CN103172404A - Three-dimensional metal-graphene composite substrate and preparation method thereof - Google Patents
Three-dimensional metal-graphene composite substrate and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional metal-graphene composite substrate and a preparation method thereof. The composite substrate disclosed by the invention is composed of a first nano layer, a graphene layer and a second nano layer, wherein the first nano layer is deposited on the surface of an amorphous carbon underlayer, the graphene layer is arranged on the surface of the first nano layer through spin coating, the second nano layer is deposited on the surface of the graphene layer, and the first nano layer and the second nano layer are gold or silver nano layers. According to the method, an active substrate with a good surface enhanced Raman effect is constructed; and the three-dimensional metal-graphene composite substrate is simple in preparation method, high in efficiency, and low in preparation cost.
Description
Technical field
The present invention relates to a kind of nano composition and preparation method, particularly based on 3-dimensional metal-graphene composite structure as surface enhanced Raman substrate and preparation method thereof.
Background technology
Surface enhanced Raman spectroscopy (SERS) technology is as highly sensitive and have the powerful light spectral technology of single molecular recognition, and verified its has important application at analytical chemistry, biomedical sector, especially to the detection of biomolecules.For the enhanced mechanism of surface enhanced Raman scattering, mainly contain two kinds of mechanism: a kind of Electromagnetic enhancement mechanism that is based on surface plasma body resonant vibration, a kind of chemical enhanced mechanism that is based on charge transfer.Adopt the surface enhanced Raman spectroscopy detection technique can effectively overcome the very weak shortcoming of normal Raman spectroscopy detection signal.
The surface enhanced Raman spectroscopy technology the most important thing is to develop take the noble metal nano structure as main active substrate, improves the intensity of probe molecule Raman signal.At present, textured metal particle, nano-structure array and the colloidal solid solution application in surface enhanced Raman spectroscopy detects based on Jin Heyin realizes.Silver nanostructured have a highest surface plasma body resonant vibration energy, and reinforced effects is best, but poor chemical stability, and the surface is easy to oxidation, is a silver nanostructured large weakness as the surface reinforced Raman active substrate.For silver, the reinforced effects of gold is slightly low, but gold has better biocompatibility and chemical stability.Recently, according to the report of NANO letter, grapheme material also can be used as the surface reinforced Raman active substrate.This has further promoted the surface reinforced Raman active research to the noble metal-graphene matrix material.The compound of Graphene and gold (silver) can obtain stronger enhancing signal, and this wherein exists the chemistry of Graphene to strengthen and the synergy of the Electromagnetic enhancement of metal Nano structure: the individual layer sheet structure of Graphene is conducive to adsorb the charge transfer of molecule and substrate; Gold (silver) nanoparticle can produce different plasma resonance patterns along with spacing of particle dwindles.When being in contact with one another on when nanoparticle particle plane, the strong coupling effect of plasma body has strengthened the electromagnetic intensity that occupy of nanoparticle, produces so-called " focus ".This is conventional graphite alkene and the mechanism and enhancement mechanism of gold (silver) matrix material as surface enhanced Raman substrate.At present, the method that preparation has the surface reinforced Raman active substrate is a lot, as: the coarse method of electrochemical redox, chemical synthesis, template etc.Aforesaid method respectively has quality.The coarse method process of chemistry redox is simple, but the electrode surface that forms is inhomogeneous, and pattern and size are all wayward; The synthetic colloidal sol nanoparticle of chemical method is all controlled at pattern and size, and reinforced effects is very good, but the tensio-active agent that adds makes enhancing signal be interfered, and preparation process is loaded down with trivial details, often needs through repeatedly centrifugal to remove unnecessary impurity.Template can access orderly nano particles array, but cost is higher, and preparation is comparatively complicated, Raman signal relatively a little less than.
Summary of the invention
The object of the present invention is to provide a kind of 3-dimensional metal-Graphene composite substrate and preparation method thereof.
For realizing above purpose, the technical solution adopted in the present invention is:
3-dimensional metal of the present invention-Graphene composite substrate is comprised of the first nanometer layer, graphene layer and the second nanometer layer, described the first nanolayer deposition is on the surface of amorphous carbon substrate, described graphene layer is spin-coated on the surface of the first nanometer layer, described the second nanolayer deposition is on the surface of graphene layer, and described the first nanometer layer and the second nanometer layer are gold nano layer or silver nanoparticle layer.
