CN104749154A - Surface enhanced Raman scattering substrate and preparation method thereof - Google Patents
Surface enhanced Raman scattering substrate and preparation method thereof Download PDFInfo
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- CN104749154A CN104749154A CN201310740306.6A CN201310740306A CN104749154A CN 104749154 A CN104749154 A CN 104749154A CN 201310740306 A CN201310740306 A CN 201310740306A CN 104749154 A CN104749154 A CN 104749154A
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- 239000000758 substrate Substances 0.000 title claims abstract description 71
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000010931 gold Substances 0.000 claims abstract description 93
- 229910052737 gold Inorganic materials 0.000 claims abstract description 92
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 37
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000013078 crystal Substances 0.000 claims description 30
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- -1 poly tetrafluoroethylene Polymers 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 17
- 238000004062 sedimentation Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 229960005070 ascorbic acid Drugs 0.000 claims description 14
- 235000010323 ascorbic acid Nutrition 0.000 claims description 14
- 239000011668 ascorbic acid Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000001338 self-assembly Methods 0.000 claims description 10
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001069 Raman spectroscopy Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 238000001514 detection method Methods 0.000 abstract description 10
- 238000004557 single molecule detection Methods 0.000 abstract description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 12
- ZVAVRBUTFWLEBK-UHFFFAOYSA-N NC1=CC(=C(C=C1)S)C1=CC=CC=C1 Chemical compound NC1=CC(=C(C=C1)S)C1=CC=CC=C1 ZVAVRBUTFWLEBK-UHFFFAOYSA-N 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
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- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention provides a surface enhanced Raman scattering substrate. The surface enhanced Raman scattering substrate comprises a hydrophobic substrate and multiple gold nanometer particles attaching to the hydrophobic substrate. The gold nanometer particle is in a shape of a cuboid. All surfaces of the gold nanometer particles are concave. The gold nanometer particle has eight tapered sharp corners. The surface enhanced Raman scattering substrate has good stability and strong Raman enhancement effects, can reduce detection concentrations of dye molecules and phenyl amine organic matters to less than 10<-10>mol/L and realizes a single molecule detection level. The invention also provides a preparation method of the surface enhanced Raman scattering substrate. The preparation method has simple processes and is convenient for operation.
Description
Technical field
The present invention relates to nano material and optical technical field, particularly relate to a kind of surface enhanced Raman scattering substrate and preparation method thereof.
Background technology
Raman spectrum is a kind of spectral technique studying molecular vibration energy level, can be widely used in molecular recognition field.But normal Raman scattered signal is very faint, detection difficulty is large, limits its application in actual production.Surface enhanced raman spectroscopy (SERS) spectral technique is by the substrate of structure special surface, and strengthening greatly normal Raman signal, thus effectively carry out low concentrations of molecular detection, is a kind of Analytical Methods of Trace with widespread use potentiality.Surface enhanced Raman scattering effect is since last century, the seventies was found, good, highly sensitive and be widely used with its selectivity.
Experiment and theoretical research show, SERS phenomenon and the surrounding environment residing for testing molecule closely related, there is high enhancing ability, the SERS active substrate of high stability be one of enlarge-effect key factor realizing high sensitivity detection utilizing SERS.The Raman scattering of molecule on substrate is strengthened, and is to put forward high molecular Raman scattering efficiency on the one hand; On the other hand, be to make testing molecule farthest be gathered in substrate surface.Therefore, develop a kind of SERS substrate of function admirable, it is easy to preparation, easy to use, has very strong enhancing ability, and testing result is repeatable highly becomes particularly important.
Summary of the invention
In view of this, embodiment of the present invention first aspect provides a kind of surface enhanced Raman scattering substrate, in order to solve textured metal structural substrates in prior art, the problem such as the substrate of nano metal colloidal sol improves that testing molecule Raman scattering efficiency is low, detection sensitivity is low, repeatability and poor stability.
