CN113588621A - Three-dimensional liquid in-situ SERS detection substrate and preparation method and application thereof - Google Patents
Three-dimensional liquid in-situ SERS detection substrate and preparation method and application thereof Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims abstract description 70
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 65
- 238000001514 detection method Methods 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 17
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 claims abstract description 13
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 26
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 19
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 15
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052782 aluminium Inorganic materials 0.000 claims description 2
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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- 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
The invention relates to a SERS substrate with a surface enhanced Raman scattering effect, in particular to a three-dimensional liquid in-situ SERS detection substrate and a preparation method and application thereof. Silver and gold salt solutions are sequentially introduced into a channel tube in which a metal wire is packaged, and a dendritic gold-silver composite multilevel structure penetrating between the metal wire and the channel tube is prepared through a displacement reaction to form a three-dimensional liquid in-situ SERS detection substrate, so that the problems that the conventional SERS substrate is difficult to fully contact with flowing liquid, the detection signal sensitivity is low, the repeatability is poor and the like are solved.
Description
Technical Field
The invention relates to a SERS substrate with a surface enhanced Raman scattering effect, in particular to a three-dimensional liquid in-situ SERS detection substrate and a preparation method and application thereof.
Background
The Surface Enhanced Raman Scattering (SERS) is a powerful and effective spectrum analysis technology, has the advantages of fingerprint identification, high sensitivity, rapidness, no damage and the like, and has great potential application value in the fields of medicine, environment, food safety, catalysis and the like. However, due to the diffusion property of the detected object, the raman detection of the liquid medium depends on the binding degree of the detected object and the hot spot region, and the practical application of the raman spectrum in the trace element detection is limited to a certain extent.
At present, a great deal of literature reports that the SERS technology is applied to the field of environmental detection. An ultrasensitive SERS detection substrate for a liquid medium is mostly of a one-dimensional and two-dimensional gold/silver nanostructure, the binding degree of a molecule to be detected and the substrate is low, and the stability, the uniformity and the signal reproduction are poor; and the circulation of the detected object is difficult to realize, and the in-situ real-time detection process of the fluid medium is seriously influenced. Due to the strong plasma-plasma coupling effect, larger signal enhancement can be generated among the noble metal nano dimers; therefore, the three-dimensional liquid in-situ SERS detection substrate is designed and prepared by utilizing the excellent chemical stability of gold and the high Raman signal enhancement performance of silver, changing the component ratio of gold to silver, adjusting a plasma band, effectively enhancing the sensitivity, stability and signal reproducibility of the substrate, and realizing the great significance for the rapid, in-situ and real-time detection of liquid pollutants.
The three-dimensional liquid in-situ SERS detection substrate designed and prepared by the invention takes a capillary glass tube with excellent optical property as a reaction channel and a flow channel, and utilizes the inherent potential difference between deposited metal gold, silver and sacrificial material copper as a reaction driving force to synthesize a multi-layer dendritic gold-silver composite nano structure embedded in the channel in situ. Compared with a single nanometer unit, the multi-dimensional highly-branched complex ordered nanometer structure can generate high-density hot spots among specific gaps, tips, surfaces and particles due to the local surface plasmon effect, and can show excellent surface enhanced Raman scattering effect.
Disclosure of Invention
The invention prepares a multi-level dendritic gold-silver composite SERS detection substrate embedded in a capillary glass tube, is successfully applied to the field of liquid in-situ real-time detection, and solves the problems that the conventional SERS substrate is difficult to be fully contacted with flowing liquid, the detection signal sensitivity is low, the repeatability is poor and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a three-dimensional liquid in-situ SERS detection substrate is characterized in that a branched gold-silver composite multilevel structure penetrating between a metal wire and a channel tube is prepared in the channel tube packaged with the metal wire through a displacement reaction, and the three-dimensional liquid in-situ SERS detection substrate is formed.
