CN107436301B - 2, 6-dichlorophenol imprinted sensor based on surface enhanced Raman technology, and preparation method and application thereof - Google Patents
2, 6-dichlorophenol imprinted sensor based on surface enhanced Raman technology, and preparation method and application thereof Download PDFInfo
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- 238000005516 engineering process Methods 0.000 title claims abstract description 23
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- 229910004613 CdTe Inorganic materials 0.000 claims abstract description 88
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
本发明属于功能材料制备技术领域，提供了一种基于表面增强拉曼技术的2,6‑二氯苯酚印迹传感器及其制备方法和用途。步骤如下：步骤1、Ag球的制备；步骤2、Ag/CdTe的制备；步骤3、Ag/CdTe/APTES的制备；步骤4、Ag/CdTe/MIPs传感器的制备。本发明将拉曼检测技术与分子印迹技术结合，使得产物具有灵敏的检测性与高度的选择性；在本发明中，将Ag/CdTe基底与分子印迹技术相结合，其中CdTe是优秀的半导体，拥有独特的光学特性，能够应用于对2,6‑二氯苯酚的检测。高灵敏度金属‑半导体异质结构的SERS材料具有更强的、更灵敏的表面增强拉曼信号。在本发明中，特异的结构使得发明产物成为了更具有竞争力的传感器，并且拓宽了表面增强拉曼散射的应用。
The invention belongs to the technical field of functional material preparation, and provides a 2,6-dichlorophenol imprinted sensor based on surface-enhanced Raman technology, and a preparation method and application thereof. The steps are as follows: step 1, preparation of Ag ball; step 2, preparation of Ag/CdTe; step 3, preparation of Ag/CdTe/APTES; step 4, preparation of Ag/CdTe/MIPs sensor. The present invention combines Raman detection technology with molecular imprinting technology, so that the product has sensitive detection and high selectivity; in the present invention, Ag/CdTe substrate is combined with molecular imprinting technology, wherein CdTe is an excellent semiconductor, With unique optical properties, it can be applied to the detection of 2,6-dichlorophenol. SERS materials with high-sensitivity metal-semiconductor heterostructures have stronger and more sensitive surface-enhanced Raman signals. In the present invention, the specific structure makes the invention product a more competitive sensor and broadens the application of surface-enhanced Raman scattering.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and relates to a high-performance composite surface-enhanced Raman scattering imprinted sensor for detecting 2, 6-dichlorophenol, and a preparation method and application thereof.
Background
In recent years, organic pollution has seriously threatened our living environment. Organic pollutants are pollutants composed of natural organic substances in the form of carbohydrates, proteins, amino acids, fats and the like, and some other biodegradable artificially synthesized organic substances. With the rapid development of economy, the chemical industry produces a large number of toxic chemical polluting emissions, of which chlorophenol is one. The compounds have low biodegradability, high toxicity and durability, can seriously affect the biological denitrification process and even can seriously affect the endocrine system of human. Therefore, the detection of parachlorophenol compounds is very important.
At present, the detection and analysis methods of the parachlorophenol include ultraviolet spectrophotometry, high performance liquid chromatography, gas chromatography, electrochemical methods and the like. However, these conventional methods have many disadvantages such as complicated operation procedures, high detection cost, and most of them require skilled working skills. Therefore, an effective method for rapidly and sensitively detecting the trace chlorophenol in the daily environment is urgently needed to be explored.