Further, gold nano layer of the present invention is made of nanoparticle, and described silver nanoparticle layer is dendritic structure or Cluster Structures.
Further, the particle diameter of the nanoparticle of gold nano layer of the present invention is 15nm～65nm.
Further, if silver nanoparticle layer Cluster Structures of the present invention, the diameter of cluster is 100～150nm.
Further, the thickness of graphene layer of the present invention is 1～8nm.
Preferably, the nanoparticle that gold nano layer of the present invention is 15nm～65nm by particle diameter consists of, and described silver nanoparticle layer is dendritic structure or Cluster Structures; If described silver nanoparticle layer is Cluster Structures, the diameter of cluster is 100～150nm; The thickness of described graphene layer is 1～8nm.
The preparation method of 3-dimensional metal of the present invention-Graphene composite substrate comprises the steps:
(1) at the amorphous carbon-film substrate surface, by constant potential electrochemical deposition method deposition the first nanometer layer;
If the first nanometer layer is the gold nano layer, mode of deposition is: electrodeposit liquid is the HAuCl of 0.6～2.4 mmol/L
4KH with 0.075～0.1 mol/L
2PO
4Mixed aqueous solution, depositing time is 300～600s, sedimentation potential is-0.5～-0.8V;
If the first nanometer layer is the silver nanoparticle layer, mode of deposition is: electrodeposit liquid is the AgNO of 3～6 mmol/L
3KNO with 0.375～0.5 mol/L
3Mixed aqueous solution, depositing time is 1200～1600s, sedimentation potential is-0.3～-0.5V;
(2) use spin coater 0.5～1 mg/mL graphite oxide aqueous solution of 40～80 μ L to be dropped in the surface of the first nanometer layer, the rotating speed of spin coater be 500 turn/min～4000 turn/min, the spin coating time is 5 seconds～30 seconds;
(3) graphene oxide that uses electrochemical reducing will be spin-coated on the first nanometer layer is reduced into Graphene, and the condition of described electrochemical reducing is: reducing solution is the KH of 20～60mmol/L
2PO
4The aqueous solution, the electrochemical workstation operating mode is cyclic voltammetry, reduction potential is-1.5V～0 V, scanning speed is 50～100 mV/s, the circulation number of turns is 10～60 circles;
(4) utilize electrochemical deposition method to deposit the second nanometer layer on described Graphene;
If the second nanometer layer is the gold nano layer, mode of deposition is: electrodeposit liquid is the HAuCl of 0.6～2.4 mmol/L
4KH with 0.075～0.1 mol/L
2PO
4Mixed aqueous solution, depositing time is 300～600s, sedimentation potential is-0.5～-0.8V;
If the second nanometer layer is the silver nanoparticle layer, mode of deposition is: electrocasting/electrodeposition liquid is the AgNO of 3～6 mmol/L
3KNO with 0.375～0.5 mol/L
3Mixed aqueous solution, depositing time is 1200～1600s, sedimentation potential is-0.3～-0.5V.
Further, amorphous carbon-film of the present invention is the amorphous carbon-film of the tetrahedral structure of doping nitrogen.
Further, the electrochemical workstation of constant potential electrochemical deposition method of the present invention and electrochemical reducing all uses three-electrode system, and the reference electrode in described three-electrode system is saturated calomel electrode.
In above-mentioned steps, graphene oxide is to obtain with the Hummers method is synthetic; Electrochemical deposition gold or silver nanoparticle layer and electrochemical reduction graphene oxide all use three-electrode system, and amorphous carbon film is working electrode, and platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode; Amorphous carbon-film in step (1) is through acetone, ethanol, ultrapure water ultrasonic cleaning successively, and every kind of solution cleaned 5 minutes, treats electrochemical deposition gold or silver nanoparticle layer use after drying.
Compared with prior art, the invention has the beneficial effects as follows:
1. the three-dimensional lamination layer structure of the first nanometer layer---graphene layer---the second nanometer layer is adopted in substrate of the present invention, and such structure not only has the coupling effect of metallic plasma in the plane, also can produce plasmon coupling on perpendicular to the direction of substrate.Graphene layer can produce the internal layer electric field in vertical direction as electron transfer layer.Compare with traditional Raman active substrate, substrate of the present invention has larger advantage on enhancing Raman scattering intensity.
2. in the present invention, the three-dimensional lamination layer structure owing to adopting the first nanometer layer---graphene layer---the second nanometer layer when the first nanometer layer is the silver nanoparticle layer, can play certain protective role to the silver that is easy to oxidation.
