CN114062455A - Molecular imprinting photoelectric chemical sensor based on MXene/bismuth sulfide composite material and preparation method and application thereof - Google Patents

Molecular imprinting photoelectric chemical sensor based on MXene/bismuth sulfide composite material and preparation method and application thereof Download PDF

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CN114062455A
CN114062455A CN202111331080.5A CN202111331080A CN114062455A CN 114062455 A CN114062455 A CN 114062455A CN 202111331080 A CN202111331080 A CN 202111331080A CN 114062455 A CN114062455 A CN 114062455A
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mxene
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chlorogenic acid
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吕海霞
范德春
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Fuzhou University
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Abstract

The invention belongs to the technical field of sensors, and particularly discloses a molecular imprinting photoelectric chemical sensor based on an MXene/bismuth sulfide composite material, and a preparation method and application thereof. The invention aims to solve the problems that the traditional chlorogenic acid detection method is complex in operation and needs operation of a professional technician. The invention uses a novel semiconductor MXene as a substrate and Bi2S3The molecular imprinting material and MXene form a heterojunction to amplify signals of the photoelectrochemical sensor, and a molecular imprinting technology is introduced, so that the problem of insufficient selectivity is solved, the recognition capability of chlorogenic acid is greatly improved, and the molecular imprinting photoelectrochemical sensor is prepared.

Description

Molecular imprinting photoelectric chemical sensor based on MXene/bismuth sulfide composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoelectric chemical sensing analysis detection and sensing, and particularly relates to a photoelectric chemical sensing device based on MXene/Bi2S3A molecular imprinting photoelectric chemical sensor of composite material.
Background
About 60-80% of antibiotics and anticancer drugs are derived from crude drugs, and therefore, quantitative analysis of the effective components of crude drugs is an important task. Chlorogenic acid is one of phenolic acids, and is composed of caffeic acid and quinic acid. It is widely found in eucommia bark, honeysuckle, dandelion, coffee and other plants. In recent years, chlorogenic acid has attracted considerable attention for its unique pharmacological actions, including anti-oxidant, anti-bacterial and anti-viral, anti-cancer and anti-tumor, protection of the cardiovascular system and reduction of blood lipids and blood glucose. Chlorogenic acid is used as a natural oxidant and polyphenol substances, is a main active ingredient of a plurality of crude drugs, and has important significance for quantitative research due to the medicinal value and the health-care function of the chlorogenic acid. Chlorogenic acid is determined by many methods, such as flow injection chemiluminescence and high efficiency liquid. Despite the wide interest in clinical studies, there is currently a lack of highly sensitive detection.
Compared to other methods, photoelectrochemical sensors have higher sensitivity and lower background signals, which are based on electrochemistry and photochemistry, which spontaneously combine the advantages of both. Under the condition of light irradiation, photo-generated electron transfer is performed between the target analyte and the electrode surface in the presence of the target analyte to amplify and reflect the change of the analysis signal. Meanwhile, the electrochemical equipment is used for detection, so that the detection and analysis method has the advantages of equipment miniaturization, quick response and the like in the future.
MXene has metalloid conductivity, good hydrophilicity, environmental friendliness, biocompatibility, excellent mechanical stability, favorable Fermi level position and no toxicity to organisms. In addition, MXenes have a larger surface area, which makes them readily and strongly interactive with a variety of analytes and photoactive materials. However, MXene material has no specific recognition performance on target substances and has certain limitation in enriching and recognizing specific target substances, and Bi2S3The material has the characteristics of narrow direct band gap, high absorption coefficient and the like, is considered to be a photoelectric material with high potential, however, the narrow band gap easily causes the rapid recombination of photogenerated electrons and holes, reduces the utilization rate of the electrons and the holes, and thus MXene and Bi are mixed2S3Combined to form a composite materialAnd a heterojunction is constructed, so that the photoelectric performance of the composite material is improved.
