detection performance of valid certificates chemically modified carbon paste electrode disclosed by the invention, by the embodiment of the present invention
1～4 chemically modified carbon paste electrodes prepared use DPASV differential pulse anodic stripping voltammetry to detect in system to be measured
Lead ion, cadmium ion and zinc ion.The instrument used is CHI660D electrochemical workstation (Shanghai occasion Hua Yi
Device company limited): three-electrode system (working electrode is the chemically modified carbon paste electrode that embodiment 1～4 prepares,
Reference electrode is saturated calomel electrode, is platinum electrode to electrode)；The reagent used is analytical pure, and water is equal
For redistilled water；The reagent used is analytical pure, and water is redistilled water.
Effect example 1
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte second is first added
Acid-sodium acetate, forms system to be measured, and the concentration of the supporting electrolyte acetic acid-sodium acetate in this system to be measured is 0.5
Mol/L, is then set to 2 by the pH value of this system to be measured；
(2) first by ready three-electrode system, (working electrode is that the chemistry that embodiment 1 prepares is repaiied
Decorations carbon paste electrode, reference electrode is saturated calomel electrode, is platinum electrode to electrode) insert this system to be measured,
It is suitable for DPASV differential pulse anodic stripping voltammetry and detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.2V
Stirring enrichment 6min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV, arteries and veins
Rushing amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, and record anode is molten
Go out volt-ampere curve.
Under above experiment condition, the chemically modified carbon paste electrode that embodiment 1 prepares is to 6 bodies to be measured
System carries out detecting that (in system 1 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 1.0 × 10-8mol/L、
1.0×10-8Mol/L and 1.0 × 10-8mol/L；In system 2 to be measured, lead ion, cadmium ion and zinc ion concentration divide
It is not 7.0 × 10-9mol/L、7.0×10-9Mol/L and 7.0 × 10-9mol/L；Lead ion, cadmium in system 3 to be measured
Ion and zinc ion concentration are respectively 5.0 × 10-9mol/L、5.0×10-9Mol/L and 5.0 × 10-9mol/L；To be measured
In system 4, lead ion, cadmium ion and zinc ion concentration are respectively 1.0 × 10-9mol/L、1.0×10-9Mol/L and
1.0×10-9mol/L；In system 5 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 5.0 × 10-10mol/L、
5.0×10-10Mol/L and 5.0 × 10-10mol/L；In system 6 to be measured, lead ion, cadmium ion and zinc ion concentration divide
It is not 2.0 × 10-10mol/L、2.0×10-10Mol/L and 2.0 × 10-10Mol/L), detection lead ion, cadmium ion and
The relative standard deviation (RSD) of zinc ion be respectively 0.9%, 1.1% and 1.1% (wherein n (lead)=n (zinc)=
N (cadmium)=6)；Illustrate that the detection of lead ion, cadmium ion and zinc ion is had well by this chemically modified carbon paste electrode
Linear.
Fig. 1 be Application Example 1 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion；Interior illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.As it is shown in figure 1,
In anodic stripping voltammetry figure, six curves from low to high, represent zinc ion, cadmium ion and lead ion successively
Concentration is 2.0 × 10-10Mol/L (system 6 to be measured), 5.0 × 10-10Mol/L (system 5 to be measured), 1.0
×10-9Mol/L (system 4 to be measured), 5.0 × 10-9Mol/L (system 3 to be measured), 7.0 × 10-9Mol/L is (to be measured
System 2) or 1.0 × 10-8Anodic stripping voltammetry curve during mol/L (system 1 to be measured)；From-1.2V to
Between-0.45V, raising with voltage, every curve occurs three peaks successively, is zinc ion, cadmium ion respectively
Stripping Currents peak with lead ion.In in figure, illustration is lead ion, cadmium ion and zinc ion dissolution peak electricity respectively
Stream ipWith the linear relationship chart of lead ion, cadmium ion and zinc ion concentration, take zinc ion, cadmium ion the most respectively
Being vertical coordinate with the peak value at the Stripping Currents peak of lead ion, corresponding ion concentration is abscissa, is drawn
Electric current-concentration curve.Via linear fit, it is known that lead ion, cadmium ion and zinc ion dissolution peak current ipWith
