CN107282918B - A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application - Google Patents
A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application Download PDFInfo
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- CN107282918B CN107282918B CN201710347677.6A CN201710347677A CN107282918B CN 107282918 B CN107282918 B CN 107282918B CN 201710347677 A CN201710347677 A CN 201710347677A CN 107282918 B CN107282918 B CN 107282918B
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
Abstract
The invention discloses a kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano materials and its preparation method and application, feature is that the core-shell nano material is made of Silver nanorod kernel, polymer covering layer and Nano silver piece outer layer three parts, the polystyrene polyacrylic acid block copolymer layer that wherein polymer covering layer is 10 nanometers of thickness；The length of Silver nanorod kernel is 400 nanometers -1.3 microns, the irregular sheet that corresponding Nano silver piece outer layer is side length 120-320 nanometers；Or the length of Silver nanorod kernel is 175-310 nanometers, the keeper shape and its half package Silver nanorod kernel that corresponding Nano silver piece outer layer is bottom side length 510-780 nanometers, the present invention uses Silver nanorod/polymer/silver nanometer sheet core-shell nano material of Seed inducement method preparation, advantage is to generate that there is the SERS signal of very high strength to export, its preparation process is simple, period is short, and yield is high, easy to spread and large-scale production.
Description
Technical field
The present invention relates to material engineering and field of nanometer technology, more particularly, to a kind of Silver nanorod/polymer/silver nanometer
Piece core-shell nano material and its preparation method and application.
Background technique
In past 20 years, due to the sensitivity with unimolecule rank, Surface enhanced Raman scattering (SERS) technology
Have been developed as life health care, the efficient analysis detection means in the fields such as environmental monitoring and food safety.In various SERS materials
In material, the advantage of noble metal nanometer material is that its surface plasma body resonant vibration (LSPR) can induce and generates extremely strong local electricity
Magnetic field shows excellent enhancing characteristic.In these noble metal nanometer materials, silver is with its preferable enhancing characteristic and simple system
Standby technique is shown one's talent.By using a plurality of types of surfactants, people have been prepared for that there is diversified silver to receive
Rice material, such as nanometer rods, nanocube, nanometer sheet and nanometer magnitude.By the structure and shape that change these silver nano materials
Looks, people can effectively adjust its surface plasma bulk properties and obtain more excellent optical property.But due to wherein not
Containing nano gap, individual silver nano-grain, SERS signal is in general too weak to for Single Molecule Detection.Meanwhile
The efficiency and reliability of SERS nano-probe is frequently subjected to the damage of dissociation of ligand or exchange.In addition, in addition to high-intensitive output
Signal, the uniformity and stability of other performances such as signal are also most important for the practical application of SERS substrate.Therefore, it uses
Advanced nano-fabrication technique makes novel Silver nanorod/polymer/silver nanometer sheet core-shell nano material, better to obtain
The technical issues of SERS performance is current detection field urgent need to resolve.
Summary of the invention
The silver nanoparticle for the SERS signal output with very high strength that technical problem to be solved by the invention is to provide a kind of
Stick/polymer/silver nanometer sheet core-shell nano material and its preparation method and application.
The technical scheme of the invention to solve the technical problem is: a kind of Silver nanorod/polymer/silver nanometer sheet
Core-shell nano material, the core-shell nano material by Silver nanorod kernel, be wrapped in Silver nanorod surface polymer covering layer and
Nano silver piece outer layer three parts positioned at cover surface form, wherein the polymer covering layer is 10 nanometers of thickness poly-
Styrene polyacrylic acid block copolymer layer；The length of the Silver nanorod kernel is 400 nanometers -1.3 microns, corresponding institute
The irregular sheet that the Nano silver piece outer layer stated is side length 120-320 nanometers；Or the length of the Silver nanorod kernel is
175-310 nanometers, described in the keeper shape and its half package that the Nano silver piece outer layer is bottom side length 510-780 nanometer
Silver nanorod kernel.