In recent years, molecular imprinting techniques have been found to have good recognition and selection properties for imprinted molecules. From the perspective of bionics, molecular imprinting techniques utilize artificial methods to prepare polymers that bind to specific template molecules, thereby achieving specific separations. The molecular imprinting layer is used as a natural antibody and has the characteristics of simple preparation, good selectivity and the like.
Disclosure of Invention
The invention aims to solve the problems that the traditional detection and analysis method for chlorogenic acid and other crude drugs is complex in detection method and needs professional personnel to guide operation. The invention mainly aims to provide a film based on MXene/Bi2S3A preparation method and application of a molecular imprinting photoelectric chemical sensor of a composite material.
In order to prepare the photoelectrochemical sensor, MXene and Bi are firstly synthesized by a hydrothermal synthesis method2S3And combining to form a heterojunction. Then the prepared material is loaded to an indium tin oxide electrode (ITO) by a drop coating method, and the composite material is combined with the ITO electrode by electrostatic attraction. And then combining the cross-linking effect of the cross-linking agent and chitosan with chlorogenic acid to be detected to form a molecular imprinting layer, and modifying the molecular imprinting layer on the surfaces of the ITO electrode and the composite material in a dripping mode. The modified working electrode is subjected to photoelectrochemical detection fitting linear equation, and then MXene/Bi-based working electrode is successfully constructed2S3A molecular imprinting photoelectric chemical sensor of composite material. The preparation method comprises the following steps:
step 1, mixing layered MXene solution, thioacetamide solution and pentahydrate bismuth nitrate solution in different proportions, performing ultrasonic stirring treatment, and pouring the obtained mixed solution into a hydrothermal reaction kettle for hydrothermal treatment. The hydrothermal synthesized material is centrifugally washed, and the composite material after vacuum drying is MXene/Bi2S3。
Step 2, putting the clean indium tin oxide glass into methanol, ethanol and ultrapure water in sequence for 10min, naturally drying, and applying an adhesive tape to an electrodeLeaving a surface of about 0.25cm2The circular area of (a) is ready for use.
Step 3, MXene/Bi prepared in step 12S3Dispersing the composite material in ultrapure water for ultrasonic treatment to obtain uniform suspension, taking a proper amount of suspension liquid to be coated on the surface of the exposed circular area of the ITO electrode in the step 2, waiting for natural drying, and obtaining MXene/Bi after drying2S3An ITO electrode of composite material.
Step 4, dissolving chitosan in acetic acid solution, adding chlorogenic acid and sulfuric acid (cross-linking agent) to stir to prepare molecular imprinting polymer film solution, taking out molecular imprinting layer liquid, and dropwise adding MXene/Bi prepared in step 32S3The composite material electrode is prepared by eluting most chlorogenic acid in the molecular imprinting layer by using an ethanol solution after natural air drying, and obtaining the molecular imprinting layer and MXene/Bi after natural air drying2S3The indium tin oxide electrode modified by the composite material is used as a working electrode and is connected into a photoelectrochemical three-electrode system to obtain the electrode based on MXene/Bi2S3A molecular imprinting photoelectric chemical sensor of composite material.
Further, MXene/Bi is prepared by the hydrothermal synthesis method in the step 12S3The mass fraction of MXene in the composite is 0-10% and not 0, preferably 1%, 3%, 5% and 10%, most preferably 5%.
Further, MXene/Bi in the suspension of the step 32S3The concentration of the composite material is 1-10mg/mL, preferably 1mg/mL, 3mg/mL, 5mg/mL, 7mg/mL, 10 mg/mL. Most preferably 5 mg/mL.
Further, the hydrothermal specific method in the step 1 comprises the steps of firstly preparing 5mg/mL MXene monolayer liquid, adding 65mg of bismuth nitrate pentahydrate into 20mL of ultrapure water, stirring for 3 hours, then adding 27mg of thioacetamide, stirring for 0.5 hour, pouring into a 50mL reaction kettle, sealing, and placing in a 160 ℃ hot blast drying box for reaction for 8 hours; after the hydrothermal reaction kettle is cooled to room temperature, taking out the solution in the hydrothermal reaction kettle, sequentially centrifugally washing the solution with ultrapure water and absolute ethyl alcohol (8000 rpm, 3 times each), and drying the precipitate in a vacuum drying oven at 60 DEG CObtaining MXene/Bi at night2S3A composite material.
