CN113447545B - Application of graphene polymer electrochemical sensor in detection of p-nitrophenol - Google Patents
Application of graphene polymer electrochemical sensor in detection of p-nitrophenol Download PDFInfo
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Abstract
The invention discloses a graphene polymer electrochemical sensor, a preparation method and application thereof in detecting p-nitrophenol. The graphene polymer electrochemical sensor provided by the invention has the advantages of low sensing detection limit, wide linear detection range, high stability and low cost, and can be used for preparing a disposable pNP test strip and also can be used for in-situ long-time continuous monitoring of pNP.
Description
Technical Field
The invention relates to the fields of electrochemical sensors, electrochemical processing technologies, nanomaterials and analytical chemistry, in particular to a graphene polymer electrochemical sensor, a preparation method and application thereof in detection of p-nitrophenol.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
P-nitrophenol (pNP, p-nitrophenol) is an important raw material and an intermediate product which are widely applied in the fields of medicine, agriculture, industry, paper making and the like, and is widely distributed in various water body environments worldwide at present. However, pNP has extremely strong toxicity and has obvious threat to animals, plants and human beings. In addition, pNP has extremely strong chemical stability, is difficult to decompose in natural environment, and can also form a food chain enrichment effect. The environmental hazard is prominent, and the environmental protection agency (USEPA) in the United states lists 114 the main pollutants, so that the analysis and detection of the pollutants are very important.
Common detection techniques for pNP include HPLC, electrophoretic analysis, fluorescence analysis, enzyme-linked immunosorbent assay, and the like. These methods all require large and expensive specialized instruments, are expensive to analyze, require long analysis times, and require professional personnel to operate. In contrast, the electrochemical analysis technology has the advantages of high sensitivity, low analysis cost, short analysis time, convenience in portable design, easiness in operation and the like, and is an ideal technical scheme for researching and developing the pNP sensor.
In the prior reports, there are many reports for developing a pNP electrochemical sensor based on nanomaterials, polymer materials, metal-based electrocatalysts, and the like. However, the inventor researches and finds that the technical schemes or the preparation are too complicated and expensive, or the problems of insufficient detection limit, detection range, stability and the like are faced, and the test requirements are often difficult to meet in the case of practical application test scenes. Therefore, there is still an urgent need for a pNP sensor with low detection limit, wide test range, high stability and low cost in the market.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a graphene polymer electrochemical sensor, a preparation method and application thereof in detection of p-nitrophenol.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the one hand, the graphene polymer electrochemical sensor comprises a carbon-based electrode, wherein a composite material is modified on the surface of the carbon-based electrode, and the composite material is formed by compounding graphene and polyarginine.
According to the invention, through research, the carbon-based electrode can carry out electrooxidation and electroreduction catalysis on pNP so as to generate an electrochemical signal for quantitative analysis. The comparison shows that the electrochemical polymerization of the pNP product can be caused by the electrooxidation process to cause electrode pollution so as to infect sensing signals; this problem can be avoided by using the electroreduction reaction. The electrochemical in-situ synthesis of the poly-arginine-graphene interface can greatly improve the electrical reduction signal of the pNP on the carbon electrode, and realize the detection of the pNP with low detection limit, wide linear detection range and high stability.
On the other hand, the preparation method of the graphene polymer electrochemical sensor comprises the steps of carrying out primary electrochemical treatment on the carbon-based electrode to enable graphene to be synthesized on the surface of the carbon-based electrode in situ, then carrying out secondary electrochemical treatment on the carbon-based electrode with the graphene synthesized on the surface to enable arginine to be condensed into poly-arginine, and enabling the poly-arginine to be compounded with graphene.
In a third aspect, the graphene polymer electrochemical sensor is applied to catalyzing the electrochemical polymerization of p-nitrophenol.
In a fourth aspect, the graphene polymer electrochemical sensor is applied to detection of p-nitrophenol.
