CN113655051A - Preparation method of nano manganese dioxide/carbon-based point/nano gold surface enhanced Raman substrate - Google Patents
Preparation method of nano manganese dioxide/carbon-based point/nano gold surface enhanced Raman substrate Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 155
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 69
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 43
- 239000000758 substrate Substances 0.000 title claims abstract description 38
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- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
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- 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 discloses a preparation method of a nano manganese dioxide/carbon base point/nano gold surface enhanced Raman substrate, which utilizes rich oxygen-containing functional groups on the surface of a single-layer carbon base point as a stabilizing agent and a wrapping agent to prepare large-size flexible manganese dioxide nano-sheets and nano gold with uniform size, and then obtains the nano manganese dioxide/carbon base point/nano gold composite material by a simple mixing and co-centrifuging method. The preparation method is simple, convenient and fast, has no pollution, and has rapid reaction and strong operability. The obtained nano manganese dioxide/carbon-based point/nano gold composite material has the advantages that gold nanoparticles are distributed on the manganese dioxide nanosheets in the state of aggregated clusters, the sub-nanometer-level gaps among the gold nanoparticles are favorable for generating a strong local electromagnetic field coupling effect, the Raman enhancement effect is high in sensitivity, the electromagnetic field enhancement effect of the noble metal nanoparticles can be enhanced by the composite semiconductor material manganese dioxide nanosheets, and the measurement sensitivity is further improved.
Description
Technical Field
The invention belongs to the field of preparation of surface enhanced Raman substrates, and relates to a preparation method of a nano manganese dioxide/carbon base point/nano gold surface enhanced Raman substrate.
Background
The surface Raman enhancement spectrum is characterized in that incident light is irradiated on noble metal materials such as gold, silver and the like at a nanometer level, the probability of inelastic collision of molecules adsorbed or bonded on the materials is increased, and therefore an obvious Raman enhancement signal is obtained. The SERS technique can greatly enhance the raman signal of the molecule, which is beneficial for observing more vibration modes that are not observed by the common raman technique. The change of molecular energy level and structural property or the change of a substrate interface can cause the change of molecular Raman signal intensity or displacement, and in addition, different types of chemical bonds show different vibration and rotation modes, so that the SERS technology has good application prospects in the aspects of sensing, catalytic mechanism research, energy application, biological medicine and the like. Mechanistic aspects the enhancement mechanism of surface enhanced raman is not discussed, but the physical enhancement mechanism and the chemical enhancement mechanism are two raman enhancement mechanisms generally accepted by academia.
The physical enhancement mechanism is mainly to research SERS enhancement from the aspect of a photo-electromagnetic field, and a phenomenon that a (< 10 nm) molecular Raman scattering signal near a metal nanoparticle is enhanced due to a huge enhanced electromagnetic field generated by incident light on a metal surface with certain roughness. Recently, a great number of workers compound noble metal nanostructures with carbon nanomaterials to prepare hybrid materials with excellent surface-enhanced raman activity, and the compound carbon nanostructures can stabilize metal nanoparticles on one hand and can produce more electromagnetic "hot spots" on the other hand to enhance raman signals. Although the chemical enhancement is weaker than the physical enhancement, it is not negligible, and the chemical enhancement mechanism is more due to the interaction between the adsorbate and the substrate. At present, various researchers pay attention to the preparation of surface enhanced raman substrate materials with both physical enhancement and chemical enhancement effects, most of which are to deposit precious metal nanoparticles on the surface of a semiconductor or wrap the precious metal nanoparticles with the semiconductor to obtain a composite material for the surface enhanced raman research, but the electromagnetic enhancement effect of the materials is weakened by wrapping the precious metal nanoparticles with the semiconductor material, and the chemical enhancement effect of the materials is also influenced by the deposition of the precious metal nanoparticles on the semiconductor. Therefore, it is important to synthesize an excellent noble metal/semiconductor nanocomposite and obtain a more sensitive raman signal from the analyte through the synergistic effect of the two materials. AuNPs in the nano manganese dioxide/carbon-based dot/nanogold prepared by the method exist on the nano manganese dioxide/carbon-based dot nanosheet in the form of an aggregate, so that more SERS 'hot points' can be generated, and the method has a good electromagnetic field enhancement effect. And the interaction between the nano manganese dioxide/carbon-based dots and molecules improves the polarizability of the system and increases the chemical enhancement effect of the system. Therefore, the nano composite material has a good SERS enhancement effect when being used as a SERS substrate, and the high-sensitivity surface-enhanced Raman active substrate has certain significance for trace detection of analytes and Raman mechanism research.
