CN111830094A - Molecularly imprinted photoelectrochemical sensor and preparation method and application thereof - Google Patents
Molecularly imprinted photoelectrochemical sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of sensors, and particularly discloses a molecularly imprinted photoelectrochemical sensor and a preparation method and application thereof. According to the invention, the traditional photocatalyst titanium dioxide is used as a substrate, the gold nanoparticles and the graphene are used for amplifying photoelectrochemical signals of the electrochemical sensor, and a molecular imprinting technology is introduced, so that the problem of insufficient selectivity of most photoelectrochemical sensors is solved, the identification capability of TBBPA is greatly improved, and the molecular imprinting photoelectrochemical sensor is prepared. The invention takes the electronic garbage dust and tap water samples as the real samples of TBBPA to detect, and achieves satisfactory results.
Description
Technical Field
The invention belongs to the technical field of sensors, and particularly relates to a molecular imprinting photoelectrochemical sensor and a preparation method and application thereof.
Background
Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants, and is widely applied to industries such as building materials, electronics, plastics, textiles and the like. Therefore, TBBPA is widely existed in many environmental fields such as air medium, soil, river sediment, electronic waste, water environment and the like. Also, because TBBPA is lipophilic, it is also present in animal or human organs. TBBPA has the activities of bioaccumulation, cytotoxicity, neurotoxicity and endocrine disturbance, and poses great threats to the ecological environment and human health. At present, a large number of methods are used for detecting TBBPA, wherein the photoelectric chemical sensing technology is widely applied to the detection of environmental pollutants and biomolecules due to the characteristics of high sensitivity, convenient carrying and low cost. However, the photoelectrochemistry generates strong hydroxyl radicals, most of the pollutants can be oxidized, and the selectivity is poor. Therefore, the technical problem solved by the invention is how to rapidly, sensitively and accurately detect TBBPA by utilizing a photoelectric sensor technology, and the defect of poor selectivity is overcome.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a molecular imprinting photoelectrochemical sensor.
The invention also aims to provide the molecularly imprinted photoelectrochemical sensor prepared by the method.
The invention further aims to provide application of the molecular imprinting photoelectric chemical sensor in TBBPA detection.
The purpose of the invention is realized by the following scheme:
a preparation method of a molecularly imprinted photoelectrochemical sensor comprises the following steps:
(1) placing tetrabutyl titanate into water, adding a TBBPA ethanol solution to obtain a mixed solution, heating the mixed solution for reaction, cooling a product after the reaction is finished, purifying and drying to obtain a precursor titanium dioxide;
(2) annealing the precursor titanium dioxide prepared in the step (1), and cooling to room temperature to obtain MI-titanium dioxide;
(3) adding the MI-titanium dioxide obtained in the step (2) into an ethylene glycol aqueous solution, uniformly mixing with a chloroauric acid aqueous solution and graphene oxide, adjusting the system to be alkaline, carrying out a heating reaction on the obtained mixed solution, and purifying and drying the obtained product after the reaction is finished to obtain an MI-gold-graphene/titanium dioxide compound;
(4) and (4) dispersing the MI-gold-graphene/titanium dioxide compound obtained in the step (3) in an aqueous solution of an organic solvent, adding a Nafion solution, uniformly mixing to obtain a suspension, dripping the suspension on the surface of a conductive electrode substrate, and drying to obtain the molecular imprinting photoelectric chemical sensor.
Preferably, the volume ratio of the tetrabutyl titanate, the water and the TBBPA ethanol solution in the step (1) is 0.3-2: 5-15: 0.1-0.5; more preferably 0.8 to 1.2: 8-12: 0.2 to 0.3; most preferably 1:10: 0.25.
Preferably, the concentration of TBBPA in the TBBPA ethanol solution in the step (1) is 0.08-0.12M; more preferably 0.1M.
Preferably, the heating reaction in the step (1) is carried out at the temperature of 100-140 ℃ for 4-6 h; more preferably, the temperature is 120 ℃ and the time is 5 h.
Preferably, the annealing treatment in the step (2) is carried out in air, the heating rate is 3-7 ℃/min, the annealing temperature is 480-520 ℃, and the annealing time is 1-3 h; more preferably, the heating rate of the annealing is 5 ℃/min, the annealing temperature is 500 ℃, and the annealing time is 2 h.