In a fifth aspect, the electrochemical detection method for p-nitrophenol uses the graphene polymer electrochemical sensor as a working electrode, and the working electrode is immersed in a solution to be detected containing p-nitrophenol for electrochemical detection.
The beneficial effects of the invention are as follows:
1. experiments show that the current intensity of a sensing signal of pNP is stagnated and even disordered by a compound of graphene modified on the surface of a carbon-based electrode and poly-arginine, and the carbon-based electrode of the compound of graphene modified on the surface of the carbon-based electrode and poly-arginine can be used as a pNP electrochemical sensor based on the phenomenon.
2. The electrochemical sensor provided by the invention has the advantages of low detection limit, wide linear detection range, high selectivity and high stability in the electrochemical detection of pNP.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a bar graph of the elemental composition of P (Arg)/eG/SPE prepared in example 1 of the present invention, eG/SPE prepared in comparative example 1 and SPE;
FIG. 2 shows XPS spectra of P (Arg)/eG/SPE prepared in example 1 of the present invention and eG/SPE prepared in comparative example 1, wherein a is eG/SPE, b is P (Arg)/eG/SPE, and c is L-arginine;
FIG. 3 is an FTIR spectrum of P (Arg) in P (Arg)/eG/SPE prepared in example 1 of the present invention;
FIG. 4 is a graph showing the results of detection and characterization of electrochemical sensing performance in Experimental example 1;
FIG. 5 is a graph showing the results of AC impedance characterization in Experimental example 1 of the present invention;
FIG. 6 is a graph showing the results of cyclic voltammetry tests in Experimental example 2 of the present invention;
FIG. 7 is a graph showing the results of the constant potential current test of the electroreduction reaction in Experimental example 3 of the present invention;
FIG. 8 is a graph showing the results of potentiostatic current testing of electrooxidation reaction in Experimental example 3 of the present invention;
FIG. 9 is a graph showing the results of SWV scan tests in Experimental example 4 of the present invention;
FIG. 10 is a graph showing the results of the selectivity test in Experimental example 4 of the present invention;
FIG. 11 is a graph showing the test results of Experimental example 6 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The invention provides a graphene polymer electrochemical sensor, which comprises a carbon-based electrode, wherein the surface of the carbon-based electrode is modified with a composite material, and the composite material is formed by compounding graphene and polyarginine.
According to the invention, the surface of the carbon-based electrode is modified by the compound of graphene and polyarginine, so that the pNP can generate an electrooxidation reaction, and the pNP electrooxidation reaction can be used for realizing the detection of the pNP with low detection limit, wide linear detection range and high stability.
In some embodiments of this embodiment, the graphene is in situ synthesized graphene.
In some examples of this embodiment, the carbon-based electrode is a carbon screen printed electrode.
The invention further provides a preparation method of the graphene polymer electrochemical sensor, the carbon-based electrode is subjected to primary electrochemical treatment, graphene is synthesized on the surface of the carbon-based electrode in situ, then the carbon-based electrode with the graphene synthesized on the surface is subjected to secondary electrochemical treatment, arginine is condensed into poly-arginine, and the poly-arginine is compounded with the graphene.
Methods of electrochemical treatment include voltammetry, amperometry, and amperometry. Voltammetry includes, but is not limited to, cyclic voltammetry, square wave pulse voltammetry, differential pulse voltammetry, linear voltammetry. The current method includes but is not limited to potentiostatic current method, differential pulse current method.
In some examples of this embodiment, the primary electrochemical treatment process is: the carbon-based electrode is firstly processed by positive direct current voltage or scanned by positive voltage, and then scanned by negative voltage or processed by negative direct current voltage.
In one or more embodiments, the positive DC voltage is 1.0-3.0V. The time for processing the carbon-based electrode by adopting the positive direct current voltage is 150-250 s.
In one or more embodiments, the positive voltage and the negative voltage are applied in a scan range of 0-2.2V during the positive voltage scan process. The scanning rate is 50-150 mV/s, and the scanning times are 5-30.
