CN107576704B - microcystin-LR molecular imprinting photoelectric chemical sensor and preparation and application thereof - Google Patents
microcystin-LR molecular imprinting photoelectric chemical sensor and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a Cu based on visible light drive2O/PPy composite material microcapsule algae toxin-LR molecular engram photoelectrochemical sensor and preparation and application thereof. ITO conductive glass is used as a substrate, a molecularly imprinted membrane is deposited by an electrochemical technology, and the molecularly imprinted membrane is Cu absorbed by visible light2The O semiconductor is used as a photoelectric material and compounded with polypyrrole containing microcystin-LR vacancy, visible light is used as an excitation light source, and the microcystin-LR concentration is detected on a CHI660e workstation by adopting an i-t technology. Compared with the prior art, the application of the microcystin-LR molecular imprinting photoelectrochemical sensor has the following advantages: sensitive photoelectrochemical response, wide detection range and capability of being 1.0 ng.L‑1～10.0ug·L‑1The detection is carried out within the concentration range of (1), and the anti-interference capability is strong; the preparation method is simple and quick, has low cost and can be suitable for quick online detection of the water body.
Description
Technical Field
The invention belongs to the field of water pollution analysis and detection, and particularly relates to Cu based on visible light drive2Micro of O/PPy composite materialA phycotoxin-LR molecular imprinting photoelectrochemical sensor and a preparation method and application thereof.
Background
Microcystins (Microcystins) are monocyclic polypeptide compounds released after death of algae, have stable structure, are difficult to degrade, are easy to enrich in organisms, are hepatotoxins with strong cancer promotion effect, and have strong inhibition effect on protein phosphatase 1A, protein phosphatase 2A and intestines and stomach. The structures of the microcystins which are separated and identified at present are more than 90, wherein the microcystin-LR is the subtype with the highest toxicity and the highest content. The World Health Organization (WHO) has also regulated that the maximum content of microcystins in drinking water must not exceed 1ug L-1. Therefore, development of a microcystin-LR sensor with high speed, high efficiency, low cost, high sensitivity and wide detection range is necessary.
At present, a plurality of methods for detecting microcystin-LR are available, such as High Performance Liquid Chromatography (HPLC), chromatography/mass spectrometry, Raman detection and the like, and although the methods are sensitive and reliable, the methods have high cost, need professional technicians to operate, and are easy to introduce toxic reagents such as acetonitrile. The sensitivity of the protease inhibition analysis method or the physiological toxicity test is low, and the timely online detection cannot be realized.
The molecular imprinting photoelectric chemical sensor combines the high selectivity of molecular imprinting technology and the high sensitivity of photoelectric chemical detection, and has the advantages of low cost, simple operation, wide detection range, high detection speed and the like. In recent years, a photoelectrochemical detection analysis method which uses a semiconductor material absorbed in a visible light range as a photoelectric material and drives excited electrons to obtain photocurrent as a detection signal by visible light is gradually developed, so that rapid on-line detection of microcystin-LR can be realized, the sensitivity is high, and the detection range is wide.
Disclosure of Invention
The invention aims to provide Cu based on visible light drive2O/PPy composite material microcystin-LR molecular imprinting photoelectrochemical sensor and preparation method and application thereof. The sensor of the invention has low preparation cost and can simply and quickly realize wide rangeAccurate and sensitive detection of the surrounding microcystin-LR.
The purpose of the invention can be realized by the following technical scheme:
a microcystin-LR molecular imprinting photoelectrochemical sensor is based on visible light driven Cu2The O/PPy composite material microcystin-LR molecular imprinting photoelectric chemical sensor takes ITO conductive glass as a substrate, a molecular imprinting film is deposited by an electrochemical deposition technology, and the molecular imprinting film is made of Cu2The O photoelectric material is compounded with polypyrrole (PPy) containing microcystin-LR vacancy.
