CN114441504A - Flexible surface-enhanced Raman substrate and preparation method thereof - Google Patents

Flexible surface-enhanced Raman substrate and preparation method thereof Download PDF

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CN114441504A
CN114441504A CN202210086944.XA CN202210086944A CN114441504A CN 114441504 A CN114441504 A CN 114441504A CN 202210086944 A CN202210086944 A CN 202210086944A CN 114441504 A CN114441504 A CN 114441504A
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polystyrene
enhanced raman
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高宇坤
杨楠
尤汀汀
殷鹏刚
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Beihang University
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Abstract

The invention provides a flexible surface enhanced Raman substrate and a preparation method thereof, relating to the technical field of surface enhanced Raman spectrum substrate preparation, wherein the preparation method of the flexible surface enhanced Raman substrate comprises the following steps: s101: taking the organic polymer film with the conductive surface as a substrate for electrodeposition, and performing electrodeposition preparation of a noble metal nano structure on the surface of the organic polymer film by using an electrolyte solution to prepare a product; s102: and (4) washing the product prepared in the step (S101) in pure water to obtain the flexible surface enhanced Raman substrate compounded by the noble metal nanostructure and the organic polymer. The preparation method provided by the invention has the characteristics of simple preparation process and convenient practical application. The silver nano tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate prepared by the preparation method provided by the invention has excellent Raman detection performance, high sensitivity and good reproducibility, and can be effectively used for detecting additives or pesticides in food.

