CN110455770A - A kind of surface enhanced Raman scattering substrate and its preparation method and application - Google Patents
A kind of surface enhanced Raman scattering substrate and its preparation method and application Download PDFInfo
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- CN110455770A CN110455770A CN201910738400.5A CN201910738400A CN110455770A CN 110455770 A CN110455770 A CN 110455770A CN 201910738400 A CN201910738400 A CN 201910738400A CN 110455770 A CN110455770 A CN 110455770A
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Abstract
The invention discloses a kind of surface enhanced Raman scattering substrate and its preparation method and application, which includes substrate and the gold nano grain for being attached to substrate surface, which is in four-headed arrow shape.In the above manner, surface enhanced Raman scattering substrate of the present invention is equipped with the gold nano grain of four-headed arrow shape, the gold nano grain has sensitive Raman detection performance, organic fragrant dye molecule can be quickly detected, Raman reinforcing effect is obvious when detection, and the detectable concentration of organic fragrance dye molecule is down to 10‑10mol/L。
Description
Technical field
The present invention relates to pollutant monitoring technical fields, and in particular to a kind of surface enhanced Raman scattering substrate and its preparation
Methods and applications.
Background technique
Organic fragrance dye molecule is the important organic pollutant of one kind present in environment, wherein such as rhodamine 6G, peacock
Malachite green, crystal violet etc. belong to organic fragrant dye molecule, their application is quite extensive, can be used for sterilizing, desinsection, have
It can also be used in biological stain in textile or even some can be also used for biomarker.But work as this kind of dye molecule
When in into human body, the recessive dye molecule with more harmfulness can be generated, such as recessive rhodamine 6G, concealed malachite green and hidden
Property crystal violet.Organic fragrance dye molecule is the severe pollutant in water body, has high residue, high carcinogenic, high toxicity and teratogenesis
The disadvantages of property, if the use of long-term, high-dose, large area, expendable harm can be caused to human body and biology.Therefore,
Organic fragrant dye molecule is classified as forbidden drugs by many countries at present, and is not useable in aquaculture.It is thus right
The detection of these pollutants seems particularly important especially in water in environment.
Method currently used for detecting organic fragrant pollutant mainly has liquid chromatography, high performance liquid chromatography, gas phase
Chromatography-Mass Spectrometry, however these methods require to be pre-processed, Gao Chengben, the deficiencies of time-consuming, high operation requirements.
Raman spectrum is a kind of spectral technique for studying molecular vibration energy level, can be widely used for molecular recognition field.But normal Raman
Scattered signal is very faint, and detection difficulty is big, limits its application in actual production.Surface enhanced Raman scattering (SERS)
Spectral technique greatly enhances normal Raman signal, by the substrate of construction special surface to be effectively performed low
Concentration molecular detection is a kind of with the Analytical Methods of Trace that potentiality are widely applied.
Experiment and theoretical research show that Surface enhanced Raman scattering (SERS) can obtain Gao Ling on low concentration test substance
The signal of sensitivity, but obtain high quality Raman signal precondition be SERS active-substrate quality, SERS enhancement effect with
SERS base material has close relationship, and pattern, type of base material etc. determine the enhancement effect of SERS substrate.Cause
This, develops a kind of SERS substrate of function admirable, particularly important with the quickly detection for realizing organic fragrant dye molecule.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of surface enhanced Raman scattering substrate and preparation method thereof and
Using.
The technical scheme adopted by the invention is that: a kind of surface enhanced Raman scattering substrate, including substrate and it is attached to institute
The gold nano grain of substrate surface is stated, the gold nano grain is in four-headed arrow shape.
Preferably, the length of the gold nano grain is 45~55nm;Preferably 50nm.
Preferably, the draw ratio of the gold nano grain is 1.0~4.36.
