CN104259475B - A kind of preparation method of Nano Silver/Graphene derivative surface-enhanced Raman matrix - Google Patents
A kind of preparation method of Nano Silver/Graphene derivative surface-enhanced Raman matrix Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of Nano Silver/Graphene derivative surface-enhanced Raman matrix, it is characterized in that using the adsorptivity of Graphene derivative ultrathin membrane, reducing agent such as glucose is uniformly adsorbed in surface, nano silver film is gone out in Graphene derivative ultrathin membrane superficial growth using silver mirror reaction.By controlling the concentration of the Graphene derivative film number of plies and silver ammino solution to the growth of nano silver film, and nano-Ag particles size, distribution is regulated and controled.The surface Raman enhancement performance of its laminated film is regulated and controled by the number of plies of Graphene derivative film and the pattern of nano silver film.Finally give the optimal technological parameter of Raman-enhancing energy.
Description
Technical field
The present invention relates to Molecular Spectral Analysis detection field, and in particular to a kind of Nano Silver/Graphene derivative surface increases
Hale the preparation method of graceful matrix.
Background technology
Raman spectrum belongs to molecular vibration spectrum, is the fingerprint of material molecule, according to the Raman spectrum that Ramam effect makes
Instrument can be used for accurate Qualitive test sample.The analysis method of Raman spectrum need not typically carry out pre-treatment to sample, and
Easy to operate during analysis, minute is short, be it is a kind of can to sample while carry out the technology of qualitative and quantitative analysis,
Biological in environment, historical relic, chemical industry, the field such as food has extremely wide application prospect.But it has the disadvantage that sensitivity is relatively low,
Especially when more complicated biological sample is detected.In low concentration, normal Raman spectroscopy is to extremely low concentration in liquid
Deleterious molecular is insensitive, it is impossible to effectively detected.The discovery of surface enhanced Raman technique, causes the world wide
General concern.Because surface enhanced Raman technique there can be a huge vibration signal, its intensity is set to improve 10 numbers
It is more than magnitude.
Nano Silver has excellent Raman enhancement effect, and is widely used on Raman enhancing probe, and Nano Silver is prepared at present
The technique of Raman reinforcing material has a lot, such as：Chemical method reducing nano-silver, electron beam lithography, nanosphere etching, vacuum evaporation
Method etc.；Then these processing steps are cumbersome, complexity, are related to high temperature, relatively costly and oxidizable or even cause dirt to environment
Dye.In order to overcome above-mentioned problem, people generally on nano-silver loaded to a suitable carrier, will obtain nano silver-group and be combined
Material.The composite can effectively improve the surface-enhanced Raman performance of Nano Silver, and reduces cost improves its stability.
Graphene (Graphene) is the Two-dimensional Carbon atomic crystal of monoatomic thickness, Graphene and the big ratio of its derivative
Surface area and layer structure have become the excellent template for preparing nano material, by in-situ synthesis, can effectively prevent
The reunion of nano particle obtains dispersed nano particle-graphene composite material.For example：Xu et al. utilizes silver mirror reaction liquid
Phase method obtains Nano Silver-graphene solution, then obtains laminated film by vacuum filtration, and there is the film obvious surface to increase
Hale graceful performance；It is that then template absorption silver ion can also obtain after a series of reducing agent is reduced using graphene oxide
Nano Silver-graphene complex is obtained,《Small》, the B of CN 102554255 disclose a kind of silver nanoparticle/graphene composite material
Preparation method, it is characterised in that prepare Graphene by peeling off the method for expanded graphite using ultrasound in nmp solution,
Then in the nmp solution of this Graphene, Ag is reduced directly using tannic acid+, the growth in situ Ag nano particles on Graphene,
Obtain silver/graphite alkene nano composite material.The method complex process is cumbersome, is unfavorable for industrialized production.CN103334096 A are public
A kind of method of nano-silver-graphenecomposite composite film is opened, it first obtains silver ion-graphene oxide and is combined with vacuum filtration method
