CN113433107A - Preparation method of surface-enhanced Raman active substrate - Google Patents
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Abstract
The invention relates to a preparation method of a surface-enhanced Raman active substrate, belonging to the cross field of processing preparation and instrument analysis and detection. Firstly, dripping 1-mercaptomethyl cyclopropyl acetic acid into a silver nitrate solution, and then dripping sodium iodide to prepare green silver iodide sol; then sequentially passing the quartz piece through a mixed solution of concentrated sulfuric acid and oxalic acid and a polymethacryloxyethyltrimethyl ammonium chloride aqueous solution; then, sequentially soaking the silver nanoparticles in silver iodide sol and sodium borohydride solution to obtain a silver nanoparticle substrate; and finally, putting the silver nanoparticle substrate into a mixed solution of diphenylamine, silver oxide, ammonia water, ethanol and a reducing solvent to obtain the surface-enhanced Raman silver nanoparticle substrate material. The preparation method has the advantages of simple operation, low cost, capability of replacing foreign imported raw materials, basically controllable structure, higher uniformity and strong reinforcing capability, and the morphology and the size of the obtained nano structure are easy to control.
Description
Technical Field
The invention relates to a preparation method of a surface-enhanced Raman active substrate, belonging to the cross field of processing preparation and instrument analysis and detection.
Background
Raman spectroscopy (Raman spectroscopy), which is a scattering spectrum, is an analysis method that analyzes a scattering spectrum having a frequency different from that of incident light to obtain information on molecular vibration and rotation, and is applied to molecular structure research. The Raman spectrum and the infrared spectrum are the same as the molecular vibration spectrum and can reflect the characteristic structure of molecules. But the Raman scattering effect is very strongWeak process with scattered light intensity of about 10 of the incident light intensity-6～10-9The application and development of raman spectroscopy are greatly limited.
The surface enhanced Raman scattering effect refers to the phenomenon that in the excitation area, the Raman scattering signals of adsorbed molecules are greatly enhanced compared with common Raman scattering signals due to the enhancement of an electromagnetic field on the surface or near the surface of a sample on the surfaces of specially prepared metal good conductors or in sol. The surface enhanced Raman overcomes the defect of low Raman spectrum sensitivity, can obtain structural information which is not easily obtained by the conventional Raman spectrum, is widely used for surface research, adsorption interface surface state research, interface orientation and configuration of biological large and small molecules, conformation research, structural analysis and the like, and can effectively analyze the adsorption orientation, adsorption state change, interface information and the like of a compound on an interface.
The surface enhanced Raman scattering is that the Raman cross-sectional area of the material can be increased by 10 under the action of metal colloidal particles or rough metal surfaces7By a factor of two, the species that occur on the directly adsorbed metal surface is increased. However, the adsorption performance of the surface enhanced substrate to different materials is different, which causes problems in quantitative analysis, and the reproducibility and stability of the substrate are difficult to control.
The preparation of the active substrate is a precondition for obtaining a surface-enhanced Raman signal, and in the research paper of the active substrate, leek et al in 2003 put forward a preparation method of a novel surface-enhanced Raman active substrate, wherein a silver reinforcing agent and an initiator used in the method are purchased from Sigma company in the United states. This technique is largely dominated by imported products.
Therefore, the invention aims at the problems, researches and innovations are carried out through active experiments, the used raw materials are all made in China, and a completely independent novel method for preparing the silver nanoparticle substrate is expected to be created, so that the silver nanoparticles can grow to the appropriate size, and the optimal Raman enhancement effect is achieved.
Disclosure of Invention
The invention aims to get rid of the problem of dependence on imported raw materials and provide a preparation method of a surface-enhanced Raman active substrate.
The purpose of the invention is realized by the following technical scheme.