The present invention also provides the preparation methods of more than one surface enhanced Raman scattering substrates, comprising the following steps:
S1, gold chloride, cetyltriethylammonium bromide, enuatrol, silver nitrate, hydrochloric acid and ultrapure water are uniformly mixed,
Ascorbic acid is added, obtains mixed solution;After the mixed solution becomes colorless, sodium borohydride is added, in 30~40 DEG C of conditions
Lower standing reaction;Centrifugation taking precipitate is then carried out, gold nanorods are obtained;The gold nanorods are dispersed in water again, obtain Jenner
Rice stick solution;
S2, under agitation, gold chloride is added in cetyl triethyl ammonium chloride solution, is then sequentially added
Silver nitrate, hydrochloric acid, ascorbic acid mix;Gold nanorods solution obtained by step S1 is added, reaction is stood after mixing, then
It is centrifuged taking precipitate, then sediment is dispersed in water, obtains four-headed arrow shape gold nano grain suspension;
S3, the suspended drop of four-headed arrow shape gold nano grain is set on substrate, it is dry.
Preferably, in step S1, gold chloride, cetyltriethylammonium bromide, enuatrol, silver nitrate, ascorbic acid and
The molar ratio of sodium borohydride is (1~4): (180~720): (2~8): (0.2~0.8): (1.12~4.48): (0.03~
1.2)。
In step S1, ultrapure water is the water that resistivity is greater than or equal to 18M Ω * cm (25 DEG C).
Preferably, in step S1, the draw ratio of the gold nanorods is 4.0~4.5;Preferably 4.36.
Preferably, in step S1, the reaction time for standing reaction is 2~4h.
Preferably, in step S1, the revolving speed of centrifugal process is 10000~13000rpm, and centrifugation time is 10~30min.
Preferably, in step S2, gold chloride, cetyl triethyl ammonium chloride, silver nitrate, hydrochloric acid and ascorbic acid rub
You are than being (0.075~0.3): (50~200): (0.075~0.3): (10~40): (0.4~1.5).
In addition, the mixing speed of stirring condition is generally 500~1000r/min in step S2.The revolving speed one of centrifugal process
As be 8000~10000rpm, centrifugation time be 10~20min.
The preparation method of the above surface enhanced Raman scattering substrate is simple, and it is convenient to operate, and utilizes the secondary of gold nanorods
Four-headed arrow shape gold nano grain is prepared in growth, i.e. the both ends of gold nano grain are in arrow shaped, preparation process reaction condition
It is mild controllable, it is pollution-free.
The above surface enhanced Raman scattering substrate can be used for detecting organic fragrant dye molecule, it can be achieved that organic fragrance dyestuff
The quick detection of molecule.Therefore, the present invention also provides more than one surface enhanced Raman scattering substrates to detect organic fragrance
Application in dye molecule.Wherein, organic fragrant dye molecule includes any one of rhodamine 6G, malachite green, crystal violet.
Specific detection method can include: drip the position on surface enhanced Raman scattering substrate equipped with four-headed arrow shape gold nano grain
Add the solution to be detected containing organic fragrant dye molecule, heating, drying;Raman spectrometer is recycled to detect four-headed arrow shape Jenner
The characteristic signal of organic fragrant dye molecule of rice grain absorption, and carry out data Collecting and dealing.
The method have the benefit that: the present invention provides a kind of surface enhanced Raman scattering substrate and preparation method thereof
And application, the surface enhanced Raman scattering substrate are equipped with the gold nano grain of four-headed arrow shape, the Jenner of the four-headed arrow shape
Rice grain has sensitive Raman detection performance, can quickly detect organic fragrant dye molecule, Raman reinforcing effect when detection
Obviously, the detectable concentration of organic fragrant dye molecule is down to 10-10mol/L。
Detailed description of the invention
For the clearer technical solution illustrated in the embodiment of the present invention, will make below to required in embodiment description
Attached drawing briefly describes.