Film, is then heat-treated reduction acquisition nano-silver-graphenecomposite composite film under hydrogen and argon gas mixed gas at high temperature, and this is thin
Film has an excellent surface-enhanced Raman performance, but the method high cost, it is impossible to the size of control nano-Ag particles well
And particle diameter distribution, this is very big to performance impact.Additionally, our seminars are found that while that solvent method can obtain Nano Silver-stone
Black alkene laminated film, but its surface-enhanced Raman performance is but influenceed by many factors and cannot obtain excellent effect.Than
Such as, Nano Silver not only causes that the Raman signal of target molecule strengthens, and graphene base body Raman signal in itself is equally also increased
By force, enhanced Graphene signal can cover the Raman signal of target molecule, cause the sensitivity of composite to decline.Equally,
Zhou et al. proves that the surface-enhanced Raman performance of graphene sheet layer is relevant with its number of plies, more its hydraulic performance declines of the number of plies
《JACS》.However, Xie et al. researchs find that graphene sheet layer has excellent photoluminescence quenching performance and strong adsorptivity, make it
With obvious surface-enhanced Raman performance《JACS》.So if the thickness of Graphene can be effectively controlled, and can be well
If loading nano silvery particle, it will prepare highly sensitive surface-enhanced Raman matrix.The A of CN 102515560 disclose one
The method for preparing Graphene/Ag composite conductive thin films is planted, it is characterized in that being presoma to graphene oxide/silver sol, is used
Transparent conductive film is obtained after czochralski method, heat treatment.The A of CN 102849730 disclose one kind, and to prepare nanometer silver-graphene bionical
The method of nanostructured laminated film, it is characterized in that being assembled into Nano Silver and graphene oxide using electrostatic self-assembled technique multiple
Film is closed, heat treatment is eventually passed and is obtained Nano Silver/graphene composite film.Two patents of invention belong to self assembly preparation and receive
The category of rice silver-graphene laminated film, can control the thickness of graphene film, but the uncontrollable Nano Silver of the method
Particle size, sensitivity is low.And if by Graphene thickness control it is very low if, causing the amount of Nano Silver also reduces, its surface
Enhancing Raman hydraulic performance decline.In addition, silver mirror reaction is the most traditional handicraft for preparing silverskin, but the method preparation is silver-colored thin
Film is blocked up.The A of CN 101187017 disclose the method for preparing silver nano antibacterial material, it is characterised in that with aluminum salt solution to base
Bottom is pre-processed；Silver mirror reaction liquid will be dipped in by the substrate of pretreatment, reaction obtains nano silver film.But should
Invention is still traditional silver mirror reaction, and nano silver film stability is poor, and serious, high cost is piled up on aluminium flake.CN
103103511 A and the A of CN 101856035 disclose one kind and prepare silicon face morphology controllable nanometer silver granuel using silver mirror reaction
The method of son, by silver to the corrasion of monocrystalline silicon so as to form nano-Ag particles in silicon face.But the complex process, its
Etching acid has very strong corrosivity, pollutes environment.
Above-mentioned Nano Silver and nano-silver-graphenecomposite composite film synthetic method and deposited in surface-enhanced Raman application
In following technological deficiency：
1st, part chemical solvent, surfactant, reducing agent etc. are used in building-up process with toxicity, with very big ring
Border pollution problem；
2nd, building-up process may be larger in temperature higher, longer time, energy consumption；
3rd, the size regulation and control to nano-Ag particles in complex matrix are more difficult, it is impossible to reach the optimum size for meeting performance.
4th, the matrix material of some laminated films, such as organic matrix can influence the performance of surface-enhanced Raman, make its sensitive
Degree and accuracy decline；
5th, distance is difficult control between nano-Ag particles in laminated film, influences its performance.
5th, for current Nano Silver/Graphene complex matrix, it is impossible to optimize influence of the Graphene to performance.
In order to overcome prior art defect, the present inventor on the basis of prior art is summarized, by lot of experiments,
Complete the present invention.