Further, the suspension concentration in the step 3 is 5mg/mL, and the volume of the solution dripped on the surface of the ITO electrode is 20 uL.
Further, the molecularly imprinted polymeric membrane solution in the step 4 is specifically obtained by adding 250mg of chitosan into 20mL of acetic acid solution (the mass ratio of acetic acid to water is 1: 99), then carrying out water bath at 60 ℃ for 2h, adding 20mg of chlorogenic acid, stirring for 4h, adding 2M sulfuric acid, and continuing to stir for 0.5 h.
Further, the eluent of the step 4 has a concentration of 5wt% to 30wt%, most preferably 10%.
Further, the elution time of the step 4 is 5-40 min, and most preferably 20 min.
Based on MXene/Bi2S3The molecular imprinting photoelectrochemical sensor made of the composite material is prepared by the method, is applied to the detection of chlorogenic acid, and comprises the following steps:
(i) establishing a standard curve of chlorogenic acid detection: absorbing 20uL of chlorogenic acid water samples with different concentrations, dripping the chlorogenic acid water samples on an electrode modified by a molecular imprinting layer, incubating for 20 minutes to absorb chlorogenic acid molecules, washing, putting the chlorogenic acid water samples into a 0.1M sodium sulfate solution, connecting a photoelectrochemical three-electrode system, establishing a standard curve with the abscissa as the concentration of the chlorogenic acid and the ordinate as the intensity of photocurrent by adopting a chronoamperometry and a bias voltage of 0V.
(ii) And (3) absorbing 20uL of a chlorogenic acid water sample with unknown concentration, dripping the chlorogenic acid water sample on an electrode modified by a molecular imprinting layer, adsorbing for 20 minutes, putting the adsorbed electrode into a 0.1M sodium sulfate solution after washing, accessing a photoelectrochemical three-electrode system, introducing the standard curve obtained in the step (i) by adopting an amperometric method and a bias voltage of 0V, and calculating a sample with unknown concentration.
Compared with the prior art, the invention has the following advantages:
1. the invention uses a novel semiconductor MXene as a substrate and Bi2S3And the molecular imprinting photoelectrochemical sensor and the substrate MXene form a heterojunction to amplify a photocurrent signal of the molecular imprinting photoelectrochemical sensor.
2. The invention solves the problem of selective adsorption of molecular structure by introducing molecular imprinting technology, and greatly improves the identification capability of chlorogenic acid.
3. The invention passes MXene/Bi2S3The composite material has a large specific surface area, can load more molecular imprinting layers and target substance adsorption capacity, chlorogenic acid can be detected by using an MXene material alone, but the photoelectric current of a substrate is reduced, the detection limit sensitivity of the molecular imprinting sensor is improved only based on a higher photoelectric current background signal, and the MXene serving as a two-dimensional material can load more molecular imprinting layers, so that the sensor can better detect the target substance.
4. The invention firstly constructs the MXene/Bi-based2S3The photoelectric chemical molecular imprinting sensor made of the composite material is used for detecting chlorogenic acid, and is used for detecting the chlorogenic acid in a water sample, the detection limit is as low as 0.24ng/mL, and the sensitivity is high.
Drawings
FIG. 1 shows MXene/Bi-based preparation of the invention2S3The process schematic diagram of the molecular imprinting photoelectric chemical sensor of the composite material for detecting the chlorogenic acid;
FIG. 2 shows MXene/Bi in example 12S3SEM topography of the composite;
FIG. 3 shows MXene/Bi in example 12S3The composite material is synthesized;
FIG. 4 is a graph of the photocurrent response and corresponding linearity of chlorogenic acid at different concentrations in example 1; wherein the concentration of chlorogenic acid is 1ng/mL, 5ng/mL, 10ng/mL, 50ng/mL, 100ng/mL, 500ng/mL, or 1000 ng/mL.
