CN114563460A - Preparation based on bismuth film and two-dimensional graphite alkyne sensor and application of sensor in one-step detection of multi-component heavy metal ions - Google Patents

Preparation based on bismuth film and two-dimensional graphite alkyne sensor and application of sensor in one-step detection of multi-component heavy metal ions Download PDF

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CN114563460A
CN114563460A CN202210183087.5A CN202210183087A CN114563460A CN 114563460 A CN114563460 A CN 114563460A CN 202210183087 A CN202210183087 A CN 202210183087A CN 114563460 A CN114563460 A CN 114563460A
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gdy
gce
sensor
electrode
heavy metal
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孙伟
艾益静
叶翔
闫丽君
姚昱岑
孙云秀
王宝丽
邵波
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Hainan Normal University
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    • G—PHYSICS
    • 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
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
    • G—PHYSICS
    • 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
    • G01N27/416—Systems
    • G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species

Abstract

The invention designs preparation of an electrochemical sensor based on a bismuth film (Bi) and two-dimensional graphite alkyne (GDY) and application of the electrochemical sensor in one-step detection of various heavy metal ions. Prepared by a dripping coating method and an electrodeposition method, can sensitively detect Zn in one step2+、Cd2+、Pb2+The electrochemical sensor (Bi/GDY/GCE). The method mainly comprises the following steps of (1) preparing a sensor: with Al2O3Polishing powder a Glassy Carbon Electrode (GCE) was polished on a chamois, and then the electrode was cleaned with ultrapure water. The GDY solution was applied drop-wise to the surface of the GCE and after drying at room temperature a bismuth film was electrodeposited. (2) Application of the sensor: the constructed electrochemical sensor is used for three heavy metal ions Zn through adsorption stripping voltammetry2+、Cd2+、Pb2+And (4) detecting in one step. The invention has simple process, low manufacturing cost, high detection efficiency and measurement effectIs remarkable in that.

Description

Preparation based on bismuth film and two-dimensional graphite alkyne sensor and application of sensor in one-step detection of multi-component heavy metal ions
Technical Field
The invention belongs to the field of preparation of electrochemical sensors and analysis of heavy metal ions, and relates to preparation of a sensor based on a bismuth film and a two-dimensional GDY and application of the sensor in one-step detection of multi-component heavy metal ions.
Background
The industries of paint, battery production, pesticide, paper making and the like can discharge a large amount of waste water and waste residue containing heavy metal ions, so that the pollution is increasingly serious. The high content of heavy metals such as zinc, cadmium and lead in the environment and food is becoming a fatal threat. These heavy metals are not biodegradable and can accumulate in human organs and tissues through the food chain and drinking water and exceed critical limits leading to serious diseases. The zinc has important function in human body, but the excessive zinc can cause the liver or the kidney to lose function, thereby causing the olfactory loss. Cadmium can be combined with protein molecules containing hydroxyl, amino and sulfhydryl groups in human bodies, so that a plurality of enzyme systems are inhibited, and various cancers, cardiovascular diseases and osteoporosis are caused. Lead ions in the environment can lead to death of the child, severe damage to the brain and kidneys, manifested as nephropathy and colic-like abdominal pain. Therefore, the development of a sensitive, simple, cheap and reliable analysis method is crucial to monitoring and early warning the concentration of heavy metal ions in the water environment.
The detection methods reported at present mainly include atomic absorption spectrometry, spectrophotometry, fluorescence, inductively coupled plasma emission spectrometry, etc., and these analysis methods often require trained analysts, precise instruments, long-time detection and tedious sample preparation, which limits their application in daily production and life. Compared with the traditional method, the Adsorption Stripping Voltammetry (ASV) is widely concerned, and has the advantages of high efficiency, simple operation, high response speed, low cost, high sensitivity and the like. Zn in water environment2+、Pb2+And Cd2+The content of (A) is usually trace level, while the existing electrochemical sensor has low sensitivity and cannot detect multi-component heavy metal ions efficiently, so that the preparation of a sensor with higher sensitivity and higher detection efficiency is urgently neededHigh and faster response speed of the electrochemical sensor.
