CN113607799A - Manganese dioxide-polypyrrole composite electrode, preparation method thereof and application thereof in heavy metal detection - Google Patents
Manganese dioxide-polypyrrole composite electrode, preparation method thereof and application thereof in heavy metal detection Download PDFInfo
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 77
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- 239000011572 manganese Substances 0.000 title claims abstract description 63
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- 150000002500 ions Chemical class 0.000 claims abstract description 39
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- 238000000034 method Methods 0.000 claims abstract description 30
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- -1 mercury ions Chemical class 0.000 description 12
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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Abstract
The invention provides a manganese dioxide-polypyrrole composite electrode, a preparation method thereof and application thereof in heavy metal detection. The invention adopts an electrochemical in-situ modification method, adopts a three-electrode system, and modifies metallic nickel, polypyrrole and manganese dioxide on the surface of an electrode to form a composite electrode. The electrode combines polypyrrole with conductivity and manganese oxide with good catalytic activity, greatly improves the speed of ion transmission and electron transfer in the oxidation-reduction reaction process, increases the sensitivity of the electrode to metal ion detection, and reduces the detection limit. Meanwhile, the composite structure of the copolymer on the surface of the electrode and the metal increases the stability of the electrode, so that the electrode can be recycled. The composite electrode can be used for simultaneously detecting trace Hg2+、Pb2+And Cu2+Ions.
Description
Technical Field
The invention belongs to the field of electrochemical sensors, particularly relates to the field of electrochemical detection of heavy metal ions, and relates to a manganese dioxide-polypyrrole composite electrode, a preparation method thereof and application thereof in heavy metal detection.
Background
Heavy metals are metals with a specific gravity greater than 5, including gold, silver, copper, iron, lead, mercury, and the like. With the exploitation, smelting and processing of heavy metals, a lot of heavy metals enter the atmosphere, water and soil, and serious environmental pollution is caused. Heavy metals discharged from wastewater, even if having a low concentration, can accumulate in algae and sediment, and are adsorbed on the body surface of fish and shellfish to cause food chain concentration, thereby causing public nuisance. Heavy metals can interact strongly with proteins and various enzymes in human bodies to cause them to lose activity, and can also be enriched in certain organs of human bodies, if the heavy metals exceed the tolerance limit of the human bodies, acute poisoning, subacute poisoning, chronic poisoning and the like of the human bodies can be caused, and great harm can be caused to the human bodies.
The activity and persistence indicate the degree of stability of the contaminant in the environment. Pollutants with high activity are easy to generate chemical reaction in the environment or in the treatment process, the toxicity is reduced, but pollutants with stronger toxicity than the original pollutants can be generated, and secondary pollution is formed. For example, mercury can be converted into methyl mercury, and the toxicity is stronger. In contrast to activity, persistence means that some contaminants can maintain their harmfulness for a long period of time, such as heavy metal lead, which is toxic and difficult to degrade in nature, can produce bioaccumulation, and threaten human health and survival for a long period of time.
The general heavy metal toxicity range in natural water is about 1-10 mg/L, and the mercury toxicity range is 0.01-0.001 mg/L. Therefore, the method is very important for the real-time detection of trace heavy metal ions.
Currently approved methods for heavy metal analysis include: ultraviolet spectrophotometry (UV), Atomic Absorption Spectroscopy (AAS), Atomic Fluorescence (AFS), Inductively Coupled Plasma (ICP), X-ray fluorescence spectroscopy (XRF), inductively coupled plasma mass spectrometry (ICP-MS) and the like, but the detection methods have the disadvantages of high instrument cost, complex operation, long detection time and incapability of ensuring the detection precision and repeatability. The electrochemical method has high detection speed and accurate numerical value, and can be used for emergency detection in the environments such as the field and the like. Therefore, it is important to develop an electrochemical sensing electrode for rapid detection of heavy metal ions.
Polypyrrole is polymerized from pyrrole monomers and is an amorphous, insoluble, and infusible, black solid. The polypyrrole has higher conductivity, biocompatibility and environmental stability, and the monomer activity is higher, so that oxidative polymerization is very easy to realize, and the polypyrrole is non-toxic and environment-friendly. The polypyrrole has wide application prospect in various fields such as sensors, electronic devices, functionalized films and the like.