Detailed description of the preferred embodiments
The invention will now be described more fully and clearly with reference to the accompanying drawings and specific examples of embodiments of the invention. It is to be understood that the following examples are only a part of the present invention and are not intended to limit the scope of the present invention.
In the examples, various reagents, reaction conditions, detection methods, and the like, which are conventionally used in the art, may be used unless otherwise specified.
Example 1
Based on MXene/Bi2S3The preparation method and the application of the molecular imprinting photoelectric chemical sensor of the composite material comprise the following steps:
(1) using ultrasonic cell grinder to process Ti3C2TxThe aqueous solution (pH =6.42) was sonicated for 30 min. Then 0.2 mM Bi (NO)3)3·5H2O is dissolved in Ti containing 1300uL 5mg/mL3C2TxThe aqueous solution was stirred in deionized water for 3 hours to ensure sufficient electrostatic adsorption time. Subsequently, 27mg of thioacetamide (C) was added2H5NS), stirring for 30 min. Transferring the mixed solution into a 50mL autoclave with a polytetrafluoroethylene lining, keeping the temperature at 160 ℃ for reaction for 8h, cooling to room temperature, washing and centrifuging the final black precipitate by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ overnight to obtain MXene/Bi2S3Composite material, and obtaining Bi2S3The properties and morphology of/MXene are shown in FIG. 2, from which Bi can be seen2S3Presents a nano-rod shape with a diameter of about 100nm, and MXene nano-lamella is Bi due to proportion2S3And (4) covering the nanorods. The specific synthetic scheme is shown in FIG. 3.
(2) Dissolving 250mg of chitosan in 20mL of acetic acid solution (the mass ratio of acetic acid to water is 1: 99), and stirring for 2h at 60 ℃; adding chlorogenic acid 25mg and sulfuric acid 25ul 10M into the chitosan solution, stirring at 60 deg.C for 4 hr, filtering to remove impurities, sealing, and storing in shade.
(3) 5mg of Bi2S3Dispersing the/MXene composite material in 1mL of ultrapure water, carrying out ultrasonic treatment for 30min, washing an ITO electrode, and leaving 0.25cm of ITO electrode by using an adhesive tape2The circular hole area of (a); 20uL of 5mg/mL Bi is taken2S3the/MXene solution is dripped in the circular hole area of the ITO electrode and is placed in the air for drying; then, 20uL of molecular imprinting layer is dripped into Bi2S3Naturally drying the electrode modified by the/MXene composite material in the air to obtain the moleculeImprinting the polymer layer, eluting in 10% ethanol water solution for 20min to remove template molecule to obtain Bi-based polymer2S3The molecular imprinting photoelectrochemical sensor of the/MXene composite material.
Firstly, establishing a standard curve for detecting chlorogenic acid; dripping 20uL of chlorogenic acid solution with different concentrations on a molecular imprinting photoelectric electrochemical sensor, continuing specific adsorption for 20min, placing an ITO electrode in 0.1M sodium sulfate solution, and introducing into a photoelectrochemical three-electrode system; adopting an amperometry method, obtaining the photocurrent signal intensity by the bias voltage of 0V, thereby establishing a chlorogenic acid detection standard curve with the abscissa as the concentration of the chlorogenic acid and the ordinate as the photocurrent signal intensity, as shown in FIG. 4, the concentrations of the chlorogenic acid are 1ng/mL, 5ng/mL, 10ng/mL, 50ng/mL, 100ng/mL, 500ng/mL and 1000ng/mL, the photocurrent response value of the sensor is reduced along with the increase of the concentration of the chlorogenic acid, and the linear relation is I =731.604-197.1543logCChlorogenic acid，R2=0.9916, minimum detection limit is 0.24 ng/mL. Then, 20uL of sample with unknown concentration is dripped on the molecular imprinting photoelectric chemical sensor for specific adsorption for 20 min; then the adsorbed electrode is connected into a 0.1M sodium sulfate solution and connected into a photoelectrochemical three-electrode system; and (3) adopting an ampere-timing method, wherein the bias voltage is 0V, obtaining the photocurrent signal intensity, and calculating the final concentration of the sample corresponding to the established chlorogenic acid detection standard curve.