3. the present invention adopts electrochemical deposition method to prepare gold nano layer or silver nanoparticle layer, pattern and size than electrochemical roughening method nanometer layer more easy to control, also more save chemical reagent and preparation section than chemical synthesis, and do not have the interference of tensio-active agent to detecting, preparation efficiency is higher, and Raman signal is stronger.
4. when the first nanometer layer of substrate of the present invention and the second nanometer layer were the gold nano layer, the chemical stability of substrate was good, and biocompatibility is good, can be used for the detection of biomolecules.
Description of drawings
Fig. 1-3 are the scanning electron microscope (SEM) photograph of three phases in the surface reinforced Raman active substrate preparation process of the golden nanometer particle-Graphene-golden nanometer particle in embodiment 1.Wherein, Fig. 1 is the scanning electron microscope (SEM) photograph of the golden nanometer particle layer of amorphous carbon-film surface deposition; Fig. 2 is the scanning electron microscope (SEM) photograph that Graphene covers the golden nanometer particle layer; Fig. 3 is the scanning electron microscope (SEM) photograph of golden nanometer particle-Graphene-golden nanometer particle.
Fig. 4 is the scanning electron microscope (SEM) photograph of surface reinforced Raman active substrate of silver nanometer tree branches-Graphene-golden nanometer particle of embodiment 2.
Fig. 5 is the scanning electron microscope (SEM) photograph of surface reinforced Raman active substrate of golden nanometer particle-Graphene-ag nano-cluster of embodiment 3.
Fig. 6-8 are reduced phenogram for graphene oxide of the present invention.Wherein, Fig. 6 is the electrochemical reduction curve of graphene oxide; Fig. 7 is the x-ray photoelectron energy spectrogram of graphene oxide and Graphene; Fig. 8 is the Raman spectrogram of graphene oxide and Graphene.
Fig. 9 is the Raman spectrogram of the upper rhodamine B of surface reinforced Raman active substrate in the step (2) that is adsorbed on embodiment 1, (3).(a) only be coated with the golden nanometer particle layer but the Raman signal of the rhodamine B that detects without the substrate of graphene layer for preparation in step (2); (b) for the Raman signal of the rhodamine B that the golden nanometer particle that covers graphene layer detects is arranged in step (3); (c) Raman signal of the rhodamine B that detects for the surface reinforced Raman active substrate of three-dimensional golden nanometer particle-Graphene-golden nanometer particle.
Figure 10 adsorbs the Raman spectrogram of the upper rhodamine B of the surface reinforced Raman active substrate of 3-dimensional metal-graphene composite structure in the present invention.Curve (a), (b), (c) are respectively the Raman signal of the rhodamine B that the surface reinforced Raman active substrate of golden nanometer particle-Graphene-golden nanometer particle, silver nanometer tree branches-Graphene-golden nanometer particle, golden nanometer particle-Graphene-ag nano-cluster detects.
Embodiment
Embodiment 1:
In the present embodiment, prepare according to the following steps 3-dimensional metal of the present invention-Graphene composite substrate:
(1) amorphous carbon-film is through the ultrasonic cleaning successively of acetone, ethanol, ultrapure water, and every kind of solution cleaned 5 minutes, treats electrochemical deposition gold nano layer use after drying.
(2) adopt electrochemical deposition method at amorphous carbon-film surface deposition golden nanometer particle layer, electrodeposit liquid used is 20ml 0.6 mmol/L HAuCl
4With 0.075 mol/L KH
2PO
4Mixed aqueous solution.Adopt three-electrode system: amorphous carbon film is working electrode, and platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode.The electrochemical workstation model was CHI630D, and operating mode is potentiostatic mode ,-0.8V deposit 600 seconds.Standby after sample drying.The scanning electron microscope (SEM) photograph of this sample such as Fig. 1.As seen from Figure 1, the golden nanometer particle of deposition is comparatively even, and particle dia is 65nm.
(3) utilize spin coater that graphene oxide is spin-coated on the sample that step (2) prepares.Detailed process is as follows: get 40 μ L 0.5 mg/mL graphene oxides, drop on the sample of step (2) preparation, regulate spin coating rotating speed 500 and turn/min, the spin coating time is 5 seconds.Spin coating is complete, uses electrochemical workstation to have the sample of graphene oxide to carry out electrochemical reduction to spin coating, and reducing solution is 20mL 20 mmol/L KH
2PO
4The aqueous solution, operating mode is cyclic voltammetry, parameter is-1.5V is to rate loop 10 circles of 0 V with 100 mV/s, namely obtained having covered the golden nanometer particle layer sample of Graphene.The scanning electron microscope (SEM) photograph of this sample as shown in Figure 2.As seen from Figure 2, Graphene covers on the golden nanometer particle layer, and thickness is between 1～8nm.