Preferably, the mass-volume ratio of the MI-titanium dioxide to the ethylene glycol aqueous solution in the step (3) is 1-2 mg/mL; the mass of the chloroauric acid aqueous solution accounts for 1-2 wt% of the ethylene glycol aqueous solution; the mass fraction of the graphene oxide aqueous solution in the ethylene glycol aqueous solution is 5-10 wt%.
Preferably, the volume ratio of water to ethylene glycol in the ethylene glycol aqueous solution in the step (3) is 1: 0.5-2, preferably 1: 1. the concentration of the chloroauric acid aqueous solution is 0.0364-0.0602M, and is more preferably 0.0486M.
Preferably, the uniform mixing in the step (3) is preferably ultrasonic dispersion for 1-2 hours. Adjusting the system in the step (3) to be alkaline, and adjusting the pH value to be 9.5-10.5; more preferably, the adjustment is carried out using sodium hydroxide at a concentration of 0.1M.
Preferably, the heating reaction in the step (3) is carried out at the temperature of 120-160 ℃ for 3-5 hours; more preferably, the temperature is 140 ℃ and the time is 4 h.
Preferably, the concentration of the MI-gold-graphene/titanium dioxide composite in the step (4) in an ethanol water solution is 1-2 mg/mL.
Preferably, the volume ratio of water to the organic solvent in the aqueous solution of the organic solvent in the step (4) is 1: 0.5-2, preferably 1: 1. the organic solvent is at least one of ethanol, methanol, acetone and the like.
Preferably, the amount of the Nafion solution in the step (4) is such that 5 to 15. mu.L of Nafion solution is added to each 1mL of the aqueous solution of the organic solvent, and more preferably 10. mu.L of Nafion solution is added.
Preferably, the concentration of the Nafion solution in the step (4) is 4-6 wt%, and more preferably 5 wt%.
Preferably, the suspension liquid in the step (4) is 25-50 mu L/cm2Is coated on the surface of the conductive substrate.
Preferably, the conductive electrode is a glassy carbon electrode, a carbon rod electrode, a titanium electrode, or the like.
The molecular imprinting photoelectrochemical sensor is prepared by the method.
The molecular imprinting photoelectric chemical sensor is applied to TBBPA detection. Preferably in the detection of TBBPA in electronic waste recycling station dust and tap water samples.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention relates to a molecular imprinting photoelectrochemical sensor which takes traditional photocatalyst titanium dioxide as a substrate and amplifies photoelectrochemical signals thereof by utilizing gold nanoparticles and graphene.
(2) By introducing the molecular imprinting technology, the invention solves the problem of insufficient selectivity of most of photoelectrochemical sensors, greatly improves the identification capability of the photoelectrochemical sensors on TBBPA, and simultaneously the detection limit of the photoelectrochemical sensors on TBBPA can reach 1 nM.
(3) The invention takes the electronic garbage dust and tap water samples as the real samples of TBBPA to detect, and achieves satisfactory results.
Drawings
Fig. 1 is a TEM topography of titanium dioxide and MI-gold-graphene/titanium dioxide composite in example 1, where panel a corresponds to titanium dioxide and panel B corresponds to MI-gold-graphene/titanium dioxide composite.
Fig. 2 is a graph of the photocurrent response of MI-gold-graphene/titanium dioxide and NI-gold-graphene/titanium dioxide in example 2. NI-gold-graphene/titania (a), MI-gold-graphene/titania (b) in 0.1M phosphate buffer (pH 7.0) and NI-gold-graphene/titania (c), MI-gold-graphene/titania (d) in 0.1M phosphate buffer (pH 7.0) containing 20 μ M TBBPA.
Fig. 3 is a graph of the photocurrent stability of MI-gold-graphene/titanium dioxide as a sensor in 0.1M phosphate buffered solution (pH 7.0) containing 20 μmtbpa in example 2.
Fig. 4 is a graph of photocurrent of the detection limit of MI-gold-graphene/titanium dioxide as a sensor in example 2 for TBBPA in 0.1M phosphate buffered solution (pH 7.0).
