CN114433867B - Dendritic symmetrical octagonal Ag nano structure and preparation method and application thereof - Google Patents

Dendritic symmetrical octagonal Ag nano structure and preparation method and application thereof Download PDF

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CN114433867B
CN114433867B CN202210117825.6A CN202210117825A CN114433867B CN 114433867 B CN114433867 B CN 114433867B CN 202210117825 A CN202210117825 A CN 202210117825A CN 114433867 B CN114433867 B CN 114433867B
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CN114433867A (en
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李路怡
范李娜
王媛媛
田钰琳
姚开胜
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Henan University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons

Abstract

The invention relates to a dendritic symmetrical octagonal Ag nano structure, a preparation method and application thereof, wherein a 2-thiopheneethylamine chloroform solution is prepared, and a certain amount of the solution is added into a cylindrical reaction container; careful addition of AgNO along the vessel wall 3 An aqueous solution; standing the reactants at room temperature for 2.0-12.0 h, extracting a lower chloroform phase by using a syringe after the reaction to deposit a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding ethanol for soaking and washing, adding tetrahydrofuran for soaking and washing, pumping the solution, and vacuum drying the product to obtain the dendritic symmetrical octagonal Ag nano structure. The preparation method is simple, easy to operate and low in energy consumption, and the prepared Ag nano structure has a dendritic symmetrical octagonal structure, is uniform in appearance and stable in structure, and has excellent SERS enhancement performance.

Description

Dendritic symmetrical octagonal Ag nano structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of noble metal nano material preparation, in particular to a method for preparing dendritic symmetrical octagonal Ag by a liquid-liquid interface and application thereof in Surface Enhanced Raman Scattering (SERS) research.
Background
Nanostructured noble metal materials have attracted considerable research enthusiasm in recent years due to their extremely attractive optical, electrical and catalytic properties. Among the numerous nanomaterials, nanoscale Au and Ag materials have shown great potential in many application fields due to unique photocatalytic, catalytic and electrocatalytic properties. Moreover, ag has a unique dielectric function, and Ag nanostructures possess the highest plasmonic activity compared to other metals. Meanwhile, the Ag nanostructure shows higher refractive index sensitivity in the visible and near infrared regions compared to Au of the nanostructure due to the combined effect of the real part of the dielectric function and its spectral dispersion. With similar morphology and size, ag nanostructures generally have greater plasmonic field enhancement than Au, which makes Ag nanostructures significantly better than Au nanostructures in surface enhanced raman and fluorescence applications. Meanwhile, the Ag nano structure has larger solar energy conversion efficiency than the Au nano structure. Thus, ag nanostructures are more attractive in plasma-based technology applications.
It is well known that the properties of nanomaterials are closely related to their morphology, structure, size and aggregation state. Thus, researchers have been working to develop different synthesis techniques to prepare Ag nanomaterials of different morphologies and structures. For example, wang et al first treat a Cu plate to Cu 2 O/Cu complex, then in an acidic aqueous environment, in Cu 2 And growing a film assembled by the Ag nano-sheets on the O/Cu plate. The Meng et al first electrodeposit micro-hemispherical Ag using ITO glass as a cathode, and then prepares Ag nanoplatelets vertically grown on the micro-hemispheres by Ostwald ripening in an aqueous solution. Pure Ag target material is placed at the bottom of an electrolytic tank by Yang et al, and dendritic Ag is prepared on a cathode by an electrochemical method by taking pure water as electrolyte. Yao et al used trioctyl methyl ammonium bis (trifluoro) sulfonimide salt ([ N ] 8881 ][Tf 2 N]) And preparing the Ag nano-belt assembled film by using an ionic liquid-water two-phase system. Although Ag nanomaterials with various morphologies and structures have been successfully synthesized, the current methods all use hard templates, multiple stepsSynthetic, expensive reagents. Moreover, to our knowledge, ag with a dendritic symmetrical octagonal structure has not been reported, and Cu is prepared by adopting a hydrothermal synthesis route under the regulatory action of PVP only in the presence of a buffering agent by Zhou et al 2 O octagon dendrites. Therefore, it is necessary to develop a mild one-pot synthetic route for preparing the Ag nano material with the symmetrical octagonal structure.