Fig. 1 is the scanning electron microscope (SEM) photograph of obtained gold nanorods in embodiment 1;
Fig. 2 is the transmission electron microscope picture of obtained four-headed arrow shape gold nano grain in embodiment 1;
Fig. 3 is the scanning electron microscope (SEM) photograph of obtained four-headed arrow shape gold nano grain in embodiment 1;
Fig. 4 is detection of the surface enhanced Raman scattering substrate obtained by embodiment 1 to the rhodamine 6G solution of various concentration
Raman signal figure;
Fig. 5 is that surface enhanced Raman scattering substrate obtained by embodiment 4 believes the detection Raman of the crystal violet of various concentration
Number figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
A kind of preparation method of surface enhanced Raman scattering substrate comprising following steps:
(1) there are the gold nanorods of high length-diameter ratio using the synthesis of no seed law, specifically include: at room temperature, by 4mL
The cetyltriethylammonium bromide that aqueous solution of chloraurate that concentration is 0.005mol/L, 18mL concentration are 0.2mol/L is water-soluble
Silver nitrate aqueous solution that aqueous solution sodium oleate that liquid, 400 μ L concentration are 0.1mol/L, 1mL concentration are 0.004mol/L, 32 μ L
The ultra-pure water solution of concentrated hydrochloric acid and 18mL that mass fraction is 37% uniformly mixes, and adding 224 μ L concentration is 0.1 mol/L
Ascorbic acid solution, obtain mixed solution;After mixed solution becomes colorless, it is 0.01mol/L that 60 μ L concentration are added thereto
Sodium borohydride aqueous solution, at 35 DEG C stand reaction 3h, be then centrifuged 10min under 12000rpm revolving speed, obtain have height
The gold nanorods of draw ratio, then be dispersed in 1mL water, obtain gold nanorods solution.
(2) four-headed arrow shape gold nano grain is prepared in gold nanorods diauxic growth: under stirring conditions, by 150 μ
The aqueous solution of chloraurate that L concentration is 0.01mol/L is added to the cetyl triethyl ammonium chloride that 10mL concentration is 0.1mol/L
In aqueous solution, the salt that silver nitrate aqueous solution, 200 μ L concentration that 150 μ L concentration are 0.01mol/L are 1mol/L is then sequentially added
Acid, the ascorbic acid that 75 μ L concentration are 0.1mol/L, are vigorously stirred 30s, add the gold nanorods that 0.5mL step (1) obtains
Solution stirs 10s, after placing 10min, is centrifuged 10min under 8000rpm revolving speed, obtains the gold nano grain of four-headed arrow shape;
It is dispersed in water again, and is concentrated into 100 μ L, obtain four-headed arrow shape gold nano grain suspension.
(3) the suspended drop of two-way gold nano grain is set in silicon chip substrate, utilizes 45 DEG C of heating, dryings of warm table.
Gold nanorods obtained by above step (1) are characterized using scanning electron microscope, and transmission electron microscope is respectively adopted
Four-headed arrow shape gold nano grain obtained by above step (2) is characterized with scanning electron microscope, acquired results such as Fig. 1-Fig. 3
It is shown.Wherein, Fig. 1 is the scanning electron microscope (SEM) photograph of the above obtained gold nanorods;Fig. 2 is the saturating of the above obtained gold nano grain
Penetrate electron microscope;Fig. 3 is the scanning electron microscope (SEM) photograph of the above obtained gold nano grain.As shown in Figure 1, the above obtained gold nano
Stick size uniformity, draw ratio with higher.By Fig. 2 and Fig. 3 it is found that obtained gold nano grain be in double-head arrow shape, i.e., two
Holding is in arrow shaped, and the size uniformity of gold nano grain.
In addition, using the organic fragrant dye molecule of the detection of surface enhanced Raman scattering substrate obtained by the present embodiment.Specifically
Ground takes 5 surface enhanced Raman scattering substrates respectively, is equipped with four-headed arrow shape on each surface enhanced Raman scattering substrate respectively
Various concentration (respectively 10 is added dropwise in the position of gold nano grain-6mol/L、10-7mol/L、10-8mol/L、10-9mol/L、10- 10Mol/L in rhodamine 6G solution), 45 DEG C of heating, dryings of warm table are utilized;Raman spectrometer is recycled to detect four-headed arrow
The characteristic signal of the adsorbed organic fragrant dye molecule of shape gold nano grain simultaneously carries out data Collecting and dealing, and acquired results are such as
Shown in Fig. 4.As shown in Figure 4, in low concentration 10-10Under the conditions of mol/L, rhodamine 6G characterization of molecules signal still can be detected, from
And it confirms the four-headed arrow shape gold nano grain material and may be implemented to rhodamine 6G down to 10-10The detection limit of mol/L.