Graphene (GDY) is a new all-carbon nanostructured material following fullerenes, carbon nanotubes, graphene. Compared with graphene, GDY has more abundant carbon chemical bonds and a large conjugated system, and an electrochemical sensor constructed based on GDY usually shows higher sensitivity and better chemical stability. Bismuth as a green metal has low toxicity and good electrochemical performance, can form an alloy with various heavy metals, and provides possibility for one-step detection of multi-component heavy metal ions. The electrochemical sensor constructed by taking the bismuth film and the two-dimensional graphdine as the substrate realizes the Zn-Zn couple2+、Cd2+、Pb2+The one-step detection has stronger application significance in the field of environmental monitoring.
Disclosure of Invention
In view of the problems of the prior art, the invention aims to provide a high-sensitivity one-step detection method for Zn2+、Cd2 +、Pb2+The electrochemical sensor and the preparation method.
The purpose of the invention can be realized by the following technical scheme:
is used for Zn2+、Cd2+、Pb2+The preparation method of the electrochemical sensor with one-step detection comprises the following steps:
(1) with Al2O3Polishing a Glassy Carbon Electrode (GCE) on chamois leather for about 1-2 minutes by using polishing powder, and then cleaning the electrode by using ultrapure water; dripping GDY suspension liquid on the surface of GCE, and drying to obtain modified electrode GDY/GCE;
(2) and (3) continuously immersing GDY/GCE into the bismuth salt solution, electrodepositing a bismuth film, and then drying by using nitrogen to obtain the modified electrode Bi/GDY/GCE.
Preferably, in step (1), the GDY/GCE preparation process comprises: 5 mu L of GDY suspension with the concentration of 5.0 mg/mL is dripped on the surface of the treated GCE, and the mixture is dried by an infrared lamp to obtain the modified electrode GDY/GCE.
Preferably, the GDY suspension is prepared by the following steps: to GDY powder, ultrapure water was added, followed by ultrasonic dispersion for 30 min with a cell disruptor, to give a GDY suspension of 5.0 mg/mL.
Preferably, in the step (2), the process of electrodepositing the bismuth film is as follows: GDY/GCE was immersed in 0.1 mM Bi (NO)3)3In the aqueous solution (2), Ag/AgCl was used as a reference electrode, a platinum wire electrode was used as a counter electrode, chronoamperometry (i-t) was used, a deposition potential was-1.1V, and a deposition time was 120 s.
The application of the Bi/GDY/GCE in one-step detection of the concentration of multi-component heavy metal ions in a water environment is based on a bismuth film and a two-dimensional GDY sensor.
Synchronous detection of Zn in water environment2+、Cd2+And Pb2+The concentration method, in the step (2), based on the application of the Bi/GDY/GCE electrochemical sensor, comprises the following steps: using a three-electrode system, taking Bi/GDY/GCE as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode and Zn2+、Cd2+、Pb2+Detection of Zn in water environment by adsorption stripping voltammetry in mixed electrolyte solution2+、Cd2+And Pb2+Electrochemical dissolution signal of (1).
Preferably, a series of Zn with different concentrations is enriched in a constant potential under the condition of stirring2+、Cd2+、Pb2+Standard buffer (the enrichment potential is preferably-1.3V, the enrichment time is preferably 150 s, the buffer solution is preferably HAc-NaAc with pH 6.0), then dissolving (the dissolution potential scanning range is-1.3V to 0.2V) to obtain anodic dissolution peak current, and according to the anodic dissolution peak current and Zn2+、Cd2+、Pb2+Drawing a working curve according to the logarithm of the concentration of each ion in the standard buffer solution, and using the drawn working curve to perform Zn treatment on Zn in the water environment2+、Cd2+、Pb2+And (6) detecting.
The Bi/GDY/GCE electrochemical sensor provided by the invention is selectively measured by the following method: adding other solution containing interfering ions to the solution containing Zn2+、Cd2+、Pb2+The HAc-NaAc (b) was subjected to adsorption and elution by the same method under the same conditions as described aboveAnd (3) performing voltammetry measurement, researching the change of the anodic dissolution characteristic peak potential and peak current of the three heavy metal ions, and inspecting the selection performance of the electrochemical sensor. Wherein the interfering ion is Ni2+、Co2+、Fe3+、Cu2+、Fe2+、Mg2+、Ca2+、Mn2+And Cl-。
The stability of the Bi/GDY/GCE electrochemical sensor is measured by the following method: the prepared Bi/GDY/GCE was stored in a refrigerator at 4 ℃ for 6 days, and Zn was investigated by performing adsorption stripping voltammetry every day under the same conditions by the same method as described above2+、Cd2+、Pb2+And observing the stability of the electrochemical sensor by the change of the anode dissolution characteristic peak potential and the peak current.