Description

Flexible surface-enhanced Raman substrate and preparation method thereof
Technical Field
The invention relates to the technical field of surface enhanced Raman spectrum substrate preparation, in particular to a flexible surface enhanced Raman substrate and a preparation method thereof.
Background
The Surface Enhanced Raman Spectroscopy (SERS) has the characteristic of nondestructive detection, thereby being a powerful detection means in the fields of analytical chemistry, biological detection, food safety and environmental monitoring. In recent years, there have been many developments in preparing SERS-active substrates for sensitive detection of food additives; for example, noble metal nanostructures are often used in the construction of SERS substrates, based on their excellent surface plasmon properties. Among them, silver nanotreeds have attracted much attention due to their pointed "hot spot" structures. In addition, the common SERS substrate fixes the nano-structure on the solid substrate, so that although the stability and the repeatability of the nano-structure substrate can be improved, the substrate is solid, so that the substrate cannot be directly attached to a detected object, and further the practicability is influenced.
Currently, there is no flexible SERS substrate that can be effectively used for non-planar object detection.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the flexible surface enhanced Raman substrate and the preparation method thereof, and the silver nano tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate prepared by the preparation method provided by the invention has excellent Raman detection performance, high sensitivity and good repeatability, and can be effectively used for detecting additives or pesticides in food. In addition, the preparation method provided by the invention has the characteristics of simple preparation process and convenience in practical application, and the prepared flexible surface enhanced Raman substrate can obtain good surface enhanced Raman signals, so that the preparation method is applied to the field of food safety detection.
One object of the present invention is to provide a method for preparing a flexible surface-enhanced raman substrate, comprising the steps of: s101: taking the organic polymer film with the conductive surface as a substrate for electrodeposition, and performing electrodeposition preparation of a noble metal nano structure on the surface of the organic polymer film by using an electrolyte solution to prepare a product; s102: and (4) washing the product prepared in the step (S101) in pure water to obtain the flexible surface enhanced Raman substrate compounded by the noble metal nanostructure and the organic polymer.
Preferably, in step S101, the electrolyte solution is a silver nitrate solution, and the concentration of the silver nitrate solution is 10 mM.
Preferably, in step S101, the method for preparing a surface-conductive organic polymer thin film includes the following steps: s201: dissolving particles of an organic polymer in dichloromethane to prepare a dichloromethane solution of the organic polymer; s202: injecting the organic polymer dichloromethane solution prepared in the step S201 into a mold, and naturally volatilizing the solvent to prepare an organic polymer film; s203: and (5) carrying out gold spraying treatment on the organic polymer film prepared in the step (S201) to prepare the organic polymer film with the conductive surface.
Further preferably, in step S201, the concentration of the organic polymer dichloromethane solution is 0.8 g/mL.
Further preferably, in step S201, the organic polymer is polystyrene-polybutadiene-polystyrene; the polymerization degree of the polystyrene-polybutadiene-polystyrene is 17% of styrene in terms of styrene content.
Further preferably, in step S202, the amount of the organic polymer dichloromethane solution is 300 μ L; the size of the injection mould is 2cm multiplied by 1cm multiplied by 0.5 cm.
Further preferably, in step S203, the duration of the metal spraying treatment is 2.5 min.
Preferably, in step S101, the electrodeposition preparation includes the following steps: connecting the organic polymer film with the conductive surface with the negative electrode of a direct-current power supply, simultaneously using a carbon rod as the positive electrode, keeping a constant-voltage mode, and performing electrodeposition preparation; wherein, the conditions of the electrodeposition preparation are as follows: the deposition voltage is 1-5V, and the deposition time is 1-5 min.
Further preferably, the conditions for the electrodeposition preparation are as follows: the deposition voltage is 3V, and the deposition time is 3 min.
The flexible surface enhanced Raman substrate prepared by the method is a silver nano tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate.
The invention also aims to protect the flexible surface enhanced Raman substrate prepared by the preparation method.
The invention has the beneficial effects that:
(1) the silver nano tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate prepared by the preparation method provided by the invention has excellent Raman detection performance, higher sensitivity and better repeatability, and can be used for detecting additives or pesticides in food.
(2) The silver nano tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate prepared by the preparation method provided by the invention has the characteristics of simple preparation process and convenience in practical application, can obtain better surface enhanced Raman signals, and can be applied to the field of food safety detection.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a transmission electron microscope image and detection 10 of the flexible surface enhanced Raman substrate prepared in embodiments 1-5 of the present invention- 6M p-MBA surface enhanced Raman spectroscopy result;
FIG. 2 is a transmission electron micrograph of the flexible surface enhanced Raman substrate prepared in example 3 and examples 6 to 9 of the present invention and inspection 10-6M p-MBA surface enhanced Raman spectroscopy results.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The experimental procedures in the following examples are conventional unless otherwise specified.
The test materials used in the following examples were purchased from a conventional reagent store unless otherwise specified.
In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
The invention provides a preparation method of a flexible surface enhanced Raman substrate, which can be used for preparing a silver nano tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate and comprises the following steps:
s101: taking the organic polymer film with the conductive surface as a substrate for electrodeposition, and performing electrodeposition preparation of a noble metal nano structure on the surface of the organic polymer film by using an electrolyte solution to prepare a product; s102: and (4) washing the product prepared in the step (S101) in pure water to obtain the flexible surface enhanced Raman substrate compounded by the noble metal nanostructure and the organic polymer.
In step S101, the electrolyte solution is a silver nitrate solution, and the concentration of the silver nitrate solution is 10 mM.
In step S101, the electrodeposition preparation includes the following steps: connecting the organic polymer film with the conductive surface with the negative electrode of a direct-current power supply, simultaneously using a carbon rod as the positive electrode, keeping a constant-voltage mode, and performing electrodeposition preparation; wherein, the conditions of the electrodeposition preparation are as follows: the deposition voltage is 1-5V, and the deposition time is 1-5 min. Preferably, the conditions for the electrodeposition preparation are as follows: the deposition voltage is 3V, and the deposition time is 3 min.
In step S101, the method for preparing a surface-conductive organic polymer thin film includes the following steps: s201: dissolving particles of an organic polymer in dichloromethane to prepare a dichloromethane solution of the organic polymer; s202: injecting the organic polymer dichloromethane solution prepared in the step S201 into a mold, and naturally volatilizing the solvent to prepare an organic polymer film; s203: and (5) carrying out gold spraying treatment on the organic polymer film prepared in the step (S201) to prepare the organic polymer film with the conductive surface.
In step S201, the concentration of the organic polymer dichloromethane solution is 0.8 g/mL.
In step S201, the organic polymer is polystyrene-polybutadiene-polystyrene; the polymerization degree of the polystyrene-polybutadiene-polystyrene accounts for 17 percent of styrene in terms of styrene content.
In step S202, the dosage of the organic polymer dichloromethane solution is 300 mu L; the size of the injection mould is 2cm multiplied by 1cm multiplied by 0.5 cm.
In step S203, the duration of the metal spraying treatment is 2.5 min.
Example 1
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (1V) and deposition time (3min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Example 2
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (2V) and deposition time (3min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Example 3
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (3V) and deposition time (3min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Example 4
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (4V) and deposition time (3min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Example 5
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (5V) and deposition time (3min) to perform an electrochemical deposition process in a constant-voltage mode. S102: and after the deposition is finished, cleaning the obtained composite film substrate in pure water, storing the cleaned composite film substrate in a mixed solution of pure water and ethanol, taking out the composite film substrate to be dried for subsequent testing when the composite film substrate is required to be used.
Example 6
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (3V) and deposition time (1min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Example 7
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (3V) and deposition time (2min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Example 8
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (3V) and deposition time (4min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Example 9
The embodiment provides a preparation method of a silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate, which comprises the following steps:
(1) firstly, a glassware related in the experimental process is soaked in aqua regia, taken out after half an hour, and washed by a large amount of deionized water.
(2) Preparing a surface-conductive polystyrene-polybutadiene-polystyrene film, comprising the steps of:
s201: polystyrene-polybutadiene-polystyrene particles were first dissolved in 10mL of methylene chloride to prepare a polystyrene-polybutadiene-polystyrene solution (0.8 g/mL). S202: and (3) injecting 300 mu L of polystyrene-polybutadiene-polystyrene solution into a polytetrafluoroethylene mold (2cm multiplied by 1cm multiplied by 0.5cm), placing the polytetrafluoroethylene mold in a fume hood for volatilization, and obtaining the transparent and flexible polystyrene-polybutadiene-polystyrene substrate when the dichloromethane solvent is completely volatilized. S203: and carrying out gold spraying treatment on the substrate by adopting an ion sputtering instrument, wherein the gold spraying time is 2.5 min.
(3) The preparation method of the silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate comprises the following steps:
s101: the method comprises the steps of taking a polystyrene-polybutadiene-polystyrene film as a substrate for electrodeposition, connecting a negative electrode of a direct-current power supply, simultaneously using a carbon rod as a positive electrode, in order to avoid the influence of citric acid on signals of subsequent SERS detection, only using 10mM silver nitrate as an electrolyte solution, and setting deposition voltage (3V) and deposition time (5min) to perform an electrochemical deposition process in a constant-voltage mode. S102: after deposition is finished, the obtained composite film substrate is washed in pure water and stored in a mixed solution of pure water and ethanol, and is taken out and dried for subsequent tests when in use.
Test examples
The flexible surface enhanced raman substrates prepared in examples 1 to 9 were subjected to a performance test.
When in use, the prepared silver nano tree branch-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate is soaked in 10-6And (3) carrying out SERS sensitivity test in M p-mercaptobenzoic acid (p-MBA) solution for 4 h.
The specific results are shown in fig. 1 and fig. 2.
In fig. 1, a to e are transmission electron microscope images of the flexible surface enhanced raman substrate prepared in examples 1 to 5 of the present invention in sequence, and f is a pair of flexible surface enhanced raman substrates 10 prepared in examples 1 to 5 of the present invention-6M p-Surface Enhanced Raman Spectroscopy (SERS) detection of MBA.
In fig. 2, a to e are transmission electron micrographs of the flexible surface-enhanced raman substrates prepared in embodiments 6, 7, 3, 8, and 9 of the present invention in sequence, and f is a pair of flexible surface-enhanced raman substrates 10 prepared in embodiments 6, 7, 3, 8, and 9 of the present invention-6M p-Surface Enhanced Raman Spectroscopy (SERS) detection of MBA.
As can be seen from the figure, by adopting the preparation method provided by the invention, the silver nanometer tree branches and the polystyrene-polybutadiene-polystyrene film can be compounded into the flexible SERS film. The relative standard deviation RSD% of the flexible surface-enhanced raman substrates prepared in examples 1 to 5 of the present invention for the p-MBA assay were 11.2%, 16.8%, 0.7%, 11.7% and 5.2%, respectively. The relative standard deviation RSD% of the flexible surface enhanced raman substrates prepared in example 3 of the present invention and examples 6 to 9 for the p-MBA assay were 16.6%, 1.3%, 0.9%, 8.0% and 10.6%, respectively.
In addition, in addition to the conditions and parameters implemented in examples 1 to 9, other conditions and parameters in the preparation process, etc. may also be used to prepare the flexible surface enhanced raman substrate provided by the present invention.
The silver nanometer tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate provided by the invention has excellent Raman detection performance, high sensitivity and good reproducibility, and can be effectively used for detecting additives or pesticides in food. In addition, the method for preparing the silver nano tree-polystyrene-polybutadiene-polystyrene flexible surface enhanced Raman substrate has the characteristics of simple preparation process and convenience in practical application, and the prepared flexible surface enhanced Raman substrate can obtain good surface enhanced Raman signals and is further applied to the field of food safety detection.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims (10)