The content of the invention
The present invention relates to a kind of preparation method of Nano Silver/Graphene derivative surface-enhanced Raman matrix, its feature exists
In the adsorptivity using Graphene derivative ultrathin membrane, by aldehydes reducing agent uniform adsorption in surface, using silver mirror reaction in stone
Black ene derivative ultrathin membrane superficial growth goes out nano silver film.By controlling the Graphene derivative film number of plies, silver ammino solution
Growth of the temperature and time of concentration and silver mirror reaction to nano silver film, and nano-Ag particles size, distribution are entered
Row regulation and control, so as to the surface Raman enhancement performance to its laminated film regulates and controls, final acquisition has excellent surface enhanced
The base film of Raman performance.
The technical scheme that solution above-mentioned technical problem is used is made up of following step：
a）The preparation of Graphene derivative film：
（1）By in Graphene derivative powder addition deionized water, the Graphene for adding 0.1 mg per mL deionized waters spreads out
Biology, ultrasonic 2 h obtains the Graphene derivative aqueous solution.
（2）The PDDA aqueous solution, deionized water and quality are obtained during deionized water is added into the PDDA that mass fraction is 20 %
Fraction is that the volume ratio of 20 % PDDA is 4:1.
（3）The pretreatment of substrate：Substrate is cleaned by ultrasonic 5 min in acetone, ethanol, deionized water successively, nitrogen is used
Drying.
（4）In the pretreated substrate immersion Graphene derivative aqueous solution deionized water rinsing, nitrogen will be used after 20 min
Immersed after air-blowing is dry（2）Deionized water rinsing is used in the PDDA aqueous solution of configuration after 20 min, the step 0 ~ 10 time are repeated.
b）By step a）The Graphene derivative film of middle acquisition is put into aldehydes reducing agent aqueous solution after 20 min vertically
Take out, nitrogen drying, aldehydes concentration of aqueous solution is 10 mg/mL.
c）The configuration of silver ammino solution：Under agitation, the ammonia spirit that mass fraction is 2 % is added dropwise to 0.2
It is completely dissolved to precipitation in the silver salt solution of ~ 0.8 mol/L concentration.
d）By step b）In Graphene derivative film be put into step c vertically）In the silver ammino solution of configuration, and 50 ~
10 ~ 60 min are incubated in 90 DEG C of water-bath, now, transparent graphite oxide film surface forms one layer of nano silver film, goes
Ionized water is rinsed, and Nano Silver/Graphene derivative surface-enhanced Raman matrix is obtained after nitrogen drying.
Step a in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix）'s（1）In
Graphene derivative is Graphene derivative, in the Graphene after the Graphene of oxidation-chemical method reduction acquisition and modification
Any one.
Step a）'s（3）In involved substrate be any one in glass, quartz, indium oxide tin glass and printing paper
Kind.
Step a）'s（4）The middle repetition number of steps is ranged preferably from 2 ~ 4 times.
Step b in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix）Middle aldehydes reduction
Agent is glucose, mannose, galactolipin, any one in lactose and maltose.
Step c in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix）Middle silver salt is nitre
Any one in sour silver, silver acetate, silver perchlorate, silver orthophosphate.
Step c in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix）Described nitric acid
Silver concentration ranges preferably from 0.2 ~ 0.4 mol/L.
Step d in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix）In water-bath temperature
Degree ranges preferably from 60 ~ 80 DEG C, and soaking time ranges preferably from 20 ~ 30 min.
Laminated film is main described in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix
For Homeland Security, environmental monitoring, food security, the field such as material foundation research and health care.
The present invention compared with prior art, has the following advantages that and beneficial effect：Nano Silver of the invention/Graphene derives
The preparation method of thing surface enhanced Raman substrate, is matrix uniform adsorption with Graphene derivative using improved silver mirror reaction
Aldehyde radical carbohydrate reducing agent, and Nano Silver is reverted into acquisition Nano Silver/Graphene derivative matrix on Graphene derivative matrix.