In recent years, Surface Enhanced Raman Scattering (SERS) technology has attracted much attention in the field of analysis and detection because of its excellent properties such as low cost, simple preparation process, and easy operation. SERS can detect, identify and quantify targets. Generally, the scattering enhancement factor of SERS is divided into two aspects, the Electromagnetic (EM) mechanism and the Charge Transfer (CT) mechanism. When the target molecule is adsorbed at or near the surface of the substrate, the raman signal will be significantly amplified. In the preparation of SERS substrates, researchers have mostly focused their attention on noble metal nanoparticles (e.g., gold, silver) which provide excellent optical and electronic properties and have strong characteristic absorption in the visible region. Particularly, silver, which is a noble metal, can exhibit more stable SERS detection performance. In view of the high cost of conventional SERS substrates, and to further facilitate and expand the use of SERS, there is a need to develop a low cost, reusable, topographically controllable SERS substrate. Recently, a high-sensitivity metal-semiconductor heterostructure substrate is receiving attention, which is a composite SERS substrate material combining a noble metal nano-material and a semiconductor. For example, Ko and collaborators prepared three-dimensional alumina thin film loaded Au nanoparticles (Au NPs), and studied the SERS enhancing property thereof, which proved that it can detect TNT and HMTD at a molecular level. Although SERS technology has rapidly developed in microchemical detection, current SERS research is mainly focused on modification of substrate materials, ignoring the disadvantage of traditional matrix materials, lack of specific selectivity for target molecules. Therefore, a method is explored as soon as possible to promote the selectivity of the traditional SERS substrate material, and the application range of SERS detection is expanded.
Disclosure of Invention
To improve the selectivity of conventional SERS substrates, the present invention combines Molecular Imprinting (MIT) with conventional SERS detection techniques. It is known that multiple action sites are formed when a template molecule in MIT contacts a polymer monomer, and the action sites are memorized through a polymerization process, and when the template molecule is removed, a cavity having multiple action sites, which can be matched with the spatial configuration of the template molecule, is formed in the polymer, and the cavity has specific selectivity to the template molecule. The defect of lack of selectivity of the traditional SERS technology can be greatly improved.
The invention combines the SERS technology with the surface molecular imprinting technology, takes Ag/CdTe as an SERS substrate and 2, 6-dichlorophenol (2,6-DCP) as a template molecule, and prepares a high-performance composite SERS imprinting sensor (Ag/CdTe/MIPs) by an Atom Transfer Radical Polymerization (ATRP) technology. Meanwhile, the specific adsorption capacity, the detection sensitivity and the selective detection of the compound are researched. Finally, the performance of the sensor for detecting the 2,6-DCP is actually detected by a sample, and the composite SERS imprinted sensor is found to show excellent detection performance in the aspect of detecting the 2,6-DCP pollutants.
The technical scheme adopted by the invention is as follows:
a preparation method of a 2, 6-dichlorophenol imprinting sensor based on a surface enhanced Raman technology comprises the following steps:
Mixing AgNO3Dispersing the solution, namely the mandelic acid solution in water, performing ultrasonic treatment for several minutes, stirring for several minutes under an ice bath condition, quickly adding the VC solution, continuously stirring, reacting for 15min, performing centrifugal separation on the synthesized product, washing and drying to obtain Ag nanospheres; standby;
step 2, preparation of Ag/CdTe
Mixing the silver nanosphere prepared in the step 1 with CdCl2TGA is dispersed in water, and the pH value is adjusted to 10-12 by NaOH solution to obtain mixed solution A;
at the same time, mixing Te powder and NaBH4Mixing with a small amount of water in a centrifuge tube, sealing and ultrasonically treating, and removing excessive gas with a needle until the solution color becomes colorless; preparing a precursor;
quickly injecting the precursor into the mixed solution A, continuously introducing nitrogen, raising the temperature to 90-110 ℃, performing reflux reaction for 23-25h, then performing centrifugal separation on the synthesized product, washing and drying to obtain Ag/CdTe; standby;
step 3, preparation of Ag/CdTe/APTES
Dispersing the Ag/CdTe prepared in the step (2) in a toluene solution, adding APTES, raising the temperature to 80-100 ℃, reacting for 23-25h, after the reaction is finished, centrifugally separating the synthesized product, washing, and drying in vacuum to obtain Ag/CdTe/APTES; standby;
step 4, preparing Ag/CdTe/MIPs sensor
Dispersing the product Ag/CdTe/APTES prepared in the step 3 into a mixed solution of TEA and Tetrahydrofuran (THF), introducing N2After several minutes, dropwise adding a THF and 2-BIB mixed solution, introducing nitrogen and carrying out ice bath in the whole process, continuously introducing the nitrogen for several minutes after the dropwise adding is finished, sealing, and continuously reacting at room temperature for 23-25 hours after 1.0-3.0 hours of ice bath; after the reaction is finished, centrifugally washing and separating the synthesized product, and drying for later use, and marking as a product A;
dispersing the product A, MAA, AM and EGDMA into acetonitrile, slowly stirring at room temperature for 2.0-4.0h, introducing nitrogen, adding cleaned CuBr and bipyridyl, continuously introducing nitrogen in the whole process, sealing, raising the temperature to 60-80 ℃, reacting for 23-25h to obtain the Ag/CdTe/MIPs sensor, repeatedly washing with acetonitrile, ethanol and water, centrifuging, separating and drying.