The stripping peak potentials of metal ions in the anodic stripping voltammetry are different, and the stripping peak current is in direct proportion to the ion concentration, so that an effective and rapid platform is provided for real-time detection of a target object.
The material modified by the electrochemical sensor prepared by the invention is Bi/GDY, has better conductivity and better property of enriching heavy metal cations, can enhance the enrichment of the working electrode on the heavy metal cations under the measured potential condition, enables the heavy metal ions to be easily deposited, prevents the working electrode from separating hydrogen, realizes one-step detection of multi-component heavy metal ions, simultaneously improves the one-step detection flux, has lower detection limit and wider linear range. In particular, the modified electrode material Bi and heavy metal ions form an alloy, so that the enrichment capacity of the heavy metal ions is enhanced. GDY has large surface area and electron transmission capability, and is beneficial to the deposition and signal transmission of bismuth film. The enrichment performance of Bi and GDY on heavy metal ions is enhanced by the synergistic effect of Bi and GDY, and Bi is uniformly dispersed on GDY with better conductivity, so that the specific surface area of the composite material is larger, the electron transfer rate is better, and the one-step high-sensitivity detection of various heavy metal ions is facilitated.
The electrochemical sensor can realize heavy metal Zn2+、Cd2+、Pb2+For Zn in a highly sensitive one-step assay2+、Cd2+、Pb2 +The detection limits of (a) are respectively: 1.46 pM, 1.15 pM, 1.71 pM, linear range 100 pM-100. mu.M.
Drawings
FIG. 1 shows Bi/GDY/GCE prepared in test example 1 at 1 mM K3[Fe(CN)6]And cyclic voltammetry curves in 0.5M KCl mixed electrolyte at different sweep rates;
FIG. 2 shows the oxidation peak current vs. upsilon of Bi/GDY/GCE prepared in test example 1 at different sweep rates1/2The linear relationship of (a);
FIG. 3 shows the results of test example 1 for (a) GCE, (b) GDY/GCE, (c) Bi/GCE, (d) Bi/GDY/GCE at 100. mu.M Zn2+、Cd2+、Pb2+ Adsorption dissolution voltammogram in HAc-NaAc mixed electrolyte with pH of 6.0;
FIG. 4 shows the different volumes of 5.0 mg/mL GDY in test example 1 of Bi/GDY/GCE at 100. mu.M Zn2+、Cd2+、Pb2+Adsorption-elution voltammogram in the HAc-NaAc (pH 6.0) mixed electrolyte solution of (1);
FIG. 5 is an optimization chart of different types of buffer solutions of test example 1;
FIG. 6 is an optimized graph of different pH values of test example 1;
FIG. 7 is an optimization plot of different enrichment potentials for test example 1;
FIG. 8 is a graph of the optimization of different enrichment times for test example 1;
FIG. 9 shows the Bi/GDY/GCE prepared in test example 2 at different concentrations of Zn2+、Cd2+、Pb2+Adsorption-elution voltammogram in HAc-NaAc (pH 6.0) mixed electrolyte;
FIG. 10 shows the prepared Bi/GDY/GCE at different concentrations of Zn2+、Cd2+、Pb2+The dissolution peak current and log in the electrolyte solution of (2)CThe linear relationship of (a);
FIG. 11 shows the results of the preparation of Bi/GDY/GCE in test example 2 in the presence of Zn without interfering ions (curve a) and with 100. mu.M interfering ions (curve b), respectively2+、Cd2+、Pb2+Adsorption and dissolution curve in HAc-NaAc (pH 6.0) mixed electrolyte, and interference ions are Ni2+、Co2+、Fe3+、Cu2+、Fe2+、Mg2+、Ca2+、Mn2+Or Cl-；
FIG. 12 shows that the Bi/GDY/GCE prepared in test example 2 was stored in a refrigerator at 4 ℃ for 6 days at 100. mu.M Zn2+、Cd2+、Pb2+The dissolution peak current in the HAc-NaAc (pH 6.0) mixed electrolyte of (1).