A preparation method of the three-dimensional liquid in-situ SERS detection substrate comprises the following steps:
step 1, preprocessing a channel tube: placing the channel tube in the piranha solution, soaking, cleaning with ultrapure water, and drying at room temperature for later use;
step 2, ultrasonically cleaning the metal wire, inserting the metal wire into a channel tube, performing end sealing treatment on two ends of the channel tube, only reserving a liquid flow channel, injecting silver salt solution into the channel tube through the liquid flow channel, and preparing to obtain a three-dimensional dendritic silver multilevel structure penetrating between the metal wire and the channel tube by using an inherent electrochemical potential difference between silver ions and the metal wire as a reaction driving force;
step 3, injecting a gold salt solution into the channel pipe through a liquid flow channel, and growing gold nanoparticles on the surface and the tip of the dendritic silver in situ by utilizing the redox reaction between silver and gold ions to finally form a three-dimensional dendritic gold-silver composite multilevel structure between the surface of the metal wire and the inner wall of the channel pipe;
and 4, blowing ultrapure water into the channel tube to clean residual gold, silver salt solution and the suspended gold-silver structure, and then drying in a vacuum and dark manner at room temperature to obtain the detection substrate.
Further, the soaking time in the step 1 is 12 hours.
Further, the step 2 of ultrasonically cleaning the metal wire comprises the following specific steps: the metal wire is placed in ethanol for ultrasonic cleaning for 10 minutes, and then is cleaned by ultrapure water and dried at room temperature for standby.
Further, the channel pipe and the liquid circulation pore passage are both capillary glass pipes. The capillary glass tube does not react with silver salt and gold salt solution, has excellent optical performance, effectively reduces fluorescence effect, and improves the purity of Raman scattering spectrum.
Further, the silver salt solution in the step 2 is a silver nitrate solution, the concentration of the silver salt solution is 0.1mol/L, and the flow rate of the silver salt solution is 1/15-1/3 mL/min.
Further, the gold salt solution in the step 3 is a chloroauric acid solution, the concentration of the gold salt solution is 0.005mol/L, and the flow rate of the gold salt solution is 1/30-1/6 mL/min.
Further, the time for vacuum dark drying in the step 4 is 12 hours.
The application of a three-dimensional liquid in-situ SERS detection substrate in detecting a fluid medium.
Compared with the prior art, the invention has the following advantages:
(1) compared with a two-dimensional substrate, the multi-layer dendritic gold-silver composite three-dimensional substrate prepared by the invention has the advantages that the effective SERS active area in the light spot detection range is greatly increased; compared with gold and silver nanoparticles, the multi-stage three-dimensional dendritic gold-silver structure can provide more abundant active sites and has more excellent surface enhanced Raman scattering effect.
(2) The dendritic silver structure prepared by the invention is embedded in the channel instead of being attached to the inner wall of the channel pipe, so that the laser transmittance can be effectively improved; and the laser spot is small, and the laser spot can be directly focused in a liquid flow micro channel provided by the channel tube, so that the detection sensitivity of the Raman signal is effectively enhanced.
(3) The built channel tube can realize liquid circulation, and the highly branched and multi-level dendritic structure can effectively target molecules of an object to be detected, so that the interaction between the substrate and the molecules of the object to be detected is greatly enhanced.
(4) The preparation method is simple and efficient, has high repetition rate and mild reaction conditions, and provides theoretical support for the practical application of the SERS technology.
(5) The invention provides the three-dimensional liquid in-situ SERS detection substrate and application of the three-dimensional liquid in-situ SERS detection substrate prepared by the preparation method of the three-dimensional liquid in-situ SERS detection substrate in rapid, in-situ, real-time and trace detection of liquid pollutants, and solves the problems of difficulty in liquid in-situ detection, complex detection steps, low detection sensitivity and poor repeatability in the prior art.
