CN110542712B - Preparation method of electrochemical sensor for detecting copper ions with high sensitivity - Google Patents

Preparation method of electrochemical sensor for detecting copper ions with high sensitivity Download PDF

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CN110542712B
CN110542712B CN201910894550.5A CN201910894550A CN110542712B CN 110542712 B CN110542712 B CN 110542712B CN 201910894550 A CN201910894550 A CN 201910894550A CN 110542712 B CN110542712 B CN 110542712B
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polyvinylpyrrolidone
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韦寿莲
黄象金
谢春生
何桦强
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Zhaoqing University
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Abstract

The invention relates to a preparation method of an electrochemical sensor for sensitively detecting copper ions, which comprises the following steps: synthesizing a polyvinylpyrrolidone (PVP)/cobalt oxyhydroxide composite material by a hydrothermal method; and dripping the polyvinylpyrrolidone/cobalt oxyhydroxide dispersion liquid on a glassy carbon electrode, and drying under an infrared lamp to obtain the electrochemical sensor. The cobalt oxyhydroxide has good electrochemical catalytic activity, the complexing action of heteroatoms (nitrogen and oxygen atoms) in the polyvinylpyrrolidone and copper ions shows high selectivity, and the combination of the two results enables the electrochemical sensor of the invention to have high specific response to the copper ions, thereby realizing the sensitive detection of trace copper ions. The electrochemical sensor provided by the invention has the advantages of simple preparation, low cost, good stability, wide linear range and high sensitivity and selectivity, and provides a quick, effective, sensitive and high-accuracy method for detecting copper in soil, water and food.

Description

Preparation method of electrochemical sensor for detecting copper ions with high sensitivity
Technical Field
The invention belongs to the field of electrochemical sensors, relates to a preparation method of a heavy metal ion electrochemical sensor, and particularly relates to a preparation method of an electrochemical sensor for detecting copper ions with high sensitivity.
Background
Over the past decades, industrial farming activities such as metallurgy and plastics production, pesticide and fertilizer use, as well as fossil fuel and mining processes, have increasingly discharged large amounts of heavy metals into agricultural soils and environmental water sources, resulting in heavy metal contamination. Heavy metals have the characteristics of high toxicity, nonbiodegradability, easy biological enrichment and the like, and even heavy metal pollution with extremely low concentration can cause serious harm to the ecological environment and human health. Copper is a heavy metal widely used by human beings and a trace element necessary for human bodies, but excessive intake of copper causes potential health problems. Therefore, the method has important significance for realizing on-site rapid, high-sensitivity and accurate monitoring of trace copper ions in environment and food.
At present, methods for detecting trace copper ions mainly include atomic absorption spectrometry, inductively coupled plasma emission spectrometry, inductively coupled plasma mass spectrometry and the like, and most of the methods have the defects of expensive and complex instruments, high detection cost, inconvenience for field analysis and the like, so that the wide application of the methods is limited. In contrast, the electrochemical sensor is considered to be an effective method for measuring heavy metal ions due to the advantages of low detection limit, high response speed, capability of simultaneously measuring multiple elements, low cost, simplicity in operation, good portability and the like. For a heavy metal ion sensor, the sensitivity, the reproducibility, the selectivity and the stability of the heavy metal ion sensor depend on the performance of a working electrode sensing interface material, so that the research and the search of a suitable modified electrode material are the key points for constructing an electrochemical sensor with excellent performance. Electrochemical sensors based on different modified materials have been applied to trace detection of copper ions, such as materials of carbon nitride, graphene, carbon nanotubes, gold and silver nanoparticles, but these materials have the problems of complex preparation process, high price, poor dispersibility and stability, easy aggregation after modification, low sensitivity and the like, and lack of application prospects. Therefore, the development of a novel material with simple preparation method, low cost, good dispersibility and excellent electrochemical performance applied to the modified electrode is a key technology for solving the problem of on-site monitoring of trace copper ions.
Disclosure of Invention
The invention solves the technical problem of overcoming the defects of the prior art and provides a novel preparation method of a copper ion electrical sensor based on polyvinylpyrrolidone/cobalt oxyhydroxide, and the prepared copper ion electrochemical sensor has the advantages of simple and practical method, low cost, high sensitivity and selectivity and good reproducibility, and can be applied to field monitoring of trace copper ions in environmental soil water and food.
