CN112903776B - Preparation of spirobifluorenyl microporous polymer membrane modified electrode, obtained product and application - Google Patents
Preparation of spirobifluorenyl microporous polymer membrane modified electrode, obtained product and application Download PDFInfo
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Abstract
The invention discloses a preparation method of a spirobifluorenyl microporous polymer membrane modified electrode, an obtained product and application thereof, wherein spirobifluorene, tetrabutylammonium perchlorate and acetonitrile are uniformly mixed to prepare an electrolyte; and putting the working electrode, the reference electrode and the counter electrode into electrolyte, and performing electropolymerization by adopting a cyclic voltammetry method to form a spirobifluorenyl microporous polymer film on the surface of the working electrode, thereby obtaining the spirobifluorenyl microporous polymer film modified electrode. The preparation process is simple and quick, the electrochemical sensor constructed by the electrode modified by the spirobifluorenyl microporous polymer membrane has excellent electrocatalytic activity and selectivity on three nitrophenol isomers, can distinguish and identify the three o-nitrophenol, m-nitrophenol and p-nitrophenol and simultaneously detect the three o-nitrophenol, m-nitrophenol and p-nitrophenol, and has high sensitivity, high detection speed, wide detection range, low detection limit, easy on-line automatic analysis and strong popularization and application prospects.
Description
Technical Field
The invention relates to a spirobifluorene-based microporous polymer membrane modified electrode and a preparation method thereof, and also relates to an electrochemical sensor taking the modified electrode as a working electrode and application thereof in selectively identifying and detecting three nitrophenol isomers, belonging to the technical field of nitrophenol isomer monitoring.
Background
In recent years, with the rapid development of chemical industry, nitrophenol isomers are applied to the aspects of chemical synthesis of dyes, pesticides, explosive materials and the like. It is difficult to be biodegraded, and remains widely present in industrial and natural wastes, and has become one of serious environmental pollutants, even at ultra-low concentration, the trace detection is very important for human beings, animals and plants because the trace detection still generates potential toxicity.
Heretofore, various methods for quantitatively analyzing nitrophenol have been developed, such as fluorescence method, high performance liquid chromatography, spectrophotometry, capillary electrophoresis, flow injection analysis, and the like. However, most of the methods are not easy to operate conventionally, require a lot of time and complicated equipment, and further, it is difficult to achieve good detection of various nitrophenol isomers at low concentrations. For example, patent CN 109239036B discloses a fluorescent gold nanocluster sensor array based on beta-cyclodextrin modification and dual ligand functionalization, which is used for detection of three nitrophenol isomers, but the fluorescent gold nanocluster sensor array is well distinguished only at a concentration as low as 10 μ M, and detection at a lower concentration cannot be realized.
The electrochemical analysis method has attracted wide attention in the field due to the characteristics of low cost, easy operation, high sensitivity, high detection speed and capability of performing trace detection. At present, the detection of related nitrophenol by adopting an electrochemical method has been reported, but because the nitrophenol isomers have similar structures and properties and are difficult to detect simultaneously, the method mainly aims at the measurement of single nitrophenol or multiple isomers at high concentration, and the single and simultaneous detection of the nitrophenol isomers at low concentration is always a challenge. For example, in patent CN110487882 a, a molecularly imprinted electrochemical sensor for selectively identifying p-nitrophenol is disclosed, in which foamed nickel is used as a substrate, a sulfuric acid solution of aniline and p-nitrophenol is used as an electrolyte, and the foamed nickel is directly polymerized on the surface under the action of an electric field to form a molecularly imprinted polymer, wherein the detection limit of p-nitrophenol is 1 × 10-9 mol/L, linear range of 2.5X 10-6-1×10-7 mol/L. However, the method cannot well identify and detect the o-nitrophenol and the m-nitrophenol simultaneously. Therefore, it is very important and valuable to develop an electrochemical analysis method which can distinguish various nitrophenol isomers with ultra-sensitivity, wide detection range and low detection limit.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a simple and efficient preparation method of a spirobifluorenyl microporous polymer film modified electrode and the modified electrode obtained by the preparation method.