Fig. 5 is a graph of the effect of MI-gold-graphene/titanium dioxide as a sensor on the selectivity to 2 μ M TBBPA in 0.1M phosphate buffered saline (pH 7.0) under an external interfering substance in example 3.
FIG. 6 is a graph showing the effect of MI-gold-graphene/titanium dioxide as a sensor in example 4 on the detection of 20. mu.M TBBPA by using 0.1M phosphoric acid buffer solutions at different pH values.
FIG. 7 shows the application of MI-gold-graphene/titanium dioxide as a sensor in the detection of TBBPA in dust of an electronic garbage collection station in example 5; wherein, the graph A corresponds to the current time curve graph of adding 2 mu M TBBPA every 20s, and the graph B corresponds to the linear relation graph between the current increment and the concentration.
FIG. 8 is a graph of the application of MI-gold-graphene/titanium dioxide as a sensor in the detection of TBBPA in tap water samples from example 6. Wherein, the graph A corresponds to the current time curve graph of adding 2 mu M TBBPA every 20s, and the graph B corresponds to the linear relation graph between the current increment and the concentration.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
The room temperature in the embodiment of the invention is 20-30 ℃.
The TBBPA solution of the present invention is dissolved in ethanol and stored at 4 ℃.
Example 1
The MI-gold-graphene/titanium dioxide provided by the embodiment of the invention is prepared by the following steps: (1) first, 2mL of tetrabutyltitanate, 20mL of distilled water, and 0.5mL of 0.1M TBBPA ethanol solution were then poured into the autoclave and mixed thoroughly. The mixture was placed in an oven and held at 120 ℃ for 5 hours. After cooling to room temperature, the white powder was washed with ethanol and distilled water, centrifuged and dried at 60 ℃. The white solid obtained is then annealed at 500 ℃ for 2 hours, followed by crystallization of the titanium dioxide; the template molecule (TBBPA) is removed, leaving a unique recognition site. The resulting material is referred to as MI-titania.
(2) 40mg of MI-titanium dioxide was added to 20mL of an aqueous ethylene glycol solution at a volume ratio of 1:1, and ultrasonically dispersed for 30 minutes. Then, 2mL of the graphene oxide solution (2mg/mL) and 0.42mL of chloroauric acid (0.0486M) were added to the above mixed solution. This was sonicated for 30min and the pH adjusted to 10.5 with 0.1M sodium hydroxide. The resulting solution was transferred to a 25mL autoclave and held at 140 ℃ for 4 hours. Finally obtaining the MI-gold-graphene/titanium dioxide nano composite material.
(3) And (2) adding 2mg of MI-gold-graphene/titanium dioxide into 1mL of ethanol-water mixed solution with the volume ratio, adding 10 mu L of Nafion solution (5 wt%, SIGMA-274704) into the solution, performing ultrasonic dispersion for 1 hour to obtain a suspension of MI-gold-graphene/titanium dioxide, dripping 5 mu L of the suspension on the surface of a glassy carbon electrode (the diameter is 3mm) by using a trace liquid feeder, and naturally airing in the air to obtain the MI-gold-graphene/titanium dioxide sensor.
(4) NI-gold-graphene/titanium dioxide without TBBPA ethanol solution added was used as the control for MI-gold-graphene/titanium dioxide. The preparation process is the same as that of the MI-gold-graphene/titanium dioxide prepared in the steps (1) to (3), and the only difference is that no TBBPA ethanol solution is added in the step (1). The NI-gold-graphene/titanium dioxide sensor is prepared through the subsequent steps.
In example 1, the TEM morphologies of the titanium dioxide and MI-gold-graphene/titanium dioxide are shown in fig. 1. In fig. a, it can be seen that the titanium dioxide is in an amorphous state, and in fig. B, it can be seen that the titanium dioxide nanoparticles and the gold nanoparticles are tightly tiled on the graphene sheet, and the gold nanoparticles are about 5-10 nm.