In one or more embodiments, the negative voltage scan process is performed in a negative voltage scan range of-1.5 to 0V. The scanning rate is 50-150 mV/s, and the scanning times are 10-40.
In one or more embodiments, the negative DC voltage is between-2.0 and-1.5V. The treatment time is 100-150 s.
In some examples of this embodiment, the electrolyte solution in the electrochemical treatment is a phosphate buffer solution. The pH of the phosphate buffer solution is 7.0-7.4.
In some embodiments of this embodiment, the secondary electrochemical treatment is a positive direct voltage treatment or a positive voltage scan treatment.
In one or more embodiments, the voltage of the secondary electrochemical treatment is 0.20-0.25V. The treatment time is 150-200 s.
In one or more embodiments, during the positive voltage scan process, the scan range of the positive voltage is 0-2.2V. The scanning rate is 50-150 mV/s, and the scanning times are 5-20.
In some examples of this embodiment, the carbon-based electrode is a carbon screen printed electrode.
The third embodiment of the invention provides an application of the graphene polymer electrochemical sensor in catalyzing electrochemical polymerization of p-nitrophenol.
In a fourth embodiment of the invention, an application of the graphene polymer electrochemical sensor in detecting p-nitrophenol is provided.
In a fifth embodiment of the present invention, an electrochemical detection method for p-nitrophenol is provided, in which the graphene polymer electrochemical sensor is used as a working electrode, and the working electrode is immersed in a solution to be detected containing p-nitrophenol to perform electrochemical detection.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
A carbon electrode of a carbon Screen Printing Electrode (SPE) is used as a working electrode, a carbon counter electrode is used as a counter electrode, an Ag electrode is used as a reference electrode to form a three-electrode system (C-C-Ag three-electrode), and 0.1M Phosphate Buffer Solution (PBS) with pH of 7.0 is used as a supporting electrolyte to carry out electrochemical in-situ graphene synthesis.
Immersing the screen printing screen under the surface of a supporting electrolyte solution, applying a working voltage of 2.0V to an electrode system through a constant potential mode, maintaining a constant voltage for 200s, taking out the working electrode, fully rinsing with deionized water, and airing for later use. Then the electrode is immersed into a supported electrolyte solution, 20 times of continuous scanning of-1.5-0V and 100mV/s are carried out by cyclic voltammetry, and the working electrode is taken out and fully rinsed by deionized water. And (3) placing the electrode in the same PBS containing 2mM arginine, carrying out constant potential treatment for 180s at 0.22V, taking out the electrode, fully rinsing and airing the working electrode by using deionized water, wherein the rinsed and aired working electrode is the pNP electrochemical sensor and is marked as P (Arg)/eG/SPE.
Example 2
A carbon electrode of a carbon Screen Printing Electrode (SPE) is used as a working electrode, a carbon counter electrode is used as a counter electrode, an Ag electrode is used as a reference electrode to form a three-electrode system (C-C-Ag three-electrode), and 0.1M Phosphate Buffer Solution (PBS) with pH of 7.0 is used as a supporting electrolyte to carry out electrochemical in-situ graphene synthesis.
The screen printing was immersed under the support electrolyte solution, a working voltage in the range of 0-2.2V was applied to the electrode system via cyclic voltammetry, a 15-cycle continuous scan was performed at a rate of 100mV/s, and the working electrode was taken out and rinsed thoroughly with deionized water. The electrode was then immersed in a supporting electrolyte solution and continuously treated at-1.8V for 120 seconds at constant potential, and the working electrode was taken out and rinsed thoroughly with deionized water. The electrode was placed in the same PBS containing 2mM arginine, and 10 consecutive scans were performed at 100mV/s in the 0-2.2V range using cyclic voltammetry, after removal the working electrode was rinsed thoroughly with deionized water and dried in the air for use, denoted as P (Arg)/eG/SPE-1.
