CN107589106B - Method for preparing surface enhanced Raman scattering substrate - Google Patents
Method for preparing surface enhanced Raman scattering substrate Download PDFInfo
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- CN107589106B CN107589106B CN201710752986.1A CN201710752986A CN107589106B CN 107589106 B CN107589106 B CN 107589106B CN 201710752986 A CN201710752986 A CN 201710752986A CN 107589106 B CN107589106 B CN 107589106B
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Abstract
The embodiment of the invention discloses a method for preparing a surface-enhanced Raman scattering substrate, which comprises the following steps: adding silicon dioxide aerogel powder into a beaker filled with deionized water, and stirring by a magnetic stirrer to obtain a silicon dioxide aerogel aqueous solution; transferring the silicon dioxide aerogel aqueous solution into a single-neck flask, adding a silver nitrate solution into the single-neck flask, stirring by a magnetic heating table, and heating to boil; adding a sodium citrate solution into the boiled solution and continuously heating for a preset time; cooling the remainder in the single-neck flask to room temperature, pouring the remainder into a centrifuge tube, and centrifugally cleaning the remainder with deionized water to obtain a precipitate at the lower layer of the centrifuge tube; and dropwise adding the precipitate onto a carrier plate, and naturally evaporating the liquid to obtain the silver nanoparticle modified silicon dioxide aerogel powder serving as the surface-enhanced Raman scattering substrate. The silicon dioxide aerogel powder modified by the silver nanoparticles realizes high enhancement and repeatability of SERS detection.
Description
Technical Field
The invention relates to the technical field of Raman spectrum detection, in particular to a method for preparing a surface-enhanced Raman scattering substrate.
Background
The phenomenon of Raman scattering, which was first observed experimentally by the physicist Raman (Raman) of india, is an inelastic scattering phenomenon that occurs when light is irradiated onto an atom or molecule, i.e. scattered light at a different frequency from the incident light. The Raman spectrum carries the fingerprint information of the substance and provides an effective means for researching the internal structures of crystals and molecules, so that the Raman spectrum technology is widely applied to substance detection.
However, the raman scattering cross-section of a molecule is usually small, and only a large number of molecules can contribute to a measurable raman signal, which makes it a significant limitation as a spectroscopic detection technique. In the 70's of the 20 th century, the discovery of Surface-Enhanced Raman Scattering (SERS) has attracted considerable attention and interest. The intensity of SERS can be enhanced by several orders of magnitude or even more than ten orders of magnitude compared with the common Raman scattering, and the method has higher detection sensitivity. Therefore, SERS has been widely used in the fields of material science, surface chemistry, biomedicine, and the like.
The high enhancement effect of SERS results mainly from local electromagnetic field enhancement. The metal nanostructure can generate surface plasmon resonance behavior under the excitation of incident light, and a huge local electric field is generated near the metal nanostructure, so that the raman scattering of molecules in the electric field is enhanced, and the metal nanostructure is called as a hot spot.
The existing SERS substrate has low hotspot density and poor stability, and high sensitivity and repeatability SERS detection is difficult to obtain.
Disclosure of Invention
The invention aims to provide a method for preparing a surface-enhanced Raman scattering substrate, and simultaneously realizes high enhancement and repeatability of surface-enhanced Raman scattering detection.
To achieve the above object, the present invention provides a method of preparing a surface-enhanced raman scattering substrate, comprising:
adding silicon dioxide aerogel powder into a beaker filled with deionized water, and stirring by a magnetic stirrer to obtain a silicon dioxide aerogel aqueous solution;
transferring the silicon dioxide aerogel aqueous solution into a single-neck flask, adding a silver nitrate solution into the single-neck flask, stirring by a magnetic heating table, and heating to boil;
adding a sodium citrate solution into the boiled solution and continuously heating for a preset time;
cooling the remainder in the single-neck flask to room temperature, pouring the remainder into a centrifuge tube, and centrifugally cleaning the remainder with deionized water to obtain a precipitate at the lower layer of the centrifuge tube;
and dropwise adding the precipitate onto a carrier plate, and naturally evaporating the liquid to obtain the silver nanoparticle modified silicon dioxide aerogel powder serving as the surface-enhanced Raman scattering substrate.
Preferably, the silica aerogel powder has a particle size of 5 to 20 μm.
Preferably, the adding of the silica aerogel powder to the beaker with deionized water comprises: and adding 1-2mg of the silicon dioxide aerogel powder into 1ml of deionized water in the beaker filled with the deionized water.
Preferably, the adding of the silver nitrate solution into the single-neck flask comprises: and 10mL of silver nitrate solution with the concentration of 0.0294-0.0412mol/L is added into the single-neck flask.
