CN106365159A - Silver nanoparticle-carbon nanotube embedded graphene oxide composite film, and preparation method and application thereof - Google Patents
Silver nanoparticle-carbon nanotube embedded graphene oxide composite film, and preparation method and application thereof Download PDFInfo
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- CN106365159A CN106365159A CN201610810543.9A CN201610810543A CN106365159A CN 106365159 A CN106365159 A CN 106365159A CN 201610810543 A CN201610810543 A CN 201610810543A CN 106365159 A CN106365159 A CN 106365159A
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- G—PHYSICS
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
Abstract
The invention discloses silver nanoparticle-carbon nanotube embedded graphene oxide composite film, and a preparation method and application thereof; the film is made mainly by orderly stacking hexadecyl trimethyl ammonium bromide functionalized silver nanoparticles, diallyldimethylammonium chloride functionalized carbon nanotubes, and graphene oxide; preparation methods of three materials are provided, wherein the silver nanoparticles provide SERS (surface enhanced Raman scattering) signal enhancement, the carbon nanotubes form special nano passages in the film, and filtering rate of a sample to be tested is effectively increased; an SERS substrate based on the composite film can be combined with a portable Raman spectrometer to provide rapid enrichment detection for antibiotic residues of different types in water, and a new means of field emergency detection is provided for antibiotic pollution events.
Description
Technical field
The present invention relates to a kind of embedded graphene oxide (go) of nano grain of silver (ag nps)-CNT (cnts) is combined
Thin film, using the nano grain of silver with positive charge, CNT and the graphene oxide with negative charge, prepares and has simultaneously
The graphene oxide film that fast enriching and Raman enhancement effect are integrated.This thin film can combined type portable Raman spectrometer,
Quick, sensitive, online, real-time, live or in-situ study are carried out to antibiotic remainss in environment, is particularly suited in water environment anti-
The Emergent detection demand of raw element residue detection, belongs to inorganic functional material technical field.
Background technology
Antibiotic is the medicine for preventing and treating infectious disease, is widely used and plays in medical treatment and animal husbandry
Irreplaceable effect.However, widely using, even abusing due to antibiotic in recent years, cause a large amount of active compounds and its spread out
Biology enters environment by various modes, and in induced environment, organism is sensitive to it, leads to the generation of drug resistant gene, serious threat
To health and ecological safety, have aroused widespread concern in all circles of society.It is commonly used for detecting antibiotic remainss in environment
Method includes GC-MS (gc-ms), tablets by HPLC-MS (hplc-ms), enzyme linked immunological
Analytic process.But, these methods all have some limitations, such as: pre-treatment is relatively complicated；Typically require to example enrichment
Or just can be detected after concentrating；Required instrument heaviness costliness, poor, the detection cycle length of portability etc. it is difficult to satisfaction live for
Quick, the sensitive detection demand of antibiotic remainss.
At present, surface enhanced raman spectroscopy (surface-enhanced raman scattering, sers) spectrum is in ring
Border contamination accident context of detection has good application prospect, and it is that a kind of analysis from molecular level is adsorbed in coarse noble metal
The characterization technique of surface species, has that detection time is short, sensitivity is high, water interference is little, required sample size is few, be provided that molecule refers to
The advantages of stricture of vagina information.It is to construct high-performance sers active nano structure that sers technology realizes one of wide variety of important prerequisite,
Research finds, Nano silver grain is the best nano material of sers performance in known noble metal, and Graphene has preferably
Sers to strengthen performance, so nano-silver-graphenecomposite composite film can be prepared as sers substrate.But this laminated film one side
There is silver nano-grain and be easy to reunite in face, on the other hand the problem of impact sers substrate performance has in water environment the anti-of residual
Raw element concentration is low, strengthens the problem that substrate surface is difficult to detect because adsorbance is few.Therefore, need one kind badly be applied to water environment
Antibiotics leftover detection, and the high technology of easy quick, low cost, sensitivity.
Content of the invention
For above-mentioned existing technical problem, the present invention provides the graphite oxide that a kind of nano grain of silver-CNT embeds
Alkene laminated film, mating surface strengthens Raman scattering (sers) technology, realizes carrying out scene to the antibiotic remainss in water environment
Quickly, the purpose of Sensitive Detection.