1. A preparation method of a flexible surface-enhanced Raman substrate is characterized by comprising the following steps: the preparation method of the flexible surface enhanced Raman substrate comprises the following steps: s101: taking the organic polymer film with the conductive surface as a substrate for electrodeposition, and performing electrodeposition preparation of a noble metal nano structure on the surface of the organic polymer film by using an electrolyte solution to prepare a product; s102: and (4) washing the product prepared in the step (S101) in pure water to obtain the flexible surface enhanced Raman substrate compounded by the noble metal nanostructure and the organic polymer.
2. The method of preparing a flexible surface-enhanced raman substrate according to claim 1, characterized in that: in step S101, the electrolyte solution is a silver nitrate solution, and the concentration of the silver nitrate solution is 10 mM.
3. The method of preparing a flexible surface-enhanced raman substrate according to claim 1, characterized in that: in step S101, the method for preparing a surface-conductive organic polymer thin film includes the following steps: s201: dissolving particles of an organic polymer in dichloromethane to prepare a dichloromethane solution of the organic polymer; s202: injecting the organic polymer dichloromethane solution prepared in the step S201 into a mold, and naturally volatilizing the solvent to prepare an organic polymer film; s203: and (5) carrying out gold spraying treatment on the organic polymer film prepared in the step (S201) to prepare the organic polymer film with the conductive surface.
4. The method of preparing a flexible surface-enhanced Raman substrate according to claim 3, wherein: in step S201, the concentration of the organic polymer dichloromethane solution is 0.8 g/mL.
5. The method of preparing a flexible surface-enhanced Raman substrate according to claim 3, wherein: in step S201, the organic polymer is polystyrene-polybutadiene-polystyrene; the polymerization degree of the polystyrene-polybutadiene-polystyrene accounts for 17 percent of styrene in terms of styrene content.
6. The method of preparing a flexible surface-enhanced Raman substrate according to claim 3, wherein: in step S202, the dosage of the organic polymer dichloromethane solution is 300 mu L; the size of the injection mould is 2cm multiplied by 1cm multiplied by 0.5 cm.
7. The method of preparing a flexible surface-enhanced raman substrate according to claim 3, wherein: in step S203, the duration of the metal spraying treatment is 2.5 min.
8. The method of preparing a flexible surface-enhanced raman substrate according to claim 1, characterized in that: in step S101, the electrodeposition preparation includes the following steps: connecting the organic polymer film with the conductive surface with the negative electrode of a direct-current power supply, simultaneously using a carbon rod as the positive electrode, keeping a constant-voltage mode, and performing electrodeposition preparation; wherein, the conditions of the electrodeposition preparation are as follows: the deposition voltage is 1-5V, and the deposition time is 1-5 min.
9. The method of preparing a flexible surface-enhanced raman substrate according to claim 8, wherein: the conditions of the electrodeposition preparation are as follows: the deposition voltage is 3V, and the deposition time is 3 min.
10. A flexible surface enhanced raman substrate produced by the production method according to any one of claims 1 to 9.
CN202210086944.XA 2022-01-25 2022-01-25 Flexible surface-enhanced Raman substrate and preparation method thereof Pending CN114441504A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101024483A (en) * 2007-03-27 2007-08-29 吉林大学 Constituting method for metal ordered structure surface reinforced base
TW201005278A (en) * 2008-07-29 2010-02-01 Nat Univ Chung Hsing Silver-carbon nanotube-perfluorinated sulfonic acid polymer thin film and electrode modified thereby
CN103411951A (en) * 2013-07-17 2013-11-27 浙江大学 Preparation method of surface enhanced Raman scattering substrate based on spirogram ordered porous membrane
CN106525808A (en) * 2016-09-21 2017-03-22 北京科技大学 Method for preparing flexible surface-enhanced raman base with polymer substrate
CN107084970A (en) * 2017-05-03 2017-08-22 中北大学 A kind of three-dimensional circulated gases SERS detections substrate and preparation method and application
CN108760717A (en) * 2018-06-19 2018-11-06 北京航空航天大学 The noble metal nano particles flexible surface enhancing Raman substrate and preparation method thereof compound with organic polymer
KR20200060578A (en) * 2018-11-21 2020-06-01 한국과학기술원 Block copolymer nanopattern and the method for preparing that