The preparation method is simple, and quickly, green and low cost, the Nano Silver size for being obtained and distribution meet surface-enhanced Raman base
The requirement of body.Overcome the shortcomings of high cost for preparing nano silver material technique at present, complexity, pollution.This side of the present invention
Method can also effectively control the thickness of Graphene derivative, can give full play to the excellent photoluminescence quenching of Graphene derivative,
Strong adsorptivity and surface-enhanced Raman performance, so as to further significantly improve the surface-enhanced Raman performance of laminated film.For
Further promote surface enhanced Raman technique in Homeland Security, environmental monitoring, the field such as food security and health care obtains more
Offer condition is provided.
Brief description of the drawings
Fig. 1 is the AFM figures of nano silver film prepared by embodiment 1.
Fig. 2 is the AFM figures of the laminated film of acquisition in (a) embodiment 2；The surface-enhanced Raman of (b) laminated film
Energy.
Fig. 3 is the AFM figures of the laminated film of acquisition in (a) embodiment 3；The surface-enhanced Raman of (b) laminated film
Energy.
Fig. 4 is the AFM figures of the laminated film of acquisition in (a) embodiment 4；The surface-enhanced Raman of (b) laminated film
Energy.
The AFM figures of the laminated film of Fig. 5 embodiments 5.
The AFM figures of the laminated film of Fig. 6 embodiments 6.
Specific embodiment
With reference to specific implementation example, the present invention will be further described.
Embodiment 1
Graphene derivative film helps to adsorb carbohydrate reducing agent, and for the growth of nano-Ag particles provides site, because
This, Graphene derivative serves vital effect；Embodiment 1 is not having Graphene derivative film with reference to forefathers' experience
Quartz substrate on prepare nano silver film with silver mirror reaction.Its experimental procedure is as follows：
1）The pretreatment of quartz substrate：Quartz substrate is cleaned by ultrasonic 5 in acetone, ethanol, deionized water successively
Min, is dried up with nitrogen.
2）By step 1）In quartz substrate take out after 20 min in the D/W of 10 mg/mL of immersion vertically, nitrogen
Air-blowing is done.
3）The configuration of silver ammino solution：The configuration of silver ammino solution：Under agitation, it is ammoniacal liquor that mass fraction is 2 % is molten
Extremely precipitation is completely dissolved during liquid is added dropwise to the silver salt solution of 0.4 mol/L concentration.
4）By step 2）In quartz substrate be put into step 3 vertically）In the silver ammino solution of configuration, and in 80 DEG C of water-bath
30 min of middle insulation, now, transparent quartz substrate forms one layer of nano silver film, and deionized water rinsing is made after nitrogen drying
Obtain Nano Silver/Graphene derivative surface-enhanced Raman matrix
It is dimmed that reaction terminates rear transparent quartz substrate, and has decorative pattern, and we characterize the shape of film with AFM
Looks.
Nano-Ag particles are grown in substrate surface as can see from Figure 1, but distribution of particles is sparse, and particle size is about
40 nm, the surface-enhanced Raman performance of the film is very weak.
Embodiment 2
Embodiment 2 first will plate Graphene derivative film with not being both for embodiment 1 on substrate.Comprise the following steps that：
a）The preparation of Graphene derivative-graphene oxide film：
（1）Graphene oxide powder is added in deionized water, the graphene oxide of 0.1 mg, ultrasound 2 are added per mL
H obtains graphene oxide colloidal solution.
（2）In being the PDDA of 20 % by deionized water addition mass fraction, the volume ratio of deionized water and 20 % PDDA
It is 4:1.
（3）The pretreatment of quartz substrate：Quartz substrate is cleaned by ultrasonic 5 in acetone, ethanol, deionized water successively
Min, is dried up with nitrogen.