The preparation method of the microcystin-LR molecular imprinting photoelectrochemical sensor specifically comprises the following steps:
(1)Cu2preparing an O photoelectric material: mixing Cu2SO4Solution with CH3Uniformly mixing CH (OH) COOH solution and PVP (polyvinyl pyrrolidone), stirring at room temperature, adjusting the pH of the mixed solution to 8-10, carrying out electrodeposition on a CHI660e workstation at 55-65 ℃ by taking ITO (indium tin oxide) conductive glass as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode to obtain Cu electrodeposited2Cleaning and then using ITO conductive glass of an O photoelectric material for later use;
(2) preparing a molecularly imprinted membrane: uniformly mixing microcystin-LR and pyrrole (Py) monomer, adding lithium perchlorate as a supporting electrolyte, and electrodepositing Cu by the electrodeposition obtained in the step (1)2Performing electropolymerization on ITO conductive glass of an O photoelectric material serving as a working electrode, a platinum sheet serving as a counter electrode and Ag/AgCl serving as a reference electrode on a CHI660e workstation, and then cleaning and drying for later use to obtain ITO glass polymerized with a molecular imprinting film;
(3) removing the template molecules: preparing dipotassium phosphate solution with a certain concentration as template removing solution, taking the ITO glass polymerized with the molecular imprinting film in the step (2) as a working electrode, taking a platinum sheet as a counter electrode and taking Ag/AgCl as a reference electrode, performing template removing treatment on a CHI660e workstation, and finally cleaning and drying the template removing ITO conductive glass to obtain the visible light drive Cu-based conductive glass2microcystin-LR molecular imprinting photoelectrochemical sensing of O/PPy composite materialA device.
In the step (1), Cu is added according to a molar ratio2SO4：CH3CH (OH) COOH: the PVP is 1:5: 0.1-1: 10:30, preferably 1:5: 0.1-1: 5: 10.
In the step (1), the stirring time is preferably 2 hours, but the stirring time is not limited to this, and may be more or less.
In the step (1), NaOH solution with a certain concentration can be used for adjusting the pH value, and other alkali liquor can also be used.
In the step (1), the conditions of electrodeposition are as follows: the electro-deposition is performed for 100-200 s at a constant potential of-0.3V, and then for 600-800 s at a constant potential of-0.2V.
In the step (1), the cleaning step is as follows: will deposit Cu2And (3) respectively putting the ITO conductive glass of the O photoelectric material in acetone, ethanol and deionized water, performing ultrasonic treatment for 10-20 minutes, and then drying the ITO conductive glass at the temperature of 40-60 ℃ for later use.
Among them, the drying environment is preferably an air-blast drying oven.
In the step (2), the molar ratio of the microcystin-LR to the pyrrole (Py) monomer is 1: 10-1: 50.
In the step (2), the concentration of the added lithium perchlorate is preferably 0.1 mol.L-1。
In the step (2), the electropolymerization conditions are as follows: and performing electropolymerization for 15-20 minutes at 0-0.8V by using a cyclic voltammetry technology.
The cyclic voltammetry technique is conventional in the art, and the process conditions of the conventional cyclic voltammetry technique are required to implement the present invention.
In the step (2), the cleaning refers to cleaning with deionized water, and then drying at 40-60 ℃ for later use.
In the step (3), the template removing treatment conditions are as follows: and removing the template for 10-30 minutes at constant potential plus 1.5V.
In the step (3), the cleaning refers to cleaning with deionized water, and then drying at 40-60 ℃ for later use.
