CN115464134A - Gold and silver composite nano-star and preparation method and application thereof - Google Patents
Gold and silver composite nano-star and preparation method and application thereof Download PDFInfo
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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
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Abstract
The application discloses a gold and silver composite nano-star and a preparation method and application thereof. The method obtains three types of nano-stars with different structural parameters through a seed-mediated method, has the advantages of high yield, good monodispersity and controllable form, verifies the SERS enhancement performance of the nano-stars through theoretical and experimental results, and has wide application prospect in the aspect of sensitive detection of trace molecules.
Description
Technical Field
The application belongs to the technical field of nano materials, and particularly relates to a gold and silver composite nano star and a preparation method and application thereof.
Background
Near-field optics is an emerging discipline for studying optical phenomena within one wavelength of the surface of an object. For example, surface Enhanced Raman Scattering (SERS) is achieved by exploiting the near-field enhancement properties of metal surfaces. Reports show that the near-field enhancement performance of metals depends on some hot spot structures, such as high curvature nanotips, nanogaps below 10nm, or nanohole structures. SERS is an ultrasensitive molecular detection technology oriented to practical application, and the detection performance of SERS strongly depends on the configuration of a hot spot structure, the substrate preparation mode and the structural stability. In recent years, nanostar structures have become important research targets in SERS substrate types due to their typical multi-configuration cascade coupling enhancement characteristics, excellent chemical stability and biocompatibility. Research shows that the near-field enhancement performance of the nanostars comes from the mixing of two plasma structures, namely a nano core and a nano branch, and particularly depends on the size ratio of the nano core and a peripheral branch. However, the high yield controllable synthesis of nanostars has not yet been effectively solved.
Disclosure of Invention
The application provides a gold-silver composite nanostars and a preparation method and application thereof, aiming at solving the technical problem of low nanostars yield.
In order to solve the technical problem, the application adopts a technical scheme that: the gold and silver composite nanostars are multi-dendritic and star-shaped, have absorption from a visible region to an ultraviolet region, wherein the core radius is greater than or equal to 25nm and less than or equal to 35nm, and the branch length is greater than or equal to 35nm and less than or equal to 55nm.
Another technical scheme adopted by the application is as follows: a preparation method of gold and silver composite nanostars comprises the following steps:
heating a chloroauric acid solution to boiling, then adding a sodium citrate solution, keeping heating and stirring to obtain a first solution;
adding an acidic mixture to the first solution and stirring to obtain a second solution;
and sequentially adding silver nitrate and ascorbic acid into the second solution for reaction, wherein the color of the reaction solution is changed from light red to dark green, and a gold nano-star colloidal solution is obtained.
Further, the concentration of the chloroauric acid solution is 0.01%.
Further, the concentration of the sodium citrate solution is 1%.
Further, the acidic mixture is chloroauric acid and hydrochloric acid in a molar ratio of 250000: 1mol ratio.
Further, the concentration of the silver nitrate is 0.1-0.3mol/ml.
Further, the concentration of the ascorbic acid is 100mol/ml.
The gold and silver composite nano star is used for preparing an SERS detection substrate, and the SERS detection substrate is used for detecting various low-concentration dye molecules and drugs.
The beneficial effect of this application is: the method obtains three types of nano-stars with different structural parameters through a seed-mediated method, has the advantages of high yield, good monodispersity and controllable form, verifies the SERS enhancement performance of the nano-stars through theoretical and experimental results, and has wide application prospect in the aspect of sensitive detection of trace molecules.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
fig. 1 is (a) scanning electron microscope images of spherical gold nanoparticles and (b) transmission electron microscope images of gold nanostars prepared with different concentrations of silver nitrate, according to the present application: 0.1mol/ml, (c) 0.2mol/ml; (d) 0.3mol/ml;
FIG. 2 (a) is an ultraviolet-visible spectrum before and after the growth of the seed of the present application (curve a: absorption spectrum of spherical gold seed; curves b to d correspond to absorption spectra of gold nanostars (b to d) in FIG. 1, respectively);
2 (b) -2 (d) are graphs of the energy spectrum scanning results of the nanostars with different configurations (ruler: 50 nm) in the application;
FIG. 3 is a graph of the results of the gold nanostar FDTD electromagnetic field theoretical simulation of the present application;
FIG. 4 shows the concentration of MB (10 concentration) in the present application -5 M) as a probe molecule and 3 Au nanostar structures as SERS substrates to obtain 1388 cm -1 A statistical plot of relative peak intensity uniformity;
FIG. 5 is a graph of a single point photostability study of the present application based on nanostars as SERS substrates;
FIG. 6 shows SERS measurements of different types of molecules based on nanostars.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The application provides a gold-silver composite nano star which is in a multi-dendritic star shape and has absorption from a visible region to an ultraviolet region, wherein the core radius is more than or equal to 25nm and less than or equal to 35nm, and the branch length is more than or equal to 35nm and less than or equal to 55nm.