Lead ion, cadmium ion and zinc ion concentration in system to be measured are 2.0 × 10-10Mol/L～1.0 × 10-8Mol/L's
In the range of the most linear, the equation of linear regression corresponding to lead ion is: ip=0.246+0.154c
(R=0.999)；Equation of linear regression corresponding to cadmium ion is: ip=0.566+0.116c (R=0.999)；Zinc from
Equation of linear regression corresponding to son is: ip=1.725+0.176c (R=0.998).Wherein dissolution peak current ipSingle
Position is μ A, and concentration c unit is 10-10mol/L.According to the signal to noise ratio universal standard equal to 3, it is calculated
The detection limit of detection lead ion, cadmium ion and zinc ion is respectively 1.5 × 10-12mol/L、1.9×10-12Mol/L and
1.3×10-12mol/L。
Under above experiment condition, 5 same batch chemically modified carbon paste electrodes that embodiment 1 prepares
It is respectively 5.0 × 10 to containing lead ion, cadmium ion and zinc ion concentration-9mol/L、5.0×10-9Mol/L and
5.0×10-9The system to be measured 7 of mol/L carries out detecting (owing to the chemically modified carbon paste electrode used is for a collection of
Secondary preparation, therefore its structure identical and only use i.e. abandon for 1 time), its relative standard deviation (RSD) point
It is not 1.8%, 1.2% and 1.6% (wherein n (lead)=n (cadmium)=n (zinc)=5), this carbon magma is described
Electrode has good preparation repeatability.
Under above experiment condition, lead ion, cadmium ion and zinc ion concentration in system 8 to be measured are respectively
5.0×10-9mol/L、5.0×10-9Mol/L and 5.0 × 10-9Mol/L, in the case of relative error is less than ± 5%, examines
Examined chaff interference on detection impact, result shows: the aluminium ion of 1500 times of concentration, manganese ion, nickel ion,
Sodium ion, calcium ion, magnesium ion, potassium ion, nitrate ion and sulfate ion, the ferrum of 500 times of concentration
Ion, bismuth ion and ammonium radical ion, the ferrous ion of 200 times of concentration, arsenic ion, mercury ion and chromium ion pair
Detection is all without impact.
Effect example 2
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte phosphorus is first added
Hydrochlorate buffer solution, forms system to be measured, the supporting electrolyte phosphate-buffered pair in this system to be measured dense
Degree is 0.001mol/L, then the pH value of this system to be measured is set to 6；
(2) by ready three-electrode system, (working electrode is the chemical modification carbon that embodiment 2 prepares
Paste electrode, reference electrode is saturated calomel electrode, is platinum electrode to electrode) insert this system to be measured, it is suitable for
DPASV differential pulse anodic stripping voltammetry detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.4V
Stirring enrichment 20min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV,
Pulse amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, record sun
Pole Stripping Voltammetry curve.
Under above experiment condition, the chemically modified carbon paste electrode that embodiment 2 prepares is to 6 bodies to be measured
System carries out detecting that (in system 1 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 1.0 × 10-8mol/L、
1.0×10-8Mol/L and 1.0 × 10-8mol/L；In system 2 to be measured, lead ion, cadmium ion and zinc ion concentration divide
It is not 7.0 × 10-9mol/L、7.0×10-9Mol/L and 7.0 × 10-9mol/L；Lead ion, cadmium in system 3 to be measured
Ion and zinc ion concentration are respectively 5.0 × 10-9mol/L、5.0×10-9Mol/L and 5.0 × 10-9mol/L；To be measured
In system 4, lead ion, cadmium ion and zinc ion concentration are respectively 1.0 × 10-9mol/L、1.0×10-9Mol/L and
1.0×10-9mol/L；In system 5 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 5.0 × 10-10
mol/L、5.0×10-10Mol/L and 5.0 × 10-10mol/L；In system 6 to be measured lead ion, cadmium ion and zinc from
Sub-concentration is respectively 2.0 × 10-10mol/L、2.0×10-10Mol/L and 2.0 × 10-10Mol/L), detection lead ion,
The relative standard deviation (RSD) of cadmium ion and zinc ion is respectively 1.9%, 2.5% and 1.1% (wherein n (lead)
=n (cadmium)=n (zinc)=6)；The detection to lead ion, cadmium ion and zinc ion of this chemically modified carbon paste electrode is described
There is good precision.