Therefore, the polypyrrole and the manganese dioxide with catalytic activity are compounded, the prepared composite electrode has the advantages of high sensitivity, good stability and the like, and the rapid detection of trace heavy metal ions is realized.
Disclosure of Invention
The invention aims to provide a heavy metal ion detection electrode capable of simultaneously detecting mercury ions, lead ions and copper ions and ensuring the reliability and stability of the heavy metal ion detection electrode.
The invention provides a manganese dioxide-polypyrrole composite electrode for heavy metal detection and a preparation method thereof.
The invention aims to provide a manganese dioxide-polypyrrole composite electrode, which takes a metal electrode as a substrate, comprises a working electrode, a reference electrode and an auxiliary electrode, and comprises an electrode substrate and an electrode modification layer, wherein the working electrode, the reference electrode and the auxiliary electrode are integrated on the same plane of the electrode, a metal nickel layer is modified on the surface of the metal electrode, and the manganese dioxide-polypyrrole modification layer is modified on the surface of the working electrode.
Polypyrrole has semiconductor properties, so detection and analysis can be achieved by using the quantitative relationship between the conductivity change of polypyrrole exposed to molecules or ions to be detected and the presence of the concentration of a detection object. In addition, the polypyrrole has good conductivity, chemical stability and biocompatibility, can be compounded with various active materials, and enhances the catalytic performance and stability of the polypyrrole. The polypyrrole and the oxide with high catalytic activity are compounded, so that the conductive environment of the catalyst can be obviously improved, the catalytic performance of the catalyst can be exerted to a greater extent, and a chemical sensor with higher sensitivity can be obtained.
The manganese dioxide-polypyrrole modifying layer has a three-dimensional bundle-shaped structure, the width of the binding belt is 1.5-2.0 mu m, manganese dioxide particles are uniformly modified on the surface of polyaniline, and the particle size is 5-20 nm.
The manganese dioxide-polypyrrole composite electrode provided by the invention compounds polypyrrole with excellent conductivity and manganese dioxide with good catalytic performance, and the synergistic effect of the composite electrode provides more channels for electron transfer and ion transmission, so that the active area of the electrode is greatly increased, the sensing characteristic and response time are improved, and the requirements of instant detection and emergency detection on a detection site can be met. Meanwhile, the three-dimensional skeleton structure of the composite electrode enhances the stability of the electrode and can realize the repeated recycling of the manganese dioxide-polypyrrole composite electrode.
The invention also aims to provide a preparation method of the manganese dioxide-polypyrrole composite electrode.
The method specifically comprises the following steps:
s1, preparation of a Ni layer: preparing a Ni buffer layer on the surface of the electrode substrate by adopting an electrodeposition method to obtain a nickel electrode;
s2, preparing a polypyrrole film layer: preparing a polypyrrole electrode by taking a nickel electrode as a substrate and adopting an electrodeposition method;
s3, preparing a manganese dioxide-polypyrrole composite electrode: and modifying manganese dioxide on the surface of the polypyrrole electrode serving as a base in situ to obtain the manganese dioxide-polypyrrole composite electrode.
Further, in step S1, the electrodeposition method is: preparing a nickel plating solution, specifically 200-300 g/L nickel sulfate, 20-30 g/L nickel chloride, 20-30 g/L boric acid and 0.1-0.2 g/L sodium dodecyl sulfate, and adjusting the pH value of the solution to 3.0-4.0; adopting a double-electrode constant current mode, taking a titanium mesh electrode as an anode and an electrode substrate as a cathode, setting the temperature to be 40-50 ℃, and the current density to be 1.0-5.0A/dm2The electrodeposition time is 5-10 min.
The synthesis method of polypyrrole mainly comprises a chemical method and an electrochemical polymerization method. The chemical method needs to consume more oxidant, and the obtained polypyrrole is easy to wrap impurities and can be utilized after further treatment. The electrochemical method is simple to operate, consumes less energy, is easy to control conditions, and the obtained polypyrrole has good conductivity and mechanical property, can be directly polymerized and modified on an electrode, and is a main method for preparing a polypyrrole modified electrode.
Further, in step S2, the method for preparing the polypyrrole film layer includes: and (2) taking a nickel electrode as a working electrode, putting the working electrode into a polypyrrole solution, taking Pt as an auxiliary electrode and Ag/AgCl as a reference electrode, applying a potential of 0.3-0.8V, performing electrodeposition for 10-50 s, and then putting the electrode into deionized water for ultrasonic cleaning for 3-5 min.