For achieving the above object, first, the present invention provides the graphene oxide that a kind of nano grain of silver-CNT embeds multiple
Close the preparation method of thin film, including the raw material of following mass parts: the Yin Na of cetyl trimethylammonium bromide (ctab) functionalization
1 part of the grain of rice (ag nps), 1 part of the CNT (cnts) of diallyl dimethyl ammoniumchloride (pdda) functionalization, oxidation stone
4 parts of black alkene (go), is superimposed film forming through orderly, specifically comprises the following steps that
(1) ag nps aqueous dispersions, the go aqueous dispersions of ctab functionalization are prepared respectively；Further, water is prepared using ultrasonic method
Dispersion liquid；
(2) in go aqueous dispersions, first stirring adds pdda functionalization cnts, and the ag nps moisture adding ctab functionalization dissipates
Liquid, and mix homogeneously；Further, described mixing requires stirring at least 10 min, or ultrasonic at least 5 min；
(3) with reference to filter paper, mixed liquor is filtered using vacuum filtration pump, be dried, that takes off from filter paper is silver nanoparticle
The graphene composite thin film that grain-CNT embeds；Further, the fenestra of described filter paper is that 0.2 mm, porosity are
10%th, effective filtering area area is 12 ~ 16 cm2；Described drying is that 5 ~ 10 mins are dried in 30 ~ 50 DEG C of vacuum drying oven.
Above-mentioned preparation method realizes constructing of the graphene oxide film that nano grain of silver-CNT embeds, and ctab work(
Ag nps, pdda functionalization cnts of energyization and tri- kinds of primary raw materials of go, can be obtained in the following manner.First, it is described
The concrete preparation process of the ag nps of ctab functionalization is as follows:
A-1, prepare crystal seed: prepare agno3With the mixed solution of sodium citrate, it is added dropwise over thereto with vigorous stirring
nabh4Solution, solution is changed into glassy yellow at once, and agno3, sodium citrate, nabh4Mass ratio be 65 ~ 70:20:1；Then hold
Continue stirring 1 h aging 7 days, prepared silver nanoparticle seed solution；
A-2, reduction reaction: prepare agno3With the mixed solution of ctab, it is added thereto to l- ascorbic acid, and agno3, 16
Alkyl trimethyl ammonium bromide, the mass ratio of l- ascorbic acid are 5:4 ~ 5:10 ~ 11；It is subsequently added silver nanoparticle seed solution 1 ~ 2
Ml, adjusting ph value is 13, promotes nano grain of silver to grow；It is centrifuged after stirring, obtain the ag nps of ctab functionalization；Enter one
Step, the time of described stirring is 30 min；The rotating speed of described centrifugation is 6000 rpm, and the time is 15 min.
Second, the concrete preparation process of described pdda functionalization cnts is as follows:
B-1, configuration pdda aqueous solution, are added thereto to CNT, prepared carbon nano tube dispersion liquid, and polydiene dimethylamine
Ammonium chloride, the mass ratio of CNT are 1:1 ~ 2；Further, using ultrasonic method dispersing Nano carbon tubes；
B-2, dispersion liquid are through filtering, washing, be dried, prepared pdda functionalization cnts；Further, described drying is at 60 ~ 70 DEG C
Vacuum drying oven in be dried 20 ~ 24 h.
Third, the concrete preparation process of described go is as follows:
C-1, pretreatment: add graphite powder, potassium peroxydisulfate, phosphorus pentoxide in concentrated sulphuric acid, stir 4.5 h at 80 DEG C, and
Graphite powder, potassium peroxydisulfate, the mass ratio of phosphorus pentoxide are 6:5:5 ~ 5.5, and the volume of concentrated sulphuric acid is calculated as with the quality of graphite powder
4.8~5.5ml/g；Then dilute, sucking filtration, wash to neutrality, be dried at room temperature for 12 h, obtain pre-oxidizing graphite powder；Enter one
Step, described sucking filtration adopts 0.2 μm of Merlon vacuum filtration；
C-2, oxidation reaction: add pre-oxidation graphite powder in concentrated sulphuric acid, stir at 0 DEG C；Then it is added thereto to height
Potassium manganate, reacts 2 h at 35 DEG C, dilution, dilutes again, be subsequently added into 30% h after sustained response 2 h2o2, mixed liquor leaves change
For glassy yellow；Wherein, pre-oxidation graphite powder, the mass ratio of potassium permanganate are 1:5 ~ 6, and the volume of concentrated sulphuric acid is to pre-oxidize graphite powder
Quality be calculated as 40 ~ 42 ml/g, h2o2Volume 6 ~ 8 ml/g are calculated as with the quality pre-oxidizing graphite powder；
C-3, post processing: by the centrifugation simultaneously pickling of glassy yellow mixed liquor, then be centrifuged and wash, be dried 2 days at 60 DEG C, obtain go；
Further, described pickling adopts 10% hydrochloric acid solution to wash 2-3 time.