Embodiment 2
A kind of preparation method of surface enhanced Raman scattering substrate comprising following steps:
(1) there are the gold nanorods of high length-diameter ratio using the synthesis of no seed law, specifically include: at room temperature, by 2mL
Cetyltriethylammonium bromide aqueous solution that aqueous solution of chloraurate that concentration is 0.005mol/L, 9mL concentration are 0.2mol/L,
Silver nitrate aqueous solution that aqueous solution sodium oleate that 200 μ L concentration are 0.1mol/L, 0.5mL concentration are 0.004mol/L, 16 μ L matter
The ultra-pure water solution of concentrated hydrochloric acid and 9mL that amount score is 37% uniformly mixes, and adding 112 μ L concentration is 0.1mol/L's
Ascorbic acid solution obtains mixed solution;After mixed solution becomes colorless, it is 0.01mol/L's that 30 μ L concentration are added thereto
Sodium borohydride aqueous solution stands reaction 2h at 35 DEG C, is then centrifuged 15min under 11000rpm revolving speed, obtains having high long
The gold nanorods of diameter ratio, then be dispersed in 3mL water, obtain gold nanorods solution.
(2) four-headed arrow shape gold nano grain is prepared in gold nanorods diauxic growth: under stirring conditions, 75 μ L are dense
It is water-soluble that the aqueous solution of chloraurate that degree is 0.01mol/L is added to the cetyl triethyl ammonium chloride that 5mL concentration is 0.1mol/L
In liquid, the hydrochloric acid, 40 that silver nitrate aqueous solution, 100 μ L concentration that 75 μ L concentration are 0.01mol/L are 1mol/L are then sequentially added
μ L concentration is the ascorbic acid of 0.1mol/L, is vigorously stirred 30s, adds the gold nanorods solution that 0.25mL step (1) obtains,
10s is stirred, after placing 10min, 10min is centrifuged under 9000rpm revolving speed, obtains four-headed arrow shape gold nano grain;Again by it
It is dispersed in water, and is concentrated into 50 μ L, obtain four-headed arrow shape gold nano grain suspension.
(3) the suspended drop of two-way gold nano grain is set in silicon chip substrate, utilizes 45 DEG C of heating, dryings of warm table.
Embodiment 3
A kind of preparation method of surface enhanced Raman scattering substrate comprising following steps:
(1) there are the gold nanorods of high length-diameter ratio using the synthesis of no seed law, specifically include: at room temperature, by 8mL
The cetyltriethylammonium bromide that aqueous solution of chloraurate that concentration is 0.005mol/L, 36mL concentration are 0.2mol/L is water-soluble
Silver nitrate aqueous solution that aqueous solution sodium oleate that liquid, 800 μ L concentration are 0.1mol/L, 2mL concentration are 0.004mol/L, 64 μ L
The ultra-pure water solution of concentrated hydrochloric acid and 36mL that mass fraction is 37% uniformly mixes, and adding 448 μ L concentration is 0.1 mol/L
Ascorbic acid solution, obtain mixed solution;After mixed solution becomes colorless, it is 0.01mol/ that 120 μ L concentration are added thereto
The sodium borohydride aqueous solution of L stands reaction 4h at 35 DEG C, is then centrifuged 15min in 12000rpm revolving speed, obtains having high long
The gold nanorods of diameter ratio, then be dispersed in 2mL water, obtain gold nanorods solution.