Disclosure of Invention
The invention aims to provide a dendritic symmetrical octagonal Ag nano structure, a preparation method and application thereof, wherein the preparation method is carried out in a liquid-liquid interface reaction system by adopting a one-pot synthesis technical route, the preparation method is simple, the operation is easy, the energy consumption is low, the prepared Ag nano structure has a dendritic symmetrical octagonal structure, the morphology is uniform, the structure is stable, the Ag nano structure has excellent enhancement performance in Surface Enhanced Raman Scattering (SERS) research, and the Ag nano structure is expected to be applied to fruit and vegetable pesticide residue detection.
The invention is realized by the following technical scheme, and the preparation method of the dendritic symmetrical octagonal Ag nano structure provided by the invention comprises the following steps:
preparing a 2-thiopheneethylamine chloroform solution for later use by taking 2-thiopheneethylamine as a solute and chloroform as a solvent;
step two, adding 4mL of the 2-thiopheneethylamine chloroform solution in the step one into a cylindrical glass reaction container, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction container in advance;
step three, preparing AgNO 3 An aqueous solution for standby;
step four, carefully adding 4mL of AgNO in step three into the cylindrical glass reaction vessel in step two along the wall of the vessel 3 An aqueous solution;
step five, standing reactants in the cylindrical glass reaction vessel in the step four at room temperature for 2.0-12.0 h, and then carrying out step six;
and step six, extracting the lower chloroform phase from the reaction system prepared in the step five by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol for soaking and washing, adding tetrahydrofuran for soaking and washing, pumping the solution, and vacuum drying the product to obtain the dendritic symmetrical octagonal Ag nano structure.
In the preparation method, the molar concentration of the 2-thiopheneethylamine in the 2-thiopheneethylamine chloroform solution is 0.05-0.15mol/L. AgNO 3 AgNO in aqueous solution 3 The molar concentration of (C) is 0.01-0.15mol/L.
In the preparation method, the step six is to add absolute ethyl alcohol for soaking and washing, 10-20mL absolute ethyl alcohol is added for soaking for one day each time, the absolute ethyl alcohol is extracted by a syringe after soaking, and then new absolute ethyl alcohol is added for soaking for 3 times; adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting tetrahydrofuran by a syringe after soaking, adding new tetrahydrofuran, soaking for 3 times, extracting solution, and vacuum drying the product to obtain the dendritic symmetrical octagonal Ag nano-structure.
In the preparation method, the vacuum drying temperature in the step six is 40-60 ℃.
The invention also provides the dendritic symmetrical octagonal Ag nano structure prepared by the method. The Ag nano structure symmetrically grows from the center to eight directions by eight petals, the root of each petal, namely the position of the center of each octagon, is wider, the outward growth gradually becomes sharp, the surface of each petal is provided with a rough dendritic structure, and the rough structure is favorable for higher SERS enhancement performance, and the edges of the petals are in a saw-tooth shape.
The invention also provides application of the dendritic symmetrical octagonal Ag nano structure in SERS research, and the dendritic symmetrical octagonal Ag nano structure can be used as an SERS active substrate, and the active substrate loaded with the dendritic symmetrical octagonal Ag nano structure is expected to be applied to fruit and vegetable pesticide residue detection.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the invention is carried out by adopting a liquid-liquid interface reaction system. The liquid-liquid interface is a heterogeneous system with some special thermodynamic properties. The heterogeneous region of the liquid-liquid interface is used as a reaction place for preparing the nano material, and the morphology and the performance of the obtained product are limited by various reaction conditions, such as reactant concentration, reaction temperature, height of a two-liquid-phase reaction column and the like. At the same time, charge transfer and reaction kinetics at the two-phase interface are also important for liquid-liquid interface and product morphology and assembly. Thus, the mechanism of nanomaterial formation at the liquid-liquid interface is substantially different from conventional methods. The application of the liquid-liquid interface is expected to regulate and synthesize the nano material with uniform appearance, novel structure and excellent performance.