Secondly, the present invention provides the oxidation stone that nano grain of silver-CNT that a kind of employing said method is obtained embeds again
Black alkene laminated film, provides new material for sudden antibiotic contamination accident scene Emergent detection.Wherein: graphene oxide has
Preferably sers to strengthen performance, it strengthens mechanism and causes mainly due to electric charge transfer between graphene oxide and tested molecule
Chemical enhancement effect；Nano grain of silver in graphene oxide layer plays the effect of sers signal enhancing, and it strengthens mechanism and comes from
The local electric field enhancement effect that silver surface plasma resonance produces；CNT is receiving by the curling of sheet Graphene
Rice material, has higher absorbability, it is special to be embedded in graphene oxide layer and be internally formed in laminated film
Nanochannel, plays the effect effectively improving testing sample filtering rate.
Based on this, present invention also offers the oxygen that a kind of nano grain of silver-CNT of employing said method preparation embeds
The application of graphite alkene laminated film, that is, be applied to the detection of antibiotic remainss in water environment.This laminated film is i.e. as sers
Substrate, can collect graphene oxide and the Chemical enhancement effect of CNT and the physics enhancement effect of nano grain of silver is one
There is pi-pi accumulation effect, on the one hand this can between body, and graphene oxide and CNT and the phenyl ring of antibiotic molecule
Solve the problems, such as silver nano-grain reunite, on the other hand can solve the problem that in water body, antibiotic concentration is low, strengthen substrate surface because
Adsorbance is few and is difficult to the problem detecting, so this laminated film can realize fast enriching and high-sensitive to antibiotic molecule
Sers detects.Therefore, the sers substrate combined type portable Raman spectrometer of this laminated film, it is possible to achieve antibiotic in water environment
Residual the detection of quick, sensitive, online, real-time, live or in-situ study.
Compared with prior art, the graphene composite thin film that the nano grain of silver-CNT of present invention preparation embeds,
The use of joint Portable Raman spectrometer, has as follows a significantly advantage:
1st, this laminated film has stronger sers enhancement effect, effectively increases the sensitivity of detection method；
2nd, this laminated film is uniform and stable, and has good sers signal reproducibility it is ensured that live real-time detection result
Stable；
3rd, this laminated film has high accumulation ability to the antibiotic in water environment, especially reaches nm rank to low concentration
Antibiotic, still can obtain obvious sers spectrogram, can quickly finish detection, and have extensive range.
In sum, the live fast qualitative of Antibiotics of Low Concentration, detection by quantitative in water body can be set up using the present invention
Antibiotic remainss different types of in environment are realized fast enriching detection by analytical technology system, are that paroxysmal antibiotic is dirty
The live Emergent detection of dye event provides new means.
Brief description
Fig. 1 is the optical photograph of go laminated film of the present invention；
Fig. 2 is the electron scanning micrograph of go laminated film of the present invention；
Fig. 3 is the sers spectrogram of the r6g that go laminated film of the present invention detects variable concentrations；
Fig. 4 is the repeated testing result figure of go laminated film of the present invention；
Fig. 5 is the sers spectrogram of the quadracycline that go laminated film of the present invention detects variable concentrations；
Fig. 6 is the sers spectrogram of the tetramycin hydrochloride that go laminated film of the present invention detects variable concentrations；
Fig. 7 is the sers spectrogram of the ampicillin that go laminated film of the present invention detects variable concentrations.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described, but does not constitute the concrete restriction to the present invention.
Embodiment 1: first prepare respectively and construct needed for the graphene composite thin film that nano grain of silver-CNT embeds
Raw material: ag nps, pdda functionalization cnts of ctab functionalization and go.
The method that the ag nps of a, ctab functionalization adopts seeded growth, on the stable silver nanoparticle seed of ctab, utilizes
Ascorbic acid reduction silver nitrate, to prepare, comprises the following steps that.
A-1, preparation comprise 0.068 g agno3, mixed solution 40 ml of 0.020 g sodium citrate, preparation comprises
0.001 g、nabh4Aqueous solution 5 ml, in mixed solution, while being stirred vigorously, be added dropwise over the nabh of fresh preparation4
Solution.Continuously stirred 1h aging 7 days again, aging for a long time is in order that nabh4Reducing power carry out completely, aging complete
After obtain a size of 5 ~ 10 nm silver nanoparticle seed solutions.
A-2, preparation comprise 0.052 g agno3, mixed solution 170 ml of 0.0416 g ctab, prepare comprise 0.104
Solution 6 ml of g l- ascorbic acid, adds l- ascorbic acid solution in mixed solution, is subsequently added silver nanoparticle seed solution 1
Ml, and add the naoh solution that 1ml, ph are 13 to adjust ph for 13, to realize the growth of nano grain of silver.After stirring 30 min, in
6000 rpm are centrifuged 15 min, to remove excessive ctab, obtain the ag nps of ctab functionalization, are redispersed in going of 40 ml
Aqueous dispersions are obtained in ionized water.