Fig. 2 be Application Example 2 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion；Interior illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.As in figure 2 it is shown,
In anodic stripping voltammetry figure, six curves from low to high, represent zinc ion, cadmium ion and lead ion successively
Concentration is 2.0 × 10-10Mol/L (system 6 to be measured), 5.0 × 10-10Mol/L (system 5 to be measured), 1.0
×10-9Mol/L (system 4 to be measured), 5.0 × 10-9Mol/L (system 3 to be measured), 7.0 × 10-9Mol/L is (to be measured
System 2) or 1.0 × 10-8Anodic stripping voltammetry curve during mol/L (system 1 to be measured), from-1.2V to
Between-0.45V, raising with voltage, every curve occurs three peaks successively, is zinc ion, cadmium ion respectively
Stripping Currents peak with lead ion.In in figure, illustration is lead ion, cadmium ion and zinc ion dissolution peak electricity respectively
Stream ipWith the linear relationship chart of lead ion, cadmium ion and zinc ion concentration, take zinc ion, cadmium ion the most respectively
Being vertical coordinate with the peak value at the Stripping Currents peak of lead ion, corresponding ion concentration is abscissa, is drawn
Electric current-concentration curve.Via linear fit, it is known that lead ion, cadmium ion and zinc ion dissolution peak current ipWith
Lead ion, cadmium ion and zinc ion concentration in system to be measured are 2.0 × 10-10Mol/L～1.0 × 10-8Mol/L's
In the range of the most linear, the equation of linear regression corresponding to lead ion is: ip=0.380+0.311c
(R=0.999)；Equation of linear regression corresponding to cadmium ion is: ip=1.250+0.235c (R=0.999)；Zinc
Equation of linear regression corresponding to ion is: ip=3.313+0.369c (R=0.998).Wherein dissolution peak current
ipUnit is μ A, and concentration c unit is 10-10mol/L.Calculate according to the signal to noise ratio universal standard equal to 3
Detection limit to detection lead ion, cadmium ion and zinc ion is respectively 0.9 × 10-12mol/L、1.2×10-12mol/L
With 0.8 × 10-12mol/L。
Under above experiment condition, 5 same batch chemically modified carbon paste electrodes that embodiment 2 prepares
It is respectively 1.0 × 10 to containing lead ion, cadmium ion and zinc ion concentration-8mol/L、1.0×10-8Mol/L and
1.0×10-8The system to be measured 7 of mol/L carries out detecting (owing to the chemically modified carbon paste electrode used is for a collection of
Secondary preparation, therefore its structure identical and only use i.e. abandon for 1 time), its relative standard deviation (RSD) point
It is not 2.5%, 1.3% and 1.6% (wherein n (lead)=n (cadmium)=n (zinc)=5), this carbon magma is described
Electrode has good preparation repeatability.
Under above experiment condition, lead ion, cadmium ion and zinc ion concentration in system 8 to be measured are respectively
2.0×10-10mol/L、2.0×10-10Mol/L and 2.0 × 10-10Mol/L, in the case of relative error is less than ± 5%,
Investigated chaff interference on detection impact, result shows: the aluminium ion of 1500 times of concentration, manganese ion, nickel from
Son, sodium ion, calcium ion, magnesium ion, potassium ion, nitrate ion and sulfate ion, 500 times of concentration
Iron ion, bismuth ion and ammonium radical ion, the ferrous ion of 200 times of concentration, arsenic ion, mercury ion and chromium from
Son is on detecting all without impact.
Effect example 3
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte vinegar is first added
Hydrochlorate, forms system to be measured, and the concentration of the supporting electrolyte acetate in this system to be measured is 0.05mol/L,
Then the pH value of this system to be measured is set to 5；
(2) by ready three-electrode system, (working electrode is the chemical modification carbon that embodiment 3 prepares
Paste electrode, reference electrode is saturated calomel electrode, is platinum electrode to electrode) insert this system to be measured, it is suitable for
DPASV differential pulse anodic stripping voltammetry detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.2V
Stirring enrichment 6min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV, arteries and veins
Rushing amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, and record anode is molten
Go out volt-ampere curve.