In the step (3), the concentration of the dipotassium hydrogen phosphate solution as the template removing solution is preferably 0.2mol · L-1。
The microcystin-LR molecular imprinting photoelectric chemical sensor is used for quickly detecting microcystin-LR and comprises the following specific steps:
(1) drawing a standard curve: preparing a series of standard solutions of microcystin-LR with concentration by using PBS phosphate buffer solution with pH of 7.2-7.4, taking a microcystin-LR molecular imprinting photoelectrochemical sensor as a working electrode, a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, visible light as an excitation light source, adding-0.2V bias voltage on a CHI660e electrochemical workstation by using an i-t technology, sequentially detecting according to the sequence of concentration from low to high to obtain different photocurrents, and finally establishing a linear relation between the photocurrent density and the concentration of the microcystin-LR to draw a standard curve;
(2) and (2) similarly preparing the microcystin-LR with unknown solubility into a PBS phosphate buffer solution with the pH value of 7.2-7.4, obtaining the photocurrent under the test condition of the step (1), and obtaining the unknown concentration of the microcystin-LR by using a drawn standard curve.
When pond water or river water is detected, the pond water or the river water is subjected to suction filtration for 3 times by using a sand core funnel, calcium and magnesium ions in the water are removed by using a precipitator, a certain amount of phosphate is added into a water sample to prepare a PBS phosphate buffer solution with the pH value of 7.2-7.4, a photocurrent is obtained under the test condition of the step (1), and the microcystic toxin-LR concentration in each water sample is obtained by using a drawn standard curve.
In the invention, a selectivity test is also carried out, and the selectivity test method comprises the following steps: adding an interferent with the concentration 100-200 times that of the known microcystin-LR into a PBS phosphate buffer solution with the known microcystin-LR concentration, obtaining photocurrent under the test condition of the step (1), and comparing the photocurrent with the photocurrent measured without the interferent to obtain the influence of the interferent on the rapid detection of the microcystin-LR molecular imprinting photoelectric chemical sensor.
The invention also simulates a detection method of pure water, pond water or river water, wherein the pond water and the river water are firstly filtered by a sand core funnel for 3 times, then calcium and magnesium ions in the water are removed by using a precipitator, the pure water does not need to be pretreated, then a certain amount of phosphate is added into a water sample to prepare PBS phosphate buffer solution with the pH value of 7.2-7.4, then two prepared water samples are taken, different amounts of microcystin-LR are respectively added to prepare entity water samples containing microcystin-LR with different concentrations, the photocurrent is obtained under the test condition of the step (1) in the same way, and the microcystin-LR concentration in each water sample is obtained by using a drawn standard curve.
The invention utilizes Cu absorbed in the visible range2The O semiconductor is used as a photoelectric material, visible light is used as an excitation light source, microcystin-LR is used as a template, a microcystin-LR binding site is created in the pyrrole polymerization process, a vacancy with a certain shape and bonding capability is left on the microcystin-LR template through a certain electrochemical technology, microcystin molecules can be specifically bonded to the vacancy after microcystin-LR with a certain concentration is added, and an i-t technical test shows that the photoelectric chemical sensor is high in detection sensitivity, high in detection speed, wide in detection range and strong in anti-interference capability on microcystin, and a new method is provided for rapid online detection of the microcystin-LR.
Compared with the traditional detection technology, the application of the microcystin-LR molecular imprinting photoelectrochemical sensor has the following advantages: sensitive photoelectrochemical response, wide detection range and capability of being 1.0 ng.L-1～10.0ug·L-1The detection is carried out within the concentration range of (1), and the anti-interference capability is strong; the preparation method is simple and quick, has low cost and can be suitable for quick online detection of the water body.
Drawings
FIG. 1 is an AC impedance spectrum of a process for preparing a microcystin-LR molecularly imprinted photoelectrochemical sensor. (a) Cu2O-modified ITO conductive glass, (b) a molecular imprinting photoelectrochemical sensor containing microcystin-LR, and (c) a molecular imprinting photoelectrochemical sensor with a template removed.
FIG. 2 is the photo current response diagram of the microcystin-LR molecular imprinting photoelectric chemical sensor in microcystin-LR solutions with different concentrations, wherein a-k represent that the concentration of the microcystin-LR is 0, 1.0 ng.L-1，5.0ng·L-1，10.0ng·L-1，50.0ng·L-1，100.0ng·L-1，300.0ng·L-1，500.0ng·L-1,1.0ug·L-1，3.0ug·L-1，10.0ug·L-1。
Figure 3 is a linear fit of photocurrent response to microcystin-LR solution concentration.