B, preparation pdda functionalization cnts, comprise the following steps that.
B-1, deionized water configuration comprise solution 400 ml of 100 mg pdda, then pass through ultrasonic method by 100 mg
CNT be dispersed therein, stable cnts dispersion liquid is obtained；
B-2, filtration gained dispersion liquid are simultaneously washed with deionized repeatedly, then 24 hs are dried in 60 DEG C of vacuum drying oven,
Obtain pdda functionalization cnts.
C, prepare graphene oxide film, comprise the following steps that.
C-1, pretreatment: 0.75 g graphite powder is added step-wise in 3.6 ml concentrated sulphuric acids, and adds 0.625 g persulfuric acid
Potassium, 0.625 g phosphorus pentoxide, mix at 80 DEG C, this mixture are maintained in the oil bath of 80 ° of c and stir 4.5 h, then
Dilute this mixed liquor with substantial amounts of deionized water.Then, with 0.2 μm of Merlon vacuum filter collecting reaction product, and spend
Ion water washing removes residual acid and 12 hs is dried until the ph value of filtrate close to neutrality, then under room temperature environment, is pre-oxidized
Powdered graphite.
C-2, oxidation: 0.7 g is pre-oxidized powdered graphite and adds 28 ml concentrated sulphuric acids and stir at 0 DEG C, when mixed
After compound is dispersed throughout, slowly careful thereto plus 3.5g potassium permanganate, whole reactant mixture is placed on 35 ° of c water
Bathe upper 2 h.Subsequently with 60 ml deionized water diluted mixtures, reaction adds 175 ml deionized waters, Ran Houhuan after continuing 2 h
The h of slow addition 4.2 ml 30%2o2, the color of mixed liquor immediately becomes glassy yellow.
C-3, post processing: will appear from jonquilleous mixed liquor centrifugation, and 10% hydrochloric acid solution washs 2 times.Afterwards by mixed liquor
Recentrifuge, deionized water is rinsed at least eight times so as to fully remove the metal ion in dispersion liquid and the acid remaining.Finally
Gains are dried 3 days under 60 ° of c, obtain graphene oxide.Take go ultrasonic 2 h in deionized water that 0.2 g prepares,
Obtain stable, that brown is transparent, concentration for 2 mg ml-1Go aqueous dispersions, stand-by.
By above-mentioned steps a, b, c be obtained the ag nps aqueous dispersions of required ctab functionalization, pdda functionalization cnts,
After go aqueous dispersions, in the go aqueous dispersions first 1.5 mg pdda functionalization cnts being added to 3 ml under conditions of stirring,
It is subsequently added into 12 ml, concentration is 0.125 mg ml-1The ag nps aqueous dispersions of ctab functionalization be mixed with stirring 10
min.Then, the filter paper filtering being 10 % using vacuum filtration pump with reference to fenestra 0.2 mm, porosity, its effective filtering area face
Amass as 12cm2.And 8 mins are dried in 40 DEG C of vacuum drying oven.Finally, will be multiple for the embedded go of Nano silver grain-CNT
Close thin film gently to take off from filter paper, target product as of the present invention.
Embodiment 2: first prepare the raw material needed for go laminated film: ag nps, pdda functionalization of ctab functionalization respectively
Cnts and go.
A, prepare the ag nps of ctab functionalization, comprise the following steps that.
A-1, preparation comprise 0.065 g agno3, mixed solution 40 ml of 0.020 g sodium citrate, preparation comprises
0.001 g、nabh4Aqueous solution 5 ml, in mixed solution, while being stirred vigorously, be added dropwise over 5 ml of fresh preparation
nabh4Solution.Continuously stirred 1h aging 7 days again, aging for a long time is in order that nabh4Reducing power carry out completely, aging
After the completion of obtain a size of 5 ~ 10 nm silver nanoparticle seed solutions.
A-2, preparation comprise 0.052 g agno3, mixed solution 170 ml of 0.046 g ctab, be added thereto to 6 ml
Concentration is the l- ascorbic acid solution of 0.1 m, is subsequently added silver nanoparticle seed solution 1.5 ml, and adds naoh solution to adjust ph
To 13, to realize the growth of nano grain of silver.After stirring 45 min, it is centrifuged 13 min in 6500rpm, to remove excessive ctab,
Obtain the ag nps of ctab functionalization, be redispersed in the deionized water of 40ml being obtained aqueous dispersions.
B, preparation pdda functionalization cnts, comprise the following steps that.
B-1, deionized water configuration comprise solution 400 ml of 65 mg pdda, then pass through ultrasonic method by 100 mg's
CNT is dispersed therein, and stable cnts dispersion liquid is obtained；
B-2, filtration gained dispersion liquid are simultaneously washed with deionized repeatedly, then 22 hs are dried in 65 DEG C of vacuum drying oven,
Obtain pdda functionalization cnts.