（4）In pretreated quartz substrate immersion graphene oxide solution deionized water rinsing, nitrogen will be used after 20 min
Immersed after air-blowing is dry and use deionized water rinsing in PDDA colloidal sols after 20 min, repeat the step 1 time.
b）By step a）The graphene oxide film of middle acquisition is put into D/W and is taken out after 20 min vertically, nitrogen
Air-blowing is done；D/W concentration is 10 mg/mL.
c）The configuration of silver ammino solution：c）The configuration of silver ammino solution：Under agitation, by ammoniacal liquor that mass fraction is 2 %
Extremely precipitation is completely dissolved during solution is added dropwise to the silver salt solution of 0.4 mol/L concentration.
d）By step b）In graphene oxide film be put into step c vertically）In the silver ammino solution of configuration, and at 80 DEG C
Water-bath in be incubated 30 min, now, transparent graphite oxide film surface forms one layer of nano silver film, deionized water punching
Wash, Nano Silver/surface of graphene oxide enhancing Raman matrix is obtained after nitrogen drying.
Fig. 2（a）For the AFM of Nano Silver/graphene oxide film schemes, AFM figures in comparative example 1, it can clearly be seen that
Nano Silver is evenly distributed in the graphene oxide layer of fold, the quantity of particle also showed increased.The chi of nano-Ag particles
It is very little to drop to 30 nm, but grain spacing is from having reduced.
Fig. 2（b）It is the crystal violet surface-enhanced Raman figure of the laminated film, the film has obvious as we can see from the figure
Raman-enhancing energy, its surface Raman enhancement factor be 2*104。
In conjunction with the embodiments in 1, we can draw, formation of the graphene oxide to Nano Silver has a huge impact；Oxygen
The growth for existing for nano-Ag particles of graphite alkene film improves site, and its big specific surface area and strong adsorptivity can be with
Adsorbent-reductant and surface, more preferable reducing nano-silver and surface, so as to improve the performance of film.
Embodiment 3
As different from Example 2, a in the step of embodiment 3）In（4）Repeat the step 2 time.
Fig. 3（a）For the AFM of the laminated film schemes, nano-Ag particles uniform fold is lived entirely as we can clearly see from the figure
Quartz substrate surface, nanoparticle size increases to 75 nm.
Fig. 3（b）It is the crystal violet molecular surface enhancing Raman figure of the laminated film, the as we can see from the figure property of the film
Can be greatly improved, its surface Raman enhancement factor brings up to 1.2*108。
Embodiment 3 again demonstrates graphene oxide film influences the growth of nano-Ag particles；Comparative example 1 and 2, real
The performance for applying the laminated film of example 3 is greatly enhanced.The size increase of nano-Ag particles is not only because, quantity increases
Many, grain spacing is from diminution, also as the excellent photoluminescence quenching performance of graphene oxide, strong adsorptivity can be improved further
The surface-enhanced Raman performance of laminated film.
Embodiment 4
As different from Example 2, a in the step of embodiment 4）'s（4）Repeat the step 3 time.
Fig. 4（a）It is the AFM figures of the laminated film, the as we can see from the figure pattern similar with embodiment 3.
Fig. 3（b）It is the crystal violet surface-enhanced Raman figure of the laminated film.Its surface Raman enhancement factor is calculated for 3.3*
107.Comparative example 1 ~ 3 as can be seen that growth effect of the graphene oxide film not only to nano silver film it is very big, but also
Influence its surface-enhanced Raman performance；The increase of graphene oxide film thickness causes that surface-enhanced Raman performance decreases；
Because Nano Silver is the key of surface-enhanced Raman performance, also increase while the Raman signal of crystal violet molecule is increased
Graphene oxide signal in itself；The Raman signal of the graphene oxide of increase can hide partially crystallizable purple Raman signal,
So as to the surface-enhanced Raman performance for causing laminated film has declined, and with the increase of film thickness, decline more obvious.
Embodiment 5
C in the step of embodiment 5 as different from Example 3）The concentration of silver nitrate is 0.8 mol/L.
Fig. 5 is the AFM figures of the laminated film, the result of comparative example 3, it may be seen that nano-Ag particles are into column
It is grown in matrix surface, particle size growth to 200 nm;The raising of silver nitrate concentration causes nano-Ag particles to reunite and formed
Bulky grain, but intergranular distance but increases, nano-Ag particles skewness, hence in so that the surface enhanced of the film draws
The reappearance of graceful performance, error increase.