First aspect, embodiments provide a kind of surface enhanced Raman scattering substrate, comprise substrate and be attached to the gold nano grain on described substrate, described gold nano grain is cuboid, each surface of described gold nano grain is all in spill, and described gold nano grain has eight taper wedge angles.
The above-mentioned gold nano grain with special construction is attached in hydrophobic substrate, makes substrate surface have the projection of even compact distribution, has high roughness, high-specific surface area; Thus surface plasma vibration frequency can be made to reach with the vibration frequency of testing molecule be coupled, effectively improve the Raman scattering efficiency of testing molecule.
Preferably, described gold nano grain uniform sequential ground self assembly is attached in described hydrophobic substrate.
Preferably, described in be attached to gold nano grain in hydrophobic substrate, the gap between adjacent two the taper wedge angles on adjacent two gold nano grains is 5 ~ 10nm.
Preferably, the length-diameter ratio of described gold nano grain is 1.3 ~ 2.2.
Preferably, the length of described gold nano grain is 85 ~ 120nm, and width is 55 ~ 65nm.
Preferably, described hydrophobic substrate is poly tetrafluoroethylene.
The surface enhanced Raman scattering substrate that embodiment of the present invention first aspect provides, utilize metal micro-nanostructure local plasmon resonance body enhancement effect, hydrophobic substrate, improve substrate enrichment testing molecule quantity, enhance testing molecule Raman scattering efficiency, efficient, the maximization that achieve testing molecule Raman scattering export, and meet high sensitivity detection demand, this surface enhanced Raman scattering substrate surface-enhanced raman scattering effect is strong, function admirable, and there is superior repeatability.
Second aspect, embodiments provides a kind of preparation method of surface enhanced Raman scattering substrate, comprises the following steps:
Jin Yuan, silver nitrate, hydrochloric acid and ascorbic acid are joined in cetyl trimethyl ammonium bromide solution, obtain mixed solution, when described mixed solution becomes colorless, add gold nanorods seed-solution, after stirring, 5 ~ 8h is left standstill in 25 ~ 30 DEG C of water-baths, centrifuging subsequently obtains solids of sedimentation, described solids of sedimentation is gold nano grain, described gold nano grain is cuboid, each surface of described gold nano grain is all in spill, and described gold nano grain has eight taper wedge angles;
After gained gold nano grain is washed 2 ~ 3 times with ethanol and deionized water respectively, then be scattered in deionized water, obtain gold nano grain suspension;
Described gold nano grain suspension is added drop-wise in hydrophobic substrate, after droplet drying, forms yellow spotting, namely obtain surface enhanced Raman scattering substrate.
Preferably, described Jin Yuan and described silver nitrate are that 1.5 ~ 5:1 adds by the mol ratio of gold ion and silver ion, described ascorbic acid is that 1 ~ 6:1 adds by the mol ratio with the gold ion in described golden source, and in described mixed solution, the gold ion final concentration in described golden source is 1.0 × 10
-4mol/L ~ 5.0 × 10
-4mol/L, the final concentration of described cetyl trimethyl ammonium bromide is 0.06 ~ 0.12mol/L, and the pH value of described mixed solution is greater than 1 and is less than 4.
Preferably, described Jin Yuan is gold chloride (HAuCl
4).
In above-mentioned preparation method, cetyl trimethyl ammonium bromide (CTAB), as surfactant, is coated on around crystal, can suppress the speed of growth of crystal; Silver nitrate is promotor, and the bromine in CTAB is combined and can generates silver bromide precipitation, is deposited on plane of crystal, can controls the growth of crystal face.Because the synergy of silver nitrate and CTAB, thus make the gold nano grain of generation form the rectangular structure with special concave surface, there is taper wedge angle; Hydrochloric acid is used for adjust ph, and the pH of above-mentioned reaction system is preferably about 2.In addition, because substrate has hydrophobicity, therefore, just the globule can be formed when gold nano grain suspension is added drop-wise on substrate, finally spot is formed after drying, the self assembly on substrate of the gold nano grain of the rectangular structure with special concave surface can be made like this, form new active substrate, and its surface-enhanced raman scattering successful strengthens (after gold nano grain self assembly, taper wedge angle densification distribution, define very many Raman active sites), function admirable, and there is superior repeatability.