C, prepare graphene oxide film, comprise the following steps that.
C-1, pretreatment: 0.75 g graphite powder is added step-wise in 3.9 ml concentrated sulphuric acids, and adds 0.625 g persulfuric acid
Potassium, 0.66 g phosphorus pentoxide, mix at 80 DEG C, this mixture are maintained in the oil bath of 80 ° of c and stir 4.5 h, then
Dilute this mixed liquor with substantial amounts of deionized water.Then, with 0.2 μm of Merlon vacuum filter collecting reaction product, and spend
Ion water washing removes residual acid and 12 hs is dried until the ph value of filtrate close to neutrality, then under room temperature environment, is pre-oxidized
Powdered graphite.
C-2, oxidation: 0.7 g is pre-oxidized powdered graphite and adds 29 ml concentrated sulphuric acids and stir at 0 DEG C, when mixed
After compound is dispersed throughout, slowly careful thereto plus 3.85 g potassium permanganate, whole reactant mixture is placed on 35 ° of c
2 h in water-bath.Subsequently with 60 ml deionized water diluted mixtures, reaction adds 175 ml deionized waters, then after continuing 2 h
The slow h adding 4.9 ml 30%2o2, the color of mixed liquor immediately becomes glassy yellow.
C-3, post processing: will appear from jonquilleous mixed liquor centrifugation, and 10% hydrochloric acid solution washs 2 ~ 3 times.To mix afterwards
Liquid recentrifuge, deionized water is rinsed at least eight times so as to fully remove the metal ion in dispersion liquid and the acid remaining.?
Afterwards gains are dried 1.5 days under 63 ° of c, obtain graphene oxide.Take the go that 0.2 g prepares ultrasonic in deionized water
2 h, obtain stable, that brown is transparent, concentration for 2 mg ml-1Go aqueous dispersions, stand-by.
In the go aqueous dispersions first 1.3 mg pdda functionalization cnts being added to 3 ml under conditions of stirring, then
13 ml, concentration is added to be 0.1 mg ml-1Ctab functionalization ag nps aqueous dispersions uniform 5 min of ultrasonic mixing therewith.
Then, the filter paper filtering being 10 % using vacuum filtration pump with reference to fenestra 0.2 mm, porosity, its effective filtering area area is
14 cm2, and 5 mins are dried in 60 DEG C of vacuum drying oven.Finally, that gently takes off from filter paper is Nano silver grain-carbon
The go laminated film that nanotube embeds.
Embodiment 3: first distinguish ag nps, pdda functionalization cnts and the go of ctab functionalization.
A, prepare the ag nps of ctab functionalization, comprise the following steps that.
A-1, preparation comprise 0.07 g agno3, mixed solution 40 ml of 0.020 g sodium citrate, and comprise 0.001
g、nabh4Aqueous solution 5 ml, while being stirred vigorously, in mixed solution, be added dropwise over nabh4Solution.Continuously stirred again
1h aging 7 days, obtain a size of 5 ~ 10 nm silver nanoparticle seed solutions.
A-2, preparation comprise 0.052 g agno3, mixed solution 170 ml of 0.052 g ctab, comprise 0.1144 g
Solution 6 ml of l- ascorbic acid, adds l- ascorbic acid solution in mixed solution, and silver nanoparticle seed solution 2 ml, and plus
Enter naoh solution and adjust ph to 13, to realize the growth of nano grain of silver.After stirring 60 min, it is centrifuged 10 min in 7000rpm, with
Remove excessive ctab, obtain the ag nps of ctab functionalization, be redispersed in the deionized water of 40ml being obtained aqueous dispersions.
B, preparation pdda functionalization cnts, comprise the following steps that.
B-1, deionized water configuration comprise solution 400 ml of 50 mg pdda, then pass through ultrasonic method by 100 mg's
CNT is dispersed therein, and stable cnts dispersion liquid is obtained；
B-2, filtration gained dispersion liquid are simultaneously washed with deionized repeatedly, then 20 hs are dried in 70 DEG C of vacuum drying oven,
Obtain pdda functionalization cnts.
C, prepare graphene oxide film, comprise the following steps that.
C-1, pretreatment: 0.75g graphite powder is added step-wise in 4.1 ml concentrated sulphuric acids, and adds 0.625 g persulfuric acid
Potassium, 0.687 g phosphorus pentoxide, mix at 80 DEG C, this mixture are maintained in the oil bath of 80 ° of c and stir 4.5 h, then
Dilute this mixed liquor with substantial amounts of deionized water.Then, with 0.2 μm of Merlon vacuum filter collecting reaction product, and spend
Ion water washing removes residual acid and 12 hs is dried until the ph value of filtrate close to neutrality, then under room temperature environment, is pre-oxidized
Powdered graphite.