In step 1, the AgNO3The dosage ratio of the solution, the mandelic acid solution, the water and the VC solution is 1.0 mL: 40-60 μ L: 5.0-15 mL: 0.5-1.5 mL;
the AgNO3The concentration of the solution was 1.0mol L-1The concentration of the mandelic acid solution is 0.25mol L-1The concentration of the VC solution is 1.0mol L-1The temperature is below zero.
In step 2, the silver nanospheres and CdCl2TGA, Te powder and NaBH4The dosage ratio is 50 mg: 300-400 mg: 300-400 mg: 50-55 mg: 70-90 mg;
the concentration of the NaOH solution is 1.0 mol.L-1。
In the step 3, the dosage ratio of the Ag/CdTe, the toluene and the APTES is 500mg:45-55mL:1.0-2.0 mL.
In step 4, when the product A is prepared,
the dosage ratio of the Ag/CdTe/APTES, TEA and THF mixed solution is as follows: the dosage ratio of Ag/CdTe/APTES, TEA and THF is 500mg: 2.0-4.0 mL: 20-40 mL;
the dosage ratio of each substance in the Ag/CdTe/APTES, THF and 2-BIB mixed solution is as follows: the dosage ratio of Ag/CdTe/APTES, THF and 2-BIB is 500mg: 10-20 mL: 2.0-4.0 mL;
in the step 4, when the Ag/CdTe/MIPs sensor is prepared, the dosage ratio of the products A, MAA, AM, EGDMA, acetonitrile, CuBr and bipyridyl is 500mg: 2.0-4.0 mmol: 3.0-5.0 mmol: 5.0-15 mmol: 70-90 mL: 0.3-0.4 mmol: 2.2-2.3 mmol.
In steps 1-4, the washing is performed 3 times with ethanol.
The Ag/CdTe sensor is used for selectively adsorbing 2, 6-DCP.
The preparation method of the corresponding non-imprinted polymer is similar to the synthesis method, but 2,6-DCP is not added, and the product is marked as Ag/CdTe/NIPs.
The invention has the technical advantages that:
the invention combines the Raman detection technology and the molecular imprinting technology, so that the product has sensitive detectability and high selectivity; in the present invention, an Ag/CdTe substrate is combined with molecular imprinting techniques, where CdTe is an excellent semiconductor possessing unique optical properties. The SERS material of the high-sensitivity metal-semiconductor heterostructure has stronger and more sensitive surface enhanced Raman signals. In the invention, the specific structure makes the product become a more competitive sensor and widens the application of surface enhanced Raman scattering.
Drawings
FIG. 1 is a scanning electron micrograph of Ag nanoparticles (a), Ag/CdTe composite material (b), Ag/CdTe composite material (c), Ag/CdTe/MIPs (d) (the upper right corner of the image in d is a transmission electron micrograph of Ag/CdTe/MIPs) (the size of the transmission electron micrograph is 1 micron, and the size of the transmission electron micrograph is 50 nm);
FIG. 2 is an infrared spectrum of Ag/CdTe/MIPs (a) and Ag/CdTe/NIPs (b);
FIG. 3 is an X-ray diffraction spectrum of Ag nanoparticles (a), Ag/CdTe composite (b), Ag/CdTe/MIPs (c), and Ag/CdTe/NIPs (d);
FIG. 4 is a graph showing the adsorption performance of Ag/CdTe/MIPs and Ag/CdTe/NIPs on different targets;
FIG. 5 Raman spectra (a) and 1596cm for detection of 2,6-DCP at different concentrations for Ag/CdTe/MIPs-1A detection linear relation graph (b) of the Raman intensity of Ag/CdTe/MIPs and the concentration change of the 2, 6-DCP;
FIG. 6 Ag/CdTe/MIPs in a concentration of 10-5mol L-1Selective detection of 2,6-dcp (a), 2,5-dcp (b) and hydroquinone (c).