FIG. 4 is a diagram of a selective test experiment of the microcystin-LR molecular imprinting photoelectrochemical sensor. S0-S10 respectively represent microcystin-LR, L-threonine, sarcosine, L-alanine, L-arginine hydrochloride, D-fructose, glucose, bisphenol A, 2,4-D, p-bromobenzaldehyde and N, N-dimethylbenzaldehyde.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Cu based on visible light drive2Preparing a microcystin-LR molecular imprinting photoelectrochemical sensor made of an O/PPy composite material:
(1)Cu2preparing an O photoelectric material: mixing Cu2SO4Solution with CH3CH (OH) COOH solution and a quantity of PVP according to a molar ratio Cu2SO4：CH3CH (OH) COOH is 1:5:0.1, uniformly mixing, stirring at room temperature for 2 hours, adjusting the pH value to 8-10 by using NaOH solution, taking ITO conductive glass as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, electrodepositing for 150s at a constant potential of-0.3V and 700s at a constant potential of-0.2V on a CHI660e working station at 60 ℃, and finally electrodepositing Cu2And respectively placing the ITO conductive glass of the O photoelectric material in a certain amount of acetone, ethanol and deionized water, performing ultrasonic treatment for 10-20 minutes, and then placing the ITO conductive glass in a blast drying oven at 40 ℃ for drying for later use.
(2) Preparing a molecularly imprinted membrane: uniformly mixing microcystin-LR and pyrrole (Py) monomers according to the molar ratio of 1:30, adding a certain concentration of lithium perchlorate as a supporting electrolyte, and electrodepositing Cu in the step (1)2ITO conductive glass of O photoelectric material as working electrode, platinum sheetAnd as a counter electrode, Ag/AgCl is used as a reference electrode, electropolymerization is carried out on a CHI660e workstation at a certain potential range of 0-0.8V for a certain time of about 15 minutes by using a cyclic voltammetry technology, and finally the ITO glass polymerized with the molecularly imprinted membrane is cleaned by deionized water and dried at 60 ℃ for standby.
(3) Removing the template molecules: preparing a dipotassium phosphate solution with a certain concentration as a template removing solution, taking ITO conductive glass electropolymerized with a molecularly imprinted membrane in the step (2) as a working electrode, a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, removing the template for 10-30 minutes at a certain constant potential plus 1.5V on a CHI660e workstation, finally cleaning the ITO conductive glass without the template with deionized water, and drying at 60 ℃ for later use to obtain visible light driven Cu2O/PPy composite material microcapsule algae toxin-LR molecule engram photoelectrochemical sensor.
FIG. 1 is the AC impedance spectrum of the microcystin-LR molecular imprinting photoelectrochemical sensor process prepared in this example. (a) Cu2O-modified ITO conductive glass, (b) a molecular imprinting photoelectrochemical sensor containing microcystin-LR, (c) a molecular imprinting photoelectrochemical sensor with a template removed, which is described in Cu2The electronic transfer speed is accelerated after polypyrrole is modified on the O semiconductor photoelectric material, and after a hole is left by removing the microcystin-LR template, the exchange transmission of electrons is facilitated, and the resistance is greatly reduced.
Example 2
Visible light driven Cu2The method for rapidly detecting the microcystin-LR by the microcystin-LR molecular imprinting photoelectrochemical sensor of the O/PPy composite material comprises the following steps:
(1) drawing a standard curve: PBS phosphate buffer solution with the pH value of 7.2-7.4 is utilized to prepare a series of standard solutions of microcystin-LR with concentration, the de-template ITO conductive glass prepared in the embodiment 1 is used as a working electrode, a platinum sheet is used as a counter electrode, Ag/AgCl is used as a reference electrode, visible light is used as an excitation light source, i-t technology is utilized on a CHI660e electrochemical workstation, 0.2V bias voltage is added, detection is sequentially carried out according to the sequence from low to high concentration to obtain different photocurrents, and finally a linear relation is established between the photocurrent density and the microcystin-LR concentration to draw a standard curve.