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The invention provides a preparation method of an electrochemical sensor for detecting multi-component heavy metal ions at one step with high sensitivity, which comprises the following steps:
(1) with Al2O3Polishing a Glassy Carbon Electrode (GCE) on chamois leather for about 1-2 minutes by using polishing powder, and then cleaning the electrode by using ultrapure water; dripping GDY suspension liquid on the surface of GCE, and drying to obtain modified electrode GDY/GCE;
(2) and (3) continuously immersing GDY/GCE into the bismuth salt solution, electrodepositing a bismuth film, and then drying by using nitrogen to obtain the modified electrode Bi/GDY/GCE.
In the step (1), the GDY/GCE preparation process comprises the following steps: 5 μ L of GDY suspension with a concentration of 5.0 mg/mL was dispensed onto the treated GCE surface and dried with an infrared lamp to obtain a modified electrode GDY/GCE.
In the step (2), the process of electrodepositing the bismuth film comprises the following steps: GDY/GCE was immersed in 0.1 mM Bi (NO)3)3In the aqueous solution (2), Ag/AgCl was used as a reference electrode, a platinum wire electrode was used as a counter electrode, and chronoamperometry (i-t) was used, with a deposition potential of-1.1V and a deposition time of 120 s.
The invention also provides an electrochemical sensor for detecting the concentration of the multi-component heavy metal ions in the water environment in one step, which is prepared by adopting the method.
The invention also provides a method for detecting Zn in water environment in one step2+、Cd2+And Pb2+The electrochemical sensor of concentration in (1), the detection method is as follows: using a three-electrode system, taking Bi/GDY/GCE as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, and adopting an adsorption stripping voltammetry to remove Zn in a water environment2+、Cd2+And Pb2+And (6) detecting. Firstly, a series of Zn with different concentrations are enriched at constant potential under the condition of stirring2+、Cd2+、Pb2+Standard buffer solution, then dissolving to obtain anode dissolving peak current, according to the anode dissolving peak current and Zn2+、Cd2+、Pb2+Drawing a working curve according to the logarithm of the concentration of each ion in the standard buffer solution, and using the drawn working curve to perform Zn treatment on Zn in the water environment2+、Cd2+、Pb2+And (6) detecting.
Example 1:
the preparation method of the electrochemical sensor for detecting the multi-component heavy metal ions in one step comprises the following steps:
(1) pretreating a glassy carbon electrode. First, 0.3 μm, 0.1 μm, 0.05 μm Al was used2O3Polishing the glassy carbon electrode on chamois by polishing powder, then performing ultrasonic treatment for 3 min by using water, ethanol and water respectively, finally cleaning the electrode by using ultrapure water, and drying the electrode by using nitrogen for later use.
(2) GDY/GCE preparation. GDY was sonicated in ultrapure water for 30 min to form a homogeneous suspension of GDY at 5.0 mg/mL. And (3) dropwise coating 5 mu L of GDY suspension on the surface of the pretreated GCE, and drying by using an infrared lamp to obtain GDY/GCE modified electrode.
(3) Preparation of Bi/GDY/GCE. 0.1 mM Bi (NO) is added into a three-electrode system with GDY/GCE as a working electrode, Ag/AgCl as a reference electrode and a platinum wire electrode as a counter electrode3)3The solution is an electrolyte solution, a bismuth film is electrodeposited on the surface of GDY/GCE by a chronoamperometry (i-t), the deposition potential is-1.1V, the deposition time is 120 s, and then the modified electrode Bi/GDY/GCE is obtained by washing with ultrapure water and drying with nitrogen.
Example 2:
zn was carried out using the Bi/GDY/GCE electrochemical sensor prepared in example 12+、Cd2+、Pb2+The step (2) of detecting.
Stripping Zn by adsorption voltammetry2+、Cd2+And Pb2+The concentration was measured in one step using a three-electrode system with Bi/GDY/GCE as the working electrode, Ag/AgCl as the reference electrode and a platinum wire as the counter electrode. Firstly, a series of Zn with different concentrations are enriched at constant potential under the condition of stirring2+、Cd2+、Pb2+Standard buffer, enrichment potential-1.3V, enrichment time 150 s, buffer solution is HAc-NaAc with pH 6.0. Then dissolving out, wherein the scanning range of the dissolving out potential is-1.3V to 0.2V, and obtaining the anode dissolving out peak current. When the concentration of the heavy metal ion is increased, the peak current value is also increased accordingly, because the amount of the heavy metal ion adsorbed to the surface of Bi/GDY/GCE is increased. According to the size of the anode dissolution peak current and Zn2+、Cd2+、Pb2+Drawing a working curve for the logarithm of each ion concentration in the standard buffer solution, namely drawing Zn in the water environment2+、Cd2+、Pb2+The quantitative detection is carried out, the detection limit is respectively 1.46 pM, 1.15 pM and 1.71 pM, and the linear range is 100 pM-100 mu M.