Detailed Description
The invention is further described with reference to the drawings and the detailed description.
Example 1:
(1) synthesis of Ag balls
In a 25mL flask, 1.0mL of AgNO was added3 Dispersing 40 μ L mandelic acid solution in 5.0mL water, ultrasonically treating for several minutes, stirring for several minutes under ice bath condition, rapidly adding 0.5mL VC, stirring, reacting for 15min, centrifuging the resultant, repeatedly washing for several times, and vacuum drying for use.
(2) Synthesis of Ag/CdTe
In a 150mL flask, 50mgAg ball, 300mgCdCl2300mg TGA dispersed in 100mL of water with 1.0mol L-1NaOH is used for adjusting the pH value to 10, and a precursor is added, namely 50mg of Te powder and 70mg of NaBH4Mixing with a small amount of water in a centrifuge tube, sealing the ultrasonic wave, and removing excessive gas with a needle until the solution color becomes colorless. And quickly injecting the precursor into the solution, continuously introducing nitrogen, raising the temperature to 90-110 ℃, carrying out reflux reaction for 23-25h, then, centrifugally separating the synthesized product, repeatedly washing for several times, and then, carrying out vacuum drying for later use.
(3) Synthesis of Ag/CdTe/APTES
In a 150mL single-neck flask, 500mg of Ag/CdTe is dispersed in 45mL of toluene solution, 1.0mL of APTES is added, and the temperature is raised to 90 ℃ to react for 24 h. Subsequently, the synthesized product was centrifuged, washed with ethanol repeatedly three times, and vacuum-dried for use.
(4) Preparation of Ag/CdTe/MIPs molecularly imprinted polymer
In a 150mL single-neck flask, 500mg of Ag/CdTe/APTES was dispersed in a mixed solution of 2.0mL of TEA and 20mL of THF, and a mixed solution of 10mL of THF and 2.0mL of 2-BIB was added dropwise under nitrogen to react for 2.0 hours under ice bath conditions and then for 24 hours at room temperature. And (4) centrifugally separating a synthesized product, washing the synthesized product with ethanol for three times, and drying the synthesized product in vacuum for later use.
Dispersing the product into 2.0mmol MAA, 3.0mmol AM, 5.0mmol EGDMA and 70mL acetonitrile in a 150mL single-neck flask, slowly stirring at room temperature for 3.0h, introducing nitrogen for 15min, adding washed CuBr 0.3mmol and 2.2mmol bipyridyl, and introducing nitrogen continuously and sealing. And raising the temperature to 70 ℃ for reaction for 24h to obtain the Ag/CdTe/MIPs sensor, then repeatedly washing with acetonitrile, ethanol and water, centrifugally separating and drying.
Wherein, in the reaction system in the step (1), the dosage ratio of the mandelic acid, the water and the VC is 40 mul: 5.0mL:0.5 mL. The washing in the step is ethanol washing for 3 times.
In the reaction system in the step (2), CdCl2TGA, Te powder and NaBH4The dosage ratio of the components is 300mg to 50mg to 70 mg. The washing in the step is ethanol washing for 3 times.
In the reaction system in the step (3), the dosage ratio of the toluene to the APTES is 45mL:1.0 mL. The washing in the step is ethanol washing for 3 times.
In the reaction system in the step (4), the dosage ratio of TEA to THF is 2.0mL to 20 mL; the dosage ratio of THF to 2-BIB is 10mL to 2.0 mL; the dosage ratio of MAA, AM, EGDMA, acetonitrile, CuBr and bipyridine is 2.0mmol, 3.0mmol, 5.0mmol, 70mL, 0.3mmol and 2.2 mmol. The washing in the step is that ethanol and water are respectively washed for 3 times.