A preparation method of a surface enhanced Raman active substrate comprises the following steps:
step one, accurately weighing a certain amount of silver nitrate, putting the silver nitrate into a beaker, slowly dropping deionized water, and preparing to obtain 0.1-10-2Continuously stirring a silver nitrate solution (with the pH value controlled to be 5.2-6.5) in mol/L, adding 1-mercaptomethylcyclopropyl acetic acid in 0.1-0.6mol/L, heating to 30-50 ℃, stirring for 10-50 min, and finally dripping 0.1-10-2mol/L sodium iodide. Stirring for 20min-60min to obtain green silver iodide sol. The mass ratio of silver nitrate, sodium iodide and 1-mercaptomethylcyclopropyl acetic acid is 1: 1: (0.2-0.6), wherein 1-mercaptomethylcyclopropyl acetic acid is used as a sol stabilizer.
Step two, preparing a mixed solution of 70% concentrated sulfuric acid and 35% oxalic acid according to the volume ratio of 3:7, putting the quartz piece into the mixed solution, boiling the quartz piece at 90-120 ℃ until no bubbles are generated, cooling, and cleaning the quartz piece with water.
And step three, putting the quartz piece into a 0.1-0.5 mass percent aqueous solution of polymethacryloxyethyl trimethyl ammonium chloride, soaking for 40-60 min, taking out, and washing with deionized water.
And step four, putting the quartz plate into the silver iodide sol prepared in the step one, soaking for 10-30 min, taking out, and washing with deionized water.
And step five, putting the quartz plate into an excessive sodium borohydride solution, soaking for 10-40 min, taking out, and washing with deionized water to obtain the silver nanoparticle substrate with the prefabricated particle size of 20-80 nm.
And step six, finally, putting the silver nanoparticle substrate into a mixed solution of diphenylamine, silver oxide, ammonia water, ethanol and a reducing solvent, wherein the mass ratio of the substances in the mixed solution is 4: 1: 4: 7: (3-6); and taking out the silver nanoparticles after the silver nanoparticles grow to a proper size, and washing the silver nanoparticles with deionized water to obtain the surface-enhanced Raman silver nanoparticle base material.
The reducing solution is ascorbic acid solvent, formic acid or ethylene glycol or cyclopropane;
advantageous effects
The preparation method of the surface-enhanced Raman active substrate is simple to operate, low in cost, capable of replacing foreign imported raw materials, basically controllable in structure, high in uniformity and strong in enhancing capability, and the morphology and the size of the obtained nano structure are easy to control.
Detailed Description
The following is a further description of the invention in conjunction with the examples
Example 1
A preparation method of a surface enhanced Raman active substrate comprises the following specific steps:
step one, weighing 1.699 g of silver nitrate, putting the silver nitrate into a beaker, slowly dropping deionized water to prepare 10-2Controlling the pH value of a silver nitrate solution of mol/L to be 5.5, simultaneously keeping a certain stirring speed, adding 0.4386 g/L1-mercaptomethylcyclopropyl acetic acid, heating to 40 ℃, stirring for 25min, and finally slowly dropping 10 g of sodium iodide prepared by 1.4989 g-2mol/L solution. Stirring for 30min to obtain green silver iodide sol. Silver nitrate: sodium iodide: the mass ratio of the 1-mercaptomethylcyclopropyl acetic acid is 1: 1: 0.3, wherein 1-mercaptomethylcyclopropyl acetic acid is used as a sol stabilizer.
Step two, preparing a mixed solution of 70% concentrated sulfuric acid and 35% oxalic acid according to the volume ratio of 3:7, putting the quartz pieces into the mixed solution, boiling the quartz pieces at 105 ℃ for 20min until no bubbles are generated, cooling, and then washing the quartz pieces with water.
And step three, putting the quartz piece into a 0.32 mass percent aqueous solution of polymethacryloxyethyltrimethyl ammonium chloride, soaking for 50min, taking out, and washing with deionized water.
And step four, putting the quartz plate into the prepared silver iodide sol, soaking for 10min, taking out, and washing with deionized water.
And step five, putting the quartz plate into an excessive sodium borohydride solution, soaking for 10min, taking out, and washing with deionized water to obtain the silver nanoparticle substrate with the prefabricated average particle size of about 35 nm.
And step six, finally, putting the silver substrate into a mixed solution of diphenylamine, silver oxide, ammonia water, ethanol and formic acid, wherein the mass ratio of all substances in the mixed solution is 4: 1: 4: 7: 5 in water. And taking out the silver nanoparticles after the silver nanoparticles grow to a proper size, and washing the silver nanoparticles with deionized water to obtain the surface-enhanced Raman silver nanoparticle base material.