The polypyrrole solution comprises the following specific components: 30-60 mmol/L pyrrole monomer, 0.1-0.5 mol/L Na2SO420-50 mmol/L sodium dodecyl sulfate.
Further, in step S3, the preparation method of the manganese dioxide-polypyrrole composite electrode includes: preparing a manganese dioxide solution, wherein the specific composition of the manganese dioxide solution is 0.01-0.05M manganese acetate and 0.01-0.05M potassium chloride solution; a three-electrode system is adopted, a polypyrrole electrode is used as a working electrode, Pt is used as a counter electrode, Ag/AgCl is used as a reference electrode, scanning deposition is carried out by adopting a cyclic voltammetry method, the potential range is 0.04-1.04V, and the scanning speed is 30-50 mV/s.
The manganese dioxide-polypyrrole composite electrode prepared by the invention is observed by scanning of an SEM electron microscope.
Fig. 1 is an SEM topography of a manganese dioxide-polypyrrole composite electrode prepared according to the present invention, wherein fig. 1(a) and 1(b) are SEM images of a polypyrrole electrode, and fig. 1(c) and 1(d) are SEM images of a manganese dioxide-polypyrrole composite electrode prepared after in-situ modification of manganese dioxide on the surface of the polypyrrole electrode. As can be seen from the figure, the polypyrrole electrodes are regularly distributed in a bundle shape, and after the in-situ modification is carried out by adopting an electrochemical method, a manganese dioxide film layer is uniformly covered on the surface of the polypyrrole, so that the roughness of the composite electrode is greatly increased, and the specific surface area of the modified electrode is effectively increased. Such a three-dimensional structure is advantageous for improving the sensing performance.
The invention also aims to provide an application of the manganese dioxide-polypyrrole composite electrode in heavy metal ion detection.
The manganese dioxide-polypyrrole composite electrode provided by the invention can be used for simultaneously detecting trace heavy metals in a liquid environment, wherein the liquid environment comprises water, sweat, urine, blood, beverage, food, soil and other environments.
The manganese dioxide-polypyrrole composite electrode provided by the invention can simultaneously monitor trace heavy metals including mercury, lead and copper ions.
The manganese dioxide-polypyrrole composite electrode prepared by the invention can be directly connected with electrochemical detection equipment, realizes the real-time detection of heavy metal ions on a sampling site, does not need a complex pretreatment procedure, and can be particularly used for a portable rapid detection sensor.
The manganese dioxide-polypyrrole composite electrode prepared by the method is tested for response performance by methods of cyclic voltammetry scanning, timing current detection and the like.
FIG. 2 is a square wave voltammetry curve of the manganese dioxide-polypyrrole composite electrode prepared by the invention for detecting mercury ions with different concentrations. As can be seen from the figure, the characteristic peak current of the manganese dioxide-polypyrrole composite electrode gradually increases with the increase of the concentration of mercury ions, and the manganese dioxide-polypyrrole composite electrode prepared by the method can realize the independent detection of the mercury ions.
FIG. 3 is a performance test curve of the manganese dioxide-polypyrrole composite electrode prepared by the invention on lead ions at different scanning speeds, wherein the scanning speeds are 60mV/s, 80mV/s, 100mV/s, 120mV/s and 140 mV/s. As can be seen from the figure, the peak current of the lead ions is gradually increased along with the increase of the scanning speed, which shows that the manganese dioxide-polypyrrole composite electrode prepared by the invention has excellent response performance to the lead ions.
FIG. 4 is a linear fitting curve of peak current and ion concentration (a) cyclic voltammetry curve and (b) peak current and cyclic voltammetry curve for detecting mercury ions, lead ions and copper ions with different concentrations by using the manganese dioxide-polypyrrole composite electrode prepared by the invention. It can be seen from the figure that as the concentrations of the three heavy metal ions are gradually increased, the corresponding peak currents are also gradually increased, and the fitted curve of the ion concentration and the peak current is in a good linear relationship, which indicates that the manganese dioxide-polypyrrole composite electrode prepared by the invention has good response performance to the three heavy metal ions. Meanwhile, as can be seen from the figure, three peak positions respectively representing mercury ions, lead ions and copper ions can be obviously distinguished, which shows that the manganese dioxide-polypyrrole composite electrode prepared by the invention can realize the simultaneous detection of the mercury ions, lead ions and copper ions of three heavy metal ions.