(2) According to the technical route for preparing the dendritic symmetrical octagonal Ag nano structure, a surfactant, a hard template agent and the like are not required to be added into a reaction system, and a metal organic precursor is not required to be used. The method can be completed in one step under the condition of room temperature and rest, and has mild experimental conditions and low energy consumption.
(3) The dendritic symmetrical octagonal Ag nano structure prepared by the invention is formed by symmetrically growing eight petals from the center to eight directions, the roots of the petals, namely the central position of the octagon, are wider, and the outward growth is gradually sharp. The edges of the petals are in a zigzag structure. The petals are rather rough in surface and have a dendritic structure, and the rough structure contributes to higher SERS enhancement performance. Each petal has a triple symmetrical structure.
(4) The dendritic symmetrical octagonal Ag nano-structure prepared by the invention can be directly used as an active substrate for SERS research. The common thiram pesticide is used as a molecular probe, the dendritic symmetrical octagon Ag nano structure is used as an active substrate, and the 10 with lower concentration is found -6 The Raman signal of the mol/L thiram is greatly enhanced. Because of the relatively low concentration of the thiram aqueous solution used, the signal is normally difficult to occur without Ag nanostructures as the active substrate. Therefore, the dendritic symmetrical octagonal Ag nano structure is expected to be potentially applied to the detection of pesticide residues on fruits and vegetables.
Drawings
FIG. 1 is an SEM image at 3500 magnification of a branched-symmetric octagonal Ag nanostructure prepared in example 3;
FIG. 2 is an SEM image at 5000 times magnification of a dendritic symmetrical octagonal Ag nanostructure prepared in example 3;
FIG. 3 is an SEM image at 18000 magnification of a dendritic symmetrical octagon Ag nanostructure prepared in example 3;
FIG. 4 is an SEM image at 12000 magnification of a dendritic symmetrical octagon Ag nanostructure prepared in example 3;
FIG. 5 is an XRD pattern of a dendritic symmetrical octagon Ag nanostructure prepared in example 3;
fig. 6 is a SERS spectrum of a probe molecule of thiram, which is a dendritic octagon Ag nanostructure prepared in example 3, as an active substrate.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings. The following examples are based on the technology of the present invention and give detailed embodiments and operation steps, but the scope of the present invention is not limited to the following examples.
A preparation method of a dendritic symmetrical octagonal Ag nano structure comprises the following steps:
taking a certain amount of 2-thiopheneethylamine as a solute, and taking chloroform as a solvent to prepare a 2-thiopheneethylamine chloroform solution with the molar concentration of 0.05-0.15mol/L for later use;
step two, adding 4mL of the 2-thiopheneethylamine chloroform solution in the step one into a cylindrical glass reaction vessel, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction vessel in advance;
step three, taking a certain amount of AgNO 3 Preparing the mixture into AgNO with the molar concentration of 0.01-0.15mol/L 3 An aqueous solution for standby;
step four, carefully adding 4mL of AgNO in step three into the cylindrical glass reaction vessel in step two along the wall of the vessel 3 An aqueous solution;
step five, standing reactants in the cylindrical glass reaction vessel in the step four at room temperature for 2.0-12.0 h, and then carrying out step six;
step six, extracting the lower chloroform phase from the reaction system prepared in the step five by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol to soak and wash, adding 10-20mL of absolute ethyl alcohol each time to soak for one day, extracting by using the syringe after soaking, adding new absolute ethyl alcohol, and soaking for 3 times; then adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting by a syringe after soaking, adding new tetrahydrofuran, and soaking for 3 times. And then the solution is pumped out, and the product is dried in vacuum at the temperature of 40-60 ℃ to obtain the dendritic symmetrical octagonal Ag nano structure.