Drawings
FIG. 1 is a schematic diagram of a reaction channel for preparing a three-dimensional liquid in-situ SERS detection substrate;
FIG. 2 shows silver nitrate concentration 0.1mol/L and chloroauric acid concentration 0.005mol/L, (a) silver nitrate solution flow rate 0.2mL/min, reaction time 15min, chloroauric acid solution flow rate 0.1mL/min, reaction time 30min, 3 pure copper wires with length 50mm and diameter 0.05 mm; (b) the flow rate of the silver nitrate solution is 0.2mL/min, the reaction time is 30min, the flow rate of the chloroauric acid solution is 0.1mL/min, and 5 pure copper wires with the lengths of 50mm and the diameters of 0.05mm are obtained; (c) the flow rate of the silver nitrate solution is 0.33mL/min, the reaction time is 30min, and 3 pure copper wires with the length of 50mm and the diameter of 0.05mm are obtained as an SEM image of the multilayer dendritic gold-silver substrate, wherein the flow rate of the silver nitrate solution is 0.33mL/min, the reaction time is 15min, the flow rate of the chloroauric acid solution is 0.17mL/min, and the reaction time is 30 min;
FIG. 3 is a SERS in-situ detection spectrum of the three-dimensional dendritic gold-silver substrate of example 2 for R6G solutions at different concentrations.
Detailed Description
Example 1
A three-dimensional liquid in-situ SERS detection substrate is characterized in that a branched gold-silver composite multilevel structure penetrating between a metal wire and a channel tube is prepared in the channel tube packaged with the metal wire through a displacement reaction, and the three-dimensional liquid in-situ SERS detection substrate is formed.
A preparation method of the three-dimensional liquid in-situ SERS detection substrate comprises the following steps:
step 1, pretreating a capillary glass tube: placing the capillary glass tube in the piranha solution, soaking for 12h, cleaning with ultrapure water, and drying at room temperature for later use;
step 2, placing the metal wire in ethanol for ultrasonic cleaning for 10 minutes, then cleaning with ultrapure water, inserting the metal wire into a capillary glass tube as shown in figure 1, carrying out end capping treatment on both ends of the capillary glass tube, only reserving a liquid flow channel, connecting one end of the channel with a micro injection pump, injecting silver salt solution into the capillary glass tube from the liquid flow channel by using the micro injection pump, and preparing to obtain a dendritic silver multilevel structure penetrating between the metal wire and the capillary glass tube by using an inherent electrochemical potential difference between silver ions and the metal wire as a reaction driving force;
step 3, taking the three-dimensional silver branches as basic units, injecting a gold salt solution into the capillary glass tube from the liquid flow channel by using a micro injection pump, and growing gold nanoparticles on the surfaces and the tips of the dendritic silver in situ by using the redox reaction between silver and gold ions to finally form a three-dimensional dendritic gold-silver composite multilevel structure between the surface of the metal wire and the inner wall of the channel tube;
and 4, blowing ultrapure water into the capillary glass tube through the liquid flowing channel to clean residual gold, silver salt solution and the suspended gold-silver structure, and then drying the ultrapure water in a vacuum and dark manner for 12 hours at room temperature, wherein the channel tube which is cleaned with the residual gold, silver salt solution and the suspended gold-silver structure and is embedded with the metal wire and the three-dimensional dendritic gold-silver structure can be directly used as a three-dimensional liquid in-situ SERS detection substrate.
In specific implementation, the outer diameter of the capillary glass tube of the reaction channel is 0.84mm, and the inner diameter of the capillary glass tube of the reaction channel is 0.7 mm; the outer diameter of the end-capped capillary glass tube is 0.4mm, and the inner diameter of the end-capped capillary glass tube is 0.3 mm.
In specific implementation, the metal wire is a copper wire, an aluminum wire, a stainless steel wire or a titanium wire, and the shape of the metal wire is a regular shape.
In specific implementation, the metal wire is a 99% pure copper wire with phi being 0.05 mm;
in specific implementation, the preferable silver salt solution is 0.1mol/L silver nitrate solution, the number of copper wires is 3, the reaction time is 15 minutes, and the flow rate of an injection pump is 0.2 mL/min.
In specific implementation, the gold salt solution is preferably 0.005mol/L chloroauric acid solution, the reaction time is 30 minutes, and the flow rate of the injection pump is 0.1 mL/min.
The invention provides the three-dimensional liquid in-situ SERS detection substrate and application of the three-dimensional liquid in-situ SERS detection substrate prepared by the preparation method of the three-dimensional liquid in-situ SERS detection substrate in rapid, in-situ, real-time and trace detection of liquid pollutants. The liquid pollutant is R6G solution.