Example 2
Based on MXene/Bi2S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material comprises the following steps:
(1) using ultrasonic cell grinder to process Ti3C2TxThe aqueous solution (pH =6.42) was sonicated for 30 minutes. Then 0.2 mM Bi (NO)3)3·5H2O dissolved in 5mg/mL Ti containing 1950uL3C2TxThe aqueous solution was stirred in deionized water for 3 hours to ensure sufficient electrostatic adsorption time. Subsequently, 27mg of thioacetamide (C) was added2H5NS), stirring for 30 min. Transferring the mixed solution into a 50mL autoclave with a polytetrafluoroethylene lining, keeping the temperature at 160 ℃ for reaction for 8h, and cooling toAfter room temperature, the final black precipitate was washed with deionized water and absolute ethanol and centrifuged and dried in a vacuum oven at 60 ℃ overnight to yield MXene/Bi2S3A composite material.
(2) 25mg of chitosan was dissolved in 20mL of acetic acid solution (acetic acid/water = 99/1) and stirred at 60 ℃ for 2 h; adding chlorogenic acid 25mg and glutaraldehyde 10% 5ul into chitosan solution, stirring at 60 deg.C for 3 hr, filtering to remove impurities, sealing, and storing in shade.
(3) 5mg of Bi2S3Dispersing the/MXene composite material in 1mL of ultrapure water, carrying out ultrasonic treatment for 30min, washing an ITO electrode, and leaving 0.25cm of ITO electrode by using an adhesive tape2The circular hole area of (a); 20uL of 5mg/mL Bi is taken2S3the/MXene solution is dripped in the circular hole area of the ITO electrode and is placed in the air for drying; then, 20uL of molecular imprinting layer is dripped into Bi2S3Naturally drying the electrode modified by the/MXene composite material in the air to obtain a molecularly imprinted polymeric layer, eluting the molecularly imprinted polymeric layer in 10% ethanol water solution for 20min to remove template molecules to obtain the electrode modified by the/MXene composite material based on Bi2S3The molecular imprinting photoelectrochemical sensor of the/MXene composite material.
Example 3
Based on MXene/Bi2S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material comprises the following steps:
(1) using ultrasonic cell grinder to process Ti3C2TxThe aqueous solution (pH =6.42) was sonicated for 30 min. Then 0.2 mM Bi (NO)3)3·5H2O is dissolved in Ti containing 1300uL 5mg/mL3C2TxThe aqueous solution was stirred in deionized water for 3 hours to ensure sufficient electrostatic adsorption time. Subsequently, 27mg of thioacetamide (C) was added2H5NS), stirring for 30 min. Transferring the mixed solution into a 50mL autoclave with a polytetrafluoroethylene lining, keeping the temperature at 160 ℃ for reaction for 8h, cooling to room temperature, washing and centrifuging the final black precipitate by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ overnight to obtain MXene/Bi2S3Composite materialAnd (5) feeding.
(2) 25mg of chitosan was dissolved in 20mL of acetic acid solution (acetic acid/water = 99/1) and stirred at 60 ℃ for 2 h; adding chlorogenic acid 25mg and sulfuric acid 25ul 10M into the chitosan solution, stirring at 60 deg.C for 4 hr, filtering to remove impurities, sealing, and storing in shade.