Preferably, described gold nanorods seed-solution is adopted and is prepared with the following method: Jiang Jinyuan, silver nitrate, hydrochloric acid and ascorbic acid join in cetyl trimethyl ammonium bromide solution, obtain mixed liquor, described Jin Yuan and described silver nitrate are that 5 ~ 25:1 adds by the mol ratio of gold ion and silver ion, described ascorbic acid is that 1 ~ 6:1 adds by the mol ratio with the gold ion in described golden source, in described mixed liquor, the gold ion final concentration in described golden source is 4.0 × 10
-4mol/L ~ 2.5 × 10
-3mol/L, the final concentration of described cetyl trimethyl ammonium bromide is 0.06 ~ 0.12mol/L, and the pH value of described mixed liquor is greater than 1 and is less than 4; When described mixed liquor becomes colorless, add the gold nano single crystal seed solution that particle diameter is 3 ~ 5nm, 12 ~ 14h is left standstill subsequently in 25 ~ 30 DEG C of water-baths, filter, after obtained solids of sedimentation being spent deionized water 2 ~ 3 times, again described solids of sedimentation is redissolved in deionized water, obtain gold nanorods seed-solution.
Preferably, described Jin Yuan is gold chloride.
Preferably, described gold nano single crystal seed solution is adopted and is prepared with the following method: join in reaction vessel by gold chloride, sodium borohydride, cetyl trimethyl ammonium bromide, mol ratio 1:1 ~ 3 of described gold chloride and described sodium borohydride; Then described reaction vessel is placed in ice bath and keeps 2 ~ 4h, obtained gold nano single crystal seed solution.
Sodium borohydride is reductive agent, and relative gold chloride is excessive to add, and cetyl trimethyl ammonium bromide is surfactant.
The preparation method of the surface enhanced Raman scattering substrate that embodiment of the present invention second aspect provides, technique is simple, simple operation.
The above-mentioned surface enhanced Raman scattering substrate provided of the embodiment of the present invention can be used for dye molecule and the organic Surface enhanced raman spectroscopy test of phenyl amines.Dye molecule can be such as rhodamine 6B, crystal violet, and phenyl amines organism can be such as p-aminophenyl thiophenol.
Surface enhanced Raman scattering substrate good stability provided by the invention, Raman enhancement effect are strong, and the detectable concentration of the material such as dye molecule, phenyl amines organism can be made to be low to moderate <10
-10mol/L, reaches Single Molecule Detection level, and enhancer can reach 10
7.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to instructions, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is that the transmission electron microscope TEM of the gold nanorods crystal seed that embodiment one is synthesized schemes;
Fig. 2 is the uv-visible absorption spectra figure of the gold nanorods crystal seed that embodiment one is synthesized;
Fig. 3 is the illustraton of model of the gold nano grain of the embodiment of the present invention;
Fig. 4 is the scanning electron microscope sem figure of the gold nano grain that embodiment one is synthesized;
Fig. 5 is that the transmission electron microscope TEM of the gold nano grain that embodiment one is synthesized schemes;
Fig. 6 is the energy spectrogram of the gold nano grain that embodiment one is synthesized;
Fig. 7 is the horizontal self assembly on poly tetrafluoroethylene of the gold nano grain of embodiment one and longitudinal self assembly figure;
Fig. 8 is the Raman enhanced spectrum figure of rhodamine 6B on embodiment of the present invention surface enhanced Raman scattering substrate;
Fig. 9 is the Raman enhanced spectrum figure of p-aminophenyl thiophenol on embodiment of the present invention surface enhanced Raman scattering substrate.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Multiple embodiment is divided to be further detailed the embodiment of the present invention below.The embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out that can be suitable is changed and implements.