C-2, oxidation: 0.7 g is pre-oxidized powdered graphite and adds 29.4 ml concentrated sulphuric acids and stir at 0 DEG C, when
After mixture is dispersed throughout, slowly careful thereto plus 4.2 g potassium permanganate, whole reactant mixture is placed on 35 °
2 h in c water-bath.Subsequently with 60 ml deionized water diluted mixtures, reaction adds 175 ml deionized waters, then after continuing 2 h
The slow h adding 5.6 ml 30%2o2, the color of mixed liquor immediately becomes glassy yellow.
C-3, post processing: will appear from jonquilleous mixed liquor centrifugation, and 10% hydrochloric acid solution washs 3 times.Afterwards by mixed liquor
Recentrifuge, deionized water is rinsed at least eight times so as to fully remove the metal ion in dispersion liquid and the acid remaining.Finally
Gains are dried 2 days under 65 ° of c, obtain graphene oxide.Take go ultrasonic 2 h in deionized water that 0.2 g prepares,
Obtain stable, that brown is transparent, concentration for 2 mg ml-1Go aqueous dispersions, stand-by.
Afterwards, in the go aqueous dispersions first 1.2 mg pdda functionalization cnts being added to 3 ml under conditions of stirring,
It is subsequently added into 12 ml, concentration is 0.1 mg ml-1The ag nps aqueous dispersions of ctab functionalization be mixed with stirring 20
min.Then, the filter paper filtering being 10 % using vacuum filtration pump with reference to fenestra 0.2 mm, porosity, its effective filtering area face
Amass as 16 cm2, and 10 mins are dried in 30 DEG C of vacuum drying oven.Finally, that gently takes off from filter paper is nano grain of silver
The go laminated film that son-CNT embeds.The optical photograph of prepared go laminated film is as shown in Figure 1.Go laminated film
Electron scanning micrograph is as shown in Figure 2 it is seen that nano grain of silver and CNT are embedded in graphene oxide layer.
Then, using rhodamine 6g(r6g) classical dyestuff to be verifying sensitivity and the repeatability of this go laminated film substrate.
Experiment 1: rhodamine 6g (r6g) be a kind of typical Raman tag molecules, for confirm go laminated film sensitivity, we with
This go laminated film is sers substrate, have recorded the sers spectrum of r6g under variable concentrations.Fig. 3 shows from 1 × 10-7To 1 ×
10-14The sers spectrum of m variable concentrations r6g is it is evident that the intensity of sers signal of r6g and resolution reduce with its concentration
And reduce.Although the concentration of r6g is very low, the Partial Feature peak of r6g still can substantially be observed, though concentration low reach 1 ×
10-12m.This illustrates that we have stronger sers enhancement effect at prepared go laminated film substrate, can effectively improve this inspection
The sensitivity of survey method.
Experiment 2: for assessing the repeatability of go laminated film, arbitrarily select 20 regions on this laminated film surface, and remember
Lower r6g(1 × 10 of record-7M) Raman Spectral Signal, is shown in Fig. 4.Result shows: the peak intensity of this 20 points and repeatability obtain very much
Stable and unified, go laminated film has good sers signal reproducibility, and the go that this further illustrates prepared by the present invention is multiple
Close uniformity of film fine.
Experiment 3: by preparing the quadracycline solution of variable concentrations, tetramycin hydrochloride, ampicillin simulating pollution water
Actual pollution concentration in body, is responded respectively with sers multiple techniques using this go laminated film substrate, to be analyzed go thin film
Detection by quantitative ability to antibiotic.By vacuum filtration method with 0.077 ml min-1Flow filtration absorption variable concentrations salt
Sour tetracycline, tetramycin hydrochloride, ampicillin solution, and with Portable Raman spectrometer, sers inspection is carried out to go laminated film
Survey, obtain the sers spectrogram of obvious quadracycline, such as Fig. 5, shown in Fig. 6, Fig. 7, the Raman signatures of quadracycline
Peak is 1275 and 1601 cm-1, the feature spectral peak of tetramycin hydrochloride is 1115 and 1600 cm-1, the feature spectral peak of ampicillin
1278 and 1533 cm-1Even if reaching nm rank, being still able to will become apparent from quadracycline solution, tetramycin hydrochloride, ammonia benzyl
The characteristic peak in XiLin, illustrates that this go laminated film have higher accumulation ability and superior sers performance to antibiosis.