Example 2
In this embodiment, the application of the prepared molecularly imprinted photoelectrochemical sensor in detecting TBBPA is specifically as follows: the detection is completed in a traditional three-electrode system, a platinum wire electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, the prepared MI-gold-graphene/titanium dioxide is used as a working electrode, and 0.1M phosphoric acid buffer solution (Na)2HPO4/NaH2PO4pH 7.0) as supporting electrolyte solution. The glassy carbon electrode is firstly subjected to grinding and polishing treatment on alumina polishing powder with the particle size of 50nm, and then is subjected to ultrasonic washing by deionized water and absolute ethyl alcohol in sequence.
The process for detecting TBBPA by the molecular imprinting photoelectric chemical sensor comprises the following steps: the specific recognition site on the titanium dioxide and the adsorption effect of the graphene adsorb TBBPA molecules on the surface of the sensor, then target molecules are oxidized through the photocatalysis effect of the gold nanoparticles and the titanium dioxide, and then a current-time curve of the process is recorded by using a photocurrent.
MI-gold-graphene/titania in 0.1M phosphate buffer solution (pH 7.0) and in 0.1M phosphate buffer solution containing 20 μmtbpa (pH 7.0). The specific detection steps are as follows: in a three-electrode system, a platinum wire electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, the prepared MI-gold-graphene/titanium dioxide and 0.1M phosphate buffer solution (Na)2HPO4/NaH2PO4pH 7.0) as supporting electrolyte solution, and an electrochemical workstation as a detection instrument, and performing current-time scanning detection by means of photocurrent, wherein the detection parameters of the current-time curve are as follows: initial potential is 0.48V (oxidation potential of TBBPA), illumination adopts full spectrum, and illumination intensity is 200mW/cm2. Taking NI-gold-graphene/titanium dioxide as a working electrodeAnd (6) comparison.
Fig. 2 is a graph of photocurrent response of MI-gold-graphene/titanium dioxide and NI-gold-graphene/titanium dioxide. The current response value of detecting TBBPA by MI-gold-graphene/titanium dioxide is obviously 1.0 times higher than that of detecting TBBPA by NI-gold-graphene/titanium dioxide, which shows that the molecular imprinting photoelectric chemical sensor has better capability of detecting TBBPA in a water sample.
Fig. 3 is a graph of photocurrent stability of MI-gold-graphene/titania in 0.1M phosphate buffered solution (pH 7.0) containing 20 μ M TBBPA. It can be seen that the MI-gold-graphene/titanium dioxide still maintains excellent stability after 48 cycles.
Fig. 4 is a graph of the photocurrent of the detection limit for TBBPA in MI-gold-graphene/titanium dioxide in 0.1M phosphate buffered solution (pH 7.0). Wherein, the concentration of tetrabromobisphenol A from low to high is 1, 3, 7, 12, 18, 26, 40, 50, 60, 80 and 100nM respectively. The detection range of the MI-gold-graphene/titanium dioxide for detecting the bisphenol A is 1-100 nM, and the lowest detection limit is 1nM, so that the MI-gold-graphene/titanium dioxide is extremely sensitive to the detection of TBBPA when the molecularly imprinted photoelectrochemical sensor is prepared.
Example 3
This example aims to explore the selectivity of MI-gold-graphene/titanium dioxide to TBBPA. To investigate the selectivity of the MI-gold-graphene/titanium dioxide sensor, potassium bromide (KBr), potassium chloride (KCl), sodium chloride (NaCl), sodium nitrate (NaNO) were selected2) Bromophenol blue (BPB) and bisphenol a ethoxylate (BPE). These classes of compounds act as interferents. The specific detection steps are as follows: in a three-electrode system, a platinum wire electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, the prepared MI-gold-graphene/titanium dioxide is used as a working electrode, and 0.1M phosphate buffer solution (Na)2HPO4/NaH2PO4pH 7.0) as supporting electrolyte solution, and an electrochemical workstation as a detection instrument, and performing current-time scanning detection under the illumination condition, wherein the detection parameters of the current-time curve are as follows: initial potential is 0.48V (oxidation potential of TBBPA), illumination adopts full spectrum, and illumination intensityIs 200mW/cm2. The percent (%) value is estimated by the following formula:
percent (%) < j/j >TBBPA×100％
Where j is the photocurrent density of a 20. mu.M interfering substrate solution (10 times the concentration of TBBPA), and jTBBPAIs the photocurrent density in a 2 μmtbpa solution. For comparison, all solutions were tested under the same conditions.