Example 3
A carbon electrode of a carbon Screen Printing Electrode (SPE) is used as a working electrode, a carbon counter electrode is used as a counter electrode, an Ag electrode is used as a reference electrode to form a three-electrode system (C-C-Ag three-electrode), and 0.1M Phosphate Buffer Solution (PBS) with pH of 7.0 is used as a supporting electrolyte to carry out electrochemical in-situ graphene synthesis.
Immersing the screen printing screen under the surface of a supporting electrolyte solution, applying a working voltage of 1.5V to an electrode system through a constant potential mode, maintaining a constant voltage for 240s, taking out the working electrode, fully rinsing with deionized water, and airing for later use. Then the electrode is immersed into a supported electrolyte solution, 25 times of continuous scanning of-1.5-0V and 120 mV/s are carried out by cyclic voltammetry, and the working electrode is taken out and fully rinsed by deionized water. And (3) placing the electrode in the same PBS containing 2mM arginine, carrying out constant potential treatment for 200s at 0.21V, taking out the electrode, fully rinsing and drying the working electrode by deionized water, wherein the rinsed and dried working electrode is the pNP electrochemical sensor.
Example 4
A carbon electrode of a carbon Screen Printing Electrode (SPE) is used as a working electrode, a carbon counter electrode is used as a counter electrode, an Ag electrode is used as a reference electrode to form a three-electrode system (C-C-Ag three-electrode), and 0.1M Phosphate Buffer Solution (PBS) with pH of 7.0 is used as a supporting electrolyte to carry out electrochemical in-situ graphene synthesis.
Immersing the screen printing screen under the surface of a supporting electrolyte solution, applying a working voltage of 2.5V to an electrode system through a constant potential mode, maintaining a constant voltage for 180s, taking out the working electrode, fully rinsing with deionized water, and airing for later use. Then the electrode is immersed into a supported electrolyte solution, 15 times of continuous scanning of-1.5-0V and 80 mV/s are carried out by cyclic voltammetry, and the working electrode is taken out and fully rinsed by deionized water. And (3) placing the electrode in the same PBS containing 2mM arginine, carrying out constant potential treatment for 160s at 0.24V, taking out the electrode, fully rinsing and drying the working electrode by deionized water, wherein the rinsed and dried working electrode is the pNP electrochemical sensor.
Comparative example 1
A carbon electrode of a carbon Screen Printing Electrode (SPE) is used as a working electrode, a carbon counter electrode is used as a counter electrode, an Ag electrode is used as a reference electrode to form a three-electrode system (C-C-Ag three-electrode), and 0.1M Phosphate Buffer Solution (PBS) with pH of 7.0 is used as a supporting electrolyte to carry out electrochemical in-situ graphene synthesis.
Immersing the screen printing screen under the surface of a supporting electrolyte solution, applying a working voltage of 2.0V to an electrode system through a constant potential mode, maintaining a constant voltage for 200s, taking out the working electrode, fully rinsing with deionized water, and airing for later use. And then immersing the electrode into a supported electrolyte solution, carrying out 20 times of continuous scanning of-1.5-0V and 100 mV/s by cyclic voltammetry, taking out the working electrode, fully rinsing the working electrode with deionized water, and airing the working electrode to obtain the working electrode marked as eG/SPE.
Comparative example 2
Firstly, aqueous phase Graphene Oxide (GO) synthesis is carried out by a classic Hummers method, a GO aqueous phase dispersion is prepared, and SPE is modified by a dripping method to obtain GO/SPE, wherein the method is carried out by referring to documents (Li, Y.W., Zhou. J., Song, J., Liang, X.S., Zhang, Z.P., Men, D.D., Wang, D.B., Zhang, X.E.,2019, Chemical nature of electrochemical activity of carbon electrodes.biosensors.144, 111534.). The GO/SPE was then immersed in 0.1M PBS pH 7.0 for 10 consecutive cycles of cyclic voltammetric sweep at a potential of-1.5-0V at a sweep rate of 0.1V/s. And taking out the electrode obtained after air drying and marking the electrode as rGO/SPE.