In sum, this go laminated film substrate has excellent sensitivity and repeatability, and being capable of fast enriching water ring
Antibiotic in border, based on this, can using the present invention set up further the live fast qualitative of Antibiotics of Low Concentration in water body,
Quantitative detecting analysis technical system, provides new means for antibiotic contamination accident scene Emergent detection.
It is specific implementation method above, all any modifications made in the range of the spirit and principles in the present invention, equivalent replace
Change and improve, should be included within the scope of the present invention.
Claims (16)
1. a kind of preparation method of the graphene composite thin film that nano grain of silver-CNT embeds is it is characterised in that include
The raw material of following mass parts: 1 part of the nano grain of silver of cetyl trimethylammonium bromide functionalization, diallyl dimethyl chlorination
1 part of the CNT of ammonium functionalization, 4～5 parts of graphene oxide, are superimposed film forming through orderly, specifically comprise the following steps that
(1) the nano grain of silver aqueous dispersions of cetyl trimethylammonium bromide functionalization are prepared respectively, graphene oxide moisture dissipates
Liquid；
(2) in graphene oxide aqueous dispersions, first stirring adds the carbon nanometer of diallyl dimethyl ammoniumchloride functionalization
Pipe, adds the nano grain of silver aqueous dispersions of cetyl trimethylammonium bromide functionalization, and mix homogeneously；
(3) with reference to filter paper, mixed liquor is filtered using vacuum filtration pump, be dried, that takes off from filter paper is silver nanoparticle
The graphene composite thin film that grain-CNT embeds.
2. the preparation of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 1 embeds
Method is it is characterised in that step (1) prepares aqueous dispersions using ultrasonic method.
3. the system of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 1 and 2 embeds
Preparation Method is it is characterised in that the mixing described in step (2) requires stirring at least 10min, or ultrasonic at least 5min.
4. the system of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 1 and 2 embeds
Preparation Method it is characterised in that filter paper described in step (3) fenestra be 0.2 μm, porosity be 10%, effective filtering area area
For 12～16cm2.
5. the system of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 1 and 2 embeds
Preparation Method is it is characterised in that the drying described in step (3) is that 5～10min is dried in 30～50 DEG C of vacuum drying oven.
6. the preparation of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 1 embeds
Method is it is characterised in that the concrete preparation process of the described nano grain of silver of cetyl trimethylammonium bromide functionalization is as follows:
A-1, prepare crystal seed: prepare agno3With the mixed solution of sodium citrate, it is added dropwise over nabh with vigorous stirring thereto4
Solution, solution is changed into glassy yellow at once, and agno3, sodium citrate, nabh4Mass ratio be 65～70:20:1；Then persistently stir
Mix 1h aging 7 days, the silver nanoparticle seed solution of a size of 5～10nm is obtained；
A-2, reduction reaction: configuration agno3With the mixed solution of cetyl trimethylammonium bromide, it is added thereto to l- Vitamin C
Acid, and agno3, cetyl trimethylammonium bromide, l- ascorbic acid mass ratio be 5:4～5:10～11；It is subsequently added silver
Nanometer seed solution 1～2ml, adjusting ph value is 13, promotes nano grain of silver to grow；It is centrifuged after stirring, obtain cetyl
The nano grain of silver of trimethylammonium bromide functionalization.
7. the preparation of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 6 embeds
Method is it is characterised in that the time of stirring described in step a-2 is 30～60min.
8. the system of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 6 or 7 embeds
It is characterised in that the rotating speed of centrifugation described in step a-2 is 6000～7000rpm, the time is 10～15min to Preparation Method.
9. the preparation of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 1 embeds
Method it is characterised in that the concrete preparation process of the described CNT of diallyl dimethyl ammoniumchloride functionalization such as
Under:
B-1, configuration diallyl dimethyl ammoniumchloride aqueous solution, are added thereto to CNT, prepared CNT dispersion
Liquid, and the mass ratio of diallyl dimethyl ammoniumchloride, CNT is 1:1～2.
B-2, dispersion liquid are through filtering, washing, be dried, the CNT of prepared diallyl dimethyl ammoniumchloride functionalization.
10. the preparation of the graphene composite thin film that a kind of nano grain of silver-CNT according to claim 9 embeds
Method is it is characterised in that adopt ultrasonic method dispersing Nano carbon tubes in step b-1.
The graphene composite thin film that a kind of 11. nano grain of silver-CNTs according to claim 9 or 10 embed
Preparation method is it is characterised in that drying described in step b-2 is that 20～24h is dried in 60～70 DEG C of vacuum drying oven.