Fig. 5 is a graph of the effect of MI-gold-graphene/titanium dioxide as a sensor on the selectivity to 2 μ M TBBPA in 0.1M phosphate buffered saline (pH 7.0) under an external interfering substance in example 3. As shown, the addition of inorganic ions did not significantly interfere with TBBPA with a relative deviation of less than 10%. The addition of BPB and BPE also did not affect the TBBPA signal too much, and the relative deviation was less than 25%. This example demonstrates that MI-gold-graphene/titanium dioxide has good selectivity for detection of TBBPA.
Example 4
This example consists in adjusting the pH of the initial TBBPA to explore the effect of MI-gold-graphene/titanium dioxide on TBBPA detection at different pH values. The specific detection steps are as follows: in a three-electrode system, a platinum wire electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, the prepared MI-gold-graphene/titanium dioxide is used as a working electrode, and 0.1M phosphate buffer solution (Na) is respectively used2HPO4/NaH2PO4pH 5.0,6.0,7.0,8.0,9.0) as supporting electrolyte solution, and an electrochemical workstation as a detection instrument, and performing current-time scanning detection by means of photocurrent, wherein the detection parameters of the current-time curve are as follows: initial potential is 0.48V (oxidation potential of TBBPA), illumination adopts full spectrum, and illumination intensity is 200mW/cm2。
As can be seen from fig. 6, the oxidation current of the MI-gold-graphene/titanium dioxide sensor in the 20 μmtbpa solution gradually increased as the pH increased from 5.0 to 7.0. Thereafter, as the pH was further increased from 7.0 to 9.0, the oxidation current gradually decreased. Therefore, at pH 7.0, the oxidation current was maintained at the highest level. This is because MI-gold-graphene/titania, when adsorbing TBBPA in acidic solutions, weakens due to surface protonation and strong electrostatic attraction, and in alkaline solutions the opposite. These results show that MI-gold-graphene/titanium dioxide has the highest photoelectrochemical response at pH 7.0 when the TBBPA molecule is neutral.
Example 5
The example shows the application of the MI-gold-graphene/titanium dioxide molecular imprinting photoelectric chemical sensor to the detection of TBBPA in dust in certain electronic garbage dump of stone corner town, Qingyuan, Guangdong province. The specific detection steps are as follows: firstly weighing a certain amount of dust, carrying out vortex aging, carrying out vortex extraction for 3 minutes by using a mixed solvent (v/v/v,1:1:1) of n-hexane, dichloromethane and acetone, and carrying out ultrasonic extraction for 15 minutes. The supernatant was then transferred to a clean glass tube by centrifugation at 5000r/min for 8 minutes. Repeating the extraction for 3 times at N2Concentrating the mixed extractive solution to about 0.5mL under flow rate, purifying the supernatant with solid phase extraction column, eluting the column with n-hexane and dichloromethane, collecting eluate, concentrating to near dryness, and diluting to 1mL with methanol. And diluting the obtained dust standard solution by 10 times for detection. The specific detection steps are as follows: in a three-electrode system, a platinum wire electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, the prepared MI-gold-graphene/titanium dioxide working electrode and the dust extracting solution are added with 0.1M phosphoric acid buffer solution (Na)2HPO4/NaH2PO4pH 7.0) diluted 10 times as supporting electrolyte solution, and performing current-time scanning detection under illumination conditions by using an electrochemical workstation as a detection instrument, wherein the detection parameters of the current-time curve are as follows: initial potential is 0.48V (oxidation potential of TBBPA), illumination adopts full spectrum, and illumination intensity is 200mW/cm2。
FIG. 7 shows the application of MI-gold-graphene/titanium dioxide as a sensor in the detection of TBBPA in dust of an electronic garbage collection station. To the solution was added 2 μ M TBBPA standard solution every 20s in the dust sample. From fig. 7A, it can be seen that MI-gold-graphene/titanium dioxide has a very strong response ability to 2 μ M TBBPA in the dust standard solution, and the current value per increment is very stable. A linear relationship between the current increment (Δ I) and the concentration (Δ C) can be obtained by expressing Δ I (μ a) as 0.03951 Δ C +3.667 × 10-6(FIG. 7B, R)20.999). Can be used forIt is shown that when MI-gold-graphene/titanium dioxide is used as a sensor to detect TBBPA in dust, the concentration of the TBBPA has strong correlation with current. Therefore, the MI-gold-graphene/titanium dioxide sensor has certain potential for detecting TBBPA in the real electronic garbage dust sample.