Example 2
A preparation method of a surface enhanced Raman active substrate comprises the following specific steps:
weighing 16.99 g of silver nitrate, putting the silver nitrate into a beaker, slowly dropping 500ml of deionized water in the dark to prepare 0.1mol/L silver nitrate solution, controlling the pH value to be 5.2, keeping a certain stirring speed, adding 4.3863 g/L1-mercaptomethylcyclopropyl acetic acid, heating to 40 ℃, stirring for 20min, and finally slowly dropping 500ml of solution prepared by dissolving 7.4945 g of sodium iodide. Stirring for 30min to obtain green silver iodide sol. Silver nitrate: sodium iodide: the mass ratio of the 1-mercaptomethylcyclopropyl acetic acid is 1: 1: 0.3, wherein 1-mercaptomethylcyclopropyl acetic acid is used as a sol stabilizer.
Step two, preparing a mixed solution of 70% concentrated sulfuric acid and 35% oxalic acid according to the volume ratio of 3:7, putting the quartz pieces into the mixed solution, boiling the quartz pieces at 102 ℃ for 20min until no bubbles are generated, cooling, and then washing the quartz pieces with water.
And step three, putting the quartz piece into a 0.26 mass percent aqueous solution of polymethacryloxyethyltrimethyl ammonium chloride, soaking for 55min, taking out, and washing with deionized water.
And step four, putting the quartz plate into the prepared silver iodide sol, soaking for 10min, taking out, and washing with deionized water.
And step five, putting the quartz plate into an excessive sodium borohydride solution, soaking for 10min, taking out, and washing with deionized water to obtain the silver nanoparticle substrate with the prefabricated average particle size of about 40 nm.
And step six, finally, putting the silver substrate into a mixed solution of diphenylamine, silver oxide, ammonia water, ethanol and glycol, wherein the mass ratio of all substances in the mixed solution is 4: 1: 4: 7: 3, in water. And taking out the silver nanoparticles after the silver nanoparticles grow to a proper size, and washing the silver nanoparticles with deionized water to obtain the surface-enhanced Raman silver nanoparticle base material.
Example 3
A preparation method of a surface enhanced Raman active substrate comprises the following specific steps:
step one, weighing 0.8495 g of silver nitrate, putting the silver nitrate into a beaker, and slowly dropping 500ml of deionized water to prepare 10- 2Adding 0.8773 g/L1-mercaptomethylcyclopropyl acetic acid into mol/L silver nitrate solution (pH 6.3 controlled) while maintaining a certain stirring speed, heating to 40 deg.C, stirring for 15min, and slowly adding 500ml solution prepared from 0.7495 g sodium iodide. Stirring for 30min to obtain green silver iodide sol. Silver nitrate: sodium iodide: the mass ratio of the 1-mercaptomethylcyclopropyl acetic acid is 1: 1: 0.3, wherein 1-mercaptomethylcyclopropyl acetic acid is used as a sol stabilizer.
Step two, preparing a mixed solution of 70% concentrated sulfuric acid and 35% oxalic acid according to the volume ratio of 3:7, putting the quartz pieces into the mixed solution, boiling the quartz pieces at 98 ℃ for 20min until no bubbles are generated, cooling, and then washing the quartz pieces with water.
And step three, putting the quartz piece into a 0.45 mass percent aqueous solution of polymethacryloxyethyltrimethyl ammonium chloride, soaking for 45min, taking out, and washing with deionized water.
And step four, putting the quartz plate into the prepared silver iodide sol, soaking for 10min, taking out, and washing with deionized water.
And step five, putting the quartz plate into an excessive sodium borohydride solution, soaking for 10min, taking out, and washing with deionized water to obtain the silver nanoparticle substrate with the prefabricated average particle size of about 60 nm.