Fig. 1 to 4 are SEM images of the prepared dendritic symmetrical octagonal Ag nanostructure at different magnifications, and the length of the nanostructure is about 4.5 μm as seen from a low-power scanning electron microscope (fig. 1 and 2), the nanostructure is formed by symmetrically growing eight petals from the center to eight directions, the roots of the petals, namely the central position of the octagon, are wider, and the outward growth is gradually sharp. The edges of the petals are in a zigzag structure. The enlarged scanning electron microscope (fig. 3) showed that the petal surfaces were not smooth, but rather rough, with dendritic structures, which contributed to their higher SERS enhancement performance. Only four symmetrical petals are seen in fig. 3, and four symmetrically growing petals are arranged below the four petals, and are just shielded by the four petals due to the view angle. Figure 4 shows a scanning electron microscope view from one petal growth direction, clearly showing its octagonal symmetry (the last corner being at the back of the middle most corner of figure 4), i.e. eight petals are grown from the centre along eight equal <111> directions. Moreover, it can be seen that each petal has a triple symmetrical structure.
Fig. 5 shows an X-ray diffraction pattern of the prepared dendritic symmetrical octagonal Ag nanostructure, which can be seen to be a face-centered cubic structure, and no other impurity peaks appear, thus proving that the purity of the purified sample is higher.
The invention is further illustrated by the following examples:
example 1:
1) Adding a certain amount of 2-thiopheneethylamine into chloroform solvent to prepare a chloroform solution of 2-thiopheneethylamine with the molar concentration of 0.05mol/L for standby;
2) Adding 4mL of the 2-thiopheneethylamine chloroform solution in the step 1) into a cylindrical glass reaction vessel, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction vessel in advance;
3) Taking a certain amount of AgNO 3 Preparing AgNO with the molar concentration of 0.01mol/L 3 An aqueous solution;
4) Into the cylindrical glass reaction vessel of step 2) 4mL of AgNO of step 3) were carefully added along the vessel wall 3 An aqueous solution;
5) Standing reactants in the cylindrical glass reaction container in the step 4) at room temperature for reaction for 12.0h, and then carrying out the step 6);
6) Extracting the lower chloroform phase in the reaction system of the step 5) by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol to soak and wash, adding 10-20mL of absolute ethyl alcohol each time to soak for one day, extracting by using the syringe after soaking, adding new absolute ethyl alcohol, and soaking for 3 times; then adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting by a syringe after soaking, adding new tetrahydrofuran, and soaking for 3 times. And then the solution is pumped out, and the product is dried in vacuum at the temperature of 40 ℃ to obtain the dendritic symmetrical octagonal Ag nano structure.
Example 2:
1) Adding a certain amount of 2-thiopheneethylamine into chloroform solvent to prepare a chloroform solution of 2-thiopheneethylamine with the molar concentration of 0.08mol/L for standby;
2) Adding 4mL of the 2-thiopheneethylamine chloroform solution in the step 1) into a cylindrical glass reaction vessel, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction vessel in advance;
3) Taking a certain amount of AgNO 3 Preparing the mixture into AgNO with the molar concentration of 0.08mol/L 3 An aqueous solution;
4) Into the cylindrical glass reaction vessel of step 2) 4mL of AgNO of step 3) were carefully added along the vessel wall 3 Water-solubleA liquid;
5) Standing reactants in the cylindrical glass reaction container in the step 4) at room temperature for reaction for 8.0h, and then carrying out the step 6);
6) Extracting the lower chloroform phase in the reaction system of the step 5) by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol to soak and wash, adding 10-20mL of absolute ethyl alcohol each time to soak for one day, extracting by using the syringe after soaking, adding new absolute ethyl alcohol, and soaking for 3 times; then adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting by a syringe after soaking, adding new tetrahydrofuran, and soaking for 3 times. And then the solution is pumped out, and the product is dried in vacuum at 50 ℃ to obtain the dendritic symmetrical octagonal Ag nano structure.