The mercury ion, lead ion and copper ion composite electrode prepared by the invention has higher sensitivity and lower detection limit for detecting heavy metal ions of mercury, lead and copper, and can realize simultaneous detection and independent instant detection of the mercury ions, the lead ions and the copper ions.
The invention adopts an electrochemical in-situ modification method, adopts a three-electrode system, and modifies metallic nickel, polypyrrole and manganese dioxide on the surface of an electrode to form a composite electrode. The electrode combines the polypyrrole with conductivity with the manganese oxide with good catalytic activity, greatly improves the speed of ion transmission and electron transfer in the oxidation-reduction reaction process, increases the sensitivity of the electrode to metal ion detection, and reduces the detection limit. Meanwhile, the composite structure of the copolymer on the surface of the electrode and the metal increases the stability of the electrode, so that the electrode can be recycled. The composite electrode can be used for simultaneously detecting trace Hg2+、Pb2+And Cu2+Ions.
The invention has the beneficial effects that:
(1) the polypyrrole/metal oxide composite electrode has the advantages that the polypyrrole with high conductivity is compounded with the manganese dioxide with catalytic activity to form a multi-layer skeleton structure of polymer/metal oxide, the synergistic effect of the structures greatly improves the response characteristic of the electrode to heavy metal ions, meanwhile, the stability of the electrode is improved, and the reliability and accuracy of detection are improved.
(2) The electrode of the invention has simple preparation process, the electrochemical method of in-situ modification can effectively avoid the agglomeration and inactivation of particles, the cost is lower, and the invention is suitable for industrial application.
(3) The electrode provided by the invention can realize independent detection and simultaneous detection of heavy metal ion mercury, lead and copper pollutants in water, food and atmospheric environment, and promotes popularization and application of the environment rapid detection sensor.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is an SEM topography of a manganese dioxide-polypyrrole composite electrode prepared by the present invention;
FIG. 2 is a square wave voltammetry curve of the manganese dioxide-polypyrrole composite electrode prepared by the invention for detecting mercury ions with different concentrations;
FIG. 3 is a graph of the performance test of the manganese dioxide-polypyrrole composite electrode prepared by the invention on lead ions at different scanning speeds;
fig. 4 is (a) a cyclic voltammogram curve and (b) a linear fit curve of peak current to ion concentration for detection of different concentrations of mercury, lead and copper ions for manganese dioxide-polypyrrole composite electrodes prepared according to the present invention.
Detailed Description
In order that the objects, aspects and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the following detailed description and the accompanying drawings.
Example 1
Preparing a manganese dioxide-polypyrrole composite electrode:
s1, electrode pretreatment: selecting PI as a substrate material, pretreating the substrate PI, specifically placing the PI in acetone, carrying out ultrasonic treatment for 5min, cleaning with deionized water, and soaking in 2.0M hydrochloric acid solution for 10 min.
S2, preparation of a Ni layer: preparing an electrodeposited nickel solution, which comprises the following specific components: 200g/L of nickel sulfate; 20g/L of nickel chloride; 20g/L of boric acid; 0.1g/L of sodium dodecyl sulfate; the pH of the solution was adjusted to 3.0. Adopting a double-electrode constant current mode, taking a titanium mesh electrode as an anode and PI as a cathode, setting the temperature at 40 ℃ and the current density at 1.0A/dm2And performing electrodeposition treatment for 5min to obtain the Ni buffer layer.
S3, preparing a polypyrrole film layer: preparing a polypyrrole solution, which specifically comprises the following components: 30mmol/L pyrrole monomer, 0.1mol/L Na2SO420mmol/L sodium dodecyl sulfate. Putting Ni/PI electrode into prepared polypyrrole solution, adopting three-electrode system, using the above-mentioned electrode as working electrode, Pt as counter electrode and Ag/AgCl as reference electrode, applying 0.3V potential, and making electrodepositionAnd (5) keeping the time for 50s, and then placing the electrode in deionized water for ultrasonic cleaning for 3min to obtain the PPy/Ni electrode.