Electropolymerization is used as a convenient, low-cost and environment-friendly electrochemical synthesis method, has inherent advantages such as easily-controlled film thickness, good adhesive force, conductivity and the like, and the polymer modified electrode has the characteristics of long service life, simplicity and convenience in preparation, high stability, good polymerization uniformity, good electrocatalytic activity, diversity of active points and the like. The polymer membrane modified electrode has wide prospects in theoretical research and application. At present, no study is available on the spiro-bifluorene electropolymerization method and the application thereof in separation and detection. As a novel electropolymerization material, the invention discovers that a spirobifluorenyl microporous polymer membrane (PSF) obtained by one-step electropolymerization does not need any template and surfactant, and the polymer shows a unique conjugated microporous structure, greatly enhances electrochemical response due to rich micropores, high surface area, good stability and adjustable and modifiable pore channel structure, and shows great potential in molecular recognition.
The specific technical scheme of the invention is as follows:
a preparation method of a spirobifluorenyl microporous polymer membrane modified electrode comprises the following steps:
(1) Spirobifluorene, tetrabutylammonium perchlorate and acetonitrile are uniformly mixed to prepare electrolyte;
(2) And (3) putting the working electrode, the reference electrode and the counter electrode into electrolyte, performing electropolymerization by adopting a cyclic voltammetry method, and forming a spirobifluorenyl microporous polymer film on the surface of the working electrode to obtain the spirobifluorenyl microporous polymer film modified electrode.
Furthermore, in the electrolyte, the content of spirobifluorene is 0.005-0.015 g/mL, and the content of tetrabutylammonium perchlorate is 0.02-0.08 mol/L.
Further, the scanning range of the electropolymerization cyclic voltammetry is-0.7V-2.5V, the scanning rate is 100-400 mV/s, and the number of scanning circles is 3-5 circles.
Further, the working electrode is a glassy carbon electrode, a gold electrode, an IPO electrode and the like, the reference electrode is an Ag/AgCl electrode or a calomel electrode, and the counter electrode is a platinum wire electrode.
Furthermore, the working electrode is subjected to surface pretreatment and then modified. The surface pretreatment refers to surface polishing, cleaning and other treatment modes, and the bare electrode can be polished by alumina powder and then cleaned by ethanol and water in an ultrasonic mode.
The spirobifluorene microporous polymer film modified electrode is obtained by electropolymerizing spirobifluorene on the surface of the electrode by adopting a cyclic voltammetry method, the modification method is convenient and fast, the obtained modified electrode has excellent electrocatalytic activity and identification performance on three nitrophenol isomers, the simultaneous quantitative detection of the three nitrophenol isomers can be realized, the sensitivity is high, the detection line is low, the performance is stable, and the application prospect is strong. The spirobifluorenyl microporous polymer membrane modified electrode obtained by the method is also in a protection range.
The invention also provides application of the spirobifluorenyl microporous polymer membrane modified electrode in selective identification and quantitative detection of nitrophenol isomers, wherein the nitrophenol isomers are o-nitrophenol, p-nitrophenol and m-nitrophenol.
The invention also provides a method for detecting the nitrophenol isomer, which comprises the following steps:
(1) Respectively preparing standard solutions of o-nitrophenol, p-nitrophenol and m-nitrophenol with different concentrations by using phosphate buffer solution with pH4.0-9.0;
(2) Taking the spirobifluorenyl microporous polymer membrane modified electrode as a working electrode, taking a saturated calomel electrode as a reference electrode and a platinum wire electrode as a counter electrode, fixing one end of each of the three electrodes in an electrolytic cell, and connecting the other end of each electrode with an electrochemical workstation;
(3) Scanning by adopting a differential pulse voltammetry method by taking various standard solutions prepared in the step (1) as electrolytes, wherein reduction peak current values of the o-nitrophenol, the p-nitrophenol and the m-nitrophenol appear at different positions, and respectively drawing working curves of the concentrations of the o-nitrophenol, the p-nitrophenol and the m-nitrophenol and the reduction peak current values;
(4) Adjusting the pH value of the sample to be detected to 4.0-9.0 by using a phosphate buffer solution with the pH value of 4.0-9.0, then measuring the reduction peak current value of the sample to be detected by adopting a differential pulse voltammetry method, and calculating the type and the content of nitrophenol in the sample to be detected according to a working curve.