Under above experiment condition, the chemically modified carbon paste electrode that embodiment 3 prepares is to 6 bodies to be measured
System carries out detecting that (in system 1 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 1.0 × 10-8mol/L、
1.0×10-8Mol/L and 1.0 × 10-8mol/L；In system 2 to be measured, lead ion, cadmium ion and zinc ion concentration divide
It is not 7.0 × 10-9mol/L、7.0×10-9Mol/L and 7.0 × 10-9mol/L；Lead ion, cadmium in system 3 to be measured
Ion and zinc ion concentration are respectively 3.0 × 10-9mol/L、3.0×10-9Mol/L and 3.0 × 10-9mol/L；To be measured
In system 4, lead ion, cadmium ion and zinc ion concentration are respectively 1.0 × 10-9mol/L、1.0×10-9Mol/L and
1.0×10-9mol/L；In system 5 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 5.0 × 10-10
mol/L、5.0×10-10Mol/L and 5.0 × 10-10mol/L；In system 6 to be measured lead ion, cadmium ion and zinc from
Sub-concentration is respectively 2.0 × 10-10mol/L、2.0×10-10Mol/L and 2.0 × 10-10Mol/L), detection lead ion,
The relative standard deviation (RSD) of cadmium ion and zinc ion is respectively 1.9%, 2.1% and 1.1% (wherein n (lead)
=n (cadmium)=n (zinc)=6)；The detection to lead ion, cadmium ion and zinc ion of this chemically modified carbon paste electrode is described
There is good precision.
Fig. 3 be Application Example 3 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion；Interior illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.As it is shown on figure 3,
In anodic stripping voltammetry figure, six curves from low to high, represent zinc ion, cadmium ion and lead ion successively
Concentration is 2.0 × 10-10Mol/L (system 6 to be measured), 5.0 × 10-10Mol/L (system 5 to be measured), 1.0
×10-9Mol/L (system 4 to be measured), 3.0 × 10-9Mol/L (system 3 to be measured), 7.0 × 10-9Mol/L is (to be measured
System 2) or 1.0 × 10-8Anodic stripping voltammetry curve during mol/L (system 1 to be measured), from-1.2V to
Between-0.45V, raising with voltage, every curve occurs three peaks successively, is zinc ion, cadmium ion respectively
Stripping Currents peak with lead ion.In in figure, illustration is lead ion, cadmium ion and zinc ion dissolution peak electricity respectively
Stream ipWith the linear relationship chart of lead ion, cadmium ion and zinc ion concentration, take zinc ion, cadmium ion the most respectively
Being vertical coordinate with the peak value at the Stripping Currents peak of lead ion, corresponding ion concentration is abscissa, is drawn
Electric current-concentration curve.Via linear fit, it is known that lead ion, cadmium ion and zinc ion dissolution peak current ipWith
Lead ion, cadmium ion and zinc ion concentration in system to be measured are 2.0 × 10-10Mol/L～1.0 × 10-8Mol/L's
In the range of the most linear, the equation of linear regression corresponding to lead ion is: ip=0.597+0.063c
(R=0.996)；Equation of linear regression corresponding to cadmium ion is: ip=0.952+0.0496c (R=0.999)；Zinc
Equation of linear regression corresponding to ion is: ip=0.353+0.097c (R=0.993).Wherein dissolution peak current
ipUnit is μ A, and concentration c unit is 10-10.It is calculated detection according to the signal to noise ratio universal standard equal to 3
The detection limit of lead ion, cadmium ion and zinc ion is respectively 3.5 × 10-12mol/L、4.2×10-12Mol/L and
3.1×10-12mol/L。
Under above experiment condition, 5 same batch chemically modified carbon paste electrodes that embodiment 3 prepares
It is 1.0 × 10 to containing lead ion, cadmium ion and zinc ion concentration-8The system to be measured 7 of mol/L detects
(chemically modified carbon paste electrode owing to using is prepared by same batch, and therefore its structure is identical and only makes
I.e. abandon with 1 time), its relative standard deviation (RSD) is respectively 2.5%, 1.9% and 2.9% (wherein n (lead)
=n (cadmium)=n (zinc)=5), illustrate that this chemically modified carbon paste electrode has good preparation repeatability.