(4) after the graphene oxide reduction is completed, on the sample that step (3) makes, use mode of deposition same in step (2) process deposited gold nanoparticle again.The 3-dimensional metal that preparation is completed-Graphene composite substrate is made of gold nano layer-Graphene-gold nano layer.The scanning electron microscope (SEM) photograph of this substrate such as Fig. 3.As seen from Figure 3, the distribution of golden nanometer particle is more fine and close than Fig. 1, and its particle diameter is 15～65nm.
(5) Graphene that covers on the golden nanometer particle layer is characterized its result such as Fig. 6.Fig. 6 is the electrochemical reduction curve of graphene oxide, and can find out at-0.8V has the reduction current peak, and this is the performance that graphene oxide is reduced.
(6) with rhodamine B as probe molecule, this 3-dimensional metal-Graphene composite substrate is characterized and the performance test of surface-enhanced Raman performance, and with the covering of the golden nanometer particle layer of step (2) preparation and step (3) preparation the sample of golden nanometer particle of Graphene do comparative group.Concrete operations are as follows: (a) this 3-dimensional metal-Graphene composite substrate is immersed in 10
-6In the aqueous solution of the rhodamine B of mol/L 24 hours; (b) substrate is taken out, use ultrapure water to rinse well, drying at room temperature is 1 hour in vacuum drying oven, is used for afterwards Raman detection (test result as shown in Figure 9).As seen from Figure 9, obviously the Raman signal of the upper rhodamine B of surface enhanced Raman substrate (being golden nanometer particle-Graphene-golden nanometer particle three-dimensional structure substrate) of 3-dimensional metal-graphene composite structure of obtaining of the present embodiment is better than the golden nanometer particle layer is only arranged (curve sample a) and covered the Raman signal of rhodamine B on golden nanometer particle (curve b) sample of Graphene.
Embodiment 2:
In the present embodiment, prepare according to the following steps 3-dimensional metal-Graphene composite substrate:
(1) electrochemical deposition silver nanoparticle layer is carried out on the amorphous carbon-film surface after the step (1) of embodiment 1 is cleaned, and electrodeposit liquid is 3mmol/L AgNO
3With 0.375mol/L KNO
3Mixed aqueous solution.Adopt three-electrode system: amorphous carbon film is working electrode, and platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode.The electrochemical workstation model was CHI630D, and operating mode is potentiostatic mode ,-0.3V deposit 1200 seconds.Standby after sample drying.
(2) utilize spin coater that graphene oxide is spin-coated on the above-mentioned sample for preparing.Detailed process is as follows: get 80uL 1mg/mL graphene oxide, drop on the sample of step (1) preparation, regulate spin coating rotating speed 4000 and turn/min, 30 seconds spin coating time.Spin coating is complete, uses electrochemical workstation to have the sample of graphene oxide to carry out electrochemical reduction to spin coating, and reducing solution is 20mmol/L KH
2PO
4The aqueous solution, the electrochemical workstation operating mode is cyclic voltammetry, parameter is-1.5V is to rate loop 60 circles of 0 V with 50 mV/s.
(3) after graphene oxide reduction was completed, the sample that step (2) is made carried out the electrochemical deposition of golden nanometer particle, and electrodeposit liquid is 2.4 mmol/L HAuCl
4With 0.1 mol/L KH
2PO
4Mixed aqueous solution.Adopt three-electrode system: amorphous carbon film is working electrode, and platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode.The electrochemical workstation model was CHI630D, and operating mode is potentiostatic mode ,-0.5V deposit 300 seconds.The 3-dimensional metal that preparation is completed-Graphene composite substrate is made of silver nanoparticle layer-Graphene-gold nano layer.This substrate scanning electron microscope (SEM) photograph such as Fig. 4, as seen from Figure 4, the silver nanoparticle layer is dendritic structure, and silver nanoparticle layer, graphene layer and golden nanometer particle layer consist of three-decker, and the particle diameter of golden nanometer particle is 15～20nm.