The corresponding non-imprinted polymers of the invention are prepared analogously to the synthesis as described above, but without the addition of 2, 6-DCP.
Example 2:
(1) synthesis of Ag balls
In a 25mL flask, 1.0mL of AgNO was added3Solutions of50 mu L of mandelic acid solution is dispersed in 10mL of water, ultrasonic treatment is carried out for several minutes, stirring is carried out for several minutes under the ice bath condition, 1.0mL of VC is rapidly added, stirring is continuously carried out, after reaction is carried out for 15min, the synthesized product is centrifugally separated, repeatedly washed for several times, and vacuum drying is carried out for standby.
(2) Synthesis of Ag/CdTe
In a 150mL flask, 50mg of silver, 365mg of CdCl2360mg TGA was dispersed in 100mL of water, using 1.0mol L-1NaOH is used for regulating the PH value to 11, and a precursor is added, namely 51mg of Te powder and 80mg of NaBH4Mixing with a small amount of water in a centrifuge tube, sealing the ultrasonic wave, and removing excessive gas with a needle until the solution color becomes colorless. And (3) quickly injecting the precursor into the solution, continuously introducing nitrogen in the whole process, raising the temperature to 90-110 ℃, carrying out reflux reaction for 23-25h, carrying out centrifugal separation on the synthesized product, repeatedly washing for several times, and carrying out vacuum drying for later use.
(3) Synthesis of Ag/CdTe/APTES
In a 150mL single-neck flask, 500mg of Ag/CdTe is dispersed in 50mL of toluene solution, 1.5mL of APTES is added, and the temperature is raised to 90 ℃ to react for 24 h. Subsequently, the synthesized product was centrifuged, washed with ethanol repeatedly three times, and vacuum-dried for use.
(4) Preparation of Ag/CdTe/MIPs molecularly imprinted polymer
In a 150mL single-neck flask, 500mg of Ag/CdTe/APTES was dispersed in a mixed solution of 3.0mL of TEA and 30mL of THF, and a mixed solution of 15mL of THF and 3.0mL of 2-BIB was added dropwise thereto under nitrogen, followed by reaction for 2.0 hours under ice bath conditions and further reaction for 24 hours at room temperature. And (4) centrifugally separating a synthesized product, washing the synthesized product with ethanol for three times, and drying the synthesized product in vacuum for later use.
In a 150mL single-neck flask, the product is dispersed into 3.0mmol MAA, 4.0mmol AM, 10mmol EGDMA and 80mL acetonitrile, slowly stirred at room temperature for 3.0h, then purged with nitrogen for 15min, washed CuBr 0.38mmol and 2.28mmol bipyridine are added, and the whole process is continued to be purged with nitrogen and sealed. And raising the temperature to 70 ℃ for reaction for 24h to obtain the Ag/CdTe/MIPs sensor, then repeatedly washing with acetonitrile, ethanol and water, centrifugally separating and drying.
Wherein, in the reaction system in the step (1), the dosage ratio of the mandelic acid, the water and the VC is 50 μ L, 10mL and 1.0 mL. The washing in the step is ethanol washing for 3 times.
In the reaction system in the step (2), CdCl2TGA, Te powder and NaBH4The dosage ratio of the components is 365mg to 360mg to 51mg to 80 mg. The washing in the step is all washing with ethanol for 3 times.
In the reaction system in the step (3), the dosage ratio of the toluene to the APTES is 50mL:1.5 mL.
In the reaction system in the step (4), the dosage ratio of TEA to THF is 3.0mL:30 mL; the dosage ratio of THF to 2-BIB is 15mL:3.0 mL; the dosage ratio of MAA, AM, EGDMA, acetonitrile, CuBr and bipyridine is 3.0mmol to 4.0mmol to 10mmol to 80mL to 0.38mmol to 2.28 mmol. The washing in the step is respectively washing with ethanol and water for 3 times.
The corresponding non-imprinted polymers of the invention are prepared analogously to the synthesis as described above, but without the addition of 2, 6-DCP.