Embodiment 6
Step 4 in the embodiment 6 unlike embodiment 3）Middle bath temperature is 90 DEG C, and the reaction time is 60 min.
Fig. 6 is the AFM figures of the laminated film., it is clear that with the raising of reaction temperature from figure, during reaction
Between extension, the thickness of nano silver film increases, the increase of nano-Ag particles size, about 250 nm；The surface enhanced of the film
Substantially, nano-Ag particles are too reunited influences surface-enhanced Raman performance to hydraulic performance decline.
Claims (8)
1. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix, it is characterised in that specific steps are such as
Under：
A) preparation of Graphene derivative film：
(1) by Graphene derivative powder addition deionized water, the Graphene derivative of 0.1mg is added per mL deionized waters,
Ultrasonic 2h obtains the Graphene derivative aqueous solution；
(2) in being the 20% diallyl dimethyl ammoniumchloride aqueous solution by deionized water addition mass fraction, deionized water
It is 4 with the volume ratio of the diallyl dimethyl ammoniumchloride aqueous solution that mass fraction is 20%:1；
(3) pretreatment of substrate；
(4) will be dried up with deionized water rinsing, nitrogen after 20min in the pretreated substrate immersion Graphene derivative aqueous solution
Afterwards deionized water rinsing, repeat step are used in the diallyl dimethyl ammoniumchloride aqueous solution of immersion (2) configuration after 20min
(4) 0~10 times；
B) the Graphene derivative film obtained in step a) is put into aldehydes reducing agent aqueous solution vertically and is taken out after 20min,
Nitrogen is dried up；
C) configuration of silver ammino solution：Under agitation, the ammonia spirit that mass fraction is 2% is added dropwise to 0.2~
It is completely dissolved to precipitation in the silver salt solution of 0.8mol/L concentration；
D) the Graphene derivative film in step b) is put into the silver ammino solution of step c) configurations vertically, and at 50~90 DEG C
Water-bath in be incubated 10~60min, now, transparent Graphene derivative film surface forms one layer of nano silver film, go from
Sub- water is rinsed, and Nano Silver/Graphene derivative surface-enhanced Raman matrix is obtained after nitrogen drying.
2. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix as claimed in claim 1, it is special
Levy and be：Graphene derivative in (1) of step a) is graphene oxide, the Graphene of oxidation-chemical method reduction acquisition with
And any one in the Graphene after modification.
3. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix as claimed in claim 1, it is special
Levy and be：Involved substrate is any one in glass, quartz, indium oxide tin glass and printing paper in (3) of step a)
Kind；The pretreatment of the substrate refers to and for substrate to be cleaned by ultrasonic 5min in acetone, ethanol, deionized water successively, dried up with nitrogen.
4. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix as claimed in claim 1, it is special
Levy and be：Repeat step (4) numbers range is 2~4 times in (4) of step a).
5. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix as claimed in claim 1, it is special
Levy and be：Aldehydes reducing agent is glucose, mannose, galactolipin, any one in lactose and maltose in step b)；Aldehydes
The concentration of reducing agent aqueous solution is 10mg/mL.
6. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix as claimed in claim 1, it is special
Levy and be：Silver salt is any one in silver nitrate, silver acetate, silver perchlorate and silver orthophosphate in step c).
7. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix as claimed in claim 6, it is special
Levy and be：The scope of the silver nitrate concentration described in step c) is 0.2~0.4mol/L.
8. the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix as claimed in claim 1, it is special
Levy and be：Bath temperature scope in step d) is 60~80 DEG C, and soaking time scope is 20~30min.
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| CN108906006A (en) * | 2018-07-13 | 2018-11-30 | 北京欧美中科学技术研究院 | It is a kind of can efficient absorption formaldehyde modified graphene sponge preparation method |
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