Example 3:
1) Adding a certain amount of 2-thiopheneethylamine into chloroform solvent to prepare a chloroform solution of 2-thiopheneethylamine with the molar concentration of 0.1mol/L for standby;
2) Adding 4mL of the 2-thiopheneethylamine chloroform solution in the step 1) into a cylindrical glass reaction vessel, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction vessel in advance;
3) Taking a certain amount of AgNO 3 Preparing the mixture into AgNO with the molar concentration of 0.1mol/L 3 An aqueous solution;
4) Into the cylindrical glass reaction vessel of step 2) 4mL of AgNO of step 3) were carefully added along the vessel wall 3 An aqueous solution;
5) Standing reactants in the cylindrical glass reaction container in the step 4) at room temperature for 4.0h, and then carrying out the step 6);
6) Extracting the lower chloroform phase in the reaction system of the step 5) by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol to soak and wash, adding 10-20mL of absolute ethyl alcohol each time to soak for one day, extracting by using the syringe after soaking, adding new absolute ethyl alcohol, and soaking for 3 times; then adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting by a syringe after soaking, adding new tetrahydrofuran, and soaking for 3 times. And then the solution is pumped out, and the product is dried in vacuum at the temperature of 60 ℃ to obtain the dendritic symmetrical octagonal Ag nano structure.
Concentration is set to 10 -6 The thiram aqueous solution of mol/L was sprayed onto the surface of an apple. After the moisture is completely evaporated, cleaning apples with acetone, collecting washing liquid, then dripping the collected washing liquid on a silicon chip loaded with the dendritic symmetrical octagonal Ag nano structure, and carrying out signal detection by adopting a Raman spectrometer with excitation wavelength of 532nm, wherein the integration time is 5s.
Fig. 6 shows a SERS spectrum of a branched symmetric octagon Ag nanostructure prepared in this example as an active substrate, and thiram as a probe molecule, and the signal was difficult to appear without Ag nanostructure under normal conditions because the concentration of the thiram aqueous solution used was relatively low. However, the typical thiram SERS enhancement signal can be clearly observed in fig. 6. Wherein the strongest peak is at 1378cm -1 Where C-N stretching vibration and symmetrical CH are given 3 Deformation vibration 1508cm -1 The absorption peak is C-N telescopic vibration 1138cm -1 The absorption peak is CH 3 Swinging vibration is coupled with C-N telescopic vibration 926cm -1 The absorption peak is CH 3 N stretching vibration 556cm -1 The absorption peak is S-S stretching vibration. Therefore, the dendritic symmetrical octagonal Ag nano-structure prepared by the method has obvious SERS enhancement characteristics, can be used as a SERS active substrate, and is expected to be applied to fruit and vegetable pesticide residue detection.
Example 4:
1) Adding a certain amount of 2-thiopheneethylamine into chloroform solvent to prepare a chloroform solution of 2-thiopheneethylamine with the molar concentration of 0.12mol/L for standby;
2) Adding 4mL of the 2-thiopheneethylamine chloroform solution in the step 1) into a cylindrical glass reaction vessel, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction vessel in advance;
3) Taking a certain amount of AgNO 3 Preparing the mixture into AgNO with the molar concentration of 0.1mol/L 3 An aqueous solution;
4) Into the cylindrical glass reaction vessel of step 2) 4mL of AgNO of step 3) were carefully added along the vessel wall 3 An aqueous solution;
5) Standing reactants in the cylindrical glass reaction container in the step 4) at room temperature for reaction for 6.0h, and then carrying out the step 6);
6) Extracting the lower chloroform phase in the reaction system of the step 5) by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol to soak and wash, adding 10-20mL of absolute ethyl alcohol each time to soak for one day, extracting by using the syringe after soaking, adding new absolute ethyl alcohol, and soaking for 3 times; then adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting by a syringe after soaking, adding new tetrahydrofuran, and soaking for 3 times. And then the solution is pumped out, and the product is dried in vacuum at the temperature of 60 ℃ to obtain the dendritic symmetrical octagonal Ag nano structure.