Example 1
The application provides a preparation method of the gold and silver composite nano star, which comprises the following steps:
s1, heating a chloroauric acid solution to boiling, then adding a sodium citrate solution, keeping heating and stirring to obtain a first solution;
s2, adding the acidic mixture into the first solution and stirring to obtain a second solution;
and S3, sequentially adding silver nitrate and ascorbic acid into the second solution for reaction, wherein the color of the reaction solution is changed from light red to dark green, and thus obtaining the gold nano-star colloidal solution.
Alternatively, the concentration of the chloroauric acid solution is 0.01%.
Alternatively, the concentration of the sodium citrate solution is 1%.
Alternatively, the acidic mixture is chloroauric acid with hydrochloric acid at 250000: 1mol ratio.
Optionally, the silver nitrate is present in a concentration of 0.1 to 0.3mol/ml.
Alternatively, the concentration of ascorbic acid is 100mol/ml.
Example 2
The preparation experiment of the gold and silver composite nano star comprises the following specific steps:
1) Preparation of gold nano-seeds
200ml of 0.01% chloroauric acid (HAuCl) was taken in a graduated cylinder 4 ) And added to a conical flask with a magnetic rotor. It was placed in a preheated oil bath, heated until boiling and stirred continuously. After boiling, 5 ml of 1% strength sodium citrate (C) are added rapidly 6 H 5 Na 3 O 7 ) The heating was maintained and stirring was continued for 20 minutes. After the reaction, the sample was refrigerated at 4 ℃ for further use.
2) Preparation of nano star
mu.L of the above seed solution was added to a mixture of 10mL (0.25 mol/mL HAuCl 4) and 10. Mu.L (1 mol/L hydrochloric acid) and stirred at a rotation speed of about 700 rpm. Then 100. Mu.L of AgNO was added 3 And 50. Mu.L of Ascorbic Acid (AA) with a concentration of 100mol/ml were sequentially added to the solution, and the color of the solution was changed from light red to dark green, thereby obtaining a gold nanostar colloidal solution. In the preparation method, agNO 3 Are 0.1, 0.2 and 0.3mol/ml, respectively.
As shown in fig. 1, fig. 1 is a scanning electron microscope image of (a) spherical gold nanoparticles and transmission electron microscope images of gold nanostars prepared with different concentrations of silver nitrate of the present application; 0.1mol/ml, (c) 0.2mol/ml and (d) 0.3mol/ml. Fig. 1 (a) is an initial gold seed morphology, where the large image is the SEM morphology of gold nanostars and the upper right small image is the TEM result. It can be clearly seen that the gold seeds prepared herein are uniform in size, have good monodispersity, and have an average size of about 20nm. The nano star with three configurations is obtained by using the nano star as a seed solution through a seed-mediated method. We used ascorbic acid as a weak reducing agent to form nucleation sites on the surface of the seed. With the intervention of Ag +, the growth of gold atoms on the nucleation sites is inhibited, which leads to anisotropic growth of the particles and the formation of multi-dendritic nanostars. The graphs (b) - (d) show the appearance of the nano star structure changing along with the change of the silver nitrate concentration. When the silver nitrate concentration is 0.1mol/ml, the core radius (R) of the gold nanostar is about 32nm and the length of the branch (B) is about 35.5nm, which we defined as model 1, as shown in fig. 1 (B). When the silver nitrate concentration is increased to 0.2mol/ml, the influence of silver ions on the growth of the gold nano-star is obviously increased, and the R of the obtained nano-star is about 30nm, and the B is about 4nm, which is expressed as a model 2. When the concentration was further increased to 0.3mol/ml, R was only about 27nm and B was about 52nm, as indicated in model 3. As can be seen from the TEM morphology in fig. 1, the yields of the three types of nanostars are high, indicating that the seed-mediated method adopted in the present application is excellent in controllability.
