CN113607646A - SERS substrate and preparation method thereof - Google Patents
SERS substrate and preparation method thereof Download PDFInfo
- Publication number
- CN113607646A CN113607646A CN202110888876.4A CN202110888876A CN113607646A CN 113607646 A CN113607646 A CN 113607646A CN 202110888876 A CN202110888876 A CN 202110888876A CN 113607646 A CN113607646 A CN 113607646A
- Authority
- CN
- China
- Prior art keywords
- electrode
- substrate
- graphene
- aao
- mass concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 90
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 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 29
- 229910052737 gold Inorganic materials 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 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
- 238000000034 method Methods 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 17
- 239000002114 nanocomposite Substances 0.000 abstract description 17
- 239000002131 composite material Substances 0.000 abstract description 6
- 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 3
- 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
- 150000001875 compounds Chemical class 0.000 description 12
- 238000001514 detection method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000007747 plating Methods 0.000 description 8
- 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
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 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
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000002708 enhancing effect Effects 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
- 238000001237 Raman spectrum Methods 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 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
- 229940100890 silver compound Drugs 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
Images
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 the AAO film to obtain an AAO substrate; (2) and (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 the SERS substrate by electrochemical deposition by using an electrochemical workstation. According to the invention, the effective regulation and control of the morphology of the graphene-gold/silver nano composite are realized by regulating the concentration of the electrolyte, the deposition voltage and the deposition time, and the SERS substrate is synthesized in one step to obtain the vertically oriented graphene and metal nano particle composite.
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 no damage, trace detection and the like, and can be applied to detection of chemical, environmental, biological and human diseases and the like. Graphene has certain advantages in SERS detection due to its many excellent properties. The surface plasmon resonance characteristics of the metal nanoparticles can improve the SERS signal intensity by several orders of magnitude, and have irreplaceable advantages. Compared with the electromagnetic enhancement Raman effect of metal particles, the enhancement effect of graphene and derivatives thereof is very weak, and on the other hand, the electromagnetic enhancement effect of the metal particles is very obvious, but disadvantages also exist, such as the metal particles are easy to agglomerate and oxidize, which causes uneven Raman signals or too strong noise ratio.
Since graphene was demonstrated to have a SERS enhancing effect, graphene and metal nanoparticles were assembled together, and the properties of graphene/metal nanocomposites and its SERS enhancing effect were studied. The conventional method is to prepare the composite material by reducing with a reducing agent, the composite material prepared by the method needs to be further prepared to form an 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, an electrochemical deposition method is utilized to prepare the graphene-gold/silver nano-composite on the porous alumina film substrate, the effective regulation and control of the morphology of the graphene-gold/silver nano-composite are realized by adjusting the concentration of electrolyte, deposition voltage and deposition time, and the SERS substrate is synthesized in one step to obtain the vertically oriented graphene and metal nano-ion composite.
The technical scheme of the invention is as follows:
a SERS substrate formed by electrochemical deposition of graphene-gold/silver complexes on AAO films.
A preparation method of the SERS substrate comprises the following steps:
(1) evaporating metal particles on one side of the AAO film to obtain an AAO substrate;
(2) and (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 the SERS substrate by electrochemical deposition by using 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: and evaporating for 10 s-5 min by a vacuum coating machine 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 and 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.
The invention can prepare different compounds according to different electrolyte solutions. When the electrolyte solution is a mixed solution prepared by adding water to boric acid, graphene oxide and chloroauric acid, preparing a graphene-gold compound; when the electrolyte solution is a mixed solution prepared by adding water to boric acid, graphene oxide and silver nitrate, preparing a graphene-silver compound; and when the electrolyte solution is a mixed solution prepared by adding water into boric acid, graphene oxide, chloroauric acid and silver nitrate, preparing the graphene-gold-silver composite.
The beneficial technical effects of the invention are as follows:
(1) the graphene-gold/silver nano composite is grown by electrochemical deposition, can be directly used as an SERS substrate without preparation again, and has the advantages of low cost, high repeatability, no pollution, simplicity in operation and the like.