(2) And (2) similarly preparing the microcystin-LR with unknown solubility into a PBS phosphate buffer solution with the pH value of 7.2-7.4, obtaining the photocurrent under the test condition of the step (1), and obtaining the unknown concentration of the microcystin-LR by using a drawn standard curve.
(3) And (3) selective testing: adding an interferent with the concentration 100-200 times that of the known microcystin-LR into a PBS phosphate buffer solution with the known microcystin-LR concentration, obtaining photocurrent under the test condition of the step (1), and comparing the photocurrent with the photocurrent measured without the interferent to obtain the influence of the interferent on the rapid detection of the microcystin-LR molecular imprinting photoelectric chemical sensor.
(4) Detection of purified water, pond water and river water: performing suction filtration on pond water and river water for 3 times by using a sand core funnel, removing part of calcium and magnesium ions in the water by using a precipitator, adding a certain amount of phosphate into a water sample to prepare a PBS phosphate buffer solution with the pH value of 7.2-7.4 without pretreatment, taking two prepared water samples, respectively adding different amounts of microcystin-LR to prepare entity water samples containing microcystin-LR with different concentrations, obtaining photocurrent under the test condition of the step (1) in the same way, and obtaining the concentration of the microcystin-LR in each water sample by using a drawn standard curve.
FIG. 2 is a diagram showing the photocurrent response of the photoelectrochemical sensor prepared in example 1 in the microcystin-LR solutions with different concentrations, wherein a-k represent the concentrations of microcystin-LR of 0, 1.0 ng.L-1，5.0ng·L-1，10.0ng·L-1，50.0ng·L-1，100.0ng·L-1，300.0ng·L-1，500.0ng·L-1,1.0ug·L-1，3.0ug·L-1，10.0ug·L-1As can be seen from fig. 2, the photocurrent gradually decreased with increasing concentration of microcystin-LR, probably because microcystin-LR blocked the electron transport after occupying the vacancy on pyrrole, resulting in the decrease of photocurrent.
FIG. 3 is a graph of FIG. 2 at different concentrationsThe linear fitting graph of the light current value measured under the microcystin-LR and the concentration of the microcystin-LR solution can be seen, the fitted straight line is divided into two sections, the linear relation is good, and the equation delta I/I can be respectively used00.2558+0.1975logC and Δ I/I00.5154+0.0597logC, wherein R20.9848 and 0.9891 respectively, with a minimum detection limit of 0.23 ng.L-1Wherein C is microcystin-LR concentration and I is photocurrent.
FIG. 4 is a diagram of a selective test experiment of the microcystin-LR molecularly imprinted photoelectrochemical sensor prepared in example 1. S0-S10 respectively represent microcystin-LR, L-threonine, sarcosine, L-alanine, L-arginine hydrochloride, D-fructose, glucose, bisphenol A, 2,4-D, p-bromobenzaldehyde and N, N-dimethylbenzaldehyde, and as can be seen from the figure, the photoelectric response of different interferents in the photoelectric chemical sensor is very small, most interferents are below 10 percent and respectively between 10 percent and 20 percent, the existence of the interferents has little influence on the test of the microcystin-LR, and the prepared microcystin-LR molecularly imprinted photoelectric chemical sensor has very high selectivity and strong anti-interference capability.
According to the test result that the microcystin-LR molecular imprinting photoelectrochemical sensor prepared in the embodiment 1 is applied to an actual water sample, the recovery rate of the microcystin-LR is between 98% and 103% in the detection of the solid water, and the detection result is accurate, so that the method can be well used for the detection of the solid water.