As shown in FIG. 2, FIG. 2 (a) is an ultraviolet-visible spectrum before and after the growth of the seeds of the present application (curve a: absorption spectrum of spherical gold seeds; curves b-d correspond to absorption spectra of gold nanostars (b-d) in FIG. 1, respectively); FIGS. 2 (b) to 2 (d) are graphs of the results of spectral scanning of nanostars of different configurations according to the present application (scale: 50 nm). Fig. 2 (a) shows the uv-vis absorption spectrum characteristics of gold seeds and nanostars. For gold nanopedes, the strong absorption peak at 532nm is due to the longitudinal local plasmon resonance of the nanoparticles (line a). For nanostars with branched tips, the strong absorption peaks of their longitudinal LSPR showed significant red- shift models 1,2 and 3, with nanostar absorption peaks at approximately 722nm (line b), 784nm (line c) and 802nm (line d), respectively. The absorbance spectrum of nanostars is significantly broader compared to seeds, with the peak red-shifted as the ratio of branch length to core radius increases. We speculate that this is due to the growth of nanostar branches and the difference in length and sharpness between the branches. The more branches, the higher the sharpness, the more pronounced the peak red shift. In order to further discuss the influence of the Ag + concentration on the morphology and the near-field enhancement characteristic of the gold nanostars, the distribution and content ratio of gold and silver on the surfaces of the three nanostars are analyzed through TEM energy spectrum scanning. FIGS. 2 (b-d) show the results of the spectrum scanning of three types of nanostar models, wherein green represents silver element and red represents gold element. It can be seen that the Ag element is uniformly distributed on the surface of each nanostar regardless of the difference of the structural parameters, which indicates that the reaction system is uniform and controllable.
Example 3
The gold and silver composite nanostars are used for preparing an SERS detection substrate, and the SERS detection substrate is used for detecting various low-concentration dye molecules and drugs.
The experimental procedure is as follows:
as shown in fig. 3, fig. 3 is a graph of the electromagnetic field theoretical simulation result of the gold nanostar FDTD of the present application. FDTD electromagnetic field simulation is carried out according to the structural parameters of the three types of nanostars, and the result is shown in figure 3. Theoretically, the wavelength of the incident light is 785nm, and the incident direction is perpendicular to the surface of the nanosatellite. It can be seen that the hot spot of nanostar near-field enhancement is close to the tip of the branch due to plasmon hybridization and cascade coupling enhancement effect between the nanonucleus and the branch. Therefore, when the gold nanostars are used as the SERS substrate, the branch tips can easily collect molecules to be detected, and thus the Raman signal of the substance to be detected can be effectively enhanced.
The near field enhancement characteristic of the model 2 nanostar can be judged to be most obvious by combining the electromagnetic field simulation and the statistical result of the content of the energy spectrum elements. In order to further verify the idea, the application further adopts a gas-liquid interface assembly method to obtain the nanostar film on the silicon wafer and detect the SERS performance of the nanostar film.
As shown in FIG. 4, FIG. 4 shows the results of MB (concentration: 10) in the present application -5 M) as a probe molecule and 3 Au nanostar structures as SERS substrates to obtain 1388 cm -1 Statistical plots of relative peak intensity uniformity. Methylene Blue (MB) is taken as an object to be detected, and SERS performance of the nanostar substrate with three configurations of the models 1,2 and 3 is evaluated through multipoint detection. The statistic result shows that the MB molecule is 1388 cm -1 The relative standard deviation values (RSD) of SERS intensities at characteristic peaks are 11.6%,4.1% and 10.0%, respectively, which indicates that the repeatability and stability of model 2 nanosatellite are more outstanding. In terms of relative intensity, the MB signal intensity measured based on the model 2 nanosatellite is obviously higher than that measured on the same detection stripThe MB signal intensity of other two types of nanosategories shows that the near-field enhancement characteristic of the model 2 is more sensitive and reliable.