(4) Graphene that covers on the silver nanoparticle layer is characterized its result such as Fig. 7.Fig. 7 be graphene oxide and Graphene x-ray photoelectron power spectrum (XPS) test result figure, can the place's of seeing carbon-oxygen bond peak intensity be obviously descended after oxidized Graphene is reduced by Fig. 7, illustrate that graphene oxide is reduced.
(5) with rhodamine B as probe molecule, this 3-dimensional metal-Graphene composite substrate is characterized and the performance test of surface-enhanced Raman performance.Concrete operations are as follows: (a) this 3-dimensional metal-Graphene composite substrate is immersed in 10
-6In the aqueous solution of the rhodamine B of mol/L 24 hours; (b) substrate is taken out, use ultrapure water to rinse well, drying at room temperature is 1 hour in vacuum drying oven, is used for afterwards Raman detection.Test result is as shown in the curve b of Figure 10.
Embodiment 3:
In the present embodiment, prepare according to the following steps 3-dimensional metal-Graphene composite substrate:
(1) adopt electrochemical deposition method at amorphous carbon-film surface deposition gold nano layer, electrodeposit liquid is 2.4 mmol/L HAuCl
4With 0.075 mol/L KH
2PO
4Mixed aqueous solution.Adopt three-electrode system: amorphous carbon film is working electrode, and platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode.The electrochemical workstation model was CHI630D, and operating mode is potentiostatic mode ,-0.5V deposit 600 seconds.Deposit complete, standby after sample drying.
(2) utilize spin coater that graphene oxide is spin-coated on the above-mentioned sample for preparing.Detailed process is as follows: get 40 μ L 0.5 mg/mL graphene oxides, drop on the sample of step (1) preparation, regulate spin coating rotating speed 4000 and turn/min, 30 seconds spin coating time.Spin coating is complete, uses electrochemical workstation to have the sample of graphene oxide to carry out electrochemical reduction to spin coating, and reducing solution is the KH of 60mmol/L
2PO
4The aqueous solution, operating mode are cyclic voltammetry, and parameter is-and 1.5V is to rate loop 60 circles of 0 V with 100 mV/s.
(3) after graphene oxide reduction was completed, the sample that step (2) is made carried out the electrochemical deposition of ag nano-cluster, and electrodeposit liquid is 6mmol/L AgNO
3With 0.5mol/L KNO
3Mixed aqueous solution.Adopt three-electrode system: amorphous carbon film is working electrode, and platinized platinum is supporting electrode, and saturated calomel electrode is reference electrode.The electrochemical workstation model was CHI630D, and operating mode is potentiostatic mode ,-0.5V deposit 1600 seconds.The 3-dimensional metal that preparation is completed-Graphene composite substrate is made of gold nano layer-Graphene-silver nanoparticle layer, its scanning electron microscope (SEM) photograph such as Fig. 5.As seen from Figure 5, the silver nanoparticle layer is nanocluster cluster and very fine and close, and particle diameter is in 100～150nm scope.
(4) Graphene that covers on the gold nano layer is characterized, its result as shown in Figure 8.Fig. 8 is the Raman spectrogram of graphene oxide and Graphene.As seen from Figure 8, to be reduced into Graphene thick when graphene oxide, represent aromatic nucleus SP
2The D peak ratio rising of breathing vibration pattern illustrates by electrochemical method and graphene oxide can be reduced.
(5) with rhodamine B as probe molecule, this 3-dimensional metal-Graphene composite substrate is characterized and the performance test of surface-enhanced Raman performance.Concrete experimentation is as follows: (a) this 3-dimensional metal-Graphene composite substrate is immersed in 10
-6In the aqueous solution of the rhodamine B of mol/L 24 hours; (b) substrate is taken out, use ultrapure water to rinse well, drying at room temperature is 1 hour in vacuum drying oven, is used for afterwards Raman detection.Test result is as shown in the curve c of Figure 10.
For the surface-enhanced Raman performance test of the 3-dimensional metal in embodiment 1-3-Graphene composite substrate, detected result such as Figure 10.As seen from Figure 10, the 3-dimensional metal in embodiment 1-3-Graphene composite substrate all has good surface-enhanced Raman performance.Wherein, the 3-dimensional metal-Graphene in embodiment 3 (curve c) composite substrate (3-dimensional metal that is made of gold nano layer-Graphene-silver nanoparticle layer-Graphene composite substrate) reinforced effects is best.Embodiment 1 (curve a) and the second layer nanometer layer of the 3-dimensional metal-Graphene composite substrate in embodiment 2 (curve b) be the gold nano layer, have satisfactory stability and biocompatibility.