S4, preparation of the composite electrode: the PPy/Ni electrode is used as a substrate, and manganese dioxide is modified on the surface in situ. 0.01M manganese acetate and 0.01M potassium chloride solution are prepared. And (2) adopting a three-electrode system, taking a PPy/Ni electrode as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, and performing scanning deposition by adopting a cyclic voltammetry, wherein the potential range is 0.04V, and the scanning speed is 30mV/s to obtain the manganese dioxide-polypyrrole composite electrode.
Example 2
Preparing a manganese dioxide-polypyrrole composite electrode:
s1, electrode pretreatment: selecting ceramic as a substrate material, pretreating the substrate ceramic, specifically placing the ceramic substrate in acetone, carrying out ultrasonic treatment for 10min, removing surface stains, cleaning with deionized water, placing in a 4.0M hydrochloric acid solution, soaking for 15min, removing an oxidation layer, and roughening the surface.
S2, preparation of a Ni layer: preparing an electrodeposited nickel solution, which comprises the following specific components: 300g/L of nickel sulfate; 30g/L of nickel chloride; 30g/L of boric acid; 0.2g/L of sodium dodecyl sulfate; the pH of the solution was adjusted to 4.0. Adopting a double-electrode constant current mode, taking a titanium mesh electrode as an anode and a ceramic substrate as a cathode, setting the temperature at 50 ℃ and the current density at 5.0A/dm2And performing electrodeposition treatment for 10min to obtain the Ni buffer layer.
S3, preparing a polypyrrole film layer: preparing a polypyrrole solution, which specifically comprises the following components: 60mmol/L pyrrole monomer, 0.5mol/L Na2SO450mmol/L sodium dodecyl sulfate. And (2) putting the electrode into the prepared polypyrrole solution, adopting a three-electrode system, taking the electrode as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, applying a 0.8V potential for electrodeposition for 10s, and then putting the electrode into deionized water for ultrasonic cleaning for 5min to obtain the PPy/Ni electrode.
S4, preparation of the composite electrode: the PPy/Ni electrode is used as a substrate, and manganese dioxide is modified on the surface in situ. 0.05M manganese acetate and 0.05M potassium chloride solution were prepared. And (2) adopting a three-electrode system, taking a PPy/Ni electrode as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, and performing scanning deposition by adopting a cyclic voltammetry, wherein the potential range is 1.04V, and the scanning speed is 50mV/s to obtain the manganese dioxide-polypyrrole composite electrode.
Example 3
Preparing a manganese dioxide-polypyrrole composite electrode:
s1, electrode pretreatment: selecting a silicon substrate as a substrate material, pretreating the substrate silicon substrate, specifically placing the silicon substrate in acetone, carrying out ultrasonic treatment for 8min, removing surface stains, cleaning with deionized water, placing in a 3.0M hydrochloric acid solution, soaking for 12min, removing an oxide layer, and roughening the surface.
S2, preparation of a Ni layer: preparing an electrodeposited nickel solution, which comprises the following specific components: 250g/L of nickel sulfate; 25g/L of nickel chloride; 25g/L of boric acid; 0.15g/L of sodium dodecyl sulfate; the pH of the solution was adjusted to 3.5. Adopting a double-electrode constant current mode, taking a titanium mesh electrode as an anode and a silicon-based electrode as a cathode, setting the temperature at 45 ℃ and the current density at 3.0A/dm2And performing electrodeposition treatment for 8min to obtain the Ni buffer layer.
S3, preparing a polypyrrole film layer: preparing a polypyrrole solution, which specifically comprises the following components: 50mmol/L pyrrole monomer, 0.3mol/L Na2SO435mmol/L sodium dodecyl sulfate. And (3) placing the electrode into a prepared polypyrrole solution, adopting a three-electrode system, taking the electrode as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, applying a 0.5V potential for electrodeposition for 30s, and then placing the electrode in deionized water for ultrasonic cleaning for 4min to obtain the PPy/Ni electrode.
S4, preparation of the composite electrode: the PPy/Ni electrode is used as a substrate, and manganese dioxide is modified on the surface in situ. 0.03M manganese acetate and 0.03M potassium chloride solution were prepared. And (2) adopting a three-electrode system, taking a PPy/Ni electrode as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, and performing scanning deposition by adopting a cyclic voltammetry, wherein the potential range is 0.08V, and the scanning speed is 40mV/s to obtain the manganese dioxide-polypyrrole composite electrode.