(2) According to the method, the graphene-gold/silver nano-composite is grown by an electrochemical deposition method, and the shape of the graphene-gold/silver nano-composite can be effectively regulated and controlled by regulating the concentration of a solution, the deposition growth voltage and the deposition growth time.
(3) The graphene-gold/silver nano composite SERS substrate prepared by the invention has uniform size, can be large in area and has good SERS effect.
(4) The metal nanoparticles prepared by the method are uniformly distributed, the growth of the graphene is in vertical orientation, the vertical graphene is adopted for separating the nanoparticles, and the nanoparticles have a large number of edges, so that a good SERS effect is obtained, and the metal nanoparticles can be prepared to be 1-10 cm in length2The substrate material of (1).
Drawings
Fig. 1 is an SEM image of a graphene-gold-silver nanocomposite on a SERS substrate prepared in example 1 of the present invention.
Fig. 2 is an SEM image of graphene-gold-silver nanocomplexes on the SERS substrate prepared in example 4 of the present invention.
Fig. 3 is a SERS graph of the SERS substrate detection R6G prepared in example 4 of the present invention.
FIG. 4 is a Raman spectrum of 5 μ M rhodamine 6G detected using the base material prepared in comparative examples 1-2.
Fig. 5 is an SEM image of graphene-gold nanocomposite prepared by using a glassy carbon electrode as a working electrode in comparative example 3.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The embodiments are carried out on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
Example 1:
the preparation method of the SERS substrate comprises the following steps:
first, a gold particle layer having a particle size of 5nm was deposited on the AAO film side by a vacuum coater at a current of 15mA for 10 seconds to obtain an AAO substrate.
Secondly, using an electrochemical workstation, adopting a three-electrode system, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode containing a saturated potassium chloride solution as a reference electrode, immersing the working electrode into 3mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of the boric acid in the mixed solution is 5g/L, the mass concentration of the chloroauric acid is 0.5g/L, the mass concentration of the silver nitrate is 0.5g/L, and the mass concentration of the graphene oxide is 0.5g/L, and depositing for 10min at-1.0V direct current voltage by adopting a constant potential method to grow the graphene-gold-silver nano compound to obtain the SERS substrate.
Fig. 1 is an SEM image of a graphene-gold-silver complex nano-composite on the SERS substrate prepared in this embodiment, and as shown in fig. 1, the perpendicular graphene in the prepared graphene-gold-silver complex is attached to the surface of the uniformly distributed gold-silver complex, which can be directly used as the SERS substrate.
Example 2:
the preparation method of the SERS substrate comprises the following steps:
firstly, a gold particle layer with the particle size of 20nm is evaporated on one side of the AAO film by a vacuum film plating 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, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode containing a saturated potassium chloride solution as a reference electrode, immersing the working 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 the boric acid in the mixed solution is 20g/L, the mass concentration of the chloroauric acid is 1g/L, the mass concentration of the silver nitrate is 2.5g/L, and the mass concentration of the graphene oxide is 2.5g/L, and depositing under-1.2V direct current voltage for 45min by adopting a constant potential method to grow the graphene-gold-silver nano compound to obtain the SERS substrate.
Example 3:
the preparation method of the SERS substrate comprises the following steps:
first, a gold particle layer having a particle size of 10nm was deposited on the AAO film side for 30 seconds by a vacuum coater at a current of 15mA to obtain an AAO substrate.
Secondly, using an electrochemical workstation, adopting a three-electrode system, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the reference electrode 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 the boric acid in the mixed solution is 30g/L, the mass concentration of the chloroauric acid is 1.5g/L, the mass concentration of the silver nitrate is 3.5g/L, and the mass concentration of the graphene oxide is 4g/L, and depositing under-1.6V direct current voltage for 80min by adopting a potentiostatic method to grow the graphene-gold-silver nano compound to obtain the SERS substrate.
Example 4:
the preparation method of the SERS substrate comprises the following steps:
first, a gold particle layer having a particle size of 5nm was deposited on the AAO film side for 10 seconds by a vacuum coater at a current of 15mA to obtain an AAO substrate.