Example 3:
the Bi/GDY/GCE electrochemical sensor prepared in example 1 was tested for selectivity and stability.
Stripping of Zn by adsorption voltammetry2+、Cd2+And Pb2+One-step detection is carried out, and the Bi/GDY/GCE electrochemical sensor is selectively measured by the following method: adding other solution containing interfering ions to the solution containing Zn2+、Cd2+、Pb2 +In HAc-NaAc, the change of the peak potential and the peak current of the anodic stripping characteristic of three heavy metal ions was investigated by performing the adsorption stripping voltammetry measurement under the same conditions by the same method as described above, and the selectivity of the electrochemical sensor was examined. Wherein the interfering ion is Ni2+、Co2+、Fe3+、Cu2+、Fe2+、Mg2+、Ca2+、Mn2+Or Cl-The concentration was 100. mu.M. After the addition of interfering ions, Zn2+、Cd2+、Pb2+The deviation of the peak potential of (2) is 3.6 percent, the peak position is not obviously changed, and other dissolution peaks do not appear, which indicates that the electrochemical sensor has good selectivity. Further, the stability of the electrochemical sensor of Bi/GDY/GCE of the present invention was measured, and the prepared Bi/GDY/GCE was stored in a refrigerator at 4 ℃ for 6 days, and then subjected to the adsorption stripping voltammetry measurement under the same conditions and daily for Zn investigation by the same method as described above2+、Cd2+、Pb2+And observing the stability of the electrochemical sensor by the change of the anode dissolution characteristic peak potential and the peak current. The peak current RSD was 5.2%, indicating that the electrochemical sensor had good stability in a 4 ℃ refrigerator.
Test example 1
GCE (a), GDY/GCE (b), Bi/GCE (c) and Bi/GDY/GCE (d) prepared in example 1 were used as working electrodes, Ag/AgCl electrode as a reference electrode and platinum wire as a counter electrode, and the three electrodes were placed in an electrolyte solution and subjected to electrochemical tests using cyclic voltammetry and adsorption stripping voltammetry.
FIG. 1 shows GDY/GCE prepared in example 1 at 1 mM K3[Fe(CN)6]And cyclic voltammograms at different sweep rates in 0.5M KCl mixed electrolyte, it can be seen from FIG. 1 that as the sweep rate increases, the redox peak potentials respectively shift to the positive direction and the negative direction, and the redox peak currents also gradually increase with the increase of the sweep rate.
FIG. 2 shows the oxidation peak current vs. upsilon of prepared GDY/GCE at different sweep rates1/2Is shown in figure 2, it can be seen that the redox peak current is related to upsilon1/2In a good linear relationship. The effective area of GDY/GCE is 0.162 cm by calculation2。
FIG. 3 shows the results of the preparation of GCE, GDY/GCE, Bi/GCE and Bi/GDY/GCE in 100. mu.M Zn in example 12+、Cd2+、Pb2+The stripping voltammogram by adsorption in the HAc-NaAc (pH 6.0) mixed electrolyte solution of (2). As shown in FIG. 3, the peak currents of the bare GCE (curve a) and GDY/GCE (curve b) do not vary much. The peak current signal of Bi/GCE (curve d) is increased compared with curves a and b, which indicates that the bismuth film is favorable for Zn2+、Cd2+、Pb2+Deposit on the surface of the electrode, thereby improving the ions to be measuredThe dissolution signal of (1). The peak current of Bi/GDY/GCE (curve d) is obviously increased because the deposited metal bismuth film and GDY have a synergistic effect, GDY can effectively increase the surface area of the electrode, and is beneficial to the formation of alloy by metal ions to be detected and bismuth elementary substance on the surface of the electrode, so that Zn is further enabled2+、Cd2+、Pb2+The dissolution signal at Bi/GDY/GCE is significantly increased.