Embodiment one
By gold chloride (10mmol/L, 250 μ L), Fresh, sodium borohydride (the 10mmol/L of cooling, 600 μ L), cetyl trimethyl ammonium bromide (0.1mol/L, 9.75mL) join in 25mL beaker, then beaker is placed in ice bath and keeps 4h, obtained brown gold nano single crystal seed solution, the particle diameter of gold nano single crystal seed is 3 ~ 5nm;
By HAuCl
4(10mmol/L, 0.5mL), CTAB (0.1mol/L, 10mL), silver nitrate (10mmol/L, 100 μ L), hydrochloric acid (1.0mol/L, 200 μ L) mixing after, add ascorbic acid (0.1mol/L again, 55 μ L), after mixing, obtain mixed solution, when solution to be mixed becomes colorless, with continuous stirring, 12 μ L above-mentioned gained gold nano single crystal seed solution is joined in above-mentioned mixed solution, after mixing, 12h is kept in 30 DEG C of water-baths, obtain gold nanorods crystal seed, after spending deionized water 2 times, gold nanorods crystal seed is redissolved again in 1mL deionized water, obtain gold nanorods seed-solution,
With continuous stirring, by HAuCl
4(10mmol/L, 0.15mL), silver nitrate (10mmol/L, 100 μ L), hydrochloric acid (1.0mol/L, 200 μ L), 10mL is joined, in 0.1mol/LCTAB solution with ascorbic acid (0.1mol/L, 80 μ L), obtain mixed solution, when solution to be mixed becomes colorless, add 100 μ L above-mentioned gained gold nanorods seed-solution, stir about 1min, after mixing, static maintenance 6h in 30 DEG C of water-baths.Taking-up after question response completes, centrifuging obtains solids of sedimentation, and this solids of sedimentation is gold nano grain, gained solids of sedimentation ethanol and water are washed three times respectively, wash away surfactant and unreacted impurity, be finally dispersed in water, obtain gold nano grain suspension;
Take diameter as the circular poly tetrafluoroethylene of 1cm be substrate, 3 μ L gained gold nano grain suspensions be added drop-wise on substrate, after droplet drying, form yellow spotting, namely obtain surface enhanced Raman scattering substrate.
Fig. 1 is that the transmission electron microscope TEM of the gold nanorods crystal seed of the present embodiment synthesis schemes, and as can be known from Fig. 1, crystal seed presents bar-shaped, and pattern is even, soilless sticking, and average aspect ratio is 2.2, and this is conducive to the superstar structure of synthesizing good dispersion.
Fig. 2 is the uv-visible absorption spectra figure of the gold nanorods crystal seed of the present embodiment synthesis, and as can be known from Fig. 2, the position at longitudinal plasmon absorption peak belongs to lateral surfaces plasmon absorption at 650nm, 525nm.
Fig. 3 is the illustraton of model of the gold nano grain of the embodiment of the present invention.As can be seen from the figure, gold nano grain is cuboid, and each surface of described gold nano grain is all in spill, and described gold nano grain has eight taper wedge angles.
Fig. 4 and Fig. 5 is respectively SEM figure and the TEM figure of the gold nano grain of the present embodiment synthesis, as we know from the figure, the crystallinity of gold nano grain sample is fine, product length-diameter ratio is about 1.8, the average length of gold nano grain is 112nm, width is 62nm, each particle is cuboid, each particle has 8 taper wedge angles, particle crystal face presents unique concave surface, makes synthesized sample have (h, k, 0) nanostructured of high miller index surface, these are characterized as and improve Raman enhancement effect achievements advantage.