(2) four-headed arrow shape gold nano grain is prepared in gold nanorods diauxic growth: under stirring conditions, 300 μ L
The aqueous solution of chloraurate that concentration is 0.01mol/L is added to the cetyl triethyl ammonium chloride water that 20mL concentration is 0.1mol/L
In solution, the salt that silver nitrate aqueous solution, 400 μ L concentration that 300 μ L concentration are 0.01mol/L are 1mol/L is then sequentially added
Acid, the ascorbic acid that 150 μ L concentration are 0.1mol/L, are vigorously stirred 30s, add the gold nanorods that 1mL step (1) obtains
Solution stirs 10s, and after placing 10min, centrifugation obtains four-headed arrow shape gold nano grain;It is dispersed in water, and is concentrated again
To 200 μ L, four-headed arrow shape gold nano grain suspension is obtained.
(3) the suspended drop of two-way gold nano grain is set in silicon chip substrate, utilizes 45 DEG C of heating, dryings of warm table.
Embodiment 4
A kind of preparation method of surface enhanced Raman scattering substrate comprising following steps:
(1) there are the gold nanorods of high length-diameter ratio using the synthesis of no seed law, specifically include: at room temperature, by 4mL
The cetyltriethylammonium bromide that aqueous solution of chloraurate that concentration is 0.005mol/L, 18mL concentration are 0.2mol/L is water-soluble
Silver nitrate aqueous solution that aqueous solution sodium oleate that liquid, 400 μ L concentration are 0.1mol/L, 1mL concentration are 0.004mol/L, 32 μ L
The ultra-pure water solution of concentrated hydrochloric acid and 18mL that mass fraction is 37% uniformly mixes, and being subsequently added into 224 μ L concentration is
The ascorbic acid solution of 0.1mol/L, obtains mixed solution;After mixed solution becomes colorless, 60 μ L concentration are added thereto is
The sodium borohydride aqueous solution of 0.01mol/L stands reaction 3h at 35 DEG C, is then centrifuged 10min in 12000rpm, is had
The gold nanorods of high length-diameter ratio, then be dispersed in 4mL water, obtain gold nanorods solution.
(2) four-headed arrow shape gold nano grain is prepared in gold nanorods diauxic growth: under stirring conditions, 150 μ L
The aqueous solution of chloraurate that concentration is 0.01mol/L is added to the cetyl triethyl ammonium chloride water that 10mL concentration is 0.1mol/L
In solution, the salt that silver nitrate aqueous solution, 200 μ L concentration that 150 μ L concentration are 0.01mol/L are 1mol/L is then sequentially added
Acid, the ascorbic acid that 75 μ L concentration are 0.1mol/L, are vigorously stirred 30s, add the gold nanorods that 0.5mL step (1) obtains
Solution stirs 10s, after placing 10min, is centrifuged 10min under 8000rpm revolving speed, obtains four-headed arrow shape gold nano grain;Again
It is dispersed in water, and is concentrated into 100 μ L, obtain four-headed arrow shape gold nano grain suspension.
(3) the suspended drop of two-way gold nano grain is set in silicon chip substrate, utilizes 45 DEG C of heating, dryings of warm table.
In addition, using the organic fragrant dye molecule of the detection of surface enhanced Raman scattering substrate obtained by the present embodiment.Specifically
Ground takes 5 surface enhanced Raman scattering substrates produced above respectively, is added dropwise on each surface enhanced Raman scattering substrate respectively
Various concentration (respectively 10-6mol/L、10-7mol/L、10-8mol/L、10-9mol/L、10-10Mol/L in crystal violet solution),
Utilize 45 DEG C of heating, dryings of warm table;Raman spectrometer is recycled to detect the adsorbed organic virtue of four-headed arrow shape gold nano grain
The characteristic signal of fragrant dye molecule simultaneously carries out data Collecting and dealing, and acquired results are as shown in Figure 5.As shown in Figure 5, in low concentration
10-10Under the conditions of mol/L, the characteristic signal of crystal violet still can be detected, to confirm the four-headed arrow shape gold nano
Grain material may be implemented to crystal violet down to 10-10The detection limit of mol/L.