Preferably, the adding the sodium citrate solution into the boiled solution comprises: 10ml of a sodium citrate solution with a concentration of 0.0051-0.0085mol/L is added to the boiled solution.
Preferably, after the sodium citrate solution is added into the boiled solution and is continuously heated for a preset time, before the residue in the single-neck flask is cooled to room temperature and poured into a centrifuge tube, the method further comprises the following steps: stopping heating to stop the solution from boiling for 5-10 min, and continuing heating to keep the solution boiling for 20-30 min.
Compared with the prior art, the invention has at least the following advantages:
the obtained silicon dioxide aerogel powder modified by the silver nanoparticles is used as a surface-enhanced Raman scattering substrate, and the silicon dioxide aerogel is used as a carrier, and a large number of silver nanoparticles are loaded by utilizing the special structural advantages of the silicon dioxide aerogel, so that a 'hot spot' with high density and high stability is generated, and the high sensitivity and repeatability detection of SERS detection is realized.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a surface-enhanced raman scattering substrate according to an embodiment of the present invention.
Fig. 2 is a schematic flow chart of a method for preparing a surface-enhanced raman scattering substrate according to an embodiment of the present invention.
Fig. 3(a) and 3(b) are scanning electron microscope views of SERS substrates prepared according to embodiments of the present invention.
Fig. 3(c) and 3(d) are views of SERS spectra obtained by SERS enhancement of the SERS substrate prepared according to the embodiment of the present invention.
Detailed Description
In the drawings, the same or similar reference numerals are used to denote the same or similar elements or elements having the same or similar functions. Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
In the description of the present invention, the terms "central", "longitudinal", "lateral", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and therefore, should not be construed as limiting the scope of the present invention.
In the present invention, the technical features of the embodiments and implementations may be combined with each other without conflict, and the present invention is not limited to the embodiments or implementations in which the technical features are located.
An embodiment of the present invention provides a method for preparing a surface-enhanced raman scattering substrate, as shown in fig. 1, including:
And step 104, cooling the remainder in the single-neck flask to room temperature, pouring the remainder into a centrifuge tube, and centrifugally cleaning the remainder with deionized water to obtain a precipitate at the lower layer of the centrifuge tube.
And 105, dripping the precipitate onto a carrier plate, and naturally evaporating the liquid to obtain the silver nanoparticle modified silicon dioxide aerogel powder serving as the surface-enhanced Raman scattering substrate.
In one embodiment, the silica aerogel powder has a particle size of 5 to 20 μm, and most preferably 15 μm.
In one embodiment, adding silica aerogel powder to a beaker of deionized water comprises: and adding 1-2mg of the silicon dioxide aerogel powder into 1ml of deionized water in the beaker filled with the deionized water. For example, 10-20 mg silicon dioxide aerogel powder was added to a beaker containing 10ml deionized water.
In one embodiment, adding the silver nitrate solution to the single-neck flask comprises: and 10mL of silver nitrate solution with the concentration of 0.0294-0.0412mol/L is added into the single-neck flask.
In one embodiment, the adding the sodium citrate solution to the boiled solution comprises: 10ml of a sodium citrate solution with a concentration of 0.0051-0.0085mol/L is added to the boiled solution. Among them, a sodium citrate solution of 0.0353mol/l is most preferable.
In one embodiment, after the sodium citrate solution is added into the boiled solution and heated for a preset time, the method further comprises the following steps of: stopping heating to stop the solution from boiling for 5-10 min, and continuing heating to keep the solution boiling for 20-30 min.
A specific example is provided below. It is to be understood that this example is provided only for better illustration of the method of preparing the surface enhanced raman scattering substrate of the present invention and is not intended to particularly limit the scope of the present invention.
As shown in fig. 2, the method for preparing a surface-enhanced raman scattering substrate provided by this example includes:
Wherein the rotating speed of the magnetic stirrer is 900 revolutions per minute.
And 204, cooling the residual reactant after heating to room temperature, pouring the reactant into a centrifugal tube, centrifugally cleaning the reactant by using deionized water, dropwise adding the precipitate on the lower layer of the centrifugal tube onto a glass sheet, and naturally evaporating the liquid to obtain the silver nanoparticle modified silicon dioxide aerogel powder, namely the SERS substrate.
In order to illustrate the SERS detection effect of the SERS substrate prepared according to the embodiment of the present invention, that is, the silver nanoparticle-modified silica aerogel powder, an electron scanning microscope (SEM) of the silver nanoparticle-modified silica aerogel powder prepared according to the method provided in the above example is shown in fig. 3(a) and fig. 3(b), a SERS detection spectrum of rhodamine (R6G) molecule is shown in fig. 3(c), and a SERS detection spectrum of 5-fluorouracil is shown in fig. 3 (d). Fig. 3(b) is an enlarged view of the sample inside the dotted frame in fig. 3 (a).