In-situ EDS element spectrum analysis is carried out on P (Arg)/eG/SPE, eG/SPE and SPE, the element composition is shown in figure 1, which shows that the O% of the eG/SPE subjected to electrochemical in-situ graphene synthesis treatment is remarkably increased and the C% is reduced compared with that of the SPE, and the generation of an interface graphene oxide structure is shown; compared with the eG/SPE, the difference of the P (Arg)/eG/SPE is smaller, and the N% is obviously increased, which shows that the interface graphene-poly-arginine interface is formed.
XPS spectrums of P (Arg)/eG/SPE, eG/SPE and L-arginine show in figure 2, peaks at 284.67eV, 285.2eV, 286.5eV and 288.8eV are only observed in the XPS C1s spectrum of the eG/SPE, and all the peaks are corresponding functional groups of graphite and adhesive; the new peak at 285.9eV is more increased in the P (Arg)/eG/SPE curve and is of a C-N structure, indicating the existence of guanidino and amide structures; in contrast, the L-arginine monomer curve is more representative of-NH 2 The 288.0eV peak of (A) was not observed in the results for P (Arg)/eG/SPE, further confirming the arginine polymerization.
As shown in FIG. 3, 1077cm appeared in the sample of polyarginine (P (Arg)) as compared with L-arginine monomer -1 New peaks are C-N and N-H stretching vibration peaks; 1524cm -1 The new peak is N-H bending vibration, which indicates the formation of the marker amido bond on the polymer.
Experimental example 1
The cyclic voltammetric responses of SPE, eG/SPE, P (Arg)/eG/SPE were tested in PBS containing 1mM potassium ferricyanide. Potassium ferricyanide is used as a representative probe molecule of an interface-dependent electrochemically active species (including pNP) to examine the potential of electrochemical sensing performance of several electrodes, as shown in fig. 4. The SPE has the lowest electro-catalysis performance, the lowest catalytic current intensity and the highest peak potential difference (delta E), and shows that the electron transfer process on the SPE is retarded dynamically; the peak current intensity of a curve corresponding to the eG/SPE is obviously increased along with the great reduction of delta E, which shows that the graphene interface synthesized in situ by electrochemistry has a remarkable advantage in the aspect of electrochemical catalytic activity on interface-dependent electrochemical active species compared with a carbon interface; the response curve of P (Arg)/eG/SPE is further obviously enhanced compared with the response current intensity of eG/SPE, and the delta E value is further reduced, so that the strong electrochemical catalytic performance is proved, and the method is extremely suitable for being used as an optimized interface scheme of a high-efficiency electrochemical sensor.
Alternating current impedance (EIS) analysis was performed on SPE, eG/SPE, and P (Arg)/eG/SPE interfaces, and equivalent circuit simulation analysis was performed on the three electrode interfaces, the results are shown in FIG. 5. The results show that: the equivalent circuit simulation contact ratio of the SPE is low, the stability of a display interface is relatively low, the uniformity is low, a composite circuit element structure is formed, and the realization of the stability of the sensor is not facilitated; the eG/SPE and the P (Arg)/eG/SPE show perfect simulation contact ratio compared with the SPE, show strong uniformity of an interface, and are beneficial to obtaining a high-stability sensor. The circuit fitting results also show that one of the main factors affecting the performance of the three electrodes is their respective interface charge transfer resistance (Rct). Wherein Rct of SPE is as high as 2136 Ω, while for the interfaces of eG/SPE and P (Arg)/eG/SPE, Rct is reduced to 258.6 and 343.5 Ω respectively, which is extremely beneficial to the fast kinetic process of the interface electron transfer process.