Fig. 6 is the energy spectrogram of the gold nano grain of the present embodiment synthesis, and as can be seen from Figure 6, synthesized sample only has Au element to form, and is proof gold structure.
Fig. 7 is the horizontal self assembly of gold nano grain on poly tetrafluoroethylene and longitudinal self assembly figure.Wherein a is horizontal self assembly figure, and as can be seen from the figure gold nano grain dense uniform is distributed on poly tetrafluoroethylene; B figure is longitudinal self assembly figure, the rectangular parallelepiped square formation as can be seen from the figure erect, and distributes in order, and each longitudinal side is spill square.
Embodiment two
By gold chloride (10mmol/L, 250 μ L), Fresh, sodium borohydride (the 10mmol/L of cooling, 600 μ L), cetyl trimethyl ammonium bromide (0.1mol/L, 9.75mL) join in 25mL beaker, then beaker is placed in ice bath and keeps 4h, obtained brown gold nano single crystal seed solution, the particle diameter of gold nano single crystal seed is 3 ~ 5nm;
By HAuCl
4(10mmol/L, 0.5mL), CTAB (0.1mol/L, 10mL), silver nitrate (10mmol/L, 80 μ L), hydrochloric acid (1.0mol/L, 200 μ L) mixing after, add ascorbic acid (0.1mol/L again, 55 μ L), after mixing, obtain mixed solution, when solution to be mixed becomes colorless, with continuous stirring, 12 μ L above-mentioned gained gold nano single crystal seed solution is joined in above-mentioned mixed solution, after mixing, 14h is kept in 30 DEG C of water-baths, obtain gold nanorods crystal seed, after spending deionized water 3 times, gold nanorods crystal seed is redissolved again in 1mL deionized water, obtain gold nanorods seed-solution,
With continuous stirring, by HAuCl
4(10mmol/L, 0.15mL), silver nitrate (10mmol/L, 80 μ L), hydrochloric acid (1.0mol/L, 200 μ L), 10mL is joined, in 0.1mol/LCTAB solution with ascorbic acid (0.1mol/L, 80 μ L), obtain mixed solution, when solution to be mixed becomes colorless, add 100 μ L above-mentioned gained gold nanorods seed-solution, stir about 1min, after mixing, static maintenance 8h in 25 DEG C of water-baths.Taking-up after question response completes, centrifuging obtains solids of sedimentation, and this solids of sedimentation is gold nano grain, gained solids of sedimentation ethanol and water are washed three times respectively, wash away surfactant and unreacted impurity, be finally dispersed in water, obtain gold nano grain suspension;
Take diameter as the circular poly tetrafluoroethylene of 1cm be substrate, 3 μ L gained gold nano grain suspensions be added drop-wise on substrate, after droplet drying, form yellow spotting, namely obtain surface enhanced Raman scattering substrate.