Under above experiment condition, lead ion, cadmium ion and zinc ion concentration in system 8 to be measured are
5.0×10-10Mol/L, in the case of relative error is less than ± 5%, has investigated the chaff interference impact on detection, knot
Fruit show: the aluminium ion of 1500 times of concentration, manganese ion, nickel ion, sodium ion, calcium ion, magnesium ion,
Potassium ion, nitrate ion and sulfate ion, the iron ion of 500 times of concentration, bismuth ion and ammonium radical ion,
The ferrous ion of 200 times of concentration, arsenic ion, mercury ion and chromium ion are on detecting all without impact.
Effect example 4
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte lemon is first added
Lemon hydrochlorate, forms system to be measured, and the concentration of the supporting electrolyte citrate in this system to be measured is 0.4mol/L,
Then the pH value of this system to be measured is set to 7；
(2) by ready three-electrode system, (working electrode is the chemical modification carbon that embodiment 4 prepares
Paste electrode, reference electrode is saturated calomel electrode, is platinum electrode to electrode) insert this system to be measured, it is suitable for
DPASV differential pulse anodic stripping voltammetry detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.2V
Stirring enrichment 6min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV, arteries and veins
Rushing amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, and record anode is molten
Go out volt-ampere curve.
Under above experiment condition, the chemically modified carbon paste electrode that embodiment 4 prepares is to 6 bodies to be measured
System carries out detecting that (in system 1 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 1.0 × 10-8mol/L、
1.0×10-8Mol/L and 1.0 × 10-8mol/L；In system 2 to be measured, lead ion, cadmium ion and zinc ion concentration divide
It is not 7.0 × 10-9mol/L、7.0×10-9Mol/L and 7.0 × 10-9mol/L；Lead ion, cadmium in system 3 to be measured
Ion and zinc ion concentration are respectively 5.0 × 10-9mol/L、5.0×10-9Mol/L and 5.0 × 10-9mol/L；To be measured
In system 4, lead ion, cadmium ion and zinc ion concentration are respectively 2.0 × 10-9mol/L、2.0×10-9Mol/L and
2.0×10-9mol/L；In system 5 to be measured, lead ion, cadmium ion and zinc ion concentration are 1.0 × 10-9mol/L；
In system 6 to be measured, lead ion, cadmium ion and zinc ion concentration are respectively 2.0 × 10-10mol/L、2.0×10-10
Mol/L and 2.0 × 10-10Mol/L), detection lead ion, cadmium ion and the relative standard deviation (RSD) of zinc ion
It is respectively 2.3%, 2.1% and 2.8% (wherein n (lead)=n (cadmium)=n (zinc)=6)；This chemical modification carbon is described
Paste electrode has good precision to the detection of lead ion, cadmium ion and zinc ion.