Experimental example 2
The results of cyclic voltammetry tests in 0.1M PBS (pH 7.0) containing 1mM pNP are shown in FIG. 6. Compared with the rGO/SPE, the rGO/SPE has low electrochemical catalytic activity, which shows the performance advantage of the electrochemical in-situ synthesis of graphene compared with the chemical synthesis of graphene; compared with P (Arg)/eG/SPE, the electrochemical signal of P (Arg)/eG/SPE is obviously higher than that of eG/SPE. The P (Arg)/eG/SPE has excellent electrochemical analysis performance on pNP, and is an ideal technical scheme for preparing the pNP electrochemical sensor.
Experimental example 3
The electroreduction reaction of the P (Arg)/eG/SPE to the pNP is utilized, the constant potential current test is carried out on the solution under different pNP concentrations, and the result shows that: the P (Arg)/eG/SPE has good linear response to pNP in the range of 5-1250 muM, and the current-concentration regression curve is that Ipc (muA) is 0.067C (muM) +8.7405 (R) 2 0.9983); the detection limit of the response was 2.4nM, read time 3s, demonstrating the powerful analytical performance of P (Arg)/eG/SPE on pNP, as shown in FIG. 7.
The electrooxidation of pNP using P (Arg)/eG/SPE, potentiostatic current measurements were performed on solutions of different pNP concentrations, as shown in FIG. 8, and the results indicated that: the P (Arg)/eG/SPE has good linear response to pNP in the range of 5-200. mu.M, and the current-concentration regression curve is Ipa (mu.A) ═ 0.041C (mu.M) -5.0597 (R) 2 0.9983); the limit of detection of the response was 3.9 nM. In the test process of more than 200 μ M, the sensor signal current intensity of pNP from P (Arg)/eG/SPE is found to be stagnated or even disordered, which is mainly because the electrooxidation process of pNP from P (Arg)/eG/SPE can cause electrochemical polymerization of pNP product and thus electrode contamination to infect the sensor signal. In comparison, the electrochemical oxidation or reduction process of the P (Arg)/eG/SPE can realize the high-sensitivity electrochemical analysis of the pNP, but the electrooxidation reaction can realize the higher-performance pNP electrochemical sensing.
Experimental example 4
The SWV scan test was performed by immersing P (Arg)/eG/SPE in 0.1M PBS (pH 7.0) containing various concentrations of pNP, and as a result, as shown in FIG. 9, it was found that the sensors all maintained a good linear response to pNP over a wide concentration range of 0.5-1250. mu.M. The corresponding regression curve is Ipc (μ a) ═ 0.0342C (μ M) +115.1 (R) 2 0.998). The lower detection limit is calculated to be 12nM, and the detection time is less than 15 s.
The sensing selectivity of the P (Arg)/eG/SPE is tested by immersing the P (Arg)/eG/SPE in the PBS solution containing 1mM pNP, wherein the mixed solution contains various interference components with different concentrations, and the result is shown in FIG. 10.
This experimental example shows that the P (Arg)/eG/SPE prepared in example 1 exhibits electrochemical sensing performance with low detection limit, wide concentration range and high selectivity on pNP.
Experimental example 5 Disposable pNP high sensitivity analysis
And performing standard addition test analysis on 3 samples of sewage (industrial wastewater) collected from a factory drain, laboratory wastewater and river water by adopting P (Arg)/eG/SPE. The detection method was as described in example 5. Adding pNP reference substances with different contents into the 3 water body samples respectively, testing the SWV response change of the P (Arg)/eG/SPE before and after the labeling, and reading the peak current value as an analysis result. The normalized concentrations, test recoveries and standard error are shown in Table 1.
TABLE 1 addition standard concentration, recovery rate and standard error conditions of P (Arg)/eG/SPE for different samples
The result shows that the performance of the labeling test of the P (Arg)/eG/SPE on 3 kinds of water bodies is ideal, the error is extremely small, the sensing accuracy of the P (Arg)/eG/SPE on the pNP is not obviously influenced due to the complexity of the water body components, and the P (Arg)/eG/SPE can make correct electrochemical response and indication on the concentration of the pNP in the water body environment.