Example 3
Cu based on visible light drive2Preparing a microcystin-LR molecular imprinting photoelectrochemical sensor made of an O/PPy composite material:
(1)Cu2preparing an O photoelectric material: mixing Cu2SO4Solution with CH3CH (OH) COOH solution and a quantity of PVP according to a molar ratio Cu2SO4：CH3CH (OH) COOH is 1:5: 5, uniformly mixing, stirring at room temperature for 2 hours, adjusting the pH to 8-10 by using NaOH solution with certain concentration, taking ITO conductive glass as a working electrode, taking a platinum sheet as a counter electrode, and taking Ag/AgCl is used as a reference electrode, the Cu is electrodeposited for 100 to 200s at a constant potential of-0.3V, then the Cu is electrodeposited for 600 to 800s at a constant potential of-0.2V on a CHI660e workstation at the temperature of 55 to 65℃, and finally the Cu is electrodeposited2And respectively placing the ITO conductive glass of the O photoelectric material in a certain amount of acetone, ethanol and deionized water, performing ultrasonic treatment for 10-20 minutes, and then placing the ITO conductive glass in a blast drying oven at 40 ℃ for drying for later use.
(2) Preparing a molecularly imprinted membrane: uniformly mixing microcystin-LR and pyrrole (Py) monomers according to the mol ratio of 1: 10-1: 50, adding lithium perchlorate with a certain concentration as a supporting electrolyte, and electrodepositing Cu in the step (1)2The method comprises the following steps of taking ITO conductive glass of an O photoelectric material as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, carrying out electropolymerization for a certain time of about 15-20 minutes on a CHI660e workstation at a certain potential range of 0-0.8V by using a cyclic voltammetry technology, finally cleaning the ITO glass polymerized with the molecularly imprinted membrane by using deionized water, and drying at 60 ℃ for later use.
(3) Removing the template molecules: preparing a dipotassium phosphate solution with a certain concentration as a template removing solution, taking the ITO conductive glass electropolymerized with the molecularly imprinted membrane in the step (2) as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, removing the template for 10-30 minutes on a CHI660e workstation at a certain constant potential plus 1.5V, finally cleaning the ITO conductive glass with deionized water, and drying at 60 ℃ for later use.
Example 4
Cu based on visible light drive2Preparing a microcystin-LR molecular imprinting photoelectrochemical sensor made of an O/PPy composite material:
(1)Cu2preparing an O photoelectric material: mixing Cu2SO4Solution with CH3CH (OH) COOH solution and a quantity of PVP according to a molar ratio Cu2SO4：CH3CH (OH) COOH is 1:5:10, the mixture is uniformly mixed, stirred at room temperature for 2 hours, the pH value is adjusted to 8-10 by NaOH solution with certain concentration, ITO conductive glass is used as a working electrode, a platinum sheet is used as a counter electrode, Ag/AgCl is used as a reference electrode, and the constant potential of-0.3V is firstly used on a CHI660e workstation at the temperature of 55-65 DEG CPerforming potential electrodeposition for 100-200 s, performing constant potential deposition at-0.2V for 600-800 s, and finally performing electrodeposition on Cu2And respectively placing the ITO conductive glass of the O photoelectric material in a certain amount of acetone, ethanol and deionized water, performing ultrasonic treatment for 10-20 minutes, and then placing the ITO conductive glass in a blast drying oven at 40 ℃ for drying for later use.
(2) Preparing a molecularly imprinted membrane: uniformly mixing microcystin-LR and pyrrole (Py) monomers according to the mol ratio of 1: 10-1: 50, adding lithium perchlorate with a certain concentration as a supporting electrolyte, and electrodepositing Cu in the step (1)2The method comprises the following steps of taking ITO conductive glass of an O photoelectric material as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, carrying out electropolymerization on the ITO conductive glass for a certain time on a CHI660e workstation at a certain potential range of 0-0.8V by using a cyclic voltammetry technology for about 20-30 minutes, finally cleaning the ITO glass polymerized with a molecularly imprinted membrane by using deionized water, and drying the ITO glass at 60 ℃ for later use.