And step six, finally, putting the silver substrate into a mixed solution of diphenylamine, silver oxide, ammonia water, ethanol and ascorbic acid, wherein the mass ratio of all substances in the mixed solution is 4: 1: 4: 7: 6 in water. And taking out the silver nanoparticles after the silver nanoparticles grow to a proper size, and washing the silver nanoparticles with deionized water to obtain the surface-enhanced Raman silver nanoparticle base material.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (2)
1. A preparation method of a surface enhanced Raman active substrate is characterized by comprising the following steps: the method comprises the following steps:
firstly, accurately weighing a certain amount of silver nitrate, putting the silver nitrate into a container, slowly dripping deionized water into the container to prepare 0.1-10-2 mol/L silver nitrate solution, controlling the pH value to be 5.2-6.5, continuously stirring the solution, adding 0.1-0.6 mol/L1-mercaptomethylcyclopropylacetic acid, heating the solution to 30-50 ℃, stirring the solution for 10min to 50min, and finally dripping 0.1-10-2 mol/L sodium iodide into the solution; stirring for 20min-60min to obtain green silver iodide sol; the mass ratio of silver nitrate, sodium iodide and 1-mercaptomethylcyclopropyl acetic acid is 1: 1: (0.2-0.6), wherein 1-mercaptomethylcyclopropyl acetic acid is used as a sol stabilizer;
step two, preparing a mixed solution of 70% concentrated sulfuric acid and 35% oxalic acid according to the volume ratio of 3:7, putting the quartz pieces into the mixed solution, boiling the quartz pieces at 90-120 ℃ until no bubbles are generated, cooling, and cleaning the quartz pieces with water;
step three, putting the quartz plate into a polymethacryloxyethyl trimethyl ammonium chloride aqueous solution with the mass fraction of 0.1-0.5%, soaking for 40-60 min, taking out, and cleaning with deionized water;
step four, putting the quartz plate into the silver iodide sol prepared in the step one, soaking for 10min-30min, taking out, and washing with deionized water;
step five, putting the quartz plate into an excessive sodium borohydride solution, soaking for 10-40 min, taking out, and washing with deionized water to obtain a prefabricated silver nanoparticle substrate with the particle size of 20-80 nm;
and step six, finally, putting the silver nanoparticle substrate into a mixed solution of diphenylamine, silver oxide, ammonia water, ethanol and a reducing solvent, wherein the mass ratio of the substances in the mixed solution is 4: 1: 4: 7: (3-6); and taking out the silver nanoparticles after the silver nanoparticles grow to a proper size, and washing the silver nanoparticles with deionized water to obtain the surface-enhanced Raman silver nanoparticle base material.
2. A method of preparing a surface-enhanced raman active substrate according to claim 1, wherein: and step six, the reducing solution is ascorbic acid solvent, formic acid or ethylene glycol or cyclopropane.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102330080A (en) * | 2011-07-14 | 2012-01-25 | 东北师范大学 | Method for preparing silver nano flower-like film |
| US20130050695A1 (en) * | 2011-08-30 | 2013-02-28 | Cornell University - Cornell Center For Technology Enterprise & Commercialization (Cctec) | Surface enhanced raman scattering (sers) apparatus, methods and applications |
| CN104132921A (en) * | 2014-07-07 | 2014-11-05 | 华南师范大学 | Chemical vapor deposition based method for preparing surface Raman enhanced active substrate |
| CN110082340A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | The flexible detection method that orderly micro-nano patterned films detect trace TNT |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102330080A (en) * | 2011-07-14 | 2012-01-25 | 东北师范大学 | Method for preparing silver nano flower-like film |
| US20130050695A1 (en) * | 2011-08-30 | 2013-02-28 | Cornell University - Cornell Center For Technology Enterprise & Commercialization (Cctec) | Surface enhanced raman scattering (sers) apparatus, methods and applications |
| CN104132921A (en) * | 2014-07-07 | 2014-11-05 | 华南师范大学 | Chemical vapor deposition based method for preparing surface Raman enhanced active substrate |
| CN110082340A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | The flexible detection method that orderly micro-nano patterned films detect trace TNT |
Non-Patent Citations (2)
| Title |
|---|
| 宿健 等: "荧光/表面增强拉曼散射双模式纳米光学探针的构建及性能研究", 《发光学报》 * |
| 李小灵: "基于新型SERS基底的功能化自组装膜研究", 《中国优秀博硕士学位论文全文数据库（博士） 基础科学辑》 * |
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