Example 5:
1) Adding a certain amount of 2-thiopheneethylamine into chloroform solvent to prepare a chloroform solution of 2-thiopheneethylamine with the molar concentration of 0.15mol/L for standby;
2) Adding 4mL of the 2-thiopheneethylamine chloroform solution in the step 1) into a cylindrical glass reaction vessel, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction vessel in advance;
3) Taking a certain amount of AgNO 3 Preparing AgNO with the molar concentration of 0.15mol/L 3 An aqueous solution;
4) Into the cylindrical glass reaction vessel of step 2) 4mL of AgNO of step 3) were carefully added along the vessel wall 3 An aqueous solution;
5) Standing reactants in the cylindrical glass reaction container in the step 4) at room temperature for 4.0h, and then carrying out the step 6);
6) Extracting the lower chloroform phase in the reaction system of the step 5) by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol to soak and wash, adding 10-20mL of absolute ethyl alcohol each time to soak for one day, extracting by using the syringe after soaking, adding new absolute ethyl alcohol, and soaking for 3 times; then adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting by a syringe after soaking, adding new tetrahydrofuran, and soaking for 3 times. And then the solution is pumped out, and the product is dried in vacuum at the temperature of 60 ℃ to obtain the dendritic symmetrical octagonal Ag nano structure.
The above description is only an individual embodiment of the present invention, and is not limited in any way, and the present invention may have other embodiments according to the above preparation method, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.

Claims (9)

1. The preparation method of the dendritic symmetrical octagonal Ag nano structure is characterized by comprising the following steps of:
preparing a 2-thiopheneethylamine chloroform solution for later use by taking 2-thiopheneethylamine as a solute and chloroform as a solvent;
step two, adding 4mL of the 2-thiopheneethylamine chloroform solution in the step one into a cylindrical glass reaction container, wherein a silicon wafer or a glass sheet is placed at the bottom of the cylindrical glass reaction container in advance;
step three, preparing AgNO 3 An aqueous solution for standby;
step four, carefully adding 4mL of AgNO in step three into the cylindrical glass reaction vessel in step two along the wall of the vessel 3 An aqueous solution;
step five, standing reactants in the cylindrical glass reaction vessel in the step four at room temperature for 2.0-12.0 h, and then carrying out step six;
and step six, extracting the lower chloroform phase from the reaction system prepared in the step five by using a syringe, depositing a reaction product on a silicon wafer or a glass sheet which is placed at the bottom of a cylindrical glass reaction container in advance, extracting an upper aqueous solution by using the syringe, adding absolute ethyl alcohol for soaking and washing, adding tetrahydrofuran for soaking and washing, pumping the solution, and vacuum drying the product to obtain the dendritic symmetrical octagonal Ag nano structure.
2. The method for preparing the dendritic symmetrical octagonal Ag nano-structure according to claim 1, wherein the molar concentration of 2-thiopheneethylamine in the 2-thiopheneethylamine chloroform solution is 0.05-0.15mol/L.
3. The method for preparing the dendritic symmetrical octagonal Ag nanostructure according to claim 1, wherein AgNO 3 AgNO in aqueous solution 3 The molar concentration of (C) is 0.01-0.15mol/L.
4. The method for preparing the dendritic symmetrical octagonal Ag nano structure according to claim 1, wherein in the sixth step, absolute ethyl alcohol is added for soaking and washing, 10-20mL absolute ethyl alcohol is added for soaking for one day each time, absolute ethyl alcohol is extracted by a syringe after soaking, and new absolute ethyl alcohol is added for soaking for 3 times; adding tetrahydrofuran for soaking and washing, adding 10-20mL of tetrahydrofuran each time for soaking for one day, extracting tetrahydrofuran by a syringe after soaking, adding new tetrahydrofuran, soaking for 3 times, extracting solution, and vacuum drying the product to obtain the dendritic symmetrical octagonal Ag nano-structure.
5. The method for preparing a dendritic symmetrical octagonal Ag nanostructure according to claim 1 or 4, wherein the vacuum drying temperature in step six is 40 ℃ to 60 ℃.
6. A dendritic symmetrical octagonal Ag nanostructure prepared by the preparation method according to any one of claims 1 to 5.
7. The dendritic symmetrical octagonal Ag nanostructure of claim 6, wherein the Ag nanostructure symmetrically grows from the center to eight directions from eight petals, the roots of the petals are wide, the outward growth becomes gradually sharp, the petal surface has a rough dendritic structure, and the petal edges are serrated.
8. The dendritic symmetrical octagon Ag nanostructure of claim 6, characterized by use as SERS active substrate.
9. The use of the dendritic symmetrical octagon Ag nanostructure according to claim 1 or 6 in the detection of pesticide residues on fruits and vegetables.
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