CN104259475A - Preparation method of nano-silver/graphene derivative surface enhanced Raman substrate - Google Patents
Preparation method of nano-silver/graphene derivative surface enhanced Raman substrate Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano-silver/graphene derivative surface enhanced Raman substrate. The preparation method is characterized by uniformly adsorbing a reducing agent such as glucose on the surface of a graphene derivative ultrathin film through the adsorption of the graphene derivative ultrathin film, and growing a nano-silver thin film on the surface of the graphene derivative ultrathin film through the silver mirror reaction. The growth of the nano-silver thin film and the particle size and distribution of nano-silver are regulated and controlled by controlling the number of layers of the graphene derivative thin film and the concentration of a silver ammonia solution. The surface Raman enhanced performance of a composite film is regulated and controlled through the number of layers of the graphene derivative thin film and the morphology of the nano-silver thin film. Finally, a technological parameter of the optimal Raman enhanced performance is obtained.
Description
Technical field
The present invention relates to Molecular Spectral Analysis detection field, be specifically related to the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix.
Background technology
Raman spectrum belongs to molecular vibration spectrum, is the fingerprint of material molecule, and the Raman spectrometer made according to Ramam effect may be used for accurate Qualitive test sample.The analytical method of Raman spectrum does not generally need to carry out pre-treatment to sample, and it is easy and simple to handle in analytic process, minute is short, it is a kind of technology simultaneously can carrying out qualitative and quantitative analysis to sample, at environment, biological, historical relic, chemical industry, the fields such as food have application prospect very widely.But it is lower that its shortcoming is sensitivity, especially when detecting the biological sample of more complicated.When low concentration, normal Raman spectroscopy is insensitive to the deleterious molecular of extremely low concentration in liquid, cannot effectively be detected.The discovery of surface enhanced Raman technique, causes the world and pays close attention to widely.This is because surface enhanced Raman technique can have a huge vibration signal, its intensity is made to improve more than 10 orders of magnitude.
Nano Silver has excellent Raman enhancement effect, and is widely used on Raman enhancing probe, and the technique preparing Nano Silver Raman reinforcing material at present has a lot, such as: chemical method reducing nano-silver, and electron beam lithography, nanosphere etching, vacuum vapor deposition method etc.; Then these processing steps are loaded down with trivial details, complicated, relate to high temperature, and cost is higher, and oxidizable even to environment.In order to overcome above-mentioned problem, people generally by nano-silver loaded on a suitable carrier, obtain nano silver-group composite.This composite effectively can improve the surface-enhanced Raman performance of Nano Silver, reduces costs, and improves its stability.
Graphene (Graphene) is the Two-dimensional Carbon atomic crystal of monoatomic thickness, Graphene and the large specific area of its derivative and layer structure have become the excellent template of preparation nano material, by in-situ synthesis, can effectively prevent the reunion of nano particle from obtaining homodisperse nano particle-graphene composite material.Such as: the people such as Xu utilize silver mirror reaction liquid phase method to obtain Nano Silver-graphene solution, and then obtain laminated film by vacuum filtration, this film has obvious surface-enhanced Raman performance; Utilize graphene oxide for template Adsorption For Ag ion is then by also obtaining Nano Silver-graphene complex after a series of reducing agent reduction, " Small ", CN 102554255 B discloses a kind of preparation method of silver nanoparticle/graphene composite material, it is characterized in that by using the method for ultrasonic stripping expanded graphite to prepare Graphene in nmp solution, then, in the nmp solution of this Graphene, tannic acid direct-reduction Ag is used