As shown in fig. 5, fig. 5 is a graph of single-point photostability studies of the present application based on nanostars as SERS substrates; wherein the probe molecule is MB with a concentration of 10 -6 And M. The present application investigated the lightfastness of model 2 nanostars itself with incident light at a wavelength of 785 nm. Similarly, MB is taken as a probe molecule, a nanostar film is taken as an SERS substrate, the laser power is 60mW, and 60 spectra are continuously collected at a fixed point. The integration time for each spectrum was 5s and the continuous illumination time was 855s. It can be seen that the SERS signal of MB fluctuates slightly over time, showing good structural and photo stability. The inset depicts 1388 cm during the 855s irradiation period -1 The change in SERS intensity, with the intensity fluctuating within a narrow range (between 489 and 605 counts), can further demonstrate good optical stability of the model 2 nanostar.
Example 4
As shown in fig. 6, fig. 6 is the SERS detection results of different types of molecules based on nanostars in the present application. The application further utilizes the model 2 nano-stars to carry out SERS spectrum collection on dye molecules and various virus molecules. The detected 3-type dye molecule concentration is 10 -7 M, as shown in FIG. 6 (a). The excitation wavelength was 785nm and the integration time was 5s. For the concentration of drug molecules in fig. 6 (b), methadone was 0.5219 mg/ml, morphine was 0.2289 mg/ml, ketamine was 0.2143 mg/ml, methamphetamine was 0.4592 mg/ml. It can be seen that the raman characteristic spectra of various molecules can be clearly detected, and have a higher signal-to-noise ratio, which indicates that the model 2 nanosatellite has certain SERS detection universality. We further diluted the methadone concentration and performed a multi-point reproducibility test on 0.261ug/ml methadone, with the results shown in fig. 6 (c). From the consistency of the peak shapes, the prepared nano-star substrate shows higher SERS uniformity and stability.
Three gold nano-stars with different structural parameters are prepared by a seed-mediated method. The ultraviolet-visible absorption spectrum covers the near infrared region, which makes it possible for biological applications. FDTD simulation shows that the near-field enhancement hot spot of the nanostars is concentrated at the branch tips, and the cascade enhancement effect of the plasma between the nano cores and the branches directly influences the performance of the SERS hot zone. When the core radius of the nano-star is 30nm and the branch length is 40nm, the local electromagnetic field enhancement property of the nano-star is relatively strong. The nanostars in this morphology also showed good structural stability in a single point photostability test. Therefore, the application provides a simple and controllable preparation method of the nano-star, and theoretical and experimental bases are provided for the near-field enhancement characteristics of the nano-star.
The above description is only an example of the present application and is not intended to limit the scope of the present application, and all modifications of equivalent structures and equivalent processes, which are made by the contents of the specification and the drawings, or which are directly or indirectly applied to other related technical fields, are intended to be included within the scope of the present application.
Claims (8)
1. A gold-silver composite nanostar, comprising: the gold and silver composite nano star is in a multi-dendritic star shape and has the absorption from a visible region to an ultraviolet region, wherein the core radius is more than or equal to 25nm and less than or equal to 35nm, and the branch length is more than or equal to 35nm and less than or equal to 55nm.
2. The preparation method of the gold-silver composite nanostar is characterized by comprising the following steps:
heating a chloroauric acid solution to boil, then adding a sodium citrate solution, keeping heating and stirring to obtain a first solution;
adding an acidic mixture to the first solution and stirring to obtain a second solution;
and sequentially adding silver nitrate and ascorbic acid into the second solution for reaction, wherein the color of the reaction solution is changed from light red to dark green, and a gold nano-star colloidal solution is obtained.
3. The method of claim 2, wherein the chloroauric acid solution has a concentration of 0.01%.
4. The method of claim 2, wherein the concentration of the sodium citrate solution is 1%.
5. The method of claim 2, wherein the acidic mixture is chloroauric acid with hydrochloric acid in a molar ratio of 250000: 1mol ratio.
6. The method according to claim 2, characterized in that the concentration of silver nitrate is 0.1-0.3mol/ml.
7. The method according to claim 2, wherein the concentration of ascorbic acid is 100mol/ml.
8. The application of the gold and silver composite nano-star is characterized in that the gold and silver composite nano-star is used for preparing an SERS detection substrate, and the SERS detection substrate is used for detecting various low-concentration dye molecules and drugs.
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