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101024483A (en) * 2007-03-27 2007-08-29 吉林大学 Constituting method for metal ordered structure surface reinforced base
TW201005278A (en) * 2008-07-29 2010-02-01 Nat Univ Chung Hsing Silver-carbon nanotube-perfluorinated sulfonic acid polymer thin film and electrode modified thereby
CN103411951A (en) * 2013-07-17 2013-11-27 浙江大学 Preparation method of surface enhanced Raman scattering substrate based on spirogram ordered porous membrane
CN106525808A (en) * 2016-09-21 2017-03-22 北京科技大学 Method for preparing flexible surface-enhanced raman base with polymer substrate
CN107084970A (en) * 2017-05-03 2017-08-22 中北大学 A kind of three-dimensional circulated gases SERS detections substrate and preparation method and application
CN108760717A (en) * 2018-06-19 2018-11-06 北京航空航天大学 The noble metal nano particles flexible surface enhancing Raman substrate and preparation method thereof compound with organic polymer
KR20200060578A (en) * 2018-11-21 2020-06-01 한국과학기술원 Block copolymer nanopattern and the method for preparing that

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAN YANG 等: "Fabrication of a Flexible Gold Nanorod Polymer Metafilm via a Phase Transfer Method as a SERS Substrate for Detecting Food Contaminants", JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY, vol. 66, pages 6889 - 6896 *

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