Example 4
Preparing a manganese dioxide-polypyrrole composite electrode:
s1, electrode pretreatment: selecting FR-4 as a substrate material, pretreating the FR-4 of the substrate, specifically placing the FR-4 in acetone, carrying out ultrasonic treatment for 6min, removing surface stains, cleaning with deionized water, placing in a 4.0M hydrochloric acid solution, soaking for 11min, removing an oxide layer, and roughening the surface.
S2, preparation of a Ni layer: preparing an electrodeposited nickel solution, which comprises the following specific components: 280g/L of nickel sulfate; 28g/L of nickel chloride; 28g/L of boric acid; 0.18g/L of sodium dodecyl sulfate; the pH of the solution was adjusted to 3.0. Adopting a double-electrode constant current mode, taking a titanium mesh electrode as an anode and a silicon-based electrode as a cathode, setting the temperature at 50 ℃ and the current density at 2.0A/dm2And performing electrodeposition treatment for 9min to obtain the Ni buffer layer.
S3, preparing a polypyrrole film layer: preparing a polypyrrole solution, which specifically comprises the following components: 40mmol/L pyrrole monomer, 0.4mol/L Na2SO425mmol/L sodium dodecyl sulfate. And putting the Ni electrode into the prepared polypyrrole solution, adopting a three-electrode system, taking the electrode as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, applying a 0.7V potential for electrodeposition for 40s, and then putting the electrode into deionized water for ultrasonic cleaning for 5min to obtain the PPy/Ni electrode.
S4, preparation of the composite electrode: the PPy/Ni electrode is used as a substrate, and manganese dioxide is modified on the surface in situ. Preparing 0.04M manganese acetate and 0.04M potassium chloride solution. And (2) adopting a three-electrode system, taking a PPy/Ni electrode as a working electrode, Pt as a counter electrode and Ag/AgCl as a reference electrode, and performing scanning deposition by adopting a cyclic voltammetry, wherein the potential range is 0.06V, and the scanning speed is 35mV/s to obtain the manganese dioxide-polypyrrole composite electrode.
Example 5
Manganese dioxide-polypyrrole composite electrode for detecting heavy metal ions Hg2+：
The manganese dioxide-polypyrrole composite electrode prepared in example 1 was used as a working electrode, the reference electrode was an Ag/AgCl electrode, and a platinum electrode was used as a counter electrode. The deposition potential is 0.2V, the deposition time is 60s, the amplitude is 0.05V, the test concentration gradient is 0.8-1.3 mg/L (0.1mg/L gradient), and a square wave voltammetry curve of the composite electrode for mercury ion detection is tested to obtain an attached figure 2.
FIG. 2 shows peak current density as a function of Hg2+Increased by increasing the concentrationTherefore, the manganese dioxide-polypyrrole composite electrode prepared in example 1 has excellent response characteristics to trace mercury ions, and can be used for individual detection of trace mercury ions.
Example 6
Manganese dioxide-polypyrrole composite electrode for detecting heavy metal ions Pb2+：
The manganese dioxide-polypyrrole composite electrode prepared in example 2 was used, and an acetic acid-sodium acetate buffer solution having a pH of 3.5 was used as a test solution, and the test was performed at scan speeds of 60mV/s, 80mV/s, 100mV/s, 120mV/s, and 140mV/s, respectively. Scan 10 rounds and take the last round as the result to show, resulting in fig. 3.
Fig. 3 shows that the peak current density increases as the scanning speed increases, and thus the manganese dioxide-polypyrrole composite electrode prepared in example 2 has an excellent response characteristic to lead ions, and can be used for separate detection of trace lead ions.
Example 7
The manganese dioxide-polypyrrole composite electrode has three heavy metal ions:
the manganese dioxide-polypyrrole composite electrode prepared in example 3 was used as a working electrode, and the working electrode was placed in a 0.1mol/L acetic acid-sodium acetate buffer solution (pH 4.5), and pb was gradually added2+、Hg2+And Cu2+The mixed solution takes platinum as a counter electrode, silver-silver chloride as a reference electrode, the deposition potential is-1.3V, the deposition time is 180s, the test concentration is 1.40-2.40 mg/L, and the change curve of the peak current is measured to obtain the attached figure 4.