+, growth in situ Ag nano particle on Graphene, obtains silver/graphite alkene nano composite material.The method complex process is loaded down with trivial details, is unfavorable for suitability for industrialized production.CN103334096 A discloses a kind of method of nano-silver-graphenecomposite composite film, it first obtains silver ion-graphene composite thin film by vacuum filtration method, then at high temperature heat treatment reduction obtains nano-silver-graphenecomposite composite film under hydrogen and argon gas mist, this film has excellent surface-enhanced Raman performance, but the method cost is high, well cannot control size and the domain size distribution of nano-Ag particles, this is very large to performance impact.In addition, although our seminar finds that solvent method can obtain nano-silver-graphenecomposite composite film, but its surface-enhanced Raman performance is subject to many factors impact and cannot obtains excellent effect.Such as, Nano Silver not only makes the Raman signal of target molecule strengthen, and equally also strengthens the Raman signal of graphene base body itself, and the Graphene signal of enhancing can cover the Raman signal of target molecule, causes the sensitivity of composite to decline.Equally, the surface-enhanced Raman performance of the bright graphene sheet layer of the testimony of a witnesies such as Zhou is relevant with its number of plies, more its hydraulic performance declines " JACS " of the number of plies.But the people such as Xie study and find that graphene sheet layer has excellent photoluminescence quenching performance and strong adsorptivity, make it have obvious surface-enhanced Raman performance " JACS ".If the thickness of Graphene therefore effectively can be controlled, again can good loaded with nano Argent grain, high-sensitive surface-enhanced Raman matrix will be prepared.CN 102515560 A discloses the method that one prepares Graphene/Ag composite conductive thin film, it is characterized in that in order to graphene oxide/silver sol be presoma, obtains transparent conductive film after adopting czochralski method, heat treatment.CN 102849730 A discloses a kind of method preparing nanometer silver-graphene bionic nanostructure composite film, it is characterized in that adopting electrostatic self-assembled technique that Nano Silver and graphene oxide are assembled into laminated film, eventually pass heat treatment and obtain Nano Silver/graphene composite film.Two patents of invention all belong to the category that nano-silver-graphenecomposite composite film is prepared in self assembly, can control the thickness of graphene film, but the uncontrollable nano-Ag particles size of the method, and sensitivity is low.And if Graphene THICKNESS CONTROL is very low, cause the amount of Nano Silver also to reduce, its surface-enhanced Raman hydraulic performance decline.In addition, silver mirror reaction prepares the most traditional handicraft of silverskin, but Ag films prepared by the method is blocked up.CN 101187017 A discloses the method preparing silver nano antibacterial material, it is characterized in that carrying out pretreatment with aluminum salt solution to substrate; To be dipped in silver mirror reaction liquid through pretreated described substrate, reaction obtains nano silver film.But this invention is still conventional silver mirror reaction, nano silver film poor stability, and pile up serious on aluminium flake, cost is high.CN 103103511 A and CN 101856035 A discloses a kind of method utilizing silver mirror reaction to prepare silicon face morphology controllable nano silver particles, by silver to the corrasion of monocrystalline silicon thus at silicon face formation nano-Ag particles.But this complex process, its etching acid has very strong corrosivity, contaminated environment.
Above-mentioned Nano Silver and nano-silver-graphenecomposite composite film synthetic method and there is following technological deficiency in surface-enhanced Raman application:
1, use partial chemical solvent, surfactant, reducing agent etc. in building-up process and there is toxicity, there is very large problem of environmental pollution;
2, building-up process may in higher temperature, longer time, and energy consumption is larger;
3, more difficult to the size regulation and control of nano-Ag particles in complex matrix, the optimum size meeting performance cannot be reached.
4, the matrix material of some laminated films, as organic matrix can affect the performance of surface-enhanced Raman, makes its sensitivity and accuracy decline;
5, in laminated film, nano-Ag particles spacing is difficult to control, and affects its performance.
5, for current Nano Silver/Graphene complex matrix, the impact of Graphene on performance cannot be optimized.
In order to overcome prior art defect, the present inventor, on the basis of summing up prior art, by lot of experiments, completes the present invention.
Summary of the invention
The present invention relates to the preparation method of a kind of Nano Silver/Graphene derivative surface-enhanced Raman matrix, it is characterized in that the adsorptivity utilizing Graphene derivative ultrathin membrane, by aldehydes reducing agent uniform adsorption in surface, silver mirror reaction is utilized to go out nano silver film in the superficial growth of Graphene derivative ultrathin membrane.By controlling the Graphene derivative film number of plies, the concentration of silver ammino solution and the temperature and time of silver mirror reaction are to the growth of nano silver film, and nano-Ag particles size, distribution regulate and control, thus the surface Raman enhancement performance of its laminated film is regulated and controled, the final base film obtaining the surface-enhanced Raman performance with excellence.