In the detection method, the differential pulse voltammetry conditions are as follows: the potential is-0.6-0.4V, and the scanning speed is 100 mV/s.
Compared with the prior art, the invention has the following beneficial effects:
1. the spirobifluorenyl microporous polymer membrane modified electrode is prepared based on a one-step electrodeposition method, the preparation process is simple and quick, the performance of the modified electrode is stable, the modified polymer membrane can provide more attachment sites for the modified electrode, the electrocatalysis effect is good, and the detection sensitivity is improved.
2. The electrochemical sensor constructed by the electrode modified by the spirobifluorenyl microporous polymer membrane has excellent electrocatalytic activity and selectivity on three nitrophenol isomers, can distinguish and identify the o-nitrophenol, the m-nitrophenol and the p-nitrophenol and simultaneously detect the o-nitrophenol, the m-nitrophenol and the p-nitrophenol, has high sensitivity, high detection speed, wide detection range and low detection limit, is easy to carry out online automatic analysis, and has strong popularization and application prospects.
3. The electrochemical sensor constructed by the electrode modified by the spirobifluorenyl microporous polymer membrane has the advantages of simple and convenient test process, short test time, low detection limit, high selectivity and sensitivity, can simultaneously detect three nitrophenol isomers by a differential pulse voltammetry, and can solve the practical application problem of quickly detecting the nitrophenol isomers in trace and ultra-trace by an electrochemical method.
Drawings
FIG. 1 is a scanning electron micrograph of a spirobifluorenyl microporous polymer film according to the present invention;
FIG. 2 is a graph of the linear relationship of reduction peak current values to the concentration of o-nitrophenol (o-NP);
FIG. 3 is a graph of the linear relationship between the reduction peak current value and the concentration of m-nitrophenol (m-NP);
FIG. 4 is a linear plot of reduction peak current values versus p-nitrophenol (p-NP) concentration.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be exemplary only and are not intended to be limiting.
Unless otherwise specified, the following concentrations are mass percent concentrations.
Example 1
Preparing a spirobifluorenyl microporous polymer membrane modified electrode, comprising the following steps of:
(1) Electrode polishing: the bare glassy carbon electrode was polished with 0.03 um alumina powder and rinsed with ultra-pure water, followed by ultrasonic cleaning in ethanol and ultra-pure water, respectively, for 5 minutes.
(2) Spirobifluorene, tetrabutylammonium perchlorate and chromatographically pure acetonitrile are mixed uniformly to prepare electrolyte, the concentration of the spirobifluorene is 0.01 g/mL, and the concentration of the tetrabutylammonium perchlorate is 0.05M (mol/L).
(3) Taking a cleaned bare electrode as a working electrode, taking a platinum electrode as a counter electrode and taking a saturated calomel electrode as a reference electrode, and carrying out electropolymerization in electrolyte by using a cyclic voltammetry method;
the scanning range of the cyclic voltammetry is-0.7-2.5V, the scanning speed is 10-400 mV/s, and the number of scanning circles is 1-7 circles.
(4) And (3) rinsing the modified electrode with ultrapure water, and removing surface impurities to obtain the spirobifluorenyl microporous polymer modified electrode.