Disclosure of Invention
The invention aims to provide a preparation method of a nano manganese dioxide/carbon-based point/nano gold surface enhanced Raman substrate aiming at the defects of the existing material, and the method has the advantages of simple operation, low cost, rapid reaction and mild conditions. Compared with the nano manganese dioxide/carbon-based dot composite material, the nano gold/carbon-based dot composite material has better Raman signals and can be used for trace detection of an object to be detected.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano manganese dioxide/carbon base point/nano gold surface enhanced Raman substrate comprises the following steps:
(1) synthesizing a nano manganese dioxide/carbon dot composite material: weighing a certain amount of carbon base points, stirring and dissolving in deionized water, sequentially adding manganous chloride after heating to be stable, continuously stirring potassium permanganate for a period of time, stopping reaction, centrifuging the mixed solution at a low rotating speed to collect supernatant, repeatedly centrifuging the supernatant at a high rotating speed to clarify the supernatant, collecting precipitate, and re-dispersing the precipitate in water to obtain the nano manganese dioxide/carbon base point composite material;
(2) and (3) synthesis of the nano gold/carbon dot composite material: mixing 1-10 mL of 0.01-0.05 mg/mL carbon-based dot solution and 0.05-1 mL of 0.1-10 mg/mL chloroauric acid solution, adding a sodium hydroxide solution to adjust the pH to 8-10, adding sodium borohydride after the solution is heated and stabilized, continuously stirring and reacting for a period of time, stopping the reaction, centrifuging the solution at a low rotating speed to collect supernatant, centrifuging the supernatant at a high rotating speed, collecting precipitate, and re-dispersing the precipitate in water to obtain the nanogold/carbon-based dot material;
(3) synthesis of the composite material: and mixing the synthesized nano manganese dioxide/carbon-based dot material and the nano gold/carbon-based dot material in water, stirring, centrifuging, and re-dispersing the precipitate in distilled water to obtain the nano manganese dioxide/carbon-based dot/nano gold composite material.
In the step (1), the carbon base point is a graphene structure nanosheet with a transverse size smaller than 100 nanometers, and the surface of the nanosheet contains a large number of oxygen-containing functional groups;
in the step (1), the medium and small rotating speed is 1000-3000 rpm, and the centrifugation time is 5-60 min; the large-speed centrifugation speed is 9000-20000 rpm, and the centrifugation time is 15-60 min.
The concentration of the carbon base point solution in the step (1) is 0.01-0.05 mg/mL; the concentration of the nano manganese dioxide/carbon-based dot composite material in the obtained composite material solution is 0.2-0.5 mg/mL.
In the step (1), the heating temperature is 120-140 ℃; the time for continuously stirring and reacting is 10-20 min.
In the step (2), the medium and small rotating speed is 1000-3000 rpm, and the centrifugation time is 5-60 min; the high-speed centrifugation rotating speed is 8000-18000 rpm, and the centrifugation time is 15-60 min.
The initial concentration of the chloroauric acid in the reaction system in the step (2) is 0.1-10 mg/ml.
The amount of sodium borohydride in the reaction system in the step (2) is 0.5-50 mg per mg of silver ions.
In the step (2), the heating temperature is 120-140 ℃; heating for 10-20 min; the time for continuously stirring and reacting is 10-30 min.
In the step (3), the mass ratio of the nano manganese dioxide/carbon base points to the nano gold/carbon base point composite material in the reaction system is controlled to be 0.01-10.
In the step (3), the rotation speed of centrifugal washing is 9000-20000 rpm.
The application comprises the following steps: the application of the nano manganese dioxide/carbon base point/nano gold composite material in preparing a surface enhanced Raman substrate.