Example 3:
(1) synthesis of Ag balls
In a 25mL flask, 1.0mL of AgNO was added3 Dispersing 60 mu L of mandelic acid solution in 15mL of water, performing ultrasonic treatment for several minutes, stirring for several minutes under the ice bath condition, rapidly adding 1.5mL of VC, continuing stirring, reacting for 15min, centrifugally separating the synthesized product, repeatedly washing for several times, and performing vacuum drying for later use.
(2) Synthesis of Ag/CdTe
In a 150mL flask, 50mg of silver, 400mg of CdCl2400mg TGA dispersed in 100mL of water with 1.0mol L-1Adjusting the pH value to 12 with NaOH, adding a precursor of 55mg of Te powder and 90mg of NaBH4Mixing with a small amount of water in a centrifuge tube, sealing the ultrasonic wave, and removing excessive gas with a needle until the solution color becomes colorless. And quickly injecting the precursor into the solution, continuously introducing nitrogen, raising the temperature to 90-110 ℃, carrying out reflux reaction for 23-25h, then carrying out centrifugal separation on the synthesized product, repeatedly washing for several times, and carrying out vacuum drying for later use.
(3) Synthesis of Ag/CdTe/APTES
In a 150mL single-neck flask, 500mg of Ag/CdTe is dispersed in 55mL of toluene solution, 2.0mL of APTES is added, and the temperature is raised to 90 ℃ to react for 24 h. Subsequently, the synthesized product was centrifuged, washed with ethanol repeatedly three times, and vacuum-dried for use.
(4) Preparation of Ag/CdTe/MIPs molecularly imprinted polymer
In a 150mL single-neck flask, 500mg of Ag/CdTe/APTES was dispersed in a mixed solution of 4.0mL of TEA and 40mL of THF, and a mixed solution of 20mL of THF and 4.0mL of 2-BIB was added dropwise under nitrogen to react for 2.0 hours under ice bath conditions and then for 24 hours at room temperature. And (4) centrifugally separating a synthesized product, washing the synthesized product with ethanol for three times, and drying the synthesized product in vacuum for later use.
Dispersing the product into 4.0mmol MAA, 5.0mmol AM, 15mmol EGDMA and 90mL acetonitrile in a 150mL single-neck flask, slowly stirring at room temperature for 3.0h, introducing nitrogen for 15min, adding washed CuBr 0.4mmol and 2.3mmol bipyridyl, and continuously introducing nitrogen and sealing in the whole process. And raising the temperature to 70 ℃ for reaction for 24h to obtain the Ag/CdTe/MIPs sensor, then repeatedly washing with acetonitrile, ethanol and water, centrifugally separating and drying.
Wherein, in the reaction system in the step (1), the dosage ratio of the mandelic acid, the water and the VC is 60 mu L, 15mL and 1.5 mL. The washing in the step is ethanol washing for 3 times.
In the reaction system in the step (2), CdCl2TGA, Te powder and NaBH4The dosage ratio of the components is 400mg to 55mg to 90 mg. The washing in the step is all washing with ethanol for 3 times.
In the reaction system in the step (3), the dosage ratio of the toluene to the APTES is 55mL to 2.0 mL.
In the reaction system in the step (4), the dosage ratio of TEA to THF is 4.0mL:40 mL; the dosage ratio of THF to 2-BIB is 20mL:4.0 mL; the dosage ratio of MAA, AM, EGDMA, acetonitrile, CuBr and bipyridine is 4.0mmol:5.0 mmol:15mmol:90mL:0.4mmol:2.3 mmol. The washing in the step is respectively washing with ethanol and water for 3 times.
The corresponding non-imprinted polymers of the invention are prepared analogously to the synthesis as described above, but without the addition of 2, 6-DCP.
The specific Raman detection of the invention is carried out according to the following method that all the Raman detection conditions are consistent in the experiment, and the wavelength of the excitation light is 633 nm. The spectral collection and exposure time for each sample was 10s, and the power of the incident laser was 0.25 mW. The SERS spectra were collected using a 50 × nikon lens. All SERS substrates are placed on a glass slide and naturally dried for detection of surface enhanced Raman spectroscopy.