Solve the problems of the technologies described above adopted technical scheme to be made up of following step:
A) preparation of Graphene derivative film:
(1) add in deionized water by Graphene derivative powder, every mL deionized water adds the Graphene derivative of 0.1 mg, and ultrasonic 2 h obtain the Graphene derivative aqueous solution.
(2) deionized water being added mass fraction is obtain the PDDA aqueous solution in the PDDA of 20 %, deionized water and quality
Mark is the volume ratio of 20 % PDDA is 4:1.
(3) pretreatment of substrate: substrate is cleaned 5 min in acetone, ethanol, deionized water for ultrasonic successively, blows with nitrogen
Dry.
(4) pretreated substrate to be immersed in the Graphene derivative aqueous solution after 20 min and to dry up in the PDDA aqueous solution that rear immersion (2) configures use deionized water rinsing after 20 min with deionized water rinsing, nitrogen, repeat this step 0 ~ 10 time.
B) take out after the Graphene derivative film obtained in step a) vertically being put into the aldehydes reducing agent aqueous solution 20 min, nitrogen dries up, and aldehydes concentration of aqueous solution is 10 mg/mL.
Mass fraction is that the ammonia spirit of 2 % dropwise joins in the silver salt solution of 0.2 ~ 0.8 mol/L concentration and dissolves completely to precipitation by the c) configuration of silver ammino solution: under agitation.
D) the Graphene derivative film in step b) is vertically put into the silver ammino solution of step c) configuration, and 10 ~ 60 min are incubated in the water-bath of 50 ~ 90 DEG C, now, transparent graphite oxide film surface forms one deck nano silver film, deionized water rinsing, nitrogen dries up rear obtained Nano Silver/Graphene derivative surface-enhanced Raman matrix.
In the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix step a) (1) in Graphene derivative be Graphene derivative, oxidation-chemical method reduction obtain Graphene and modify after Graphene in any one.
Substrate involved in (3) of step a) is any one in glass, quartz, indium oxide tin glass and printing paper.
Repeat this number of steps in (4) of step a) and range preferably from 2 ~ 4 times.
In the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix, in step b), aldehydes reducing agent is glucose, mannose, galactolipin, any one in lactose and maltose.
In the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix, in step c), silver salt is any one in silver nitrate, silver acetate, silver perchlorate, silver orthophosphate.
Silver nitrate concentration in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix described in step c) range preferably from 0.2 ~ 0.4 mol/L.
Bath temperature in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix in step d) ranges preferably from 60 ~ 80 DEG C, and temperature retention time ranges preferably from 20 ~ 30 min.
Described in the preparation method of Nano Silver of the present invention/Graphene derivative surface-enhanced Raman matrix, laminated film is mainly used in Homeland Security, environmental monitoring, food security, the fields such as material foundation research and health care.
The present invention compared with prior art, tool has the following advantages and beneficial effect: the preparation method of Nano Silver of the present invention/Graphene derivative surface enhanced Raman substrate, adopt the silver mirror reaction improved, take Graphene derivative as matrix uniform adsorption aldehyde radical carbohydrate reducing agent, and Nano Silver is reverted on Graphene derivative matrix and obtain Nano Silver/Graphene derivative matrix.This preparation method is simple, and fast, green and cost is low, the Nano Silver size obtained and distribution meet the requirement of surface-enhanced Raman matrix.Overcome prepare at present nano silver material technique high cost, complicated, the shortcomings such as pollution.This method of the present invention effectively can also control the thickness of Graphene derivative, the photoluminescence quenching of Graphene derivative excellence can be given full play to, strong adsorptivity and surface-enhanced Raman performance, thus the surface-enhanced Raman performance significantly improving laminated film further.For promoting that surface enhanced Raman technique is at Homeland Security further, environmental monitoring, the field such as food security and health care is more widely used and provides condition.
Accompanying drawing explanation
Fig. 1 is the AFM figure of nano silver film prepared by embodiment 1.
Fig. 2 is the AFM figure of the laminated film obtained in (a) embodiment 2; The surface-enhanced Raman performance of (b) laminated film.
Fig. 3 is the AFM figure of the laminated film obtained in (a) embodiment 3; The surface-enhanced Raman performance of (b) laminated film.
Fig. 4 is the AFM figure of the laminated film obtained in (a) embodiment 4; The surface-enhanced Raman performance of (b) laminated film.