Example 6
The present example describes the application of a MI-gold-graphene/titanium dioxide molecularly imprinted photoelectrochemical sensor to TBBPA detection of tap water in a laboratory. Tap water was mixed with 0.1M phosphate buffer (1:1) for testing. The specific detection steps are as follows: in a three-electrode system, a platinum wire electrode is used as a counter electrode, a calomel electrode is used as a reference electrode, the prepared MI-gold-graphene/titanium dioxide is used as a working electrode, tap water and 0.1M phosphate buffer solution (Na)2HPO4/NaH2PO4pH 7.0) as supporting electrolyte solution, and performing current-time scanning detection under illumination conditions by using an electrochemical workstation as a detection instrument, wherein detection parameters of a current-time curve are as follows: initial potential is 0.48V (oxidation potential of TBBPA), illumination adopts full spectrum, and illumination intensity is 200mW/cm2。
Fig. 8 shows the effect of MI-gold-graphene/titanium dioxide as a sensor for TBBPA detection in laboratory tap water. To the solution was added 2 μ M TBBPA standard solution every 20s in a tap water sample. From fig. 8A, it can be seen that MI-gold-graphene/titanium dioxide has a very strong response ability to 2 μ M TBBPA in the dust standard solution, and the current value per increment is also very stable. A linear relationship between the current increment (Δ I) and the concentration (Δ C) can be obtained by expressing Δ I (μ a) as 0.05389 Δ C +3.667 × 10-6(FIG. 8B, R)20.999). Therefore, when the MI-gold-graphene/titanium dioxide is used as a sensor to detect TBBPA in tap water, the concentration of the TBBPA has strong correlation with the current. Thus, the MI-gold-graphene/titanium dioxide sensor has certain potential for detecting TBBPA in real tap water samples.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a molecular imprinting photoelectrochemical sensor is characterized by comprising the following steps:
(1) placing tetrabutyl titanate into water, adding a TBBPA ethanol solution to obtain a mixed solution, heating the mixed solution for reaction, cooling a product after the reaction is finished, purifying and drying to obtain a precursor titanium dioxide;
(2) annealing the precursor titanium dioxide prepared in the step (1), and cooling to room temperature to obtain MI-titanium dioxide;
(3) adding the MI-titanium dioxide obtained in the step (2) into an ethylene glycol aqueous solution, uniformly mixing with a chloroauric acid aqueous solution and graphene oxide, adjusting the system to be alkaline, carrying out a heating reaction on the obtained mixed solution, and purifying and drying the obtained product after the reaction is finished to obtain an MI-gold-graphene/titanium dioxide compound;
(4) and (4) dispersing the MI-gold-graphene/titanium dioxide compound obtained in the step (3) in an aqueous solution of an organic solvent, adding a Nafion solution, uniformly mixing to obtain a suspension, dripping the suspension on the surface of a conductive electrode substrate, and drying to obtain the molecular imprinting photoelectric chemical sensor.
2. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the method comprises the steps of:
the volume ratio of the tetrabutyl titanate, the water and the TBBPA ethanol solution in the step (1) is 0.3-2: 5-15: 0.1-0.5.
3. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the method comprises the steps of:
the volume ratio of the tetrabutyl titanate to the water to the TBBPA ethanol solution in the step (1) is 0.8-1.2: 8-12: 0.2 to 0.3;
the concentration of TBBPA in the TBBPA ethanol solution in the step (1) is 0.08-0.12M.
4. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 1, 2 or 3, wherein:
the mass-volume ratio of the MI-titanium dioxide to the ethylene glycol aqueous solution in the step (3) is 1-2 mg/mL; the mass of the chloroauric acid aqueous solution accounts for 1-2 wt% of the ethylene glycol aqueous solution; the mass fraction of the graphene oxide aqueous solution in the ethylene glycol aqueous solution is 5-10 wt%.
5. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the method comprises the steps of:
and (3) the volume ratio of water to ethylene glycol in the ethylene glycol aqueous solution in the step (3) is 1: 0.5 to 2; the concentration of the chloroauric acid aqueous solution is 0.0364-0.0602M;
and (3) adjusting the system to be alkaline, namely adjusting the pH value to be 9.5-10.5.
6. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the method comprises the steps of:
the concentration of the MI-gold-graphene/titanium dioxide compound in the aqueous solution of the organic solvent in the step (4) is 1-2 mg/mL;
and (4) the dosage of the Nafion solution in the step (4) is such that 5-15 mu of the Nafion solution is correspondingly added into each 1mL of the aqueous solution of the organic solvent.
7. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the method comprises the steps of: the concentration of the Nafion solution in the step (4) is 4-6 wt%; the suspension liquid in the step (4) is mixed at 25-50 mu L/cm2The amount of the coating is coated on the surface of the conductive substrate; the volume ratio of water to the organic solvent in the aqueous solution of the organic solvent in the step (4) is 1: 0.5 to 2.
8. The method for preparing a molecularly imprinted photoelectrochemical sensor according to claim 1, wherein the method comprises the steps of:
the heating reaction in the step (1) is carried out at the temperature of 100-140 ℃ for 4-6 h;
the annealing treatment in the step (2) is carried out in air, the heating rate is 3-7 ℃/min, the annealing temperature is 480-520 ℃, and the annealing time is 1-3 h;
and (3) heating to react at 120-160 ℃ for 3-5 h.
9. A molecularly imprinted photoelectrochemical sensor prepared by the method of any one of claims 1 to 8.
10. The use of the molecularly imprinted photoelectrochemical sensor according to claim 9 in TBBPA detection.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112903767A (en) * | 2021-01-25 | 2021-06-04 | 郑州轻工业大学 | WO (WO)3Molecular imprinting type photoelectrochemical sensor and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102735720A (en) * | 2011-04-07 | 2012-10-17 | 同济大学 | Photoelectric chemical analysis method adopting molecular imprinting functionalization modified electrode |
| CN105738445A (en) * | 2016-05-06 | 2016-07-06 | 华东交通大学 | Molecular imprinting sensor and detection method for bisphenol A |
| CN110441380A (en) * | 2019-08-07 | 2019-11-12 | 暨南大学 | A kind of electrochemical sensor and its preparation method and application based on molecular engram electrode technology |
| CN110527039A (en) * | 2019-08-29 | 2019-12-03 | 陕西科技大学 | A kind of magnetic surface molecularly imprinted polymer and its preparation method and application |
-
2020
- 2020-07-02 CN CN202010626200.3A patent/CN111830094B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102735720A (en) * | 2011-04-07 | 2012-10-17 | 同济大学 | Photoelectric chemical analysis method adopting molecular imprinting functionalization modified electrode |
| CN105738445A (en) * | 2016-05-06 | 2016-07-06 | 华东交通大学 | Molecular imprinting sensor and detection method for bisphenol A |
| CN110441380A (en) * | 2019-08-07 | 2019-11-12 | 暨南大学 | A kind of electrochemical sensor and its preparation method and application based on molecular engram electrode technology |
| CN110527039A (en) * | 2019-08-29 | 2019-12-03 | 陕西科技大学 | A kind of magnetic surface molecularly imprinted polymer and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| RANDA AHMAD等: "Nanocomposites of Gold Nanoparticles@Molecularly Imprinted Polymers: Chemistry, Processing, and Applications in Sensors", 《CHEM. MATER.》 * |
| 冯莎莎 等: "二氧化钛分子印迹膜传感器光电流法检测克百威", 《分析测试学报》 * |
| 蔡蓉等: "石墨烯修饰四溴双酚S印迹电化学传感器研究", 《化学通报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112903767A (en) * | 2021-01-25 | 2021-06-04 | 郑州轻工业大学 | WO (WO)3Molecular imprinting type photoelectrochemical sensor and preparation method and application thereof |
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