Example 2
A preparation method of a three-dimensional liquid in-situ SERS detection substrate comprises the following specific steps:
respectively dissolving 0.85g of silver nitrate powder and 0.1g of chloroauric acid in 50mL of ultrapure water at room temperature, magnetically stirring at 2000rpm for 5min to obtain a silver nitrate solution with the concentration of 0.1mol/L and a chloroauric acid solution with the concentration of 0.005mol/L, and storing in a dark place for later use. Ultrasonically cleaning 3 pure copper wires with the length of 50mm and the diameter of 0.05mm, and drying for later use. And (3) building a reaction channel, injecting a silver nitrate solution, setting the flow rate of an injection pump to be 0.2mL/min, and reacting for 15 min. Subsequently, the chloroauric acid solution was continuously injected through a syringe pump at a flow rate of 0.1mL/min for a reaction time of 30 min. After the reaction is finished, adjusting the speed of an injection pump to be 2mL/min, injecting 30mL of ultrapure water at a constant speed, cleaning for 3 times, drying for 12 hours at room temperature in a dark place, and separating the injection pump and the capillary glass tube to obtain the multilayer dendritic gold-silver SERS substrate embedded in the capillary glass tube, which is shown in an attached drawing 2 (a).
Example 3
A preparation method of a three-dimensional liquid in-situ SERS detection substrate comprises the following specific steps:
respectively dissolving 0.85g of silver nitrate powder and 0.1g of chloroauric acid in 50mL of ultrapure water at room temperature, magnetically stirring at 2000rpm for 5min to obtain a silver nitrate solution with the concentration of 0.1mol/L and a chloroauric acid solution with the concentration of 0.005mol/L, and storing in a dark place for later use. Ultrasonically cleaning 5 pure copper wires with the length of 50mm and the diameter of 0.05mm, and drying for later use. And (3) building a reaction channel, injecting a silver nitrate solution, setting the flow rate of an injection pump to be 0.2mL/min, and reacting for 15 min. Subsequently, the chloroauric acid solution was continuously injected through a syringe pump at a flow rate of 0.1mL/min for a reaction time of 30 min. After the reaction is finished, adjusting the speed of an injection pump to be 2mL/min, injecting 30mL of ultrapure water at a constant speed, cleaning for 3 times, drying for 12 hours at room temperature in a dark place, and separating the injection pump and the capillary glass tube to obtain the multilayer dendritic gold-silver SERS substrate embedded in the capillary glass tube, which is shown in an attached drawing 2 (b).
Example 4
A preparation method of a three-dimensional liquid in-situ SERS detection substrate comprises the following specific steps:
respectively dissolving 0.85g of silver nitrate powder and 0.1g of chloroauric acid in 50mL of ultrapure water at room temperature, magnetically stirring at 2000rpm for 5min to obtain a silver nitrate solution with the concentration of 0.1mol/L and a chloroauric acid solution with the concentration of 0.005mol/L, and storing in a dark place for later use. Ultrasonically cleaning 3 pure copper wires with the length of 50mm and the diameter of 0.05mm, and drying for later use. And (3) building a reaction channel, injecting a silver nitrate solution, setting the flow rate of an injection pump to be 0.33mL/min, and reacting for 15 min. Subsequently, the chloroauric acid solution was continuously injected through a syringe pump at a flow rate of 0.17mL/min for a reaction time of 30 min. After the reaction is finished, adjusting the speed of an injection pump to be 2mL/min, injecting 30mL of ultrapure water at a constant speed, cleaning for 3 times, drying for 12 hours at room temperature in a dark place, and separating the injection pump and the capillary glass tube to obtain the multilayer dendritic gold-silver SERS substrate embedded in the capillary glass tube, which is shown in an attached drawing 2 (c).