In order to solve the technical problem, the invention provides a method for preparing an electrochemical sensor for sensitively detecting copper ions, which comprises the following steps:
s1, adding soluble cobalt salt, an oxidant and a precipitator into the ethanol-water mixed solution, stirring and dissolving, then adding polyvinylpyrrolidone, and stirring for 5min to obtain a mixed solution;
s2, transferring the mixed solution obtained in the step S1 to a high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at constant temperature;
s3, cooling the reaction liquid obtained in the step S2 to room temperature, washing the reaction liquid for a plurality of times by using ultrapure water, and drying the reaction liquid at a certain temperature to obtain the polyvinylpyrrolidone/cobalt oxyhydroxide composite material;
s4, grinding the composite material obtained in the step S3 into powder, dissolving a certain amount of powder in ultrapure water, and uniformly dispersing by ultrasonic to prepare a dispersion liquid of 0.5 mg/mL;
s5, grinding and polishing the glassy carbon electrode on 0.05 mu m alumina powder, washing the polished glassy carbon electrode with ultrapure water, and airing; and (4) sucking 3-6 mu L of the dispersion liquid obtained in the step S4, coating the dispersion liquid on the treated glassy carbon electrode, and drying under an infrared lamp to obtain the electrochemical sensor.
In the above method for manufacturing an electrochemical sensor, the soluble cobalt salt in step S1 is one or more of cobalt sulfate, cobalt chloride, and cobalt nitrate.
In the above method for manufacturing an electrochemical sensor, the oxidant in step S1 is one of sodium nitrate, potassium nitrate, sodium hypochlorite, potassium hypochlorite, sodium chlorate, and potassium chlorate.
In the above method for manufacturing an electrochemical sensor, the precipitant in step S1 is one of urea, hexamethylenetetramine, hexamethylenediamine, and ethylenediamine.
In the preparation method of the electrochemical sensor, the polyvinylpyrrolidone in the step S1 is one of K-15, K-30, K-60 and K-90, the mass ratio of the polyvinylpyrrolidone to the cobalt salt is 1: 1-2: 1, and the volume fraction of ethanol in the ethanol-water mixed solution is 10-30%.
In the above electrochemical sensor manufacturing method, the oxidizing agent in step S1: cobalt salt: the molar ratio of the precipitant is 1 (3-6) to 10-15.
In the preparation method of the electrochemical sensor, the reaction temperature in the step S2 is 100-150 ℃, and the reaction time is 1-5 hours.
In the preparation method of the electrochemical sensor, the drying temperature in the step S3 is 60-80 ℃, and the drying time is 12-15 hours.
In the preparation method of the electrochemical sensor, the ultrasonic time in the step S4 is 20-40 min.
In the preparation method of the electrochemical sensor, in the step S5, the power of the infrared lamp is 250-300W, the height is 7-9cm, and the baking time is 3-5 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polyvinylpyrrolidone/cobalt oxyhydroxide compound is used as the modified electrode material, and a hydrothermal method for preparing the compound has the advantages of mild synthesis conditions, low cost, easy commercialization and the like, so that the prepared electrochemical sensor has the advantage of low cost. Meanwhile, polyvinylpyrrolidone is used as a surfactant to control the aperture and the morphology of the material, and the dispersibility of the compound is improved.
(2) The cobalt oxyhydroxide has good electrochemical catalytic activity and can obviously improve current signals; the polyvinylpyrrolidone contains a large amount of nitrogen and oxygen atoms which can be combined with copper ions in a coordination manner, so that the selectivity and the sensitivity of the electrode are improved, and the detection capability of the electrochemical sensor is enhanced.
(3) The preparation method of the electrochemical sensor provided by the invention has the advantages of few preparation steps, simple and easy operation, good reproducibility and low cost, and the obtained modified electrode pair NO3 -、Cl-、SO4 2-、K+、Na+、Mn2+、Co2+、Fe3+、Zn2+、Ca2+、Mg2+The equal interference factors show strong anti-interference capability; the prepared electrochemical sensor maintains a high response current after being stored for one week. In addition, the electrochemical sensor of the invention realizes the sensitive detection of trace copper ions, the linear range is 0.1-90 mug/L, the detection limit is as low as 0.01 mug/L, and the electrochemical sensor is successfully applied to the detection of the copper content in soil, water and food.
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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 XRD pattern of a polyvinylpyrrolidone/cobalt oxyhydroxide composite prepared according to an exemplary embodiment of the present invention.