Solutions of o-nitrophenol, M-nitrophenol and p-nitrophenol at a concentration of 10. Mu.M were prepared with phosphate buffered saline PBS (pH 6.5), respectively. The prepared spirobifluorenyl microporous polymer membrane modified electrode is used as a working electrode, and forms a three-electrode system with a platinum wire electrode and a saturated calomel reference electrode, and the three-electrode system is connected with an electrochemical workstation for electrochemical performance detection, so that the scanning rate and the number of scanning cycles of the cyclic voltammetry are optimized.
Optimizing the number of scanning turns
Keeping the scanning range of the cyclic voltammetry to be-0.7-2.5V, the scanning speed to be 100 mV/s, the scanning circles to be 1, 2, 3, 4, 5, 6 and 7 respectively, and obtaining different spirobifluorenyl microporous polymer film modified electrodes.
And scanning by adopting the obtained different spirobifluorenyl microporous polymer film modified electrodes as working electrodes and adopting an o-nitrophenol, M-nitrophenol and p-nitrophenol solution with the concentration of 10 mu M as an electrolyte by adopting a cyclic voltammetry method to obtain reduction peak current values of the different spirobifluorenyl microporous polymer film modified electrodes. The results show that the reduction peak current values of the solutions for detecting o-nitrophenol, m-nitrophenol and p-nitrophenol increase and then decrease with the increase of the number of scanning cycles, and the reduction peak current value is maximum when the number of scanning cycles is 5, so that the number of scanning cycles is preferably 3-5, and most preferably 5.
Optimizing scan rate
The scanning range of the cyclic voltammetry is-0.7-2.5V, the scanning number is 5 circles, and the scanning speeds are 10 mV/s, 30 mV/s, 50 mV/s, 80 mV/s, 100 mV/s, 200 mV/s, 300 mV/s and 400 mV/s respectively, so that different spirobifluorenyl microporous polymer film modified electrodes are obtained.
And scanning by adopting the obtained different spirobifluorenyl microporous polymer film modified electrodes as working electrodes and adopting an o-nitrophenol, M-nitrophenol and p-nitrophenol solution with the concentration of 10 mu M as an electrolyte by adopting a cyclic voltammetry method to obtain reduction peak current values of the different spirobifluorenyl microporous polymer film modified electrodes. The results show that the reduction peak current value increases with the increase of the scanning rate, which indicates that the reduction of three nitrophenol isomers on the spirobifluorenyl microporous polymer membrane modified electrode belongs to the adsorption control process, and this is probably due to the fact that the high specific surface area of the conjugated microporous polymer membrane has abundant electrons and is related to the strong interaction of electron-poor nitrophenol analytes. In general terms, the scan rate is selected to be 100-400 mV/s, preferably 100V/s.
Example 2
The spirobifluorenyl microporous polymer membrane modified electrode is prepared by the following steps:
(1) Polishing the electrode: the bare glassy carbon electrode was polished with 0.03 um alumina powder and rinsed with ultra-pure water, followed by ultrasonic cleaning in ethanol and ultra-pure water, respectively, for 5 minutes.
(2) Spirobifluorene, tetrabutylammonium perchlorate and chromatographically pure acetonitrile are mixed uniformly to prepare electrolyte, the concentration of the spirobifluorene is 0.01 g/mL, and the concentration of the tetrabutylammonium perchlorate is 0.05M (mol/L).
(3) Performing electropolymerization in electrolyte by using a cyclic voltammetry method by taking a cleaned bare electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode;
the scanning range of the cyclic voltammetry is-0.7-2.5V, the scanning rate is 100 mV/s, and the number of scanning circles is 5.
(4) And (3) washing the modified electrode with ultrapure water, and removing surface impurities to obtain the spirobifluorenyl microporous polymer membrane modified electrode. The scanning electron micrograph of the obtained spirobifluorenyl microporous polymer membrane is shown in figure 1. It can be seen from the figure that the polyspirobifluorene film is uniformly electro-deposited on the electrode with a large number of apertures in the surface, most of the apertures being about 1-2 um and a few of the apertures being 3-5 um, exhibiting a large specific surface area.