Experimental example 1 As shown in FIG. 5(a), 2,6-DCP was used as a template molecule to detect the SERS activity of Ag/CdTe/MIPS and determine the detection limit. The graph shows that it is 1596cm-1The intensity of the surface enhanced raman spectrum is the strongest. As can be seen from the data, the 2,6-DCP concentration varied from 10-5mol L-1To 10-9mol L-1The intensity of SERS also changes. When the concentration of the 2,6-DCP is 10-10mol L-1The raman signal almost disappeared. Further, as shown in FIG. 5(b), the change in the characteristic peak intensity is linear with the change in the concentration of 2, 6-DCP. The concentration of 2,6-DCP is 10-5mol L-1To 10-9mol L-1In the middle (R)2) The detection coefficient of (3) was 0.96.
Experimental example 2 to investigate the specific selectivity of Ag/CdTe/MIPS to 2,6-DCP, we used 2,5-DCP and benzenediol, which have a structure similar to that of 2,6-DCP, for further investigation. As shown in FIG. 6, the adsorption concentration of Ag/CdTe/MIPS is 10-5mol L-1The 2,6-DCP, 2,5-DCP and benzenediol have different molecular structures from the 2,6-DCP and cannot be selectively adsorbed by Ag/CdTe/MIPS, so that only weak surface enhanced Raman spectrum intensity can be observed.
FIG. 1 is a scanning electron microscope image of Ag nanoparticles (a), Ag/CdTe composite material (b), Ag/CdTe composite material scanning mapping image (c), and Ag/CdTe/MIPs (d), and it can be seen from FIG. 1 that the prepared material has uniform size and good dispersibility;
FIG. 2 is an infrared spectrum of Ag/CdTe/MIPs (a) and Ag/CdTe/NIPs (b), from FIG. 2 it can be seen that the polymerization reaction was successfully initiated;
FIG. 3 is an X-ray diffraction spectrum of Ag nanoparticles (a), Ag/CdTe composite (b), Ag/CdTe/MIPs (c), and Ag/CdTe/NIPs (d), it can be seen from FIG. 3 that the Ag nanoparticles have been successfully prepared and successfully loaded with CdTe;
FIG. 4 is a graph showing the adsorption performance of Ag/CdTe/MIPs and Ag/CdTe/NIPs on different targets, and it can be seen from FIG. 4 that Ag/CdTe/MIPs exhibits more excellent selective adsorption performance than Ag/CdTe/NIPs.
Claims (9)
1. A preparation method of a 2, 6-dichlorophenol imprinting sensor based on a surface enhanced Raman technology is characterized by comprising the following steps:
step 1, preparing Ag nanospheres for later use;
step 2, preparation of Ag/CdTe:
mixing the silver nanosphere prepared in the step 1 with CdCl2Thioglycolic acid TGA is dispersed in water, and the pH value is adjusted to 10-12 by NaOH solution to obtain mixed solution A;
at the same time, mixing Te powder and NaBH4Mixing with a small amount of water in a centrifuge tube, sealing and ultrasonically treating, and removing excessive gas with a needle until the solution color becomes colorless; preparing a precursor;
quickly injecting the precursor into the mixed solution A, continuously introducing nitrogen, raising the temperature to 90-110 ℃, performing reflux reaction for 23-25h, then performing centrifugal separation on the synthesized product, washing and drying to obtain Ag/CdTe; standby;
step 3, preparing Ag/CdTe/APTES:
dispersing the Ag/CdTe prepared in the step 2 in a toluene solution, adding 3-aminopropyl triethoxysilane APTES, heating to 80-100 ℃, reacting for 23-25h, after the reaction is finished, centrifugally separating the synthesized product, washing, and drying in vacuum to obtain Ag/CdTe/APTES; standby;
step 4, preparing the Ag/CdTe/MIPs sensor:
dispersing the product Ag/CdTe/APTES prepared in the step 3 into a mixed solution of triethanolamine TEA and Tetrahydrofuran (THF), introducing N2After several minutes, dropwise adding a mixed solution of THF and bromoisobutyryl bromide 2-BIB, introducing nitrogen and carrying out ice bath in the whole process, continuously introducing nitrogen for several minutes after the dropwise adding is finished, sealing, and continuously reacting at room temperature for 23-25 hours after 1.0-3.0 hours of ice bath; after the reaction is finished, centrifugally washing and separating the synthesized product, and drying the synthesized productUsed, as product A;
dispersing the product A, methacrylic acid MAA, acrylamide AM and ethylene glycol dimethacrylate EGDMA into acetonitrile by taking 2, 6-dichlorophenol as template molecules, slowly stirring for 2.0-4.0h at room temperature, introducing nitrogen, adding cleaned CuBr and bipyridyl, continuously introducing nitrogen in the whole process, sealing, raising the temperature to 60-80 ℃, reacting for 23-25h to obtain the Ag/CdTe/MIPs sensor, and repeatedly washing, centrifugally separating and drying the sensor by using acetonitrile, ethanol and water.