The AFM figure of the laminated film of Fig. 5 embodiment 5.
The AFM figure of the laminated film of Fig. 6 embodiment 6.
Detailed description of the invention
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1
Graphene derivative film contributes to absorption carbohydrate reducing agent, and provides site for the growth of nano-Ag particles, and therefore, Graphene derivative serves vital effect; Embodiment 1 prepares nano silver film by silver mirror reaction with reference to forefathers' experience on the quartz substrate not having Graphene derivative film.Its experimental procedure is as follows:
1) pretreatment of quartz substrate: quartz substrate is cleaned 5 min in acetone, ethanol, deionized water for ultrasonic successively, dries up with nitrogen.
2) vertically immersed by the quartz substrate in step 1) in the D/W of 10 mg/mL and take out after 20 min, nitrogen dries up.
3) mass fraction is that the ammonia spirit of 2 % dropwise joins in the silver salt solution of 0.4 mol/L concentration and dissolves completely to precipitation by the configuration of silver ammino solution: the configuration of silver ammino solution: under agitation.
4) by step 2) in quartz substrate vertically put into step 3) configuration silver ammino solution, and in the water-bath of 80 DEG C, be incubated 30 min, now, transparent quartz substrate forms one deck nano silver film, deionized water rinsing, nitrogen dries up rear obtained Nano Silver/Graphene derivative surface-enhanced Raman matrix
It is dimmed that reaction terminates rear transparent quartz substrate, and have decorative pattern, and we characterize the pattern of film with AFM.
Nano-Ag particles growth is at substrate surface as can see from Figure 1, but distribution of particles is sparse, and particle size is about 40 nm, and the surface-enhanced Raman performance of this film is very weak.
embodiment 2
Embodiment 2 and not being both of embodiment 1 first substrate will plate Graphene derivative film.Concrete steps are as follows:
A) preparation of Graphene derivative-graphene oxide film:
(1) join in deionized water by graphene oxide powder, every mL adds the graphene oxide of 0.1 mg, and ultrasonic 2 h obtain graphene oxide colloidal solution.
(2) deionized water being added mass fraction is in the PDDA of 20 %, and the volume ratio of deionized water and 20 % PDDA is 4:1.
(3) pretreatment of quartz substrate: quartz substrate is cleaned 5 min in acetone, ethanol, deionized water for ultrasonic successively, dries up with nitrogen.
(4) pretreated quartz substrate is immersed in graphene oxide solution to dry up in rear immersion PDDA colloidal sol with deionized water rinsing, nitrogen after 20 min and use deionized water rinsing after 20 min, repeat this step 1 time.
B) take out after the graphene oxide film obtained in step a) vertically being put into D/W 20 min, nitrogen dries up; D/W concentration is 10 mg/mL.
Mass fraction is that the ammonia spirit of 2 % dropwise joins in the silver salt solution of 0.4 mol/L concentration and dissolves completely to precipitation by the c) configuration of silver ammino solution: the c) configuration of silver ammino solution: under agitation.
D) graphene oxide film in step b) is vertically put into the silver ammino solution of step c) configuration, and in the water-bath of 80 DEG C, be incubated 30 min, now, transparent graphite oxide film surface forms one deck nano silver film, deionized water rinsing, nitrogen dries up rear obtained Nano Silver/surface of graphene oxide and strengthens Raman matrix.
The AFM that Fig. 2 (a) is Nano Silver/graphene oxide film schemes, and in comparative example 1, AFM figure, obviously can see that Nano Silver is evenly distributed on the graphene oxide lamella of fold, the quantity also showed increased of particle.The size of nano-Ag particles drops to 30 nm, but grain spacing is from reducing to some extent.
The crystal violet surface-enhanced Raman figure that Fig. 2 (b) is this laminated film, this film has obvious Raman-enhancing energy as we can see from the figure, and its surface Raman enhancement factor is 2*10
4.
In conjunction with the embodiments in 1, we can draw, the formation of graphene oxide to Nano Silver has a huge impact; The growth existing for nano-Ag particles of graphene oxide film improves site, and its large specific area and strong adsorptivity can adsorbent-reductant and surfaces, better reducing nano-silver and surface, thus improve the performance of film.
embodiment 3
As different from Example 2, in embodiment 3 step a) in (4) repeat this step 2 time.