Example 3
A spirobifluorenyl microporous polymer membrane modified electrode was prepared according to the method of example 2, except that: the scanning range of the cyclic voltammetry is-0.7-2.5V, the scanning rate is 200 mV/s, and the number of scanning circles is 4.
Example 4
A spirobifluorenyl microporous polymer membrane modified electrode was prepared according to the method of example 2, except that: the sweep range of cyclic voltammetry is-0.7-2.5V, the sweep rate is 400 mV/s, and the number of sweep turns is 3.
Example 5 detection Properties of Spirobifluorenyl microporous Polymer Membrane-modified electrode
The spirobifluorene-based microporous polymer membrane modified electrode prepared in example 2 was used as a working electrode, and a three-electrode system was formed with a platinum wire electrode and a saturated calomel reference electrode, and connected to an electrochemical workstation for electrochemical performance detection.
Phosphate buffer solution with pH4.0-9.0 is used to prepare o-nitrophenol, M-nitrophenol and p-nitrophenol solutions with concentration of 10 μ M respectively. Adopting a differential pulse voltammetry to investigate the reduction peak current change condition of nitrophenol isomer solution with different pH values, wherein the conditions of the differential pulse voltammetry are as follows: the potential is-0.6-0.4V, and the scanning speed is 100 mV/s.
The results show that more obvious reduction peaks appear in the range of pH value of 4.0-9.0, and the current of the three peaks reaches the maximum value when the pH value is =6.5, which indicates that the spirobifluorenyl microporous polymer membrane modified electrode has the best electrochemical detection effect on nitrophenol isomer under the condition of pH value of 6.5.
Example 6
(1) Respectively preparing standard solutions of o-nitrophenol, p-nitrophenol and m-nitrophenol with different concentrations by using a phosphate buffer solution with the pH value of 6.5;
(2) Taking the spirobifluorenyl microporous polymer membrane modified electrode in the embodiment 2 as a working electrode, taking a saturated calomel electrode as a reference electrode and taking a platinum wire electrode as a counter electrode, fixing one end of each of the three electrodes in an electrolytic cell, and connecting the other end of each electrode with an electrochemical workstation;
(3) Adding 10 mL standard solutions of nitrophenol isomers with different concentrations prepared in the step (1) into an electrolytic bath, respectively measuring the reduction peak current values of the three nitrophenol isomers by using a differential pulse voltammetry method, respectively drawing the reduction peak current values of the o-nitrophenol, the p-nitrophenol and the m-nitrophenol at different positions, and respectively drawing working curves of the concentrations and the reduction peak current values of the o-nitrophenol, the p-nitrophenol and the m-nitrophenol.
The conditions of the differential pulse voltammetry are: the potential is-0.6-0.4V, and the scanning speed is 100 mV/s.
The detection results and the working curves of the o-nitrophenol, the p-nitrophenol and the m-nitrophenol are shown in figures 2-4, and it can be seen from the detection results that the spiro-dibenzoyl microporous polymer membrane modified electrode can simultaneously identify the o-nitrophenol (o-NP), the m-nitrophenol (m-NP) and the p-nitrophenol (p-NP), and the nitrophenol isomer concentration and the reduction peak current value are in a linear relationship within a certain concentration range. Wherein the linear equation of the o-nitrophenol (o-NP) in the range of 0.1-100 mu M is Ip (o-NP) = -0.10798c-1.3646 (R)2= 0.9991); the linear equation of M-nitrophenol (M-NP) in the range of 0.2-100 μ M is Ip (M-NP) = -0.15627c-1.14575 (R)2= 0.9957); linear formula of p-nitrophenol (p-NP) in the range of 0.1-120. Mu.MThe process is Ip (p-NP) = -0.05857c-0.9037 (R)2= 0.9988). Wherein c in the linear equation is the concentration of three nitrophenol isomers, the unit is mol/L, and Ip is the reduction peak current value obtained by the differential pulse voltammetry, and the unit is muA. This shows that the prepared modified electrode has a wider detection range for three nitrophenol isomers.