(3) 5mg of Bi2S3Dispersing the/MXene composite material in 1mL of ultrapure water, carrying out ultrasonic treatment for 30min, washing an ITO electrode, and leaving 0.25cm of ITO electrode by using an adhesive tape2The circular hole area of (a); 20uL of 5mg/mL Bi is taken2S3the/MXene solution is dripped in the circular hole area of the ITO electrode and is placed in the air for drying; then, 20uL of molecular imprinting layer is dripped into Bi2S3Naturally drying the electrode modified by the/MXene composite material in the air to obtain a molecularly imprinted polymeric layer, eluting the molecularly imprinted polymeric layer in 30% ethanol water solution for 30min to remove template molecules to obtain the electrode modified by the/MXene composite material based on Bi2S3The molecular imprinting photoelectrochemical sensor of the/MXene composite material.
Example 4
Based on MXene/Bi2S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material comprises the following steps:
(1) using ultrasonic cell grinder to process Ti3C2TxThe aqueous solution (pH =6.42) was sonicated for 30 min. Then 0.2 mM Bi (NO)3)3·5H2O is dissolved in Ti containing 650uL 5mg/mL3C2TxThe aqueous solution was stirred for 4h in deionized water to ensure sufficient electrostatic adsorption time. Subsequently, 27mg of thioacetamide (C) was added2H5NS), stirring for 30 min. Transferring the mixed solution into a 50mL autoclave with a polytetrafluoroethylene lining, keeping the temperature at 140 ℃ for reaction for 12h, cooling to room temperature, washing and centrifuging the final black precipitate by using deionized water and absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ overnight to obtain MXene/Bi2S3A composite material.
(2) 25mg of chitosan was dissolved in 20mL of acetic acid solution (acetic acid/water = 99/1) and stirred at 60 ℃ for 2 h; adding chlorogenic acid 25mg and sulfuric acid 25ul 10M into the chitosan solution, stirring at 60 deg.C for 4 hr, filtering to remove impurities, sealing, and storing in shade.
(3) 5mg of Bi2S3Dispersing the/MXene composite material in 1mL of ultrapure water, carrying out ultrasonic treatment for 30min, washing an ITO electrode, and leaving 0.25cm of ITO electrode by using an adhesive tape2The circular hole area of (a); 20uL of 5mg/mL Bi is taken2S3the/MXene solution is dripped in the circular hole area of the ITO electrode and is placed in the air for drying; then, 20uL of molecular imprinting layer is dripped into Bi2S3Naturally drying the electrode modified by the/MXene composite material in the air to obtain a molecularly imprinted polymeric layer, eluting the molecularly imprinted polymeric layer in 10% ethanol water solution for 20min to remove template molecules to obtain the electrode modified by the/MXene composite material based on Bi2S3The molecular imprinting photoelectrochemical sensor of the/MXene composite material.
The above embodiments are illustrative of the present invention, but the present invention is not limited to the above embodiments, and any changes, modifications, substitutions, combinations, and simplifications made without departing from the scope of the present invention shall be considered as equivalent replacements within the scope of the present invention.

Claims (9)

1. Based on MXene/Bi2S3The preparation method of the molecular imprinting photoelectrochemical sensor of the composite material is characterized in that the sensor is obtained by sequentially modifying MXene/Bi on the surface of an electrode2S3The composite material and the molecular imprinting layer, wherein the electrode is an indium tin oxide electrode; the preparation method comprises the following steps:
step 1, adding thioacetamide into a mixed solution of single-layer MXene and bismuth nitrate, and ultrasonically stirring uniformly;
step 2, preparing MXene/Bi by adopting a hydrothermal synthesis method2S3Composite material and MXene/Bi2S3The composite material is sealed and stored for later use after being dried in vacuum;
step 3, performing surface pretreatment on the indium tin oxide electrode;
step 4, MXene/Bi obtained in the step 22S3Dispersing the composite material in ultrapure water, uniformly mixing, dripping the mixed liquid on the surface of an indium tin oxide electrode substrate, and drying in air to obtain MXene/Bi2S3Indium tin oxide electrode modified by photoelectric conversion layer;
step 5, dissolving chitosan in acetic acid solution, adding chlorogenic acid and sulfuric acid, stirring to prepare a molecular imprinting polymerization membrane solution, and dropwise adding the solution to MXene/Bi obtained in step 42S3The indium tin oxide electrode modified by the photoelectric conversion layer utilizes ethanol solution to elute chlorogenic acid molecules to obtain a molecular imprinting layer and MXene/Bi2S3The indium tin oxide electrode modified by the composite material is dried in the air and then is used as a working electrode to be connected into a photoelectrochemical three-electrode system, and the MXene/Bi-based indium tin oxide electrode is obtained2S3A molecular imprinting photoelectric chemical sensor modified by a composite material.
2. MXene/Bi-based according to claim 12S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material is characterized by comprising the following steps: step 2 obtaining MXene/Bi2S3The MXene mass fraction of the composite material is 0-10% and is not 0.
3. MXene/Bi-based according to claim 22S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material is characterized by comprising the following steps: in the step 1, the concentration of the single-layer MXene is 5mg/mL, the dosage is 1300uL, the dosage of thioacetamide is 27mg, the dosage of bismuth nitrate is 65mg, and the total volume of the mixed solution is 20 mL.
4. MXene/Bi-based according to claim 12S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material is characterized by comprising the following steps: the hydrothermal synthesis method is to hermetically place the mixture in a hot blast drying oven at 160 ℃ for reaction for 8 hours.
5. MXene/Bi-based according to claim 12S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material is characterized by comprising the following steps: the surface pretreatment in the step 3 comprises the following specific steps: wiping the surface of an indium tin oxide electrode with cotton with alcohol, and sequentially putting the indium tin oxide electrode into acetone, ethanol and ultrapure water for ultrasonic treatment for 10min respectively; after the electrode was removed, it was naturally dried in air and a circular area was reserved with tape for use.
6. MXene/Bi-based according to claim 12S3The preparation method of the molecular imprinting photoelectric chemical sensor of the composite material is characterized by comprising the following steps: MXene/Bi in the mixed solution of the step 42S3The concentration of the composite material is 1-10 mg/mL.
7. MXene/Bi-based products obtained by the process according to any one of claims 1 to 62S3A molecular imprinting photoelectric chemical sensor of composite material.
8. MXene/Bi-based optical fiber according to claim 72S3The application of the molecular imprinting photoelectric chemical sensor of the composite material is characterized in that: used for the analysis and detection of chlorogenic acid.
9. MXene/Bi-based according to claim 82S3The application of the molecular imprinting photoelectric chemical sensor of the composite material is characterized in that: the method comprises the following steps:
(i) drawing a standard curve: the MXene/Bi-based electrolyte is prepared by using 0.1M sodium sulfate solution as an electrolyte2S3The molecular imprinting photoelectrochemical sensor made of the composite material is used as a working electrode, a platinum wire electrode is used as a counter electrode, Ag/AgCl is used as a reference electrode, a 300W xenon lamp is used as an excitation light source, a chronoamperometry method is utilized at a CHI760D electrochemical workstation, no bias voltage is applied, chlorogenic acid solution is detected according to the sequence from low concentration to high concentration, different photocurrent signal intensities are obtained, and finally a standard curve is drawn by taking the chlorogenic acid concentration as an abscissa photocurrent signal intensity as an ordinate;
(ii) determining the content of chlorogenic acid: loading chlorogenic acid solution sample with unknown concentration to MXene/Bi-based2S3And (3) testing the photocurrent signal intensity on the molecular imprinting photoelectrochemical sensor of the composite material under the test condition of the step (i), and obtaining the concentration of the chlorogenic acid by using the standard curve obtained in the step (i).
CN202111331080.5A 2021-11-11 2021-11-11 Molecular imprinting photoelectric chemical sensor based on MXene/bismuth sulfide composite material and preparation method and application thereof Pending CN114062455A (en)

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