The invention has the following remarkable advantages:
1) the invention utilizes the water solubility and stability of the carbon-based points as a wrapping agent in the process of preparing the manganese dioxide nano-sheets and the nano-gold, so that the manganese dioxide nano-sheets and the nano-gold are uniformly wrapped on the nano-material, and the stable carbon-based point wrapped thin large-size flexible manganese dioxide nano-sheets and the nano-gold with uniform size are obtained. The preparation method is simple to operate, complex synthetic steps are not needed, few reagents are used, no pollution is caused, and the product stability is good.
2) The nano manganese dioxide nanosheet adopted by the invention is large in transverse size, the preparation method of the nano manganese dioxide/carbon base point/nano gold surface enhanced Raman substrate is simple to operate, the nano manganese dioxide/carbon base point/nano gold surface enhanced Raman substrate is compounded together by a simple mixing and co-centrifuging method, the steps are simple, no pollution is caused, and the experimental result is stable.
3) The nano-gold in the nano-manganese dioxide/carbon-based point/nano-gold composite material prepared by the invention is distributed on manganese dioxide nano-chips in the form of aggregated clusters, the distribution is uniform, the size is relatively uniform, and the gaps at the sub-nanometer level among the gold nano-particles are beneficial to generating strong local electromagnetic field coupling effect. The semiconductor nano material and the noble metal nano material are compounded to prepare a novel surface enhanced Raman substrate with high sensitivity, crystal violet is taken as a probe molecule, and the Raman substrate has a stronger Raman signal compared with a single gold nano particle.
4) The interaction between the nano manganese dioxide/carbon-based dots and molecules improves the polarizability of a system and increases the chemical enhancement effect of the system, the manganese dioxide nanosheets have higher dielectric constants, and when noble metals are compounded with semiconductors with high dielectric constants, stronger plasma resonance can be caused, so that the signals of molecules to be detected adsorbed in the manganese dioxide nanosheets are enhanced, and the high-sensitivity surface-enhanced Raman active substrate has certain significance for trace detection of analytes and Raman mechanism research.
Drawings
FIG. 1 is a transmission electron microscope image of a carbon-based dot-coated manganese dioxide nanosheet composite prepared in example 1;
FIG. 2 is a transmission electron microscope image of the nano-Au/carbon-based dot composite material prepared in example 1;
FIG. 3 is a transmission electron microscope image of the nano manganese dioxide/carbon-based dot/nano gold composite material prepared in example 2;
FIG. 4 is a diagram showing an ultraviolet-visible absorption spectrum of a nano manganese dioxide/carbon-based dot composite material, and an ultraviolet absorption spectrum of a nano manganese dioxide/carbon-based dot/nano gold composite material in which a mass ratio of manganese dioxide/carbon-based dot to nano gold/carbon-based dot is 0.2;
FIG. 5 shows Raman signal intensity of crystal violet detected on different active substrates, wherein a curve is a nano manganese dioxide/carbon base point/nano gold composite substrate, and b curve is a nano gold/carbon base point composite substrate; the curve c is a nano manganese dioxide/carbon-based point composite substrate; the d curve is a pure crystal violet substrate;
fig. 6 shows raman signal intensity of crystal violet detected by the nano manganese dioxide/carbon base point/nano gold composite material substrate with different mass ratios of manganese dioxide/carbon base point and nano gold/carbon base point, wherein the nano manganese dioxide/carbon base point/nano gold composite material substrate with different mass ratios is 0.1, 0.2, 0.3 and 0.4 from bottom to top.
Detailed Description
For a better understanding of the present invention, it is further illustrated by way of example, but the present invention is not limited thereto.
Preparation of the carbon quantum dots: 5g of carbon black (350 mL) concentrated HNO is taken3Stirring and heating to 130 ℃ in a three-neck flask, refluxing for 48 h, cooling to room temperature, filtering unreacted carbon black in a funnel in vacuum, taking supernatant, distilling under reduced pressure for multiple times to remove acid, washing with deionized water for multiple times, and drying at 100-120 ℃ to finally obtain the reddish brown solid carbon quantum dots.