Detection limit =3S according to the standard deviation method0/k，S0Is the standard deviation of a blank (n = 0), k is the regression equation slope, k = -0.10798 for o-nitrophenol, k = -0.15627 for m-nitrophenol, k = -0.05857 for p-nitrophenol, and S for o-nitrophenol was detected0=0.000359, S of m-nitrophenol0= 0.00156S of p-nitrophenol0If =0.000195, the detection limit of o-nitrophenol is calculated to be 0.01 μ M, the detection limit of M-nitrophenol is calculated to be 0.03 μ M, and the detection limit of p-nitrophenol is calculated to be 0.01 μ M. This indicates that the prepared modified electrode has lower detection limit for three nitrophenol isomers.
Example 7
Phosphate buffered saline PBS (pH 6.5) was prepared to prepare o-, M-and p-nitrophenol solutions at a concentration of 10. Mu.M.
The spirobifluorenyl microporous polymer film modified electrode in example 2 was used as a working electrode, a saturated calomel electrode was used as a reference electrode, a platinum wire electrode was used as a counter electrode, 10 μ M solution of o-nitrophenol, M-nitrophenol, and p-nitrophenol was used as an electrolyte, and the stability of the modified electrode was examined by differential pulse voltammetry, where the scanning range of differential pulse voltammetry was-0.6 to 0.4V, the scanning rate was 100 mV/s, and the number of scanning cycles was 5 cycles. The response current of the modified electrode is measured every other day and is regularly measured for one month, the result shows that the current signal has no obvious change, and the error is less than 90 percent, which proves that the modified electrode prepared by the invention has good stability.
5 spirobifluorenyl microporous polymer membrane modified electrodes are prepared according to the method of the embodiment 2, the 5 modified electrodes are used as working electrodes, a saturated calomel electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, 10 mu M o-nitrophenol, M-nitrophenol and p-nitrophenol solution are used as electrolyte, the reproducibility of the modified electrodes is inspected by using a differential pulse voltammetry, the scanning range of the differential pulse voltammetry is-0.6-0.4V, the scanning rate is 100 mV/s, and the number of scanning turns is 5. The results show that the average relative standard deviation of the detection results of the 5 modified electrodes is less than 6.0, which indicates that the material has good reproducibility.
mu.M Ag was added to 10. Mu.M o-, M-and p-nitrophenol solutions, respectively, at pH6.5+, Zn2+, Cu2+, Fe3+, Ca2+, Hg+, Ni3+ Scanning interferents by using differential pulse voltammetry, detecting reduction peak current values under the same scanning conditions, and displaying that the interferents do not obviously interfere the detection (P)<5%), which shows that the modified electrode prepared by the invention has excellent selectivity and can be used for detecting the o-nitrophenol in the actual sample.
EXAMPLE 8 actual sample testing
The spirobifluorenyl microporous polymer membrane modified electrode prepared in this example 2 was used as a working electrode, and a phosphate buffer solution with a pH of 6.5 was used as a supporting electrolyte to perform quantitative analysis and test on lake water and local tap water samples by using differential pulse voltammetry. Before use, the actual water sample is filtered by a 0.45 mu m membrane, then the solution is adjusted to pH6.5 by PBS, and the water sample is treated by a standard addition method, which comprises the following steps: tap water was divided into six portions, lake water was divided into three portions, pH was adjusted to 6.5 with a phosphate buffer of pH6.5, and a nitrophenol standard solution was added to each of the tap water and the lake water to the original concentration in table 1.