The AFM that Fig. 3 (a) is this laminated film schemes, and nano-Ag particles uniform fold lives whole quartz substrate surface as we can clearly see from the figure, and nanoparticle size increases to 75 nm.
The crystal violet molecular surface that Fig. 3 (b) is this laminated film strengthens Raman figure, and the performance of this film is greatly improved as we can see from the figure, and its surface Raman enhancement factor brings up to 1.2*10
8.
Embodiment 3 again demonstrates the growth that graphene oxide film affects nano-Ag particles; Comparative example 1 and 2, and the performance of the laminated film of embodiment 3 is greatly enhanced.This size be not only because of nano-Ag particles increases, increasing number, and grain spacing is from reducing, and also because the photoluminescence quenching performance of graphene oxide excellence, strong adsorptivity can improve the surface-enhanced Raman performance of laminated film further.
embodiment 4
As different from Example 2, in embodiment 4 step, this step 3 time is repeated in (4) a).
The AFM that Fig. 4 (a) is this laminated film schemes, as we can see from the figure with similar pattern in embodiment 3.
The crystal violet surface-enhanced Raman figure that Fig. 3 (b) is this laminated film.Calculating its surface Raman enhancement factor is 3.3*10
7.Comparative example 1 ~ 3 can find out, graphene oxide film is not only very large to the growth effect of nano silver film, but also affects its surface-enhanced Raman performance; The increase of graphene oxide film thickness makes surface-enhanced Raman performance decrease; This is because Nano Silver is the key of surface-enhanced Raman performance, while the Raman signal increasing crystal violet molecule, also increase the signal of graphene oxide itself; The Raman signal of graphene oxide increased can cover the purple Raman signal of partially crystallizable, thus causes the surface-enhanced Raman performance of laminated film to decline to some extent, and along with the increase of film thickness, declines more obvious.
embodiment 5
In embodiment 5 step, c) concentration of silver nitrate is 0.8 mol/L as different from Example 3.
Fig. 5 is the AFM figure of this laminated film, the result of comparative example 3, and we can see that nano-Ag particles becomes columnar growth at matrix surface, and particle size rises to 200 nm; The raising of silver nitrate concentration makes nano-Ag particles reunite and forms bulky grain, but intergranular distance but increases, nano-Ag particles skewness, therefore makes the reappearance of the surface-enhanced Raman performance of this film, and error increases.
Embodiment 6
Be 90 DEG C unlike bath temperature in step 4) in embodiment 6 in embodiment 3, the reaction time is 60 min.
Fig. 6 is the AFM figure of this laminated film.Can see clearly from figure, along with the raising of reaction temperature, the prolongation in reaction time, the thickness of nano silver film increases, and nano-Ag particles size increases, and is about 250 nm; The surface enhanced hydraulic performance decline of this film is obvious, and nano-Ag particles is too reunited affects surface-enhanced Raman performance.
Claims (9)
1. the preparation method of Nano Silver/Graphene derivative surface-enhanced Raman matrix, it is characterized in that: the adsorptivity utilizing Graphene derivative ultrathin membrane, by aldehydes reducing agent uniform adsorption in surface, silver mirror reaction is utilized to go out nano silver film in the superficial growth of Graphene derivative ultrathin membrane; By controlling the Graphene derivative film number of plies, the concentration of silver ammino solution and the temperature and time of silver mirror reaction are to the growth of nano silver film, and nano-Ag particles size, distribution regulate and control, thus the surface Raman enhancement performance of its laminated film is regulated and controled, the final base film obtaining the surface-enhanced Raman performance with excellence.