Embodiment three
By gold chloride (10mmol/L, 250 μ L), Fresh, sodium borohydride (the 10mmol/L of cooling, 500 μ L), cetyl trimethyl ammonium bromide (0.1mol/L, 9.75mL) join in 25mL beaker, then beaker is placed in ice bath and keeps 6h, obtained brown gold nano single crystal seed solution, the particle diameter of gold nano single crystal seed is 3 ~ 5nm;
By HAuCl
4(10mmol/L, 0.5mL), CTAB (0.1mol/L, 10mL), silver nitrate (10mmol/L, 20 μ L), hydrochloric acid (1.0mol/L, 200 μ L) mixing after, add ascorbic acid (0.1mol/L again, 55 μ L), after mixing, obtain mixed solution, when solution to be mixed becomes colorless, with continuous stirring, 12 μ L above-mentioned gained gold nano single crystal seed solution is joined in above-mentioned mixed solution, after mixing, 12h is kept in 30 DEG C of water-baths, obtain gold nanorods crystal seed, after spending deionized water 2 times, gold nanorods crystal seed is redissolved again in 1mL deionized water, obtain gold nanorods seed-solution,
With continuous stirring, by HAuCl
4(10mmol/L, 0.15mL), silver nitrate (10mmol/L, 30 μ L), hydrochloric acid (1.0mol/L, 200 μ L), 10mL is joined, in 0.1mol/LCTAB solution with ascorbic acid (0.1mol/L, 80 μ L), obtain mixed solution, when solution to be mixed becomes colorless, add 100 μ L above-mentioned gained gold nanorods seed-solution, stir about 1min, after mixing, static maintenance 6h in 30 DEG C of water-baths.Taking-up after question response completes, centrifuging obtains solids of sedimentation, and this solids of sedimentation is gold nano grain, gained solids of sedimentation ethanol and water are washed three times respectively, wash away surfactant and unreacted impurity, be finally dispersed in water, obtain gold nano grain suspension;
Take diameter as the circular poly tetrafluoroethylene of 1cm be substrate, 3 μ L gained gold nano grain suspensions be added drop-wise on substrate, after droplet drying, form yellow spotting, namely obtain surface enhanced Raman scattering substrate.
Effect example is the beneficial effect providing powerful support for the embodiment of the present invention, provides effect example as follows, in order to evaluate and test the performance of the product that the embodiment of the present invention provides.
Adopt dye, rhodamine 6B and p-aminophenyl thiophenol as testing molecule, adopt the surface enhanced Raman scattering substrate of the embodiment of the present invention to detect.
The detection of dye, rhodamine 6B:
Get seven poly tetrafluoroethylenes, drip the gold nano grain suspension of 3 μ L embodiment 1 gained respectively, because poly tetrafluoroethylene has hydrophobic effect, water polo is formed at its surperficial suspension, until water polo at room temperature slowly after drying, form a circular fleck, spot diameter is 3mm, then by a series of concentration (1 × 10
-6mol/L, 1 × 10
-7mol/L, 1 × 10
-8mol/L, 1 × 10
-9mol/L, 1 × 10
-10mol/L, 1 × 10
-11mol/L, 1 × 10
-12mol/L) each 3 μ L of rhodamine 6B solution drop on seven circular flecks, allow its natural drying, can be directly used in Raman spectrum and detect and strengthen effect.As shown in Figure 8, Fig. 8 is the Raman enhanced spectrum figure of rhodamine 6B to testing result, and wherein, curve 1, curve 2, curve 3 be correspondence 1 × 10 respectively
-10mol/L, 1 × 10
-11mol/L, 1 × 10
-12mol/L concentration.As can be seen from Figure 8, the surface enhanced Raman scattering substrate prepared by the embodiment of the present invention detects rhodamine 6B, and strengthen effective, enhancer is 1.2 × 10
7, detectable concentration is low to moderate <10
-10mol/L, reaches Single Molecule Detection level.
The detection of p-aminophenyl thiophenol:
Get three poly tetrafluoroethylenes, drip the gold nano grain suspension of 3 μ L embodiment 1 gained respectively, because poly tetrafluoroethylene has hydrophobic effect, water polo is formed at its surperficial suspension, until water polo at room temperature slowly after drying, form a circular fleck, spot diameter is 3mm, then by a series of concentration (1 × 10
-6mol/L, 1 × 10
-8mol/L, 1 × 10
-10mol/L) each 3 μ L of p-aminophenyl thiophenol solution drop on three circular flecks, allow its natural drying, can be directly used in Raman spectrum and detect and strengthen effect.As shown in Figure 9, Fig. 9 is the Raman enhanced spectrum figure of p-aminophenyl thiophenol to testing result, and wherein, curve 1, curve 2, curve 3 be correspondence 1 × 10 respectively
-6mol/L, 1 × 10
-8mol/L, 1 × 10
-10mol/L concentration.As can be known from Fig. 9, the surface enhanced Raman scattering substrate prepared by the embodiment of the present invention detects p-aminophenyl thiophenol, has equally and well strengthens effect.