Fig. 4 be Application Example 4 electrode detection system to be measured 1 to lead ion in system 6 solution to be measured,
The anodic stripping voltammetry figure of cadmium ion and zinc ion；Interior illustration be respectively lead ion, cadmium ion and zinc from
Sub-dissolution peak current ipLinear relationship chart with lead ion, cadmium ion and zinc ion concentration.As shown in Figure 4,
In anodic stripping voltammetry figure, six curves from low to high, represent zinc ion, cadmium ion and lead ion successively
Concentration is 2.0 × 10-10Mol/L (system 6 to be measured), 1.0 × 10-9Mol/L (system 5 to be measured), 2.0
×10-9Mol/L (system 4 to be measured), 5.0 × 10-9Mol/L (system 3 to be measured), 7.0 × 10-9Mol/L is (to be measured
System 2) or 1.0 × 10-8Anodic stripping voltammetry curve during mol/L (system 1 to be measured), from-1.2V to
Between-0.45V, raising with voltage, every curve occurs three peaks successively, is zinc ion, cadmium ion respectively
Stripping Currents peak with lead ion.In in figure, illustration is lead ion, cadmium ion and zinc ion dissolution peak electricity respectively
Stream ipWith the linear relationship chart of lead ion, cadmium ion and zinc ion concentration, take zinc ion, cadmium ion the most respectively
Being vertical coordinate with the peak value at the Stripping Currents peak of lead ion, corresponding ion concentration is abscissa, is drawn
Electric current-concentration curve.Via linear fit, it is known that lead ion, cadmium ion and zinc ion dissolution peak current ipWith
Lead ion, cadmium ion and zinc ion concentration in system to be measured are 2.0 × 10-10Mol/L～1.0 × 10-8Mol/L's
In the range of the most linear, the equation of linear regression corresponding to lead ion is: ip=0.258+0.114c
(R=0.999)；Equation of linear regression corresponding to cadmium ion is: ip=0.887+0.0857c (R=0.988)；Zinc
Equation of linear regression corresponding to ion is: ip=2.75+0.106c (R=0.989).Wherein dissolution peak current ip
Unit is μ A, and concentration c unit is 10-10mol/L.It is calculated according to the signal to noise ratio universal standard equal to 3
The detection limit of detection lead ion, cadmium ion and zinc ion is respectively 9.2 × 10-12mol/L、7.2×10-12mol/L
With 8.1 × 10-12mol/L。
Under above experiment condition, 5 same batch chemically modified carbon paste electrodes that embodiment 4 prepares
It is 2.0 × 10 to containing lead ion, cadmium ion and zinc ion concentration-9The system to be measured 7 of mol/L detects
(chemically modified carbon paste electrode owing to using is prepared by same batch, and therefore its structure is identical and only makes
I.e. abandon with 1 time), its relative standard deviation (RSD) is respectively 1.8%, 1.3% and 2.3% (wherein n (lead)
=n (cadmium)=n (zinc)=5), illustrate that this chemically modified carbon paste electrode has good preparation repeatability.
Under above experiment condition, in system 8 to be measured, lead ion, cadmium ion and zinc ion concentration are
1.0×10-9Mol/L, in the case of relative error is less than ± 5%, has investigated the chaff interference impact on detection, knot
Fruit show: the aluminium ion of 1500 times of concentration, manganese ion, nickel ion, sodium ion, calcium ion, magnesium ion,
Potassium ion, nitrate ion and sulfate ion, the iron ion of 500 times of concentration, bismuth ion and ammonium radical ion,
The ferrous ion of 200 times of concentration, arsenic ion, mercury ion and chromium ion are on detecting all without impact.
Comparative example 1
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte lemon is first added
Lemon hydrochlorate, forms system to be measured, and the concentration of the supporting electrolyte citrate in this system to be measured is 0.4mol/L,
Then the pH value of this system to be measured is set to 5；
(2) first by ready three-electrode system, (working electrode is the chemistry prepared with embodiment 2
Decorating carbon paste electrode is compared, and lacks bismuth oxide powder component in carbon paste, other components and component in carbon paste
Quality is the most identical, and the electrode shell used is the most identical with specification with the material of lead-in wire, and reference electrode is
Saturated calomel electrode, is platinum electrode to electrode) insert this system to be measured, it is suitable for Differential Pulse Anodic Stripping Voltammetry volt
Peace method detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.2V
Stirring enrichment 6min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV, arteries and veins
Rushing amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, and record anode is molten
Go out volt-ampere curve.
Comparative example 2
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte lemon is first added
Lemon hydrochlorate, forms system to be measured, and the concentration of the supporting electrolyte citrate in this system to be measured is 0.4mol/L,
Then the pH value of this system to be measured is set to 5；
(2) first by ready three-electrode system, (working electrode is the chemistry prepared with embodiment 2
Decorating carbon paste electrode is compared, and lacks dithizone component in carbon paste, other components and the quality of component in carbon paste
The most identical, and the electrode shell used is the most identical with specification with the material of lead-in wire, and reference electrode is saturated
Calomel electrode, is platinum electrode to electrode) insert this system to be measured, it is suitable for DPASV differential pulse anodic stripping voltammetry
Detect the lead ion in system to be measured, cadmium ion and zinc ion；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.2V
Stirring enrichment 6min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV, arteries and veins
Rushing amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, and record anode is molten
Go out volt-ampere curve.
