CN113607646B - SERS substrate and preparation method thereof - Google Patents
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- CN113607646B CN113607646B CN202110888876.4A CN202110888876A CN113607646B CN 113607646 B CN113607646 B CN 113607646B CN 202110888876 A CN202110888876 A CN 202110888876A CN 113607646 B CN113607646 B CN 113607646B
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- 239000000758 substrate Substances 0.000 title claims abstract description 106
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 45
- 239000010931 gold Substances 0.000 claims abstract description 28
- 229910052737 gold Inorganic materials 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 238000004070 electrodeposition Methods 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000002923 metal particle Substances 0.000 claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 54
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 31
- 239000004327 boric acid Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 13
- 238000001771 vacuum deposition Methods 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002114 nanocomposite Substances 0.000 abstract description 28
- 238000000151 deposition Methods 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 6
- 239000002082 metal nanoparticle Substances 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 4
- 229940021013 electrolyte solution Drugs 0.000 description 4
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
Abstract
The invention discloses a SERS substrate and a preparation method thereof, wherein the preparation method of the SERS substrate comprises the following steps: (1) Evaporating metal particles on one side of an AAO film to obtain an AAO substrate; (2) And (3) taking the AAO substrate prepared in the step (1) as a working electrode, forming a three-electrode system with a counter electrode and a reference electrode, immersing the three-electrode system into electrolyte, and obtaining the SERS substrate through electrochemical deposition by utilizing an electrochemical workstation. According to the invention, the concentration, the deposition voltage and the deposition time of the electrolyte are regulated, so that the morphology of the graphene-gold/silver nano-composite is effectively regulated, the SERS substrate is synthesized in one step, and the vertically oriented graphene and metal nano-particle composite is obtained.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a SERS substrate and a preparation method thereof.
Background
The Surface Enhanced Raman Scattering (SERS) detection technology has the advantages of nondestructive detection, trace detection and the like, and can be applied to detection of chemical, environmental, biological, human diseases and the like. Graphene has certain advantages in SERS detection due to its many good properties. The surface plasmon resonance characteristic of the metal nanoparticles can improve the SERS signal intensity by several orders of magnitude, and has irreplaceable advantages. The enhancement effect of graphene and its derivatives is very weak compared with the electromagnetic enhancement raman effect of metal particles, on the other hand, the electromagnetic enhancement effect of metal particles is very obvious, but there are drawbacks such as easy agglomeration and oxidation of metal particles, resulting in uneven raman signal or too strong noise ratio.
Since graphene proved to have SERS enhancement effect, graphene was assembled with metal nanoparticles, and the performance of graphene/metal nanocomposite and its SERS enhancement effect were studied. The method is used for preparing the composite material by adopting the reducing agent reduction, the composite material prepared by the method needs to be further prepared to form a SERS substrate, and the distribution uniformity of the material in the substrate is poor by using the method.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a graphene-gold/silver nanocomposite SERS substrate. According to the invention, the graphene-gold/silver nano-composite is prepared on the porous alumina film substrate by using an electrochemical deposition method, and the effective regulation and control of the morphology of the graphene-gold/silver nano-composite are realized by adjusting the concentration of electrolyte, the deposition voltage and the deposition time, so that the SERS substrate is synthesized in one step, and the vertically oriented graphene and metal nano-ion composite are obtained.
The technical scheme of the invention is as follows:
a SERS substrate formed by electrochemical deposition of graphene-gold/silver complexes on an AAO film.
The preparation method of the SERS substrate comprises the following steps:
(1) Evaporating metal particles on one side of an AAO film to obtain an AAO substrate;
(2) And (3) taking the AAO substrate prepared in the step (1) as a working electrode, a counter electrode and a reference electrode to form a three-electrode system, immersing the three-electrode system into electrolyte, and obtaining the SERS substrate through electrochemical deposition by utilizing an electrochemical workstation.
Further, in the step (1), the metal particles are one or more of gold particles and silver particles, and the particle size is 5-20 nm.
Further, in the step (1), the evaporation is: the vacuum coating machine is used for vapor deposition for 10s to 5min under the current of 15 mA.
Further, in the step (2), the counter electrode is a platinum electrode, and the reference electrode is an Ag/AgCl electrode.