(3) Removing the template molecules: preparing a dipotassium phosphate solution with a certain concentration as a template removing solution, taking the ITO conductive glass electropolymerized with the molecularly imprinted membrane in the step (2) as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, removing the template for 10-30 minutes on a CHI660e workstation at a certain constant potential plus 1.5V, finally cleaning the ITO conductive glass with deionized water, and drying at 60 ℃ for later use.
Example 5
Cu based on visible light drive2Preparing a microcystin-LR molecular imprinting photoelectrochemical sensor made of an O/PPy composite material:
(1)Cu2preparing an O photoelectric material: mixing Cu2SO4Solution with CH3CH (OH) COOH solution and a quantity of PVP according to a molar ratio Cu2SO4：CH3CH (OH) COOH is 1:5:10, the mixture is uniformly mixed, stirred at room temperature for 2 hours, the pH value is adjusted to 8-10 by NaOH solution with certain concentration, ITO conductive glass is used as a working electrode, a platinum sheet is used as a counter electrode, Ag/AgCl is used as a reference electrode, electrodeposition is carried out on the mixture for 100-200 s at constant potential of-0.3V and 600-800 s at constant potential of-0.2V on a CHI660e working station at the temperature of 55-65 ℃, and finally the electrodeposition is carried outCu2And respectively placing the ITO conductive glass of the O photoelectric material in a certain amount of acetone, ethanol and deionized water, performing ultrasonic treatment for 10-20 minutes, and then placing the ITO conductive glass in a blast drying oven at 40 ℃ for drying for later use.
(2) Preparing a molecularly imprinted membrane: uniformly mixing microcystin-LR and pyrrole (Py) monomers according to the mol ratio of 1: 10-1: 50, adding lithium perchlorate with a certain concentration as a supporting electrolyte, and electrodepositing Cu in the step (1)2The method comprises the following steps of taking ITO conductive glass of an O photoelectric material as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, carrying out electropolymerization for a certain time of about 15-20 minutes on a CHI660e workstation at a certain potential range of 0-0.8V by using a cyclic voltammetry technology, finally cleaning the ITO glass polymerized with the molecularly imprinted membrane by using deionized water, and drying at 60 ℃ for later use.
(3) Removing the template molecules: preparing a dipotassium phosphate solution with a certain concentration as a template removing solution, taking the ITO conductive glass electropolymerized with the molecularly imprinted membrane in the step (2) as a working electrode, taking a platinum sheet as a counter electrode, taking Ag/AgCl as a reference electrode, removing the template for 30-40 minutes on a CHI660e workstation at a certain constant potential plus 1.5V, finally cleaning the ITO conductive glass with deionized water, and drying at 60 ℃ for later use.