Comparative example 3
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte lemon is first added
Lemon hydrochlorate, forms system to be measured, and the concentration of the supporting electrolyte citrate in this system to be measured is 0.4mol/L,
Then the pH value of this system to be measured is set to 5；
(2) first by ready three-electrode system, (working electrode is the chemistry prepared with embodiment 2
Decorating carbon paste electrode is compared, and lacks bismuth oxide powder component and dithizone component in carbon paste, other groups in carbon paste
Divide and the quality of component be the most identical, and the electrode shell used is the most identical with specification with the material of lead-in wire,
Reference electrode is saturated calomel electrode, is platinum electrode to electrode) insert this system to be measured, it is suitable for differentiated pulse
Anodic stripping voltammetry detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.2V
Stirring enrichment 6min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV, arteries and veins
Rushing amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, and record anode is molten
Go out volt-ampere curve.
Comparative example 4
Lead ion, cadmium ion and the method for zinc ion in a kind of chemically modified carbon paste electrode detection environment, including
Following steps:
(1) in the test solution to be measured containing lead ion, cadmium ion and zinc ion, supporting electrolyte lemon is first added
Lemon hydrochlorate, forms system to be measured, and the concentration of the supporting electrolyte citrate in this system to be measured is 0.4mol/L,
Then the pH value of this system to be measured is set to 5；
(2) first by ready three-electrode system, (working electrode is that the chemistry that embodiment 2 prepares is repaiied
Decorations carbon paste electrode, reference electrode is saturated calomel electrode, is platinum electrode to electrode) insert this system to be measured,
It is suitable for DPASV differential pulse anodic stripping voltammetry and detects lead ion, cadmium ion and the zinc ion in system to be measured；
The most ready three-electrode system is inserted this system to be measured, then under the accumulating potential of-1.2V
Stirring enrichment 6min, static after, potential range is set for-1.2V～-0.45V, current potential increment is 4mV, arteries and veins
Rushing amplitude is 50mV, and pulse width is 0.2s, and the pulse period is 0.5s, does Anodization scan, and record anode is molten
Go out volt-ampere curve.
Fig. 5 be the lead ion of same concentrations in comparative example 1 of the present invention～comparative example 4, cadmium ion and
Anodic stripping voltammetry figure in zinc ion solution.The chemically modified carbon paste electrode that wherein comparative example 1 uses
Dressing agent be dithizone, the dressing agent of chemically modified carbon paste electrode that comparative example 2 uses is bismuth oxide,
The carbon paste electrode that comparative example 3 uses or not any dressing agent, and the chemistry that comparative example 4 uses is repaiied
The dressing agent of decorations carbon paste electrode is composite modified dose be made up of bismuth oxide and dithizone.As it is shown in figure 5, it is right
The electrode of any dressing agent is not used, in the solution almost without dissolution peak than embodiment 3 only has carbon paste
Occur, it is impossible to detect the lead of this concentration, cadmium, zinc.Comparative example 1 use bismuth oxide as dressing agent
Electrode, and in comparative example 2 use dithizone as the electrode of dressing agent, have obvious dissolution peak,
Can detect the lead ion of this concentration, cadmium ion and zinc ion, but the height at peak is on the low side, Monitoring lower-cut is inclined
High.Comparative example 4 uses the electrode of composite modified dose be made up of bismuth oxide and dithizone, same to batten
Under part, its dissolution peak significantly increases, and the chemically modified carbon paste electrode that the present invention uses is described, to lead ion, cadmium
Ion increases significantly with the power of test of zinc ion tool compared with existing electrode, it is possible to obtain lower inspection
Survey limit.
It should be appreciated that the above-mentioned statement for present pre-ferred embodiments is more detailed, therefore can not be
And it being considered the restriction to scope of patent protection of the present invention, the scope of patent protection of the present invention should be with appended right
Requirement is as the criterion.
Claims (10)
1. a chemically modified carbon paste electrode, including electrode shell, is filled in the carbon paste in described electrode shell,
And contact and by the contact conductor drawn in described electrode shell with described carbon paste, described carbon paste includes conduction
Material with carbon element, binding agent and composite modified dose, it is characterised in that described composite modified dose includes bismuth-containing solid powder
End and chelating agen；Described bismuth-containing pressed powder is water-fast solid bi-containing substance；Described chelating agen is thin
Aqueous, can be with the reagent of at least one ion formation chelate in lead ion, cadmium ion and zinc ion.