Example 1
35 mg of carbon quantum dots are weighed and dissolved in 100 mL of deionized water with stirring, heated to 130 ℃, and then 1.2mL of 0.1M manganous chloride is added. And continuously stirring and heating for 5 min, quickly adding 1mL of 0.1M potassium permanganate solution, instantly changing the added solution from orange to brown-black instantly, continuously and stably heating for 15 min, stopping heating, and cooling to room temperature. Centrifuging the obtained solution at a low rotating speed (3000 rpm) for 10 min to remove large particles, centrifuging at a high rotating speed (12000 rpm) for 10 min to remove unreacted solvent, and obtaining precipitate, namely the obtained product nano manganese dioxide/carbon base point.
Weighing 23 mL of deionized water, 1mL of 5mg/mL carbon quantum dot solution, 200 μ L of 0.05M chloroauric acid and a 50mL round-bottom flask, adding 0.1M sodium hydroxide under stirring to adjust the pH to be alkalescent (pH = 9), heating to 130 ℃ for stabilization for 15 min, then quickly adding 600 μ L of 0.1M sodium borohydride solution into the reaction system, continuously reacting for 20min, and then turning off the heating to obtain the nanogold/carbon quantum dot composite material by the same centrifugal means as the above.
Taking 1000 mu L of nano manganese dioxide/carbon-based point composite material solution (the concentration is 0.356 mg/mL), 166 mu L of nano gold/carbon-based point composite material solution (the concentration is 0.214 mg/mL) into 20mL of deionized water, stirring for 12h, centrifuging for 10 min at 12000 rpm, washing precipitates with water, and dissolving the precipitates in the deionized water again to obtain the nano manganese dioxide/carbon-based point/nano gold composite material with the mass ratio of the nano manganese dioxide/carbon-based point to the nano gold/carbon-based point equal to 0.1, wherein the writing is 0.1-nano manganese dioxide/carbon-based point/nano gold composite material, and the following steps are the same.
Example 2
35 mg of carbon quantum dots are weighed and dissolved in 100 mL of deionized water with stirring, heated to 130 ℃, and then 1.2mL of 0.1M manganous chloride is added. And continuously stirring and heating for 5 min, quickly adding 1mL of 0.1M potassium permanganate solution, instantly changing the added solution from orange to brown-black instantly, continuously and stably heating for 15 min, stopping heating, and cooling to room temperature. Centrifuging the obtained solution at a low rotating speed (3000 rpm) for 10 min to remove large particles, centrifuging at a high rotating speed (12000 rpm) for 10 min to remove unreacted solvent, and obtaining precipitate, namely the obtained product nano manganese dioxide/carbon base point.
Weighing 23 mL of deionized water, 1mL of 5mg/mL carbon quantum dot solution, 200 μ L of 0.05M chloroauric acid and a 50mL round-bottom flask, adding 0.1M sodium hydroxide under stirring to adjust the pH to be alkalescent (pH = 9), heating to 130 ℃ for stabilization for 15 min, then quickly adding 600 μ L of 0.1M sodium borohydride solution into the reaction system, continuously reacting for 20min, and then turning off the heating to obtain the nanogold/carbon quantum dot composite material by the same centrifugal means as the above.
And (3) putting 1000 mu L of nano manganese dioxide/carbon-based point composite material solution (with the concentration of 0.356 mg/mL) and 332 mu L of nano gold/carbon-based point composite material solution (with the concentration of 0.214 mg/mL) into 20mL of deionized water, stirring for 12h, centrifuging for 10 min at 12000 rpm, washing precipitates with water once, and dissolving the precipitates in the deionized water again to obtain the 0.2-nano manganese dioxide/carbon-based point/nano gold composite material.
Example 3
35 mg of carbon quantum dots are weighed and dissolved in 100 mL of deionized water with stirring, heated to 130 ℃, and then 1.2mL of 0.1M manganous chloride is added. And continuously stirring and heating for 5 min, quickly adding 1mL of 0.1M potassium permanganate solution, instantly changing the added solution from orange to brown-black instantly, continuously and stably heating for 15 min, stopping heating, and cooling to room temperature. Centrifuging the obtained solution at a low rotating speed (3000 rpm) for 10 min to remove large particles, centrifuging at a high rotating speed (12000 rpm) for 10 min to remove unreacted solvent, and obtaining precipitate, namely the obtained product nano manganese dioxide/carbon base point.