Embodiment 5
A kind of preparation method of surface enhanced Raman scattering substrate comprising following steps:
(1) there are the gold nanorods of high length-diameter ratio using the synthesis of no seed law, specifically include: at room temperature, by 2mL
Cetyltriethylammonium bromide aqueous solution that aqueous solution of chloraurate that concentration is 0.005mol/L, 9mL concentration are 0.2mol/L,
Silver nitrate aqueous solution that aqueous solution sodium oleate that 200 μ L concentration are 0.1mol/L, 0.5mL concentration are 0.004mol/L, 16 μ L matter
The ultra-pure water solution of concentrated hydrochloric acid and 9mL that amount score is 37% uniformly mixes, and being subsequently added into 112 μ L concentration is 0.1 mol/L
Ascorbic acid solution, obtain mixed solution;After mixed solution becomes colorless, it is 0.01mol/L that 30 μ L concentration are added thereto
Sodium borohydride aqueous solution, at 35 DEG C stand reaction 2h, be then centrifuged 15min under 11000rpm revolving speed, obtain have height
The gold nanorods of draw ratio, then be dispersed in 1.5mL water, obtain gold nanorods solution.
(2) four-headed arrow shape gold nano grain is prepared in gold nanorods diauxic growth: under stirring conditions, 75 μ L are dense
It is water-soluble that the aqueous solution of chloraurate that degree is 0.01mol/L is added to the cetyl triethyl ammonium chloride that 5mL concentration is 0.1mol/L
In liquid, the hydrochloric acid, 40 that silver nitrate aqueous solution, 100 μ L concentration that 75 μ L concentration are 0.01mol/L are 1mol/L are then sequentially added
μ L concentration is the ascorbic acid of 0.1mol/L, is vigorously stirred 30s, adds the gold nanorods solution that 0.25mL step (1) obtains,
10s is stirred, after placing 10min, 10min is centrifuged under 9000rpm revolving speed, obtains four-headed arrow shape gold nano grain;Again by it
It is dispersed in water, and is concentrated into 50 μ L, obtain four-headed arrow shape gold nano grain suspension.
(3) the suspended drop of two-way gold nano grain is set in silicon chip substrate, utilizes 45 DEG C of heating, dryings of warm table.
Embodiment 6
A kind of preparation method of surface enhanced Raman scattering substrate comprising following steps:
(1) there are the gold nanorods of high length-diameter ratio using the synthesis of no seed law, specifically include: at room temperature, by 8mL
The cetyltriethylammonium bromide that aqueous solution of chloraurate that concentration is 0.005mol/L, 36mL concentration are 0.2mol/L is water-soluble
Silver nitrate aqueous solution that aqueous solution sodium oleate that liquid, 800 μ L concentration are 0.1mol/L, 2mL concentration are 0.004mol/L, 64 μ L
The ultra-pure water solution of concentrated hydrochloric acid and 36mL that mass fraction is 37% uniformly mixes, and being subsequently added into 448 μ L concentration is
The ascorbic acid solution of 0.1mol/L, obtains mixed solution;After mixed solution becomes colorless, 120 μ L concentration are added thereto is
The sodium borohydride aqueous solution of 0.01mol/L stands reaction 4h at 35 DEG C, is then centrifuged 15min under 12000rpm revolving speed, obtains
It to the gold nanorods with high length-diameter ratio, then is dispersed in 2mL water, obtains gold nanorods solution.
(2) four-headed arrow shape gold nano grain is prepared in gold nanorods diauxic growth: under stirring conditions, 300 μ L
The aqueous solution of chloraurate that concentration is 0.01mol/L is added to the cetyl triethyl ammonium chloride water that 20mL concentration is 0.1mol/L
In solution, the salt that silver nitrate aqueous solution, 400 μ L concentration that 300 μ L concentration are 0.01mol/L are 1mol/L is then sequentially added
Acid, the ascorbic acid that 150 μ L concentration are 0.1mol/L, are vigorously stirred 30s, add the gold nanorods that 1mL step (1) obtains
Solution stirs 10s, and after placing 10min, centrifugation obtains four-headed arrow shape gold nano grain;It is dispersed in water, and is concentrated again
To 200 μ L, four-headed arrow shape gold nano grain suspension is obtained.
(3) the suspended drop of two-way gold nano grain is set in silicon chip substrate, utilizes 45 DEG C of heating, dryings of warm table.