As can be seen from FIG. 2, the overall morphology of the reaction product is close to that of the dendrite, the branches are highly symmetrically arranged, the reaction product has an obvious hierarchical structure (main stem-side branch-secondary branch-tertiary branch), and rich sharp protrusions and nano gaps exist. Under the same reaction condition, the number of copper wires is increased to 5, the appearance of the product does not show obvious high-branching characteristics, the main trunk and the side branches are thickened to different degrees, and silver dendrites with the micrometer as the main trunk and the branches from a few nanometers to a few micrometers are formed, as shown in figure 2 (b). By changing the amount of silver salt or gold salt injected (fig. 2(c)), the sharp dendritic structure is significantly deformed, and a large number of blunt projections are formed around the trunk, resulting in a significant decrease in surface roughness.
Example 5
A method for detecting R6G solutions with different concentrations by using a three-dimensional liquid in-situ SERS detection substrate comprises the following specific steps:
dissolving 0.24g R6G powder in 50mL of ultrapure water at room temperature, magnetically stirring at 2000rpm for 5min to obtain 0.01mol/L R6G solution, and diluting to obtain 10-8And storing the solution of R6G in mol/L in a sealed and light-proof manner. Will 10-8The mol/L of the R6G solution was pumped into the channel of the substrate prepared in example 2 by a syringe pump at a flow rate of 0.2mL/min and was continuously flowed through the substrate for 60 min. Selecting laser with the wavelength of 785nm and the intensity of 110mW for Raman detection, focusing the laser on the surface of the three-dimensional dendritic gold-silver SERS substrate in the capillary glass tube to obtain in-situ real-time detection data of the multi-level dendritic gold-silver SERS substrate, wherein a Raman detection spectrogram is shown in an attached figure 3 (a highest curve in the figure 3).
Example 6:
a method for detecting R6G solutions with different concentrations by using a three-dimensional liquid in-situ SERS detection substrate comprises the following specific steps:
dissolving 0.24g R6G powder in 50mL of ultrapure water at room temperature, magnetically stirring at 2000rpm for 5min to obtain 0.01mol/L R6G solution, and diluting to obtain 10-10And storing the solution of R6G in mol/L in a sealed and light-proof manner. Will 10-10The mol/L of the R6G solution was pumped into the channel of the substrate prepared in example 2 by a syringe pump at a flow rate of 0.2mL/min and was continuously flowed through the substrate for 60 min. Selecting laser with the wavelength of 785nm and the intensity of 110mW for Raman detection, focusing the laser on the surface of the three-dimensional dendritic gold-silver SERS substrate in the capillary glass tube to obtain in-situ real-time detection data of the multi-level dendritic gold-silver SERS substrate, wherein a Raman detection spectrogram is shown in an attached figure 3 (a curve in the middle of the figure 3).
Example 7:
a method for detecting R6G solutions with different concentrations by using a three-dimensional liquid in-situ SERS detection substrate comprises the following specific steps:
dissolving 0.24g R6G powder in 50mL of ultrapure water at room temperature, magnetically stirring at 2000rpm for 5min to obtain 0.01mol/L R6G solution, and diluting to obtain 10-12And storing the solution of R6G in mol/L in a sealed and light-proof manner. Will 10-12The mol/L of the R6G solution was pumped into the channel of the substrate prepared in example 2 by a syringe pump at a flow rate of 0.2mL/min and was continuously flowed through the substrate for 60 min. Selecting laser with the wavelength of 785nm and the intensity of 110mW for Raman detection, focusing the laser on the surface of the three-dimensional dendritic gold-silver SERS substrate in the capillary glass tube to obtain in-situ real-time detection data of the multi-level dendritic gold-silver SERS substrate, wherein a Raman detection spectrogram is shown in an attached figure 3 (a lowest curve in the figure 3).
As can be seen from FIG. 3, the characteristic Raman peaks of R6G appear at 764, 1124, 1187, 1312, 1367, 1514, 1579 and 1662cm, respectively-1The data found are consistent with the typical raman peaks reported in the literature. The detection of the SERS substrate by using R6G as a probe molecule at different concentrations shows that even the concentration is as low as 10-12The M and R6G molecules still show good signal-to-noise ratio and have high sensitivity, and the rapid, in-situ and real-time detection of the liquid medium is realized.