Chemically modified carbon paste electrode the most according to claim 1, it is characterised in that described bismuth-containing solid
Powder is bismuth meal, bismuth oxide powder or Bismuth hydrate. powder.
Chemically modified carbon paste electrode the most according to claim 1, it is characterised in that described chelating agen is
8-hydroxyquinoline, benzoin oxime, diacetyldioxime or dithizone.
Chemically modified carbon paste electrode the most according to claim 1, it is characterised in that institute in described carbon paste
Stating conductive carbon material, described bismuth-containing pressed powder, described chelating agen is (20 with the mass ratio of described binding agent
～90): (0.5～50): (0.5～30): (10～50).
Chemically modified carbon paste electrode the most according to claim 1, it is characterised in that institute in described carbon paste
Stating conductive carbon material, described bismuth-containing pressed powder, described chelating agen is (60 with the mass ratio of described binding agent
～80): (0.5～10): (0.5～5): (10～30).
Chemically modified carbon paste electrode the most according to claim 1, it is characterised in that institute in described carbon paste
Stating conductive carbon material, described bismuth-containing pressed powder, described chelating agen is 70:2 with the mass ratio of described binding agent:
2:30.
7. the preparation method of a chemically modified carbon paste electrode, it is characterised in that comprise the steps:
(1) by conductive carbon material, binding agent and composite modified dose of mixing, described composite modified dose includes bismuth-containing
Pressed powder and chelating agen, obtain carbon paste；Described bismuth-containing pressed powder is water-fast solid bi-containing substance；
Described chelating agen is hydrophobic, can be formed with at least one ion in lead ion, cadmium ion and zinc ion
The reagent of chelate；
(2) described carbon paste is filled in electrode shell；
(3) one end of contact conductor is loaded on described electrode shell inside and is connected with described carbon paste, by described
The other end of contact conductor, from the internal extraction of described electrode shell, obtains described chemically modified carbon paste electrode.
The preparation method of chemically modified carbon paste electrode the most according to claim 7, it is characterised in that step
Suddenly, in (1), described bismuth-containing pressed powder is bismuth meal, bismuth oxide powder or Bismuth hydrate. powder.
The preparation method of chemically modified carbon paste electrode the most according to claim 7, it is characterised in that step
Suddenly, in (1), described chelating agen is 8-hydroxyquinoline, benzoin oxime, diacetyldioxime or dithizone.
The preparation method of chemically modified carbon paste electrode the most according to claim 7, it is characterised in that
In step (1), conductive carbon material described in described carbon paste, described bismuth-containing pressed powder, described chelating agen with
The mass ratio of described binding agent is (20～90): (0.5～50): (0.5～30): (10～50).
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| CN201410541908.3A CN104267086B (en) | 2014-10-14 | 2014-10-14 | Chemically modified carbon paste electrode as well as preparation method and application thereof |
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| CN201410541908.3A CN104267086B (en) | 2014-10-14 | 2014-10-14 | Chemically modified carbon paste electrode as well as preparation method and application thereof |
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| CN105866212B (en) * | 2016-05-26 | 2018-11-30 | 江西农业大学 | A kind of electrochemical sensor and preparation method thereof selectively detecting mercury ion, copper ion simultaneously |
| CN107389762B (en) * | 2017-07-24 | 2020-07-31 | 宁德师范学院 | Catechol sensor, preparation method thereof and catechol detection method |
| CN110441363A (en) * | 2019-08-27 | 2019-11-12 | 济南大学 | A kind of preparation method of titanium nitride/carbon nanotube composite paste electrode sensor |
| CN115047053A (en) * | 2022-04-13 | 2022-09-13 | 哈尔滨工业大学 | Preparation method of bismuth-containing screen-printed electrode and application of bismuth-containing screen-printed electrode in heavy metal ion detection |
| CN115078497B (en) * | 2022-05-30 | 2023-07-14 | 宁德师范学院 | Amino carbon nano tube carbon paste electrode, preparation method and application |
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