Further, in the step (2), the electrolyte is a mixed solution prepared by mixing boric acid, graphene oxide, chloroauric acid and/or silver nitrate and then adding water.
Further, the mass concentration of boric acid in the mixed solution is 5-40 g/L, the mass concentration of chloroauric acid is 0.5-2 g/L, the mass concentration of silver nitrate is 0.5-5 g/L, and the mass concentration of graphene oxide is 0.5-5 g/L.
Further, in the step (2), the volume of the electrolyte is 3-50 mL.
Further, in the step (2), the direct current voltage of the electrochemical workstation is-1.6 to-1.0V.
Further, in the step (2), the time of the electrochemical deposition is 10-120 min.
According to the invention, different compounds can be prepared according to different electrolyte solutions. When the electrolyte solution is a mixed solution prepared by adding water into boric acid, graphene oxide and chloroauric acid, preparing a graphene-gold compound; when the electrolyte solution is a mixed solution prepared by adding water into boric acid, graphene oxide and silver nitrate, preparing a graphene-silver compound; when the electrolyte solution is a mixed solution prepared by adding water into boric acid, graphene oxide, chloroauric acid and silver nitrate, the graphene-gold-silver compound is prepared.
The beneficial technical effects of the invention are as follows:
(1) The graphene-gold/silver nanocomposite is grown by electrochemical deposition, can be directly used as an SERS substrate without being prepared again, and has the advantages of low cost, high repeatability, no pollution, simplicity in operation and the like.
(2) The graphene-gold/silver nanocomposite is grown by using an electrochemical deposition method, and the morphology of the graphene-gold/silver nanocomposite can be effectively regulated and controlled by regulating the concentration of the solution, the deposition growth voltage and the deposition growth time.
(3) The graphene-gold/silver nanocomposite SERS substrate prepared by the method is uniform in size, large in area and good in SERS effect.
(4) The metal nano particles prepared by the method are uniformly distributed, the graphene grows to be in vertical orientation, the nano particles are separated by adopting vertical graphene, and a large number of edges are provided, so that a good SERS effect is obtained, and 1-10 cm of the metal nano particles can be prepared 2 Is a substrate material of the substrate.
Drawings
Fig. 1 is an SEM image of graphene-gold-silver nanocomposite on SERS substrate prepared in example 1 of the present invention.
Fig. 2 is an SEM image of graphene-gold-silver nanocomposite on SERS substrate prepared in example 4 of the present invention.
Fig. 3 is a SERS diagram of a SERS substrate prepared in example 4 of the present invention for detecting R6G.
FIG. 4 is a Raman spectrum of 5. Mu.M rhodamine 6G detected by the base material prepared in comparative example 1-2.
Fig. 5 is an SEM image of a graphene-gold nanocomposite prepared in comparative example 3 using a glassy carbon electrode as a working electrode.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
The embodiments and specific operation procedures are given on the premise of implementing the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
Example 1:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 5nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 10s, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode containing saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 3mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 5g/L, the mass concentration of chloroauric acid is 0.5g/L, the mass concentration of silver nitrate is 0.5g/L, the mass concentration of graphene oxide is 0.5g/L, and depositing for 10min under-1.0V direct current voltage by adopting a potentiostatic method to grow the graphene-gold-silver nanocomposite, thus obtaining the SERS substrate.
Fig. 1 is an SEM image of a graphene-gold-silver composite nanocomposite on a SERS substrate prepared in this embodiment, and as shown in fig. 1, in the prepared graphene-gold-silver composite, graphene attached to the surface of the uniformly distributed gold-silver composite can be directly used as the SERS substrate.
Example 2:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 20nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 1min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode containing saturated potassium chloride solution as a reference electrode, immersing the Ag/AgCl electrode into 10mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 20g/L, the mass concentration of chloroauric acid is 1g/L, the mass concentration of silver nitrate is 2.5g/L, the mass concentration of graphene oxide is 2.5g/L, and depositing for 45min under-1.2V direct current voltage by adopting a potentiostatic method to grow the graphene-gold-silver nanocomposite, thus obtaining the SERS substrate.
Example 3:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 10nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 30s, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 10mL of a mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 30g/L, the mass concentration of chloroauric acid is 1.5g/L, the mass concentration of silver nitrate is 3.5g/L, the mass concentration of graphene oxide is 4g/L, and depositing for 80min under-1.6V direct current by adopting a potentiostatic method to grow the graphene-gold-silver nanocomposite, thus obtaining the SERS substrate.
Example 4:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 5nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 10s, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 20mL of a mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 30g/L, the mass concentration of chloroauric acid is 2g/L, the mass concentration of silver nitrate is 5g/L, the mass concentration of graphene oxide is 5g/L, and depositing for 2h under-1.6V direct current voltage by adopting a potentiostatic method to grow the vertical graphene-gold-silver nanocomposite, thus obtaining the SERS substrate.
Fig. 2 is an SEM image of graphene-gold-silver nanocomposite on SERS substrate prepared in this example. As shown in fig. 2, a large amount of vertically oriented graphene exists in the prepared graphene-gold-silver composite, and is attached to the surface of the uniformly distributed gold-silver composite, and compared with fig. 1, the amount of vertically oriented graphene on the SERS substrate prepared in this example is larger.
Example 5:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 30nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 2min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 30mL of a mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 40g/L, the mass concentration of chloroauric acid is 0.5g/L, the mass concentration of silver nitrate is 2.5g/L, the mass concentration of graphene oxide is 2.5g/L, and adopting a potentiostatic method to deposit for 2h under-1.6V direct current voltage to grow a vertical graphene-gold-silver nano composite, thus obtaining the SERS substrate.
Example 6:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 40nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 4min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 40mL of a mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 30g/L, the mass concentration of chloroauric acid is 0.5g/L, the mass concentration of silver nitrate is 0.5mol/L, the mass concentration of graphene oxide is 5g/L, and depositing for 2h under-1.2V direct current by adopting a potentiostatic method to grow a vertical graphene-gold-silver nano composite, thus obtaining the SERS substrate.
Example 7:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 5min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 30g/L, the mass concentration of chloroauric acid is 0.5g/L, the mass concentration of silver nitrate is 0.5mol/L, the mass concentration of graphene oxide is 5g/L, and depositing for 2h under-1.6V direct current by adopting a potentiostatic method to grow a vertical graphene-gold-silver nano composite, thus obtaining the SERS substrate.
Example 8:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 5min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 30g/L, the mass concentration of chloroauric acid is 0.5g/L, the mass concentration of graphene oxide is 5g/L, and depositing for 2 hours under-1.6V direct current voltage by adopting a potentiostatic method to grow a vertical graphene-gold nanocomposite, thereby obtaining the SERS substrate.
Example 9:
a SERS substrate, the method of making comprising the steps of:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 5min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of boric acid in the mixed solution is 30g/L, the mass concentration of silver nitrate is 0.5mol/L, the mass concentration of graphene oxide is 5g/L, and depositing for 2 hours under-1.6V direct current voltage by adopting a potentiostatic method to grow a vertical graphene-silver nanocomposite, thereby obtaining the SERS substrate.
Comparative example 1:
the preparation method of the SERS substrate without graphene oxide comprises the following steps:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 5min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the AAO substrate into 50mL of a mixed solution prepared by adding boric acid, chloroauric acid and silver nitrate into water, wherein the mass concentration of the boric acid in the mixed solution is 30g/L, the mass concentration of the chloroauric acid is 0.5g/L, the mass concentration of the silver nitrate is 0.5mol/L, and depositing for 2 hours under-1.6V direct current voltage by adopting a potentiostatic method to grow a gold-silver nanocomposite, thereby obtaining the SERS substrate without graphene oxide.
Comparative example 2:
the SERS substrate without graphene oxide and silver nitrate is prepared by the following steps:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of an AAO film by a vacuum coating machine under the current of 15mA, and the evaporation time is 5min, so that the AAO substrate is obtained.
Secondly, using an electrochemical workstation, adopting a three-electrode system, taking the AAO substrate prepared in the step (1) as a working electrode, taking a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing 50mL of a mixed solution prepared by adding water into boric acid and chloroauric acid, wherein the mass concentration of the boric acid is 30g/L, the mass concentration of the chloroauric acid is 0.5g/L, adopting a potentiostatic method, and depositing for 2 hours under-1.6V direct current voltage to grow a gold nano film, thus obtaining the SERS substrate without adding graphene oxide and silver nitrate.