Those skilled in the art will appreciate that the invention may be practiced without these specific details. Although illustrative embodiments of the present invention have been described above to facilitate the understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, and various changes may be made apparent to those skilled in the art as long as they are within the spirit and scope of the present invention as defined and defined by the appended claims, and all matters of the invention which utilize the inventive concepts are protected.
Claims (10)
1. A three-dimensional liquid in-situ SERS detection substrate is characterized in that a branched gold-silver composite multilevel structure penetrating between a metal wire and a channel tube is prepared in the channel tube packaged with the metal wire through a displacement reaction to form the three-dimensional liquid in-situ SERS detection substrate.
2. A method for preparing the three-dimensional liquid in-situ SERS detection substrate according to claim 1, comprising the following steps:
step 1, preprocessing a channel tube: placing the channel tube in the piranha solution, soaking, cleaning with ultrapure water, and drying at room temperature for later use;
step 2, ultrasonically cleaning the metal wire, inserting the metal wire into a channel tube, performing end sealing treatment on two ends of the channel tube, only reserving a liquid flow channel, injecting silver salt solution into the channel tube through the liquid flow channel, and preparing to obtain a three-dimensional dendritic silver multilevel structure penetrating between the metal wire and the channel tube by using an inherent electrochemical potential difference between silver ions and the metal wire as a reaction driving force;
step 3, injecting a gold salt solution into the channel pipe through a liquid flow channel, and growing gold nanoparticles on the surface and the tip of the dendritic silver in situ by utilizing the redox reaction between silver and gold ions to finally form a three-dimensional dendritic gold-silver composite multilevel structure between the surface of the metal wire and the inner wall of the channel pipe;
and 4, blowing ultrapure water into the channel tube to clean residual gold, silver salt solution and the suspended gold-silver structure, and then drying in a vacuum and dark manner at room temperature to obtain the detection substrate.
3. The method for preparing the three-dimensional liquid in-situ SERS detection substrate according to claim 2, wherein the soaking time in the step 1 is 12 hours.
4. The method for preparing the three-dimensional liquid in-situ SERS detection substrate according to claim 2, wherein the step 2 of ultrasonically cleaning the metal wire comprises the following specific steps: the wire was ultrasonically cleaned in ethanol for 10 minutes, followed by rinsing with ultra pure water.
5. The preparation method of the three-dimensional liquid in-situ SERS detection substrate according to claim 2, wherein the metal wire is one of a copper wire, an aluminum wire, a stainless steel wire or a titanium wire, the shape of the metal wire is a regular shape, and the number of the metal wires is 3-5.
6. The method for preparing the three-dimensional liquid in-situ SERS detection substrate according to claim 2, wherein the channel tube and the liquid flow channel are both capillary glass tubes.
7. The preparation method of the three-dimensional liquid in-situ SERS detection substrate as claimed in claim 2, wherein the silver salt solution in the step 2 is silver nitrate solution, the concentration of the silver salt solution is 0.1mol/L, and the flow rate of the silver salt solution is 1/15-1/3 mL/min.
8. The method for preparing the three-dimensional liquid in-situ SERS detection substrate as recited in claim 2, wherein the gold salt solution in the step 3 is a chloroauric acid solution, the concentration of the gold salt solution is 0.005mol/L, and the flow rate of the gold salt solution is 1/30-1/6 mL/min.
9. The method for preparing the three-dimensional liquid in-situ SERS detection substrate according to claim 2, wherein the drying time in step 4 in vacuum and protected from light is 12 hours.
10. The application of the three-dimensional liquid in-situ SERS detection substrate is characterized by being applied to detection of a fluid medium.
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| CN116728909A (en) * | 2023-06-13 | 2023-09-12 | 中北大学 | High-sensitivity composite SERS substrate with self-cleaning function and preparation method thereof |
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| CN103994991A (en) * | 2014-05-21 | 2014-08-20 | 华东理工大学 | Preparation method of surface-enhanced raman spectrum (SERS) substrate based on capillary monolithic column |
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| CN103994991A (en) * | 2014-05-21 | 2014-08-20 | 华东理工大学 | Preparation method of surface-enhanced raman spectrum (SERS) substrate based on capillary monolithic column |
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