Taking the spirobifluorenyl microporous polymer membrane modified electrode prepared in example 2 as a working electrode, a saturated calomel electrode as a reference electrode, a platinum wire electrode as a counter electrode, and tap water or lake water as electrolyte, and respectively measuring the concentrations of three nitrophenol isomers by using differential pulse voltammetry under the conditions that: the potential is-0.6-0.4V, and the scanning speed is 100 mV/s.
And (3) respectively detecting three groups of parallel samples by each sample, taking the average electrochemical signal value of the three groups of parallel samples as a final value, and respectively substituting the electrochemical signal value into three linear regression equations for calculation to obtain the concentration of the sample. The detection results are shown in table 1, and it can be seen from table 1 that the average recovery rate of the p-nitrophenol isomer is 92.0% -104.2%, and the relative deviation is-8.0% -4.2%, which indicates that the modified electrode can be effectively applied to the simultaneous detection of three nitrophenol isomers in an actual sample.
Claims (9)
1. The application of the spirobifluorenyl microporous polymer membrane modified electrode in the selective recognition and quantitative detection of nitrophenol isomers is characterized in that: the preparation method of the spirobifluorenyl microporous polymer membrane modified electrode comprises the following steps:
(1) Spirobifluorene, tetrabutylammonium perchlorate and acetonitrile are uniformly mixed to prepare electrolyte;
(2) And putting the working electrode, the reference electrode and the counter electrode into electrolyte, and performing electropolymerization by adopting a cyclic voltammetry method to form a spirobifluorenyl microporous polymer film on the surface of the working electrode, thereby obtaining the spirobifluorenyl microporous polymer film modified electrode.
2. Use according to claim 1, characterized in that: the nitrophenol isomers are o-nitrophenol, p-nitrophenol and m-nitrophenol.
3. Use according to claim 1, characterized in that: in the electrolyte, the content of spirobifluorene is 0.005-0.015 g/mL, and the content of tetrabutylammonium perchlorate is 0.02-0.08 mol/L.
4. Use according to claim 1, characterized in that: the sweep range of cyclic voltammetry is-0.7V-2.5V, the sweep rate is 100-400 mV/s, and the number of sweep turns is 3-5.
5. Use according to claim 1, characterized in that: the working electrode is a glassy carbon electrode, a gold electrode or an IPO electrode, the reference electrode is an Ag/AgCl electrode or a calomel electrode, and the counter electrode is a platinum wire electrode.
6. Use according to claim 1, characterized in that: the working electrode is polished and then put into the electrolyte.
7. A method for detecting nitrophenol isomers is characterized by comprising the following steps:
(1) Respectively preparing standard solutions of o-nitrophenol, p-nitrophenol and m-nitrophenol with different concentrations by using a phosphate buffer solution with pH of 4.0-9.0;
(2) Taking the spirobifluorenyl microporous polymer membrane modified electrode as claimed in claim 1 as a working electrode, taking a saturated calomel electrode as a reference electrode and taking a platinum wire electrode as a counter electrode, fixing one end of the three electrodes in an electrolytic cell, and connecting the other end of the three electrodes with an electrochemical workstation;
(3) Scanning by adopting a differential pulse voltammetry method by taking various standard solutions prepared in the step (1) as electrolytes, wherein reduction peak current values of the o-nitrophenol, the p-nitrophenol and the m-nitrophenol appear at different positions, and respectively drawing working curves of the concentrations of the o-nitrophenol, the p-nitrophenol and the m-nitrophenol and the reduction peak current values;
(4) Adjusting the pH value of the sample to be detected to 4.0-9.0 by using a phosphate buffer solution with the pH value of 4.0-9.0, then measuring the reduction peak current value of the sample to be detected by adopting a differential pulse voltammetry method, and calculating the type and the content of nitrophenol in the sample to be detected according to a working curve.
8. The method of claim 7, wherein: the differential pulse voltammetry conditions were: the potential is-0.6-0.4V, and the scanning speed is 100 mV/s.
9. The method of claim 7, wherein: in steps (1) and (4), the pH of the phosphate buffer was 6.5.
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