Fig. 2 is an SEM image of a polyvinylpyrrolidone/cobalt oxyhydroxide composite prepared according to an exemplary embodiment of the present invention.
FIG. 3 is a differential pulse stripping voltammogram of the electrochemical sensor according to an exemplary embodiment of the present invention, wherein curve a is a bare glassy carbon electrode; and b is a polyvinylpyrrolidone/cobalt oxyhydroxide modified glassy carbon electrode.
Fig. 4 is a differential pulse stripping voltammogram and a corresponding working curve of the electrochemical sensor for testing different concentrations of copper ions according to an exemplary embodiment of the present invention.
Detailed Description
The present invention will be further illustrated by the following specific examples, but the present invention is not limited to these examples.
Example 1
The preparation method of the electrochemical sensor for sensitively detecting the copper ions provided by the embodiment of the invention comprises the following steps:
(1) 0.10g of potassium nitrate, 0.714g of cobalt chloride hexahydrate and 1.40g of hexamethylenetetramine are placed in a beaker according to the molar ratio of 1:3:10, 50mL of 10% (V/V) ethanol-water mixed solution is added, and the mixture is stirred and dissolved uniformly. Then 0.714g of polyvinylpyrrolidone (K-30) is added, stirred for 5min, and the mixed solution is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene lining and reacted for 3h at a constant temperature of 110 ℃. And cooling the reaction liquid to room temperature, filtering, washing the solid product with ultrapure water for 3 times, and drying at the temperature of 60 ℃ to obtain the polyvinylpyrrolidone/cobalt oxyhydroxide compound.
(2) Grinding the synthesized polyvinylpyrrolidone/cobalt oxyhydroxide compound into powder, dissolving 1mg of the powder in 2mL of ultrapure water, and performing ultrasonic treatment for 30min to obtain polyvinylpyrrolidone/cobalt oxyhydroxide compound dispersion liquid. And absorbing 4 mu L of dispersion liquid to be coated on the treated glassy carbon electrode, and baking for 4min at 8cm under a 275W infrared lamp to obtain the polyvinylpyrrolidone/cobalt oxyhydroxide modified glassy carbon electrode.
Example 2
The preparation method of the electrochemical sensor for sensitively detecting the copper ions provided by the embodiment of the invention comprises the following steps:
(1) 0.10g of potassium nitrate, 0.952g of cobalt chloride hexahydrate and 1.682g of hexamethylenetetramine are placed in a beaker according to the molar ratio of 1:4:12, 50mL of 10% (V/V) ethanol-water mixed solution is added, and the mixture is stirred and dissolved uniformly. Then 0.952g polyvinylpyrrolidone (K-30) is added, stirred for 5min, and the mixed solution is transferred to a high-pressure reaction kettle with a polytetrafluoroethylene lining and reacts for 3h at a constant temperature of 140 ℃. And cooling the reaction liquid to room temperature, filtering, washing the solid product with ultrapure water for 3 times, and drying at the temperature of 60 ℃ to obtain the polyvinylpyrrolidone/cobalt oxyhydroxide compound. FIG. 1 is an XRD pattern of the polyvinylpyrrolidone/cobalt oxyhydroxide composite prepared. Referring to fig. 1, it can be seen that characteristic peaks of cobalt oxyhydroxide appear at 17.7 °, 21.8 °, 34.5 °, 38.4 °, and 45.3 °, and a characteristic peak of PVP appears at 11.1 °, with no other impurity peaks. As shown in fig. 2, by SEM characterization, we can observe that the prepared polyvinylpyrrolidone/cobalt oxyhydroxide composite is composed of a large number of spherical particles with uniform morphology, and the spherical particles have good dispersibility.
(2) Grinding the synthesized polyvinylpyrrolidone/cobalt oxyhydroxide compound into powder, dissolving 1mg of the powder in 2mL of ultrapure water, and performing ultrasonic treatment for 30min to obtain polyvinylpyrrolidone/cobalt oxyhydroxide compound dispersion liquid. Absorbing 4 mu L of dispersion liquid to be coated on the treated glassy carbon electrode, drying for 3min under a 275W infrared lamp at 7cm, and drying under the infrared lamp to obtain the polyvinylpyrrolidone/cobalt oxyhydroxide modified glassy carbon electrode.
The electrochemical behavior of the electrochemical sensor of example 2 was investigated as follows.