2. the preparation method of a kind of Nano Silver as claimed in claim 1/Graphene derivative surface-enhanced Raman matrix, is characterized in that concrete steps are as follows:
A) preparation of Graphene derivative film:
(1) add in deionized water by Graphene derivative powder, every mL deionized water adds the Graphene derivative of 0.1 mg, and ultrasonic 2 h obtain the Graphene derivative aqueous solution;
(2) deionized water being added mass fraction is obtain the PDDA aqueous solution in the PDDA of 20 %, deionized water and matter
Amount mark is the volume ratio of 20 % PDDA is 4:1;
(3) pretreatment of substrate;
(4) pretreated substrate to be immersed in the Graphene derivative aqueous solution after 20 min and to dry up in the PDDA aqueous solution that rear immersion (2) configures use deionized water rinsing after 20 min with deionized water rinsing, nitrogen, repeat this step 0 ~ 10 time;
B) take out after the Graphene derivative film obtained in step a) vertically being put into the aldehydes reducing agent aqueous solution 20 min, nitrogen dries up;
Mass fraction is that the ammonia spirit of 2 % dropwise joins in the silver salt solution of 0.2 ~ 0.8 mol/L concentration and dissolves completely to precipitation by the c) configuration of silver ammino solution: under agitation;
D) the Graphene derivative film in step b) is vertically put into the silver ammino solution of step c) configuration, and 10 ~ 60 min are incubated in the water-bath of 50 ~ 90 DEG C, now, transparent graphite oxide film surface forms one deck nano silver film, deionized water rinsing, nitrogen dries up rear obtained Nano Silver/Graphene derivative surface-enhanced Raman matrix.
3. the preparation method of a kind of Nano Silver as claimed in claim 2/Graphene derivative surface-enhanced Raman matrix, it is characterized in that: the Graphene derivative in (1) of step a) is Graphene derivative, oxidation-chemical method reduction obtain Graphene and modify after Graphene in any one.
4. the preparation method of a kind of Nano Silver as claimed in claim 2/Graphene derivative surface-enhanced Raman matrix, it is special
Levy and be: substrate involved in (3) of step a) is any one in glass, quartz, indium oxide tin glass and printing paper; The pretreatment of described substrate refers to substrate to clean 5 min in acetone, ethanol, deionized water for ultrasonic successively, dries up with nitrogen.
5. the preparation method of a kind of Nano Silver as claimed in claim 2/Graphene derivative surface-enhanced Raman matrix, it is special
Levy and be: repeat this number of steps in (4) of step a) and range preferably from 2 ~ 4 times.
6. the preparation method of a kind of Nano Silver as claimed in claim 2/Graphene derivative surface-enhanced Raman matrix, it is special
Levy and be: in step b), aldehydes reducing agent is glucose, mannose, galactolipin, any one in lactose and maltose; The concentration of the aldehydes reducing agent aqueous solution is 10 mg/mL.
7. the preparation method of a kind of Nano Silver as claimed in claim 2/Graphene derivative surface-enhanced Raman matrix, it is special
Levy and be: in step c), silver salt is any one in silver nitrate, silver acetate, silver perchlorate and silver orthophosphate.
8. the preparation method of a kind of Nano Silver as claimed in claim 2/Graphene derivative surface-enhanced Raman matrix, it is special
Levy and be: the scope of the silver nitrate concentration described in step c) is 0.2 ~ 0.4 mol/L.
9. the preparation method of a kind of Nano Silver as claimed in claim 2/Graphene derivative surface-enhanced Raman matrix, it is special
Levy and be: the bath temperature scope in step d) is 60 ~ 80 DEG C, temperature retention time scope is 20 ~ 30 min.
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| CN108593607A (en) * | 2018-01-12 | 2018-09-28 | 中国计量大学 | A kind of preparation method of nickel foam/GO/ nano silver SERS substrates |
| CN108535235A (en) * | 2018-04-02 | 2018-09-14 | 湖南大学 | A kind of SERS test strips and preparation method thereof, application |
| CN108535235B (en) * | 2018-04-02 | 2021-06-08 | 湖南大学 | SERS test strip and preparation method and application thereof |
| CN109001178A (en) * | 2018-06-26 | 2018-12-14 | 中国科学院合肥物质科学研究院 | Surface enhanced Raman scattering detects device and preparation method thereof |
| CN109001178B (en) * | 2018-06-26 | 2020-09-25 | 中国科学院合肥物质科学研究院 | Surface enhanced Raman scattering detection device and preparation method thereof |
| 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 |
| CN109722881A (en) * | 2018-12-14 | 2019-05-07 | 杭州纳尔森精细化工有限公司 | A kind of medical antistatic new textile |
| CN110028689A (en) * | 2019-03-06 | 2019-07-19 | 宁波大学 | A kind of preparation method of graphene oxide membrane/poly 4 vinyl pyridine/three-dimensional flower-shaped micron silver composite material |
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