Weighing 23 mL of deionized water, 1mL of 5mg/mL carbon quantum dot solution, 200 μ L of 0.05M chloroauric acid and a 50mL round-bottom flask, adding 0.1M sodium hydroxide under stirring to adjust the pH to be alkalescent (pH = 9), heating to 130 ℃ for stabilization for 15 min, then quickly adding 600 μ L of 0.1M sodium borohydride solution into the reaction system, continuously reacting for 20min, and then turning off the heating to obtain the nanogold/carbon quantum dot composite material by the same centrifugal means as the above.
And (3) putting 1000 mu L of nano manganese dioxide/carbon-based dot composite material solution (with the concentration of 0.356 mg/mL) and 498 mu L of nano gold/carbon-based dot composite material solution (with the concentration of 0.214 mg/mL) into 20mL of deionized water, stirring for 12h, centrifuging at 12000 rpm for 10 min, washing precipitates with water once, and dissolving the precipitates in the deionized water again to obtain the 0.3-nano manganese dioxide/carbon-based dot/nano gold composite material.
FIG. 1 is a transmission electron microscope image of a carbon-based dot-coated manganese dioxide nanosheet composite prepared in example 1; fig. 1 illustrates that the thin-layer manganese dioxide nanosheet is a relatively thin large-size flexible nanosheet, and the nanosheet has a large number of wrinkles and is dispersed with non-obvious nanodots.
FIG. 2 is a transmission electron microscope image of the nano-Au/carbon-based dot composite material prepared in example 1; FIG. 2 shows that: the transverse size of the gold nanoparticles prepared by the method is about 30 +/-2 nm, the gold nanoparticles are uniformly dispersed and do not obviously aggregate, and probably because the carbon base points have a large number of oxygen-containing functional groups which can be used as a wrapping agent to stabilize the uniform monodispersion of the gold nanoparticles.
FIG. 3 is a transmission electron microscope image of the nano manganese dioxide/carbon-based dot/nano gold composite material prepared in example 2; FIG. 3 shows: most of the nano gold/carbon-based points are distributed on the nano manganese dioxide/carbon-based point nanosheets in an aggregated form, and few monodisperse nano gold/carbon-based points exist in the system. The gaps between the nano-gold/carbon-based dot particles are about 1-2 nm, and even some gaps reach sub-nanometer level.
FIG. 4 is a graph showing the UV-VIS absorption spectrum of the nano-manganese dioxide/carbon based dot composite, the UV-VIS absorption spectrum of the nano-gold/carbon based dot composite, and the UV absorption spectrum of the 0.2-nano-manganese dioxide/carbon based dot/nano-gold composite; as can be seen from fig. 4, compared with the ultraviolet-visible absorption spectrum of the nano manganese dioxide/carbon-based dot composite material, a new ultraviolet absorption peak appears around 650 nm, which may be caused by the aggregation of gold nanoparticles, but the absorption peaks around 530 nm and 650 nm do not change greatly, which indicates that the gold nanoparticles are aggregated in the nano manganese dioxide/carbon-based dot/nano gold composite material and the relative content of the manganese dioxide/carbon-based dot in the composite material hardly affects the morphology of the gold nanoparticles.
FIG. 5 shows Raman signal intensity of crystal violet detected on different active substrates, wherein a curve is a nano manganese dioxide/carbon base point/nano gold composite substrate, and b curve is a nano gold/carbon base point composite substrate; the curve c is a nano manganese dioxide/carbon-based point composite substrate; the d curve is a pure crystal violet substrate. As can be seen from FIG. 5, the crystal violet can generate the strongest Raman signal on the nano manganese dioxide/carbon-based point/nano gold composite material substrate compared with other substrates, and the Raman enhancement on the crystal violet can reach 3.9 multiplied by 10 through calculation8。
Fig. 6 shows raman signal intensity of crystal violet detected by using the nano manganese dioxide/carbon-based dot/nano gold composite material substrate with different mass ratios of manganese dioxide/carbon-based dot and nano gold/carbon-based dot, wherein the raman signal intensity is 0.1, 0.2, 0.3 and 0.4-nano manganese dioxide/carbon-based dot/nano gold composite substrate material from bottom to top in sequence. It is evident from FIG. 6 that: when 0.2-nano manganese dioxide/carbon base point/nanogold is used as an SERS substrate, the Raman signal of crystal violet is strongest.