There is the gold nano in four-headed arrow shape on surface enhanced Raman scattering substrate obtained by the above various embodiments
Grain can be used for organic fragrant dye molecule (including rhodamine 6G, malachite green, crystallization with sensitive Raman detection performance
It is purple) detection detection, organic fragrant dye molecule can be quickly detected, Raman reinforcing effect is obvious when detection, organic fragrance dye
Expect the detectable concentration of molecule down to 10-10mol/L.Specific detection method includes: to be equipped on surface enhanced Raman scattering substrate
The solution to be detected containing organic fragrant dye molecule, heating, drying is added dropwise in the position of four-headed arrow shape gold nano grain;It recycles
Raman spectrometer detects the characteristic signal of organic fragrant dye molecule of four-headed arrow shape gold nano grain absorption, and carries out data
Collecting and dealing.
Although specifically showing and describing the present invention in conjunction with preferred embodiment, those skilled in the art should be bright
It is white, it is not departing from the spirit and scope of the present invention defined by described claims, it in the form and details can be right
The present invention makes a variety of changes, and is protection scope of the present invention.
Claims (10)
1. a kind of surface enhanced Raman scattering substrate, which is characterized in that including substrate and the Jenner for being attached to the substrate surface
Rice grain, the gold nano grain are in four-headed arrow shape.
2. surface enhanced Raman scattering substrate according to claim 1, which is characterized in that the length of the gold nano grain
For 45~55nm.
3. surface enhanced Raman scattering substrate according to claim 1 or 2, which is characterized in that the gold nano grain
Draw ratio is 1.0~4.36.
4. the preparation method of surface enhanced Raman scattering substrate described in any one of claim 1-3, which is characterized in that including with
Lower step:
S1, gold chloride, cetyltriethylammonium bromide, enuatrol, silver nitrate, hydrochloric acid and ultrapure water are uniformly mixed, are added
Ascorbic acid obtains mixed solution;After the mixed solution becomes colorless, sodium borohydride is added, it is quiet under the conditions of 30~40 DEG C
Set reaction;Centrifugation taking precipitate is then carried out, gold nanorods are obtained;The gold nanorods are dispersed in water again, obtain gold nanorods
Solution;
S2, under agitation, gold chloride is added in cetyl triethyl ammonium chloride solution, nitric acid is then sequentially added
Silver, hydrochloric acid, ascorbic acid mix;Gold nanorods solution obtained by step S1 is added, reaction is stood after mixing, is then centrifuged
Taking precipitate, then sediment is dispersed in water, obtain four-headed arrow shape gold nano grain suspension;
S3, the suspended drop of four-headed arrow shape gold nano grain is set on substrate, it is dry.
5. the preparation method of surface enhanced Raman scattering substrate according to claim 4, which is characterized in that in step S1, chlorine
Auric acid, cetyltriethylammonium bromide, enuatrol, silver nitrate, ascorbic acid and sodium borohydride molar ratio be (1~4):
(180~720): (2~8): (0.2~0.8): (1.12~4.48): (0.03~1.2).
6. the preparation method of surface enhanced Raman scattering substrate according to claim 5, which is characterized in that in step S1, institute
The draw ratio for stating gold nanorods is 4.0~4.5.
7. the preparation method of surface enhanced Raman scattering substrate according to claim 4, which is characterized in that quiet in step S1
The reaction time for setting reaction is 2~4h.
8. the preparation method of surface enhanced Raman scattering substrate according to claim 4, which is characterized in that in step S1, from
The revolving speed of heart process is 10000~13000rpm, and centrifugation time is 10~30min.
9. the preparation method of surface enhanced Raman scattering substrate according to claim 4, which is characterized in that in step S2, chlorine
Auric acid, cetyl triethyl ammonium chloride, silver nitrate, hydrochloric acid and ascorbic acid molar ratio be (0.075~0.3): (50~
200): (0.075~0.3): (10~40): (0.4~1.5).
10. surface enhanced Raman scattering substrate described in any one of claim 1-3 is in detecting organic fragrant dye molecule
Using.
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