Claims (9)
1. 3-dimensional metal-Graphene composite substrate, it is characterized in that: formed by the first nanometer layer, graphene layer and the second nanometer layer, described the first nanolayer deposition is on the surface of amorphous carbon substrate, described graphene layer is spin-coated on the surface of the first nanometer layer, described the second nanolayer deposition is on the surface of graphene layer, and described the first nanometer layer and the second nanometer layer are gold nano layer or silver nanoparticle layer.
2. 3-dimensional metal according to claim 1-Graphene composite substrate, it is characterized in that: described gold nano layer is made of nanoparticle, and described silver nanoparticle layer is dendritic structure or Cluster Structures.
3. 3-dimensional metal according to claim 2-Graphene composite substrate, it is characterized in that: the particle diameter of the nanoparticle of described gold nano layer is 15nm～65nm.
4. 3-dimensional metal according to claim 2-Graphene composite substrate, it is characterized in that: if described silver nanoparticle layer Cluster Structures, the diameter of cluster is 100～150nm.
5. 3-dimensional metal according to claim 2-Graphene composite substrate, it is characterized in that: the thickness of described graphene layer is 1～8nm.
6. 3-dimensional metal according to claim 1-Graphene composite substrate, it is characterized in that: the nanoparticle that described gold nano layer is 15nm～65nm by particle diameter consists of, and described silver nanoparticle layer is dendritic structure or Cluster Structures; If described silver nanoparticle layer is Cluster Structures, the diameter of cluster is 100～150nm; The thickness of described graphene layer is 1～8nm.
7. the preparation method of the 3-dimensional metal of any one-Graphene composite substrate in a claim 1 to 6, is characterized in that, comprises the steps:
(1) at the amorphous carbon-film substrate surface, by constant potential electrochemical deposition method deposition the first nanometer layer;
If the first nanometer layer is the gold nano layer, mode of deposition is: electrodeposit liquid is the HAuCl of 0.6～2.4 mmol/L
4KH with 0.075～0.1 mol/L
2PO
4Mixed aqueous solution, depositing time is 300～600s, sedimentation potential is-0.5～-0.8V;
If the first nanometer layer is the silver nanoparticle layer, mode of deposition is: electrodeposit liquid is the AgNO of 3～6 mmol/L
3KNO with 0.375～0.5 mol/L
3Mixed aqueous solution, depositing time is 1200～1600s, sedimentation potential is-0.3～-0.5V;
(2) use spin coater 0.5～1 mg/mL graphite oxide aqueous solution of 40～80 μ L to be dropped in the surface of the first nanometer layer, the rotating speed of spin coater be 500 turn/min～4000 turn/min, the spin coating time is 5 seconds～30 seconds;
(3) graphene oxide that uses electrochemical reducing will be spin-coated on the first nanometer layer is reduced into Graphene, and the condition of described electrochemical reducing is: reducing solution is the KH of 20～60mmol/L
2PO
4The aqueous solution, the electrochemical workstation operating mode is cyclic voltammetry, reduction potential is-1.5V～0 V, scanning speed is 50～100 mV/s, the circulation number of turns is 10～60 circles;
(4) utilize electrochemical deposition method to deposit the second nanometer layer on described Graphene;
If the second nanometer layer is the gold nano layer, mode of deposition is: electrodeposit liquid is the HAuCl of 0.6～2.4 mmol/L
4KH with 0.075～0.1 mol/L
2PO
4Mixed aqueous solution, depositing time is 300～600s, sedimentation potential is-0.5～-0.8V;
If the second nanometer layer is the silver nanoparticle layer, mode of deposition is: electrocasting/electrodeposition liquid is the AgNO of 3～6 mmol/L
3KNO with 0.375～0.5 mol/L
3Mixed aqueous solution, depositing time is 1200～1600s, sedimentation potential is-0.3～-0.5V.
8. preparation method according to claim 7 is characterized in that: described amorphous carbon-film is the amorphous carbon-film of the tetrahedral structure of doping nitrogen.
9. according to claim 7 or 8 described preparation methods, it is characterized in that: the electrochemical workstation of described constant potential electrochemical deposition method and electrochemical reducing all uses three-electrode system, and the reference electrode in described three-electrode system is saturated calomel electrode.
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