Comparative example 3:
a SERS substrate without AAO material, the method of making comprising the steps of:
and (3) using an electrochemical workstation, adopting a three-electrode system, taking a glassy carbon electrode as a working electrode, a platinum electrode as a counter electrode, taking an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing 50mL of a mixed solution prepared by adding water into boric acid, chloroauric acid and graphene oxide, wherein the mass concentration of boric acid is 30g/L, the mass concentration of chloroauric acid is 0.5g/L, the mass concentration of graphene oxide is 5g/L, adopting a potentiostatic method, and depositing for 2 hours under-1.6V direct current to grow the graphene-gold nanocomposite, thus obtaining the SERS substrate without using an AAO material.
Fig. 5 is an SEM image of the graphene-gold nanocomposite prepared in this comparative example, and as shown in fig. 5, au nanoparticles are unevenly distributed on the surface of graphene, and graphene is tiled on the surface of an electrode.
Test example:
the SERS substrate material containing the graphene-gold-silver nano compound prepared in the embodiment 4 of the invention is used for detecting rhodamine 6G dye with different concentrations to obtain a Raman spectrum chart shown in the figure 3, and as can be seen from the figure 3, when the rhodamine 6G dye is increased from 0.5 mu M to 10 mu M, the detection effect of the SERS substrate material prepared in the embodiment 4 is always obvious, and the deviation of the 10 times of repeated detection of the dye SERS signal intensity is less than 4%; the prepared SERS substrate is stored at room temperature for 30 days for rhodamine 6G dye detection, and the deviation of the obtained SERS signal intensity is less than 3.2%, which indicates that the SERS substrate material prepared in the embodiment 4 of the invention has good stability and repeatability and is a good SERS substrate material.
The SERS substrate materials prepared in comparative examples 1-2 are used for respectively detecting 5 mu M rhodamine 6G dye to obtain a Raman spectrum chart shown in figure 4, which shows that the substrate materials containing gold-silver nano-composites or gold nano-films have certain SERS enhancement effects, but compared with figures 3 and 4, the detection signal intensity of the graphene-gold-silver nano-composites as the SERS substrate materials is more obvious, the enhancement factors are larger, and the composite is proved to be an excellent SERS substrate material.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A SERS substrate, wherein the SERS substrate is formed by electrochemical deposition onto an AAO film to form a graphene-gold/silver complex;
the preparation method of the SERS substrate comprises the following steps:
(1) Evaporating metal particles on one side of an AAO film to obtain an AAO substrate;
(2) Taking the AAO substrate prepared in the step (1) as a working electrode, forming a three-electrode system with a counter electrode and a reference electrode, immersing the three-electrode system into electrolyte, and obtaining an SERS substrate through electrochemical deposition by utilizing an electrochemical workstation;
in the step (2), the electrolyte is a mixed solution prepared by mixing boric acid, graphene oxide, chloroauric acid and/or silver nitrate and then adding water;
the mass concentration of boric acid in the mixed solution is 5-40 g/L, the mass concentration of chloroauric acid is 0.5-2 g/L, the mass concentration of silver nitrate is 0.5-5 g/L, and the mass concentration of graphene oxide is 0.5-5 g/L.
2. The SERS substrate according to claim 1 wherein in step (1), the metal particles are one or more of gold particles and silver particles, and have a particle size of 5 to 20nm.
3. The SERS substrate of claim 1 wherein in step (1) the evaporation is: the vacuum coating machine is used for evaporating for 10 s-5 min under the current of 15 mA.
4. The SERS substrate of claim 1 wherein in step (2) the counter electrode is a platinum electrode and the reference electrode is an Ag/AgCl electrode.
5. The SERS substrate of claim 1 wherein in step (2) the volume of electrolyte is 3 to 50ml.
6. The SERS substrate of claim 1 wherein in step (2) the electrochemical workstation has a dc voltage of-1.6 to-1.0V.
7. The SERS substrate according to claim 1 wherein in step (2) the electrochemical deposition is for a period of 10 to 120 minutes.
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