The polyvinylpyrrolidone/cobalt oxyhydroxide modified glassy carbon electrode obtained in example 2 was used as a working electrode, a platinum wire as a counter electrode, a saturated calomel electrode as a reference electrode, and the electrode was placed in a container containing 50. mu.g/L Cu2+The current-voltage curve was obtained by scanning the acetic acid buffer solution (0.2mol/L, pH 5.0) with differential pulse voltammetry and recording the current-voltage change by an electrochemical workstation. Differential pulseThe parameters of the impulse voltammetry are as follows: the potential increment is 0.01V, the enrichment potential is-0.8V, the enrichment time is 180s, the stirring speed is 1000r/min, the detection potential range is-0.3V, the standing time is 0s, and the pulse period is 0.5 s. As shown in fig. 3, after the polyvinylpyrrolidone/cobalt oxyhydroxide composite material is modified by the glassy carbon electrode, the dissolution peak current is significantly increased, which is attributed to the synergistic effect of polyvinylpyrrolidone and cobalt oxyhydroxide that more adsorption sites and electrocatalytic active sites are provided for copper ions.
The linear range and detection limit of the electrochemical sensor prepared by the embodiment of the present invention will be specifically described below. The following experiment was performed using the polyvinylpyrrolidone/cobalt oxyhydroxide modified glassy carbon electrode prepared in example 2.
The standard stock solution of copper ions was diluted with 0.2mol/L acetic acid buffer solution (pH 5.0) to a copper ion concentration of 0.10. mu.g/L, 1.0. mu.g/L, 10.0. mu.g/L, 20.0. mu.g/L, 40.0. mu.g/L, 60.0. mu.g/L, 80.0. mu.g/L, 90.0. mu.g/L. Detecting copper ion solutions with different concentrations according to the electrochemical test conditions of the embodiment 2, recording the differential pulse voltammetry curve of the copper ions, making the peak current-concentration working curve by the copper ions with different concentrations in the solution to be detected corresponding to different peak current values, and obtaining a linear equation i as shown in fig. 4p0.0741c +0.0142(R ═ 0.998). The electrochemical sensor of the present invention detects copper ions in a linear range of 0.1 to 90 μ g/L with a detection limit of 0.01 μ g/L (S/N ═ 3).
The reproducibility and stability of the electrochemical sensor according to the present invention prepared by the above-described method will be specifically described below.
60 mu g/L Cu-carbon electrode pair modified by polyvinylpyrrolidone/cobalt oxyhydroxide prepared in example 22+The solution was subjected to continuous parallel measurement 11 times with a dissolution peak current of 8.6% for standard deviation (RSD), and 6 electrodes were prepared under the same conditions to detect 60. mu.g/L Cu, respectively2+The relative standard deviation of the peak currents obtained for the solutions was 1.7%, indicating a better reproducibility of the sensor. The newly prepared 6 electrodes were left for 7 days and then Cu of the same concentration was detected2+Solution, peak current remaining at initial value98.3%, indicating that the stability of the sensor is good.
The following specifically describes the results of the anti-interference test performed on the prepared electrochemical sensor.
1000-fold NO investigation using polyvinylpyrrolidone/cobalt oxyhydroxide modified glassy carbon electrode prepared in example 23 -、K+、SO4 2-、Mn2+、Ca2+、Mg2+2000 times of Na+、Cl-150 times Fe3+、Zn2+100 times of Co2+For detection of 10 mug/L Cu2+The influence of (c). As can be seen from Table 1, the influence of the 11 interfering ions on the dissolution peak current of the copper ions is within 5%, which indicates that the electrochemical sensor of the invention has good anti-interference capability.
TABLE 1 different coexistent ion pairs Cu2+Influence of the detection result
Figure BDA0002209794420000051
The electrochemical sensor provided by the invention is applied to the detection of the copper content in soil water and food as follows:
water sample determination: water samples are respectively taken from tap water, barreled drinking water and school lake water, 5.00mL of water sample is taken and is subjected to constant volume to 50mL by using acetic acid buffer solution (0.2mol/L, pH is 5.0) for electrochemical analysis. And simultaneously performing a standard adding recovery test.