FIG. 4 shows that the peak current density increases with the concentration of the mixed solution, and three completely different oxidation peaks appear, corresponding to Pb, respectively2+、Hg2+And Cu2+Three heavy metal elements, therefore, the manganese dioxide-polypyrrole composite electrode prepared in example 3 can simultaneously detect trace heavy metal elements of lead ions, mercury ions and copper ions.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single technical solution, and such description is for clarity only, and those skilled in the art should take the description as a whole, and the technical solutions in the embodiments may be combined appropriately to form other embodiments that those skilled in the art can understand. The technical details not described in detail in the present invention can be implemented by any of the prior arts in the field. In particular, all technical features of the invention which are not described in detail can be achieved by any prior art.
Claims (10)
1. A manganese dioxide-polypyrrole composite electrode takes a metal electrode as a substrate, comprises a working electrode, a reference electrode and an auxiliary electrode, and comprises an electrode substrate and an electrode modification layer.
2. The manganese dioxide-polypyrrole composite electrode according to claim 1, wherein the manganese dioxide-polypyrrole modification layer has a three-dimensional bundle structure, the width of the binding band is 1.5-2.0 μm, and manganese dioxide particles are uniformly modified on the surface of polyaniline and have a particle size of 5-20 nm.
3. The method for preparing a manganese dioxide-polypyrrole composite electrode according to claim 1 or 2, characterized by comprising the following steps:
s1, preparation of a Ni layer: preparing a Ni buffer layer on the surface of the electrode substrate by adopting an electrodeposition method to obtain a nickel electrode;
s2, preparing a polypyrrole film layer: preparing a polypyrrole electrode by taking a nickel electrode as a substrate and adopting an electrodeposition method;
s3, preparing a manganese dioxide-polypyrrole composite electrode: and modifying manganese dioxide on the surface of the polypyrrole electrode serving as a substrate in situ to obtain the manganese dioxide-polypyrrole composite electrode.
4. The method of claim 3, wherein in step S1, the electrodeposition process comprises: preparing a nickel plating solution, specifically 200-300 g/L nickel sulfate, 20-30 g/L nickel chloride, 20-30 g/L boric acid and 0.1-0.2 g/L sodium dodecyl sulfate, and adjusting the pH value of the solution to 3.0-4.0; adopting a double-electrode constant current mode, taking a titanium mesh electrode as an anode and an electrode substrate as a cathode, setting the temperature to be 40-50 ℃, and the current density to be 1.0-5.0A/dm2The electrodeposition time is 5-10 min.
5. The method for preparing a manganese dioxide-polypyrrole composite electrode according to claim 3, wherein in step S2, the method for preparing the polypyrrole film layer is: and (3) taking the nickel electrode as a working electrode, putting the nickel electrode into a polypyrrole solution, taking Pt as an auxiliary electrode and Ag/AgCl as a reference electrode, applying a potential of 0.3-0.8V for electrodeposition time of 10-50 s, and then placing the nickel electrode in deionized water for ultrasonic cleaning for 3-5 min.
6. The method of claim 5, wherein the polypyrrole solution comprises: 30-60 mmol/L pyrrole monomer, 0.1-0.5 mol/L Na2SO420-50 mmol/L sodium dodecyl sulfate.
7. The method of claim 3, wherein in step S3, the method of preparing the manganese dioxide-polypyrrole composite electrode is: preparing a manganese dioxide solution, wherein the specific composition of the manganese dioxide solution is 0.01-0.05M manganese acetate and 0.01-0.05M potassium chloride solution; a three-electrode system is adopted, the polypyrrole electrode is used as a working electrode, Pt is used as a counter electrode, Ag/AgCl is used as a reference electrode, scanning deposition is carried out by adopting a cyclic voltammetry method, the potential range is 0.04-1.04V, and the scanning speed is 30-50 mV/s.
8. Use of a manganese dioxide-polypyrrole composite electrode according to any one of claims 1 to 7 in heavy metal ion detection.
9. The use of the manganese dioxide-polypyrrole composite electrode according to claim 8, wherein the manganese dioxide-polypyrrole composite electrode can simultaneously detect trace heavy metals in liquid environments, including water, sweat, urine, blood and beverage, food and soil.
10. The use of manganese dioxide-polypyrrole composite electrode according to claim 9, wherein said trace heavy metals include mercury, lead and copper ions.
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