When detecting p-aminophenyl thiophenol, select arbitrarily six regions as duplicate detection point, the experiment as signal repeatability proves.Duplicate detection result shows: surface enhanced Raman scattering substrate prepared by the embodiment of the present invention has fine repeatability, and standard deviation is about 10%.
Claims (10)
1. a surface enhanced Raman scattering substrate, it is characterized in that, comprise hydrophobic substrate and be attached to the gold nano grain in described hydrophobic substrate, described gold nano grain is cuboid, each surface of described gold nano grain is all in spill, and described gold nano grain has eight taper wedge angles.
2. surface enhanced Raman scattering substrate as claimed in claim 1, it is characterized in that, described gold nano grain uniform sequential ground self assembly is attached in described hydrophobic substrate.
3. surface enhanced Raman scattering substrate as claimed in claim 1, is characterized in that, described in be attached to gold nano grain in hydrophobic substrate, the gap between adjacent two the taper wedge angles on adjacent two gold nano grains is 5 ~ 10nm.
4. surface enhanced Raman scattering substrate as claimed in claim 1, it is characterized in that, the length-diameter ratio of described gold nano grain is 1.3 ~ 2.2.
5. surface enhanced Raman scattering substrate as claimed in claim 1, it is characterized in that, the length of described gold nano grain is 85 ~ 120nm, and width is 55 ~ 65nm.
6. surface enhanced Raman scattering substrate as claimed in claim 1, it is characterized in that, described hydrophobic substrate is poly tetrafluoroethylene.
7. a preparation method for surface enhanced Raman scattering substrate, is characterized in that, comprises the following steps:
Jin Yuan, silver nitrate, hydrochloric acid and ascorbic acid are joined in cetyl trimethyl ammonium bromide solution, obtain mixed solution, when described mixed solution becomes colorless, add gold nanorods seed-solution, after stirring, 5 ~ 8h is left standstill in 25 ~ 30 DEG C of water-baths, centrifuging subsequently obtains solids of sedimentation, described solids of sedimentation is gold nano grain, described gold nano grain is cuboid, each surface of described gold nano grain is all in spill, and described gold nano grain has eight taper wedge angles;
After gained gold nano grain is washed 2 ~ 3 times with ethanol and deionized water respectively, then be scattered in deionized water, obtain gold nano grain suspension;
Described gold nano grain suspension is added drop-wise in hydrophobic substrate, after droplet drying, forms yellow spotting, namely obtain surface enhanced Raman scattering substrate.
8. the preparation method of surface enhanced Raman scattering substrate as claimed in claim 7, is characterized in that,
Described Jin Yuan and described silver nitrate are that 1.5 ~ 5:1 adds by the mol ratio of gold ion and silver ion, described ascorbic acid is that 1 ~ 6:1 adds by the mol ratio with the gold ion in described golden source, in described mixed solution, the gold ion final concentration in described golden source is 1.0 × 10
-4mol/L ~ 5.0 × 10
-4mol/L, the final concentration of described cetyl trimethyl ammonium bromide is 0.06 ~ 0.12mol/L, and the pH value of described mixed solution is greater than 1 and is less than 4.
9. the preparation method of surface enhanced Raman scattering substrate as claimed in claim 7, is characterized in that,
Described gold nanorods seed-solution is adopted and is prepared with the following method: Jiang Jinyuan, silver nitrate, hydrochloric acid and ascorbic acid join in cetyl trimethyl ammonium bromide solution, obtain mixed liquor, described Jin Yuan and described silver nitrate are that 5 ~ 25:1 adds by the mol ratio of gold ion and silver ion, described ascorbic acid is that 1 ~ 6:1 adds by the mol ratio with the gold ion in described golden source, in described mixed liquor, the gold ion final concentration in described golden source is 4.0 × 10
-4mol/L ~ 2.5 × 10
-3mol/L, the final concentration of described cetyl trimethyl ammonium bromide is 0.06 ~ 0.12mol/L, and the pH value of described mixed liquor is greater than 1 and is less than 4; When described mixed liquor becomes colorless, add the gold nano single crystal seed solution that particle diameter is 3 ~ 5nm, 12 ~ 14h is left standstill subsequently in 25 ~ 30 DEG C of water-baths, filter, after obtained solids of sedimentation being spent deionized water 2 ~ 3 times, again described solids of sedimentation is redissolved in deionized water, obtain gold nanorods seed-solution.
10. the preparation method of the surface enhanced Raman scattering substrate as described in any one of claim 7 ~ 9, is characterized in that, described Jin Yuan is gold chloride.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105973866A (en) * | 2016-05-05 | 2016-09-28 | 吉林大学 | Method for producing low-friction super hydrophobic surface enhanced Raman substrate by using micro-nano particle coating layer |
| CN106442460A (en) * | 2016-09-05 | 2017-02-22 | 山东师范大学 | Gold @ silver nano-particles/pyramidal silicon three-dimensional Raman reinforced substrate and preparing method and application thereof |
| CN107199349A (en) * | 2016-03-17 | 2017-09-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of simple and quick method for preparing gold nano star |
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| CN108994314A (en) * | 2018-07-06 | 2018-12-14 | 中国科学院近代物理研究所 | A kind of gold nano star preparation method with excellent surface enhancing Raman trait |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090225310A1 (en) * | 2003-07-28 | 2009-09-10 | The Regents Of The University Of California | Surface-enhanced raman spectroscopy substrate for arsenic sensing in groundwater |
| CN102156118A (en) * | 2011-03-22 | 2011-08-17 | 中国科学院长春应用化学研究所 | Method for detecting melamine |
| CN102944543A (en) * | 2012-11-05 | 2013-02-27 | 中物院成都科学技术发展中心 | Method and device for detecting ultra trace sample based on surface-enhanced Raman spectroscopy |
| CN103048307A (en) * | 2012-12-23 | 2013-04-17 | 吉林大学 | Enhanced Raman detection substrate based on natural biology super-hydrophobic structure surface and preparation method thereof |
| CN103350234A (en) * | 2013-07-05 | 2013-10-16 | 浙江大学 | Preparation method of platinum copper concave alloy nanometer crystal, and platinum copper concave alloy nanometer crystal prepared through preparation method of platinum copper concave alloy nanometer crystal |
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090225310A1 (en) * | 2003-07-28 | 2009-09-10 | The Regents Of The University Of California | Surface-enhanced raman spectroscopy substrate for arsenic sensing in groundwater |
| CN102156118A (en) * | 2011-03-22 | 2011-08-17 | 中国科学院长春应用化学研究所 | Method for detecting melamine |
| CN102944543A (en) * | 2012-11-05 | 2013-02-27 | 中物院成都科学技术发展中心 | Method and device for detecting ultra trace sample based on surface-enhanced Raman spectroscopy |
| CN103048307A (en) * | 2012-12-23 | 2013-04-17 | 吉林大学 | Enhanced Raman detection substrate based on natural biology super-hydrophobic structure surface and preparation method thereof |
| CN103350234A (en) * | 2013-07-05 | 2013-10-16 | 浙江大学 | Preparation method of platinum copper concave alloy nanometer crystal, and platinum copper concave alloy nanometer crystal prepared through preparation method of platinum copper concave alloy nanometer crystal |
Non-Patent Citations (2)
| Title |
|---|
| LIN-FEI ZHANG等: "Controlled growth of concave gold nanobars with high surface-enhanced Raman-scattering and excellent catalytic activities", 《NANOSCALE》 * |
| 许苗军: "几种材料表面微纳米复合结构的构筑与应用", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
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