FIG. 4 is an optimization plot of drop volume for a 5.0 mg/mL GDY suspension as described in example 1. The drop volumes were 1. mu.L, 2. mu.L, 3. mu.L, 4. mu.L, 5. mu.L, 6. mu.L, 7. mu.L, respectively, and the infrared lamp was baked to obtain 7 kinds of GDY/GCE electrodes. Then containing 100 μ M Zn2+、Cd2+、Pb2+The electrochemical performance of the electrode is tested by an adsorption stripping voltammetry method in HAc-NaAc (pH 6.0) mixed electrolyte, the enrichment potential is-1.3V, and the enrichment time is 150 s. As a result, the optimum volume of the GDY suspension was found to be 5. mu.L.
Test example 2
FIG. 5 is an optimization chart of the kind of buffer solution in example 2. The experiment optimizes 4 kinds of buffer solutions, namely BR, HAc-NaAc, PBS and Tris-HCl. As shown in FIG. 5, Bi/GDY/GCE showed the highest dissolution signal among HAc-NaAc, so HAc-NaAc was selected as the optimal buffering environment for this experiment.
FIG. 6 is a graph of pH optimization for HAc-NaAc in example 2. The test was conducted on the detection performance of Bi/GDY/GCE in HAc-NaAc with pH values of 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, respectively. As shown in FIG. 6, Bi/GDY/GCE showed the highest dissolution signal when HAc-NaAc had a pH of 6.0, so that the optimum pH was 6.0 in this experiment.
FIG. 7 shows Zn mapping of example 22+、Cd2+、Pb2+The enrichment potential of (2) optimizes the graph. In the experiment, Bi/GDY/GCE is enriched in a solution to be detected for 150 s at a potential of-0.9, -1.0, -1.1, -1.2, -1.3, -1.4, -1.5V respectively, and dissolution signals of the Bi/GDY/GCE are detected. As shown in FIG. 7, Bi/GDY/GCE showed the highest dissolution signal when the enrichment potential was-1.3V, so that-1.3V was selected as the optimum enrichment potential in this experiment.
FIG. 8 shows Zn mapping of example 22+、Cd2+、Pb2+The enrichment time of (2) is optimized. In the experiment, Bi/GDY/GCE is used for enriching 60 s, 90 s, 120 s, 150 s, 180 s, 210 s and 240 s in a solution to be detected at a potential of-1.3V respectively, and dissolution signals of the solution are detected. As shown in FIG. 8, Bi/GDY/GCE showed the highest dissolution signal at an enrichment time of 150 s, so that 150 s was the optimal enrichment time for this experiment.
FIG. 9 shows Bi/GDY/GCE prepared in example 2 with Zn concentrations of 100 pM, 1 nM, 10 nM, 100 nM, 1. mu.M, 2. mu.M, 4. mu.M, 6. mu.M, 8. mu.M, 10. mu.M, 20. mu.M, 40. mu.M, 60. mu.M, 80. mu.M, 100. mu.M, respectively2+、Cd2+、Pb2+The stripping voltammetry by adsorption in the mixed electrolyte of (1). The result is shown in FIG. 9, the current signal increases with the increase of the metal ion concentration, which shows that Bi/GDY/GCE has good one-step Zn detection2+、Cd2+、Pb2+The ability of the cell to perform.
FIG. 10 shows the prepared Bi/GDY/GCE at different concentrations of Zn2+、Cd2+、Pb2+The dissolution peak current and log in the electrolyte solution of (2)CFrom FIG. 10, it can be seen that the peak current is related to the logCThe detection limits are 1.46 pM, 1.15 pM and 1.71 pM respectively, and the linear range is 100 pM-100 mu M.
Test example 3
FIG. 11 shows the presence or absence of interfering ions (Ni) in the electrochemical sensor of Bi/GDY/GCE prepared in example 32+、Co2 +、Fe3+、Cu2+、Fe2+、Mg2+、Ca2+、Mn2+Or Cl-) Zn of (2)2+、Cd2+、Pb2+The adsorption stripping voltammogram in the mixed electrolyte of (1) was 100. mu.M in ion concentration. The results are shown in FIG. 11, Zn2+、Cd2+、Pb2+The current deviation of the dissolution peak is not more than 3.6%, the peak position is not obviously changed, and other dissolution peaks do not appear, which indicates that the electrochemical sensor has good selectivity.