And (3) rice and potato sample determination: crushing rice by a crusher, and sieving by a 100-mesh sieve; cutting potato, placing in a drying oven at 110 deg.C, baking for 3 hr, pulverizing with a pulverizer, sieving with 100 mesh sieve, and mixing; accurately weighing 0.500g of sample into a crucible, heating the sample on an electric hot plate by small fire to fully carbonize the sample to be smokeless, then burning the sample in a muffle furnace at 550 ℃ for 3-4 h, cooling the sample, taking the sample out, dissolving the sample by using a proper amount of 50% (V/V) nitric acid aqueous solution, evaporating the dissolved solution by small fire to dryness, and finally diluting the solution to 50mL by using acetic acid buffer solution (0.2mol/L, pH 5.0) to perform electrochemical analysis. And simultaneously performing a standard adding recovery test.
Soil determination: naturally drying and crushing the collected farmland soil, and sieving the farmland soil with a 100-mesh sieve for later use.Accurately weighing 0.500g of soil into a microwave digestion tank, and adding 6mL of 65% HNO3(guaranteed reagent) 1mL of 30% H2O2(super grade purity) and 1mL of 40% HF (super grade purity), placing the materials into a microwave digestion instrument for digestion, filtering, driving acid, evaporating to dryness, finally fixing the volume to 50mL by using an acetic acid buffer solution (0.2mol/L, pH 5.0), and carrying out electrochemical analysis. And simultaneously performing a standard adding recovery test.
The polyvinylpyrrolidone/cobalt oxyhydroxide modified glassy carbon electrode prepared in example 2 is used for detecting the content of copper ions of the sample and the standard sample, and the measurement results are shown in tables 2 and 3. As can be seen from tables 2 and 3, the measured Relative Standard Deviation (RSD) is between 0.8 and 4.5%, and the average recovery rate is between 92.0 and 103%, which shows that the electrochemical sensor of the invention has high accuracy and stability.
TABLE 2 Cu in samples2+(n is 3)
Figure BDA0002209794420000061
TABLE 3 Cu in samples2+(n is 3)
Figure BDA0002209794420000062
Figure BDA0002209794420000071
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (4)

1. A preparation method of an electrochemical sensor for sensitively detecting copper ions is characterized by comprising the following steps:
s1, adding soluble cobalt salt, an oxidant and a precipitator into the ethanol-water mixed solution, stirring and dissolving, then adding polyvinylpyrrolidone, and stirring for 5min to obtain a mixed solution;
s2, transferring the mixed solution obtained in the step S1 to a high-pressure reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction at constant temperature;
s3, cooling the reaction liquid obtained in the step S2 to room temperature, washing the reaction liquid for a plurality of times by using ultrapure water, and drying the reaction liquid at a certain temperature to obtain the polyvinylpyrrolidone/cobalt oxyhydroxide composite material;
s4, grinding the composite material obtained in the step S3 into powder, dissolving a certain amount of powder in ultrapure water, and uniformly dispersing by ultrasonic to prepare a dispersion liquid of 0.5 mg/mL;
s5, grinding and polishing the glassy carbon electrode on 0.05 mu m alumina powder, washing the polished glassy carbon electrode with ultrapure water, and airing; absorbing 3-6 mu L of the dispersed liquid obtained in the step S4, coating the dispersed liquid on a treated glassy carbon electrode, and drying under an infrared lamp to obtain the electrochemical sensor;
in the step S1, the polyvinylpyrrolidone is one of K-15, K-30, K-60 and K-90, the mass ratio of the polyvinylpyrrolidone to the cobalt salt is 1: 1-2: 1, and the volume fraction of ethanol in the ethanol-water mixed solution is 10-30%; the oxidant in step S1: cobalt salt: the molar ratio of the precipitant is 1 (3-6) to 10-15; in the step S2, the reaction temperature is 100-150 ℃, and the reaction time is 1-5 h; in the step S3, the drying temperature is 60-80 ℃, and the drying time is 12-15 h; the ultrasonic time in the step S4 is 20-40 min; in the step S5, the power of the infrared lamp is 250-300W, the height is 7-9cm, and the baking time is 3-5 min.
2. The method for manufacturing an electrochemical sensor according to claim 1, wherein: the soluble cobalt salt in the step S1 is one or more of cobalt sulfate, cobalt chloride and cobalt nitrate.
3. The method for manufacturing an electrochemical sensor according to claim 1, wherein: in the step S1, the oxidant is one of sodium nitrate, potassium nitrate, sodium hypochlorite, potassium hypochlorite, sodium chlorate and potassium chlorate.
4. The method for manufacturing an electrochemical sensor according to claim 1, wherein: in the step S1, the precipitant is one of urea, hexamethylenetetramine, hexamethylenediamine, and ethylenediamine.
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