Experimental example 6 high-sensitivity analysis of Disposable pNP of real Water sample
The P (Arg)/eG/SPE-1 was placed in 0.1M PBS, different concentrations of pNP standard were started to be introduced, and the current response of P (Arg)/eG/SPE was tested at-0.8V working potential. As shown in the results of FIG. 11, as the pNP concentration in the solution environment increases, the P (Arg)/eG/SPE can rapidly respond to the pNP concentration, and the current increment and the corresponding pNP concentration increment are in strict corresponding relation. Meanwhile, when the pNP concentration is reduced in the solution environment, the P (Arg)/eG/SPE can also respond quickly and quantitatively indicate the change.
Therefore, by using the current analysis technology, the P (Arg)/eG/SPE-1 can realize the in-situ continuous monitoring of the pNP concentration in the water body environment, and the real-time information grasping requirements of the water body long-term pollution condition, the sewage discharge amount monitoring, the environment improvement and the restoration condition and the like can be well met.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A graphene polymer electrochemical sensor is characterized by comprising a carbon-based electrode, wherein the surface of the carbon-based electrode is modified with a composite material, and the composite material is formed by compounding graphene and polyarginine;
the graphene is in-situ synthesized graphene;
the carbon-based electrode is a carbon screen printing electrode;
carrying out primary electrochemical treatment on the carbon-based electrode to synthesize graphene on the surface of the carbon-based electrode in situ, then carrying out secondary electrochemical treatment on the carbon-based electrode with the graphene synthesized on the surface to polycondensing arginine into polyarginine, and compounding the polyarginine and the graphene;
the primary electrochemical treatment process comprises the following steps: processing the carbon-based electrode by adopting positive direct-current voltage or applying positive voltage to scan the carbon-based electrode, and then applying negative voltage to scan or adopting negative direct-current voltage to process;
The positive direct current voltage is 1.0-3.0V; the time for processing the carbon-based electrode by adopting positive direct current voltage is 150-250 s;
when positive voltage scanning treatment is applied, the scanning range of positive voltage and negative voltage is 0-2.2V; the scanning rate is 50-150 mV/s, and the scanning times are 5-30;
during negative voltage scanning treatment, the scanning range of the negative voltage is-1.5-0V; the scanning rate is 50-150 mV/s, and the scanning times are 10-40;
the negative direct current voltage is-2.0 to-1.5V; the treatment time is 100-150 s;
the electrolyte solution in the electrochemical treatment is phosphate buffer solution; the pH value of the phosphate buffer solution is 7.0-7.4;
the secondary electrochemical treatment is positive direct-current voltage treatment or positive voltage scanning treatment;
the voltage of the secondary electrochemical treatment is 0.20-0.25V; the treatment time is 150-200 s;
during positive voltage scanning treatment, the scanning range of positive voltage is 0-2.2V; the scanning rate is 50-150 mV/s, and the scanning times are 5-20;
the graphene polymer electrochemical sensor is applied to catalyzing the electrochemical polymerization of p-nitrophenol.
2. Use of the graphene polymer electrochemical sensor according to claim 1 in the detection of p-nitrophenol.
3. An electrochemical detection method of p-nitrophenol, which is characterized in that the graphene polymer electrochemical sensor of claim 1 is used as a working electrode, and the working electrode is immersed in a solution to be detected containing the p-nitrophenol for electrochemical detection.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110594678.7A CN113447545B (en) | 2021-05-28 | 2021-05-28 | Application of graphene polymer electrochemical sensor in detection of p-nitrophenol |
| AU2021447399A AU2021447399A1 (en) | 2021-05-28 | 2021-09-04 | Graphene polymer electrochemical sensor, and manufacturing method therefor and application thereof in detection of p-nitrophenol |
| PCT/CN2021/116572 WO2022247048A1 (en) | 2021-05-28 | 2021-09-04 | Graphene polymer electrochemical sensor, and manufacturing method therefor and application thereof in detection of p-nitrophenol |
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