2. The method for preparing a 2, 6-dichlorophenol imprinted sensor based on the surface enhanced raman technology according to claim 1, wherein the method for preparing the Ag nanospheres in step 1 comprises: mixing AgNO3Dispersing the solution and the mandelic acid solution in water, performing ultrasonic treatment for several minutes, stirring for several minutes under an ice bath condition, quickly adding the vitamin C solution, continuously stirring, reacting for 15min, performing centrifugal separation on the synthesized product, washing and drying to obtain the Ag nanospheres.
3. The method for preparing the 2, 6-dichlorophenol imprinting sensor based on the surface enhanced Raman technology according to claim 2, wherein the AgNO is3The dosage ratio of the solution, the mandelic acid solution, the water and the VC solution is 1.0 mL: 40-60 μ L: 5.0-15 mL: 0.5-1.5 mL;
the AgNO3The concentration of the solution was 1.0mol L-1The concentration of the mandelic acid solution is 0.25mol L-1The concentration of the VC solution is 1.0mol L-1The temperature is below zero ℃; the washing is ethanol washing for 3 times.
4. The method for preparing a 2, 6-dichlorophenol imprinted sensor based on the surface-enhanced raman technique according to claim 1, wherein in the step 2, the silver nanospheres and the CdCl are prepared2TGA, Te powder and NaBH4The dosage ratio is 50 mg: 300-400 mg: 300-400 mg: 50-55 mg: 70-90 mg;
the concentration of the NaOH solution is 1.0 mol.L-1。
5. The method for preparing a 2, 6-dichlorophenol imprinting sensor based on the surface enhanced Raman technology according to claim 1, wherein in the step 3, the dosage ratio of Ag/CdTe, toluene and APTES is 500mg:45-55mL:1.0-2.0 mL.
6. The method for preparing the 2, 6-dichlorophenol imprinting sensor based on the surface enhanced Raman scattering technology according to claim 1, wherein in the step 4, when preparing the product A,
the dosage ratio of the Ag/CdTe/APTES, TEA and THF mixed solution is as follows: the dosage ratio of Ag/CdTe/APTES, TEA and THF is 500mg: 2.0-4.0 mL: 20-40 mL;
the dosage ratio of each substance in the Ag/CdTe/APTES, THF and 2-BIB mixed solution is as follows: the dosage ratio of Ag/CdTe/APTES, THF and 2-BIB is 500mg: 10-20 mL: 2.0-4.0 mL.
7. The method for preparing a 2, 6-dichlorophenol imprinting sensor based on the surface enhanced Raman scattering technology according to claim 1, wherein in the step 4, when preparing the Ag/CdTe/MIPs sensor,
the dosage ratio of the product A, MAA, AM, EGDMA, acetonitrile, CuBr and bipyridine is 500mg: 2.0-4.0 mmol: 3.0-5.0 mmol: 5.0-15 mmol: 70-90 mL: 0.3-0.4 mmol: 2.2-2.3 mmol.
8. The method for preparing the 2, 6-dichlorophenol imprinting sensor based on the surface enhanced raman technology according to claim 1, wherein in steps 2 to 4, all the washings are 3 times of ethanol washing.
9. A2, 6-dichlorophenol imprinting sensor based on a surface enhanced Raman technology is characterized by being prepared by the preparation method of any one of claims 1-8.
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