Above-mentioned Silver nanorod/polymer/silver nanometer sheet core-shell nano material preparation method, comprising the following steps:
1) preparation of Silver nanorod: gold chloride, sodium citrate and sodium borohydride are dissolved in deionized water, are mixed 10
2 hours, which are stood, after minute obtains gold seeds aqueous solution；CTAB, gold chloride, silver nitrate, ascorbic acid, hydrochloric acid and gold seeds are molten
Liquid is dissolved in deionized water, and after being mixed 1 minute after static 12 hours, centrifugation obtains gold nano bipyramid；By gold nano bipyramid,
CTAC, silver nitrate and ascorbic acid are dissolved in be mixed evenly in deionized water after, at 60 DEG C heating reaction 4 hours, centrifugation
Collect precipitating afterwards to get Silver nanorod；
2) Silver nanorod/polymer core shell nanometer material preparation: take Silver nanorod made from step 1) be added to containing
In the dimethylformamide deionized water mixed solution of Raman molecular 2- thionaphthol and polystyrene polyacrylic acid block copolymer,
And heated 2 hours at 110 DEG C after being vigorously stirred, be slowly dropped to room temperature later, be collected after centrifugation precipitating to get Silver nanorod/
Polymer core shell nanometer material；
3) Silver nanorod/polymer/silver nanometer sheet core-shell nano material preparation: by Silver nanorod made from step 2/
Polymer core shell nanometer material is dissolved in be dissolved in mixed liquor made of water silver nitrate and sodium citrate, is slowly added dropwise while stirring
Aqueous ascorbic acid reacts 1 hour at room temperature, after reaction, precipitating is collected after centrifugation to get Silver nanorod/polymerization
Object/Nano silver piece core-shell nano material；
Or Silver nanorod made from step 2/polymer core shell material is dissolved in by sodium citrate, ascorbic acid and double
In the water-soluble mixed liquor made of water of oxygen, silver nitrate aqueous solution is slowly added dropwise while stirring, react 1 hour terminates at room temperature
Afterwards, precipitating is collected after centrifugation to get Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
Step 1) specifically:
A. by 0.5-1.5 milligrams of gold chlorides, 0.735-2.205 milligrams of sodium citrates and 0.0567-0.1701 milligrams of boron hydrogen
Change sodium to be dissolved in 9.65-28.95 ml deionized water, standing after ten minutes is mixed and obtains gold seeds aqueous solution within 2 hours；
B. by 2.92-8.76 grams of CTAB, 16-48 milligram gold chloride, 1.36-4.08 milligrams of silver nitrates, 11.26-33.78 milli
Gram ascorbic acid, 1.33-3.99 milliliters of hydrochloric acid and 0.4-1.2 milliliters of gold seeds solution mix in 85-255 ml deionized water
Centrifugation obtains gold nano bipyramid after static 12 hours after stirring 1 minute；
C. whole gold nano bipyramids, 6.14-18.42 grams of CTAC, 81.6-244.8 milligrams of nitric acid for taking above-mentioned steps to prepare
Silver and 422.4-1267.2 milligrams of ascorbic acid are dissolved in 400-1200 ml deionized water, after being mixed evenly, in 60 DEG C
Lower heating is reacted 4 hours, and precipitating is collected after centrifugation to get Silver nanorod.
Step 2 specifically: Silver nanorod made from step 1) is taken to be added to containing 0.05-0.15 milligrams of Raman molecular 2-
Thionaphthol and 0.5-1.5 milligrams of polystyrene polyacrylic acid block copolymers by 900-2700 microlitres of dimethylformamide and
It in the mixed liquor of 200-600 microlitres of deionized water composition, and heats 2 hours at 110 DEG C after being vigorously stirred, is slowly dropped to later
Precipitating is collected after centrifugation to get Silver nanorod/polymer core shell nanometer material in room temperature.