When SERS detection is carried out, firstly, a solution of an object to be detected is prepared, for example, the silver nanoparticle modified silica aerogel powder prepared according to the above example method is poured into the solution of the object to be detected for full mixing, a small amount of mixed solution is dripped onto a glass slide, for example, and SERS spectrum detection is carried out after the mixed solution is dried.
The concentrations of R6G in FIG. 3(c) were 10 respectively-10、10-13M, 5-Fluorouracil concentration in FIG. 3(d) is 10-10、10-13M。
As can be seen from fig. 3(a) and 3(b), a large number of silver nanoparticles are densely distributed on the silica aerogel powder, and the shape thereof meets the condition of forming hot spots. FIG. 3(c) andthe abscissa X in 3(d) is the Raman shift in cm-1The ordinate Y represents intensity in a.u (Arbitrary Unit).
As can be seen from fig. 3(c) and 3(d), the silica aerogel powder modified with silver nanoparticles has very good reinforcing effect for both molecules at both concentrations.
Finally, it should be pointed out that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Those of ordinary skill in the art will understand that: modifications can be made to the technical solutions described in the foregoing embodiments, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A method of making a surface enhanced raman scattering substrate, comprising:
adding silicon dioxide aerogel powder into a beaker filled with deionized water, and stirring by a magnetic stirrer;
transferring the solution obtained after stirring into a single-neck flask, adding a silver nitrate solution into the single-neck flask, stirring by a magnetic heating table, and heating to boil;
adding a sodium citrate solution into the boiled solution and continuously heating for a preset time;
cooling the remainder in the single-neck flask to room temperature, pouring the remainder into a centrifuge tube, and centrifugally cleaning the remainder with deionized water to obtain a precipitate at the lower layer of the centrifuge tube;
dripping the precipitate onto a carrier plate, and naturally evaporating the liquid to obtain silicon dioxide aerogel powder modified by silver nanoparticles used as a surface-enhanced Raman scattering substrate; wherein, silver nano-particles are densely distributed on the silicon dioxide aerogel powder, and the shapes of the silver nano-particles meet the condition of forming hot spots;
when the surface enhanced Raman scattering detection is carried out, the silicon dioxide aerogel powder modified by the silver nanoparticles is taken, the powder is poured into the solution of the object to be detected and fully mixed, and a proper amount of mixed solution is taken and placed on a glass slide for surface enhanced Raman spectrum detection.
2. The method of claim 1, wherein the silica aerogel powder has a particle size of 5 to 20 μ ι η.
3. The method of claim 2, wherein adding the silica aerogel powder to the beaker of deionized water comprises:
and adding 1-2mg of the silicon dioxide aerogel powder into 1mL of deionized water in the beaker filled with the deionized water.
4. The method of claim 1, wherein the adding of the silver nitrate solution to the single-neck flask comprises:
and 10mL of silver nitrate solution with the concentration of 0.0294-0.0412mol/L is added into the single-neck flask.
5. The method of claim 4, wherein adding the sodium citrate solution to the boiled solution comprises:
10ml of a sodium citrate solution with a concentration of 0.0051-0.0085mol/L is added to the boiled solution.
6. The method of claim 1, wherein after the adding the sodium citrate solution into the boiled solution and heating for the preset time, before the cooling the remainder in the single-neck flask to room temperature and pouring the remainder into a centrifuge tube, the method further comprises:
stopping heating to stop the solution from boiling for 5-10 min, and continuing heating to keep the solution boiling for 20-30 min.
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| CN113552114A (en) * | 2021-08-09 | 2021-10-26 | 首都师范大学 | Preparation method and detection method of surface-enhanced Raman scattering substrate |
| CN114280029A (en) * | 2022-01-04 | 2022-04-05 | 朱媛媛 | Method for detecting western medicine components in Chinese patent medicine |
| CN116297389B (en) * | 2023-02-15 | 2023-12-26 | 中国人民解放军空军特色医学中心 | Drug detection method capable of causing driving operation disability in biological sample at accident site |
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| CN103278492A (en) * | 2013-05-31 | 2013-09-04 | 黑龙江大学 | Preparation method of surface-enhanced Raman substrate |
| CN103868908A (en) * | 2014-02-26 | 2014-06-18 | 江南大学 | Surface enhanced Raman substrate based on sepharose gel as well as preparation method of substrate |
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