The preparation of the graphene composite thin film that a kind of 12. nano grain of silver-CNTs according to claim 1 embed
Method is it is characterised in that the concrete preparation process of described graphene oxide is as follows:
C-1, pretreatment: add graphite powder, potassium peroxydisulfate, phosphorus pentoxide in concentrated sulphuric acid, at 80 DEG C, stir 4.5h, and stone
Powdered ink, potassium peroxydisulfate, the mass ratio of phosphorus pentoxide are 6:5:5～5.5, and the volume of concentrated sulphuric acid is calculated as with the quality of graphite powder
4.8～5.5ml/g；Then dilute, sucking filtration, wash to neutrality, be dried at room temperature for 12h, obtain pre-oxidizing graphite powder；
C-2, oxidation reaction: add pre-oxidation graphite powder in concentrated sulphuric acid, stir at 0 DEG C；Then it is added thereto to height
Potassium manganate, reacts 2h, dilution at 35 DEG C, dilutes again, be subsequently added into 30% h after sustained response 2h2o2, mixed liquor becomes at once
For glassy yellow；Wherein, pre-oxidation graphite powder, the mass ratio of potassium permanganate are 1:5～6, and the volume of concentrated sulphuric acid is to pre-oxidize graphite
The quality of powder is calculated as 40～42ml/g, h2o2Volume 6～8ml/g is calculated as with the quality pre-oxidizing graphite powder；
C-3, post processing: by the centrifugation simultaneously pickling of glassy yellow mixed liquor, then it is centrifuged and washes, be dried 2～3 days at 60～65 DEG C,
Obtain graphene oxide.
The system of the graphene composite thin film that a kind of 13. nano grain of silver-CNTs according to claim 12 embed
Preparation Method is it is characterised in that the sucking filtration described in step c-1 adopts 0.2 μm of Merlon vacuum filtration.
The graphene composite thin film that a kind of 14. nano grain of silver-CNTs according to claim 12 or 13 embed
Preparation method it is characterised in that the pickling described in step c-3 adopt 10% hydrochloric acid solution wash 2-3 time.
The oxidation stone that nano grain of silver-CNT that method described in a kind of 15. employing claim 1,6,9 or 12 is obtained embeds
Black alkene laminated film.
The oxidation stone that nano grain of silver-CNT that method described in a kind of 16. employing claim 1,6,9 or 12 is obtained embeds
The application of black alkene laminated film is it is characterised in that this laminated film is applied to the detection of antibiotic remainss in water environment.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500271A (en) * | 2017-08-31 | 2017-12-22 | 北京化工大学 | Flexible graphene film and Flexible graphene based composites film and preparation method thereof |
| CN108535235A (en) * | 2018-04-02 | 2018-09-14 | 湖南大学 | A kind of SERS test strips and preparation method thereof, application |
| CN110052257A (en) * | 2019-03-06 | 2019-07-26 | 宁波大学 | A kind of preparation method of the flower-shaped micron silver composite material of graphene oxide membrane/poly 4 vinyl pyridine/porous three-dimensional |
| CN111208113A (en) * | 2020-02-28 | 2020-05-29 | 中国地质大学（北京） | Self-powered SERS substrate based on flexible piezoelectric film loaded with nano Ag and application |
| CN113522038A (en) * | 2021-07-27 | 2021-10-22 | 华北理工大学 | Preparation method and application of composite membrane for removing pollutants in water |
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| CN102408094A (en) * | 2011-11-11 | 2012-04-11 | 华东理工大学 | Preparation method for highly repetitive surface enhanced Raman spectrum (SERS) active substrate |
| CN102773495A (en) * | 2012-07-30 | 2012-11-14 | 中国科学院宁波材料技术与工程研究所 | Composite material of graphene oxide/ nanometer precious metal with surface enhanced Raman effect and preparation thereof |
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| CN102408094A (en) * | 2011-11-11 | 2012-04-11 | 华东理工大学 | Preparation method for highly repetitive surface enhanced Raman spectrum (SERS) active substrate |
| CN102773495A (en) * | 2012-07-30 | 2012-11-14 | 中国科学院宁波材料技术与工程研究所 | Composite material of graphene oxide/ nanometer precious metal with surface enhanced Raman effect and preparation thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107500271A (en) * | 2017-08-31 | 2017-12-22 | 北京化工大学 | Flexible graphene film and Flexible graphene based composites film and preparation method thereof |
| 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 |
| CN110052257A (en) * | 2019-03-06 | 2019-07-26 | 宁波大学 | A kind of preparation method of the flower-shaped micron silver composite material of graphene oxide membrane/poly 4 vinyl pyridine/porous three-dimensional |
| CN111208113A (en) * | 2020-02-28 | 2020-05-29 | 中国地质大学（北京） | Self-powered SERS substrate based on flexible piezoelectric film loaded with nano Ag and application |
| CN113522038A (en) * | 2021-07-27 | 2021-10-22 | 华北理工大学 | Preparation method and application of composite membrane for removing pollutants in water |
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