Step 3) specifically: Silver nanorod made from step 2/polymer core shell nanometer material is taken to be dissolved in by 2-6 milligrams of nitre
Sour silver and 6-18 milligrams of sodium citrates are dissolved in 9-27 made of water milliliters of mixed liquor, and 2-6 milliliters are slowly added dropwise while stirring
The aqueous ascorbic acid that concentration is 2 milligrams every milliliter reacts 1 hour at room temperature, and after reaction, it is heavy to be collected after centrifugation
It forms sediment to get Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
Step 1) -3) in centrifugal speed be 5000-10000 revs/min, centrifugation time be 5-10 minutes.
Step 3) specifically: Silver nanorod made from step 2/polymer core shell nanometer material is taken to be dissolved in by 2-4 milligrams of nitre
Sour silver, 4-8 milligrams of ascorbic acid and 12-36 microlitres of hydrogen peroxide are dissolved in 9-27 made of water milliliters of mixed liquor, are delayed while stirring
The silver nitrate aqueous solution that the slow concentration for being added dropwise 3-9 milliliters is 2 milligrams every milliliter, after reacting 1 hour at room temperature, after centrifugation
Precipitating is collected to get Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
Rapid 1) -3) centrifugal speed is 8000-16000 revs/min in, and centrifugation time is 10-20 minutes.
The application of above-mentioned Silver nanorod/polymer/silver nanometer sheet core-shell nano material, the core-shell nano material are increasing
The purposes of strong SERS signal output facet.
Compared with the prior art, the advantages of the present invention are as follows: present invention firstly discloses one kind to have the active silver of SERS
Nanometer rods/polymer/silver nanometer sheet core-shell nano material and its preparation method and application, the core-shell nano material is by Silver nanorod
Kernel, the Nano silver piece outer layer three parts composition positioned at the polymer covering layer on Silver nanorod surface and on Silver nanorod,
The Silver nanorod of Raman molecular is coated with using polystyrene acrylic acid block copolymer package, and former in shell copolymers layer surface
Position reduction silver nitrate forms Nano silver piece outer layer, obtains a kind of novel three-decker with excellent SERS characteristic wherein two
The block copolymer of parent's property, especially polystyrene acrylic acid block copolymer are due to good translucency, without influencing
The output of SERS signal.In addition, exposed hydrophilic functional group can adsorb silver ion and also after it forms clad
External silver-colored shell is formed under the action of former agent, by very thin polymer shell, the plasmon coupling of inside and outside silver layer will cause
Strong electromagnetic hotspot causes the extreme of SERS signal to enhance.Especially in core-shell nano keeper material, external silver-colored shell
Half package is formd to Silver nanorod kernel, electromagnetic coupling effect between the two is more preferable, and obtained SERS signal intensity is higher.
The present invention has phase using Silver nanorod/polymer/silver nanometer sheet core-shell nano material of Seed inducement method preparation
Two layers of noble silver nanometer layer away from only 10nm or so, under the action of external exciting light, the surface local that they are generated is electric
The effect of intercoupling more by force can occur between magnetic field, generate hot spot region, so that this material has very high strength
SERS signal output.The preparation process that the present invention uses is simple, does not use any toxic reagent, and green high-efficient, the period is short, yield
Height, easy to spread and large-scale production.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of the Silver nanorod kernel prepared in the embodiment of the present invention 1；
Fig. 2 is the larger range of transmission electron microscope photo of Silver nanorod kernel prepared in the embodiment of the present invention 1；
Fig. 3 is that the Silver nanorod/polymer core shell material transmission electron microscope prepared in the embodiment of the present invention 1 shines
Piece；
Fig. 4 is the Silver nanorod/larger range of transmitted electron of polymer core shell material prepared in the embodiment of the present invention 1
Microscope photo；
Fig. 5 is the Silver nanorod/polymer/silver nanometer sheet core-shell nano material transmission prepared in the embodiment of the present invention 1
Electron micrograph；
Fig. 6 is to utilize the silver-colored Silver nanorod prepared in the embodiment of the present invention 1/polymer/silver nanometer sheet core-shell nano material
Raman detection result；
Fig. 7 is the Silver nanorod/polymer/silver nanometer sheet core-shell nano material transmission prepared in the embodiment