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 (7)
1. A microcystin-LR molecular imprinting photoelectric chemical sensor is characterized in that the sensor is based on visible light driving Cu2The O/polypyrrole composite material microcystin-LR molecular imprinting photoelectric chemical sensor takes ITO conductive glass as a matrix and is prepared by electrochemical depositionDepositing a molecularly imprinted membrane made of Cu2The O photoelectric material is compounded with polypyrrole containing microcystin-LR vacancy;
the preparation method specifically comprises the following steps:
(1)Cu2preparing an O photoelectric material: mixing Cu2SO4Solution with CH3Uniformly mixing CH (OH) COOH solution and PVP (polyvinyl pyrrolidone), stirring at room temperature, adjusting the pH of the mixed solution to 8-10, carrying out electrodeposition on a CHI660e workstation at 55-65 ℃ by taking ITO (indium tin oxide) conductive glass as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode to obtain Cu electrodeposited2Cleaning and then using ITO conductive glass of an O photoelectric material for later use;
(2) preparing a molecularly imprinted membrane: uniformly mixing microcystin-LR and pyrrole monomer, adding lithium perchlorate as a supporting electrolyte, and electrodepositing Cu obtained in the step (1)2Performing electropolymerization on ITO conductive glass of an O photoelectric material serving as a working electrode, a platinum sheet serving as a counter electrode and Ag/AgCl serving as a reference electrode on a CHI660e workstation, and then cleaning and drying for later use to obtain ITO glass polymerized with a molecular imprinting film;
(3) removing the template molecules: taking dipotassium phosphate solution as template removing solution, taking the ITO glass polymerized with the molecular imprinting film in the step (2) as a working electrode, taking a platinum sheet as a counter electrode and taking Ag/AgCl as a reference electrode, performing template removing treatment on a CHI660e workstation, and finally cleaning and drying the template removing ITO conductive glass to obtain visible light driven Cu2A microcystin-LR molecular imprinting photoelectrochemical sensor made of an O/PPy composite material;
in the step (1), the conditions of electrodeposition are as follows: performing electrodeposition for 100-200 s at-0.3V potential constant potential, and then performing electrodeposition for 600-800 s at-0.2V potential constant potential;
in the step (2), the electropolymerization conditions are as follows: and performing electropolymerization for 15-20 minutes at 0-0.8V by using a cyclic voltammetry technology.
2. The method for preparing the microcystin-LR molecularly imprinted photoelectrochemical sensor according to claim 1, comprising the steps ofIn step (1), Cu is added in a molar ratio2SO4：CH3CH (OH) COOH: the PVP is 1:5: 0.1-1: 10: 30.
3. The preparation method of the microcystin-LR molecularly imprinted photoelectrochemical sensor according to claim 1, wherein in the step (2), the molar ratio of microcystin-LR to pyrrole monomer is 1: 10-1: 50.
4. The method for preparing a microcystin-LR molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the concentration of lithium perchlorate added in the step (2) is 0.1 mol-L-1。
5. The method for preparing a microcystin-LR molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the template removing process is performed under the following conditions in step (3): and removing the template for 10-30 minutes at constant potential plus 1.5V.
6. The application of the microcystin-LR molecularly imprinted photoelectric chemical sensor as claimed in claim 1, wherein the microcystin-LR molecularly imprinted photoelectric chemical sensor is used for rapidly detecting microcystin-LR, and comprises the following steps:
(1) drawing a standard curve: preparing a series of standard solutions of microcystin-LR with concentration by using PBS phosphate buffer solution with pH of 7.2-7.4, taking a microcystin-LR molecular imprinting photoelectrochemical sensor as a working electrode, a platinum sheet as a counter electrode, Ag/AgCl as a reference electrode, visible light as an excitation light source, adding-0.2V bias voltage on a CHI660e electrochemical workstation by using an i-t technology, sequentially detecting according to the sequence of concentration from low to high to obtain different photocurrents, and finally establishing a linear relation between the photocurrent density and the concentration of the microcystin-LR to draw a standard curve;
(2) and (2) similarly preparing the microcystin-LR with unknown solubility into a PBS phosphate buffer solution with the pH value of 7.2-7.4, obtaining the photocurrent under the test condition of the step (1), and obtaining the unknown concentration of the microcystin-LR by using a drawn standard curve.
7. The application of the microcystin-LR molecular imprinting photoelectrochemical sensor according to claim 6 is characterized in that when pond water or river water is detected, the pond water or river water is subjected to suction filtration for 3 times by using a sand core funnel, calcium and magnesium ions in the water are removed by using a precipitator, a certain amount of phosphate is added into a water sample to prepare a PBS phosphate buffer solution with the pH value of 7.2-7.4, a photocurrent is obtained under the test condition of the step (1), and the microcystin-LR concentration in each water sample is obtained by using a drawn standard curve.
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