FIG. 12 shows Bi/G prepared in example 3DY/GCE was stored in a refrigerator at 4 ℃ for 6 days, and the stability of the electrochemical sensor was examined by performing adsorption stripping voltammetry every day under the same conditions using the same method as described above. As a result, Zn is shown in FIG. 122+、Cd2+、Pb2+The RSD of the dissolution peak current of (a) was 5.2%, indicating that the electrochemical sensor has good stability in a refrigerator at 4 ℃.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (8)

1. Preparation of a sensor based on a bismuth film and two-dimensional GDY and application of the sensor in one-step detection of multi-component heavy metal ions, characterized in that the method comprises the following steps:
(1) with Al2O3Polishing a Glassy Carbon Electrode (GCE) on chamois leather for about 1-2 minutes by using polishing powder, and then cleaning the electrode by using ultrapure water; dripping GDY suspension liquid on the surface of GCE, and drying to obtain modified electrode GDY/GCE;
(2) immersing the modified electrode GDY/GCE obtained in the step (1) into a bismuth salt solution, electrodepositing a bismuth film, and then drying by using nitrogen to obtain a modified electrode Bi/GDY/GCE;
(3) soaking the modified electrode Bi/GDY/GCE obtained in the step (2) into Zn2+、Cd2+、Pb2+And detecting a stripping electrochemical signal in a sample to be detected by using an adsorption stripping voltammetry method in the mixed electrolyte solution.
2. The preparation of a two-dimensional GDY sensor based on a bismuth film according to claim 1, wherein the GDY suspension concentration in step (1) is 5.0 mg/mL, the drop volume is 5 μ L, and the drying is infrared lamp drying.
3. The GDY suspension configuration process of claim 2, being: GDY was added ultrapure water, followed by sonication for 30 min with a cell disruptor to give a homogeneous suspension of GDY at 5.0 mg/mL.
4. The preparation of the Bi/GDY/GCE sensor according to claim 1, 2 and 3, wherein the bismuth salt solution in step (2) is 0.1 mM Bi (NO)3)3The method for electrodepositing the bismuth film by using the solution is a chronoamperometry (i-t), the deposition potential is-1.1V, and the deposition time is 120 s.
5. A bismuth film and two-dimensional GDY based sensor as claimed in claims 1, 2, 3, and 4 for detecting Zn in one step2+、Cd2+、Pb2+Characterized in that Zn is contained in the step (3)2+、Cd2+、Pb2+The mixed electrolyte solution is metal ion concentration of 100 pM-100 μ M, and the buffer solution is acetic acid-sodium acetate (HAc-NaAc, pH 6.0).
6. The use of a bismuth-based membrane and a two-dimensional GDY sensor for the detection of multi-component heavy metal ions in one step according to claim 5, wherein the method in step (3) comprises: a three-electrode system is used, a sensor is used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode, the enrichment potential of adsorption stripping voltammetry is-1.3V, and the enrichment time is 150 s.
7. A method of making a bismuth film based and two dimensional GDY sensor, wherein the electrochemical sensor is made by the method of claims 1 to 4.
8. Use of an electrochemical sensor according to claim 7 for the single-step detection of heavy metal ions Zn in an aqueous environment2+、Cd2+、Pb2+The sensor has good selectivity and stability during application.
CN202210183087.5A 2022-02-27 2022-02-27 Preparation based on bismuth film and two-dimensional graphite alkyne sensor and application of sensor in one-step detection of multi-component heavy metal ions Pending CN114563460A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115266866A (en) * 2022-08-08 2022-11-01 兰州大学 Graphite alkyne/bismuth nanodot composite electrode and method for electrochemically detecting lead ions by using same
CN116726908A (en) * 2023-08-14 2023-09-12 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) Bismuth-doped high-performance electrocatalytic composite material, preparation method and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115266866A (en) * 2022-08-08 2022-11-01 兰州大学 Graphite alkyne/bismuth nanodot composite electrode and method for electrochemically detecting lead ions by using same
CN116726908A (en) * 2023-08-14 2023-09-12 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) Bismuth-doped high-performance electrocatalytic composite material, preparation method and application
CN116726908B (en) * 2023-08-14 2023-11-10 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) Bismuth-doped high-performance electrocatalytic composite material, preparation method and application

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