The invention has the advantages of cheap and easily obtained raw materials, simple and convenient experimental operation, no need of special experimental instruments, rapid reaction, mild conditions and good dispersibility of the finished product.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of a nano manganese dioxide/carbon base point/nano gold surface enhanced Raman substrate is characterized by comprising the following steps: the method comprises the following steps:
(1) synthesizing a nano manganese dioxide/carbon dot composite material: weighing a certain amount of carbon base points, stirring and dissolving in deionized water, sequentially adding manganous chloride after heating to be stable, continuously stirring potassium permanganate for a period of time, stopping reaction, centrifuging the mixed solution at a low rotating speed to collect supernatant, repeatedly centrifuging the supernatant at a high rotating speed to clarify the supernatant, collecting precipitate, and re-dispersing the precipitate in water to obtain the nano manganese dioxide/carbon base point composite material;
(2) and (3) synthesis of the nano gold/carbon dot composite material: mixing 1-10 mL of 0.01-0.05 mg/mL carbon-based dot solution and 0.05-1 mL of 0.1-10 mg/mL chloroauric acid solution, adding sodium hydroxide solution to adjust the pH value to 8-10, adding sodium borohydride after the solution is heated and stabilized, continuously stirring and reacting for a period of time, stopping reaction, centrifuging the solution at a low rotating speed to collect supernatant, centrifuging the supernatant at a high rotating speed, collecting precipitate, and re-dispersing the precipitate in water to obtain the nanogold/carbon-based dot material;
(3) synthesis of the composite material: and mixing the synthesized nano manganese dioxide/carbon-based dot material and the nano gold/carbon-based dot material in water, stirring, centrifuging, and re-dispersing the precipitate in distilled water to obtain the nano manganese dioxide/carbon-based dot/nano gold composite material.
2. The method for preparing nano manganese dioxide/carbon-based point/nano gold surface-enhanced Raman substrate according to claim 2, wherein the method comprises the following steps: in the step (1), the carbon base point is a graphene structure nanosheet with a transverse size smaller than 100 nanometers, and the surface of the nanosheet contains a large number of oxygen-containing functional groups; the small-speed centrifugal speed is 1000-3000 rpm, and the centrifugal time is 5-60 min; the large-speed centrifugation speed is 9000-20000 rpm, and the centrifugation time is 15-60 min.
3. The method of claim 1, wherein: the concentration of the carbon base point solution in the step (1) is 0.01-0.05 mg/mL; the concentration of the nano manganese dioxide in the obtained composite material solution is 0.2-0.5 mg/mL.
4. The method of claim 1, wherein: in the step (1), the heating temperature is 120-140 ℃; adding 1.2mL of 0.1mol/L manganous chloride and 1mL of 0.1mol/L potassium permanganate, and continuously stirring for reaction for 10-20 min.
5. The method of claim 1, wherein: the initial concentration of the chloroauric acid in the reaction system in the step (2) is 0.1-10 mg/ml; the amount of sodium borohydride in the reaction system in the step (2) is 0.5-50 mg per mg of silver ions.
6. The method of claim 1, wherein: in the step (2), the heating temperature is 120-140 ℃; heating for 10-20 min; the time for continuously stirring and reacting is 10-30 min.
7. The method of claim 1, wherein: in the step (2), the medium and small rotating speed is 1000-3000 rpm, and the centrifugation time is 5-60 min; the high-speed centrifugation rotating speed is 8000-18000 rpm, and the centrifugation time is 15-60 min.
8. The production method according to claim 1, characterized in that; in the step (3), the mass ratio of the nano manganese dioxide/carbon base points to the nano gold/carbon base point material AuNPs/CDs in the reaction system is controlled to be 0.01-10.
9. The production method according to claim 1, characterized in that; in the step (3), the rotation speed of centrifugal washing is 9000-20000 rpm.
10. Use of the nano manganese dioxide/carbon-based dot/nano gold composite material prepared by the preparation method according to any one of claims 1 to 8 in the preparation of a surface enhanced raman substrate.
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