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 reference electrode into 20mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of the boric acid in the mixed solution is 30g/L, the mass concentration of the chloroauric acid is 2g/L, the mass concentration of the silver nitrate is 5g/L, and the mass concentration of the graphene oxide is 5g/L, and depositing for 2h under-1.6V direct current voltage by adopting a constant potential method to grow the vertical graphene-gold-silver nano compound to obtain the SERS substrate.
Fig. 2 is an SEM image of graphene-gold-silver nanocomposite on the 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 complex and is attached to the surface of the uniformly distributed gold-silver complex, and compared with fig. 1, the amount of vertically-oriented graphene on the SERS substrate prepared in this example is greater.
Example 5:
the preparation method of the SERS substrate comprises the following steps:
firstly, a gold particle layer with the particle size of 30nm is evaporated on one side of the AAO film by a vacuum film plating 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, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the reference electrode 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 the boric acid in the mixed solution is 40g/L, the mass concentration of the chloroauric acid is 0.5g/L, the mass concentration of the silver nitrate is 2.5g/L, and the mass concentration of the graphene oxide is 2.5g/L, and depositing for 2 hours under-1.6V direct current voltage by adopting a constant potential method to grow a vertical graphene-gold-silver nano compound to obtain the SERS substrate.
Example 6:
the preparation method of the SERS substrate comprises the following steps:
firstly, a gold particle layer with the particle size of 40nm is evaporated on one side of the AAO film by a vacuum film plating 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, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the working electrode into 40mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, 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 the mass concentration of the graphene oxide is 5g/L, and depositing for 2 hours under-1.2V direct current voltage by adopting a potentiostatic method to grow a vertical graphene-gold-silver nano compound to obtain the SERS substrate.
Example 7:
the preparation method of the SERS substrate comprises the following steps:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of the AAO film by a vacuum film plating 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, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the working electrode into 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, 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 the mass concentration of the 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-silver nano compound to obtain the SERS substrate.
Example 8:
the preparation method of the SERS substrate comprises the following steps:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of the AAO film by a vacuum film plating 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, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the working electrode into 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, 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, and the mass concentration of the graphene oxide is 5g/L, and depositing for 2h under-1.6V direct current voltage by adopting a constant potential method to grow the vertical graphene-gold nano compound to obtain the SERS substrate.
Example 9:
the preparation method of the SERS substrate comprises the following steps:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of the AAO film by a vacuum film plating 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, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the working electrode into 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid, silver nitrate and graphene oxide, wherein the mass concentration of the boric acid in the mixed solution is 30g/L, the mass concentration of the silver nitrate is 0.5mol/L, and the mass concentration of the graphene oxide is 5g/L, and depositing for 2h under a direct current voltage of-1.6V by adopting a potentiostatic method to grow a vertical graphene-silver nano compound to obtain the SERS substrate.
Comparative example 1:
the preparation method of the SERS substrate without the addition of the graphene oxide comprises the following steps:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of the AAO film by a vacuum film plating 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, using the AAO substrate prepared in the step (1) as a working electrode, a platinum electrode as a counter electrode, using an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the working electrode into 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid and silver nitrate, 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, and the mass concentration of the silver nitrate is 0.5mol/L, and depositing for 2h under a direct current of-1.6V by adopting a potentiostatic method to grow a gold-silver nano compound, thereby obtaining the SERS substrate without the addition of the graphene oxide.
Comparative example 2:
the preparation method of the SERS substrate without adding graphene oxide and silver nitrate comprises the following steps:
firstly, a gold particle layer with the particle size of 50nm is evaporated on one side of the AAO film by a vacuum film plating 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, a platinum electrode as a counter electrode, an Ag/AgCl electrode of a saturated potassium chloride solution as a reference electrode, immersing the working electrode into 50mL of 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, and depositing for 2h under a direct current voltage of-1.6V by adopting a constant potential method to grow a gold nano-film to obtain the SERS substrate without adding graphene oxide and silver nitrate.
Comparative example 3:
the preparation method of the SERS substrate without using the AAO material comprises the following steps:
an electrochemical workstation is used, a three-electrode system is adopted, a glassy carbon electrode is used as a working electrode, a platinum electrode is used as a counter electrode, an Ag/AgCl electrode of a saturated potassium chloride solution is used as a reference electrode, 50mL of mixed solution prepared by adding water into boric acid, chloroauric acid and graphene oxide is immersed, wherein the mass concentration of the boric acid is 30g/L, the mass concentration of the chloroauric acid is 0.5g/L, the mass concentration of the graphene oxide is 5g/L, a potentiostatic method is adopted, and the graphene-gold nano compound is deposited for 2h under the direct current voltage of-1.6V to grow out, so that the SERS substrate without the AAO material is obtained.
Fig. 5 is an SEM image of the graphene-gold nanocomposite prepared according to the present comparative example, 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:
by using the SERS substrate material containing the graphene-gold-silver nanocomposite prepared in embodiment 4 of the present invention to detect rhodamine 6G dye with different concentrations, a raman spectrogram shown in fig. 3 is obtained, as can be seen from fig. 3, when the rhodamine 6G dye is increased from 0.5 μ M to 10 μ M, the detection effect of the SERS substrate material prepared in embodiment 4 is always significant, and the deviation of SERS signal intensity is less than 4% after the dye is repeatedly detected for 10 times; the prepared SERS substrate is stored at room temperature for 30 days and used for rhodamine 6G dye detection, and the deviation of the obtained SERS signal intensity is less than 3.2%, which shows 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 spectrogram shown in figure 4, which shows that the substrate materials containing the gold-silver nano composite or the gold-containing nano film have certain SERS enhancement effect, but the comparison between figures 3 and 4 shows that the graphene-gold-silver nano composite as the SERS substrate material has more obvious detection signal intensity and larger enhancement factor, and the composite is proved to be an excellent SERS substrate material.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that 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 (10)
1. A SERS substrate, wherein the SERS substrate is formed by electrochemical deposition of a graphene-gold/silver complex on an AAO film.
2. A method for preparing the SERS substrate according to claim 1, wherein the method comprises the steps of:
(1) evaporating metal particles on one side of the AAO film to obtain an AAO substrate;
(2) and (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 the SERS substrate by electrochemical deposition by using an electrochemical workstation.
3. The treatment method according to claim 1, wherein in the step (1), the metal particles are one or more of gold particles and silver particles, and the particle size is 5 to 20 nm.
4. The process according to claim 1, wherein in step (1), the evaporation is: and evaporating for 10 s-5 min by a vacuum coating machine under the current of 15 mA.
5. The process of claim 1, wherein in step (2), the counter electrode is a platinum electrode and the reference electrode is an Ag/AgCl electrode.
6. The treatment method according to claim 1, wherein 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.
7. The treatment method according to claim 6, wherein the mixed solution contains boric acid at a mass concentration of 5 to 40g/L, chloroauric acid at a mass concentration of 0.5 to 2g/L, silver nitrate at a mass concentration of 0.5 to 5g/L, and graphene oxide at a mass concentration of 0.5 to 5 g/L.
8. The treatment method according to claim 1, wherein in the step (2), the volume of the electrolyte is 3 to 50 mL.
9. The process of claim 1, wherein in step (2), the DC voltage of the electrochemical workstation is from-1.6V to-1.0V.
10. The treatment method according to claim 1, wherein in the step (2), the time for electrochemical deposition is 10-120 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110888876.4A CN113607646B (en) | 2021-08-03 | 2021-08-03 | SERS substrate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110888876.4A CN113607646B (en) | 2021-08-03 | 2021-08-03 | SERS substrate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113607646A true CN113607646A (en) | 2021-11-05 |
| CN113607646B CN113607646B (en) | 2023-12-26 |
Family
ID=78339342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110888876.4A Active CN113607646B (en) | 2021-08-03 | 2021-08-03 | SERS substrate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113607646B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174702A (en) * | 2011-01-11 | 2011-09-07 | 湖南大学 | Preparation method for metallic nano-particle and graphene composite |
| CN103172404A (en) * | 2013-04-05 | 2013-06-26 | 浙江理工大学 | Three-dimensional metal-graphene composite substrate and preparation method thereof |
| CN104833714A (en) * | 2015-04-02 | 2015-08-12 | 湖北大学 | Preparation method of gold-graphene composite nanomaterial, and application of composite nanomaterial in glucose detection |
| US20150284517A1 (en) * | 2014-04-02 | 2015-10-08 | The Florida State University Research Foundation, Inc. | Polymer ligands for nanoparticles |
| CN105092556A (en) * | 2015-07-15 | 2015-11-25 | 哈尔滨工业大学深圳研究生院 | Preparation method for G-SERS (Graphene surface enhanced Raman spectra) substrate and cancer cell detection method |
| CN105158227A (en) * | 2015-06-05 | 2015-12-16 | 中物院成都科学技术发展中心 | Method for preparing surface-enhanced Raman scattering (SERS) substrate |
| CN105405663A (en) * | 2015-10-30 | 2016-03-16 | 东南大学 | Electrochemical preparation method of MoS<2>/graphene composite counter electrode |
| KR20160144069A (en) * | 2015-06-08 | 2016-12-16 | 서울대학교산학협력단 | Graphene bioelectronic device |
| CN106383158A (en) * | 2016-11-10 | 2017-02-08 | 安阳师范学院 | Hydrogen peroxide non-enzyme sensor based on silver-graphene nano composite and manufacturing method thereof |
| CN111761073A (en) * | 2020-07-09 | 2020-10-13 | 江苏省特种设备安全监督检验研究院 | Preparation method of Au-Ag-graphene oxide composite material with high SERS activity |
-
2021
- 2021-08-03 CN CN202110888876.4A patent/CN113607646B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174702A (en) * | 2011-01-11 | 2011-09-07 | 湖南大学 | Preparation method for metallic nano-particle and graphene composite |
| CN103172404A (en) * | 2013-04-05 | 2013-06-26 | 浙江理工大学 | Three-dimensional metal-graphene composite substrate and preparation method thereof |
| US20150284517A1 (en) * | 2014-04-02 | 2015-10-08 | The Florida State University Research Foundation, Inc. | Polymer ligands for nanoparticles |
| CN104833714A (en) * | 2015-04-02 | 2015-08-12 | 湖北大学 | Preparation method of gold-graphene composite nanomaterial, and application of composite nanomaterial in glucose detection |
| CN105158227A (en) * | 2015-06-05 | 2015-12-16 | 中物院成都科学技术发展中心 | Method for preparing surface-enhanced Raman scattering (SERS) substrate |
| KR20160144069A (en) * | 2015-06-08 | 2016-12-16 | 서울대학교산학협력단 | Graphene bioelectronic device |
| CN105092556A (en) * | 2015-07-15 | 2015-11-25 | 哈尔滨工业大学深圳研究生院 | Preparation method for G-SERS (Graphene surface enhanced Raman spectra) substrate and cancer cell detection method |
| CN105405663A (en) * | 2015-10-30 | 2016-03-16 | 东南大学 | Electrochemical preparation method of MoS<2>/graphene composite counter electrode |
| CN106383158A (en) * | 2016-11-10 | 2017-02-08 | 安阳师范学院 | Hydrogen peroxide non-enzyme sensor based on silver-graphene nano composite and manufacturing method thereof |
| CN111761073A (en) * | 2020-07-09 | 2020-10-13 | 江苏省特种设备安全监督检验研究院 | Preparation method of Au-Ag-graphene oxide composite material with high SERS activity |
Non-Patent Citations (9)
| Title |
|---|
| HAO, R: "Preparation and Surface-Enhanced Raman Scattering Effect of Graphene Oxide/(Au/Ag) Hybrid Materials", 《PROGRESS IN CHEMISTRY》, vol. 28, no. 8, pages 1186 - 1195 * |
| WANG, L: "Strong Dependence of Surface Enhanced Raman Scattering on Structure of Graphene Oxide Film", 《MATERIALS》, vol. 11, no. 7, pages 1 - 3 * |
| 刘彦培;张艳丽;杨应彩;庞鹏飞;: "抗坏血酸在纳米金/石墨烯复合物修饰电极上的电化学行为研究", 云南民族大学学报(自然科学版), no. 04, pages 21 - 25 * |
| 刘洁;丁金龙;赵肃清;秦静;胡青青;: "非共价作用石墨烯-金纳米复合材料修饰电极的制备及检测双酚A的方法研究", 现代食品科技, no. 04, pages 201 - 205 * |
| 张倩: "基于LSPR效应的高活性SERS基底研究进展", 《应用化工》, vol. 49, no. 3, pages 709 - 714 * |
| 晋晓勇: "两种DNA分子同时检测的逻辑门及半加器的构建", 《分析科学学报》, vol. 33, no. 6, pages 763 - 768 * |
| 李英姿: "荧光金纳米簇/单壁碳纳米管(AuNCs/SWNTs)复合材料制备及体外细胞毒性研究", 《中国实验诊断学》, vol. 21, no. 12, pages 2180 - 2184 * |
| 王勤生: "GO/Au/Ag复合材料表面形貌调控及其表面增强拉曼效应", 《上海工程技术大学学报》, vol. 34, no. 4, pages 314 - 319 * |
| 郑艳苹;邴欣;周建华;张鸿雁;: "石墨烯-金纳米复合物的制备及应用研究进展", 化工新型材料, no. 01, pages 199 - 203 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113607646B (en) | 2023-12-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Murray et al. | Shape-and size-selective electrochemical synthesis of dispersed silver (I) oxide colloids | |
| Sivasubramanian et al. | A facile formation of silver dendrites on indium tin oxide surfaces using electrodeposition and amperometric sensing of hydrazine | |
| CN112505019B (en) | Preparation method of surface enhanced Raman scattering substrate based on bimetal nano lamination | |
| CN107976431B (en) | Surface enhanced Raman substrate based on metal nanoparticles and preparation method thereof | |
| Fu et al. | Carbon nanotube and graphene oxide directed electrochemical synthesis of silver dendrites | |
| Hou et al. | Synthesis, optical and electrochemical properties of ZnO nanorod hybrids loaded with high-density gold nanoparticles | |
| Stojko et al. | Stripping voltammetric determination of mercury at modified solid electrodes: I. Development of the modified electrodes | |
| Shi et al. | Chemical bath deposition of ZnO on functionalized self-assembled monolayers: selective deposition and control of deposit morphology | |
| CN108226138A (en) | A kind of hollow pipe array surface enhancing Raman scattering substrate of Ag nanometer sheets assembling | |
| CN104259475A (en) | Preparation method of nano-silver/graphene derivative surface enhanced Raman substrate | |
| Nunes et al. | The influence of the electrodeposition conditions on the electroanalytical performance of the bismuth film electrode for lead determination | |
| Balci et al. | Catalytic coating of virus particles with zinc oxide | |
| CN109612975B (en) | Surface-enhanced Raman substrate and preparation method thereof | |
| Korotcenkov et al. | Synthesis by successive ionic layer deposition (SILD) methodology and characterization of gold nanoclusters on the surface of tin and indium oxide films | |
| CN113607646B (en) | SERS substrate and preparation method thereof | |
| Jin et al. | Novel and Green Chemical Compound of HAu (Cys) 2: Toward a Simple and Sustainable Electrolyte Recipe for Cyanide-Free Gold Electrodeposition | |
| Carmo et al. | Direct preparation and characterization of copper pentacyanonitrosylferrate nanoparticles | |
| Nguyen et al. | Functional palladium tetrapod core of heterogeneous palladium–platinum nanodendrites for enhanced oxygen reduction reaction | |
| Gao et al. | A simple template method for hierarchical dendrites of silver nanorods and their applications in catalysis | |
| CN108411285B (en) | Quick green synthesis of graphene oxide modified popcorn-shaped silver SERS composite structure | |
| KR102002400B1 (en) | Graphene oxide reformed nanocomposite, laminate comprising the same, and method for preparing the same | |
| Junaid et al. | Band gap analysis of zinc oxide for potential bio glucose sensor | |
| Si et al. | Investigation of photoelectrochemical oxidation of Fe2+ ions on porous nanocrystalline TiO2 electrodes using electrochemical quartz crystal microbalance | |
| CN114990489B (en) | Preparation method and application of ordered gold @ silver nanoparticle @ cobalt hydroxide nanoflower array | |
| Xiao et al. | Electrodeposition of Pd–Ag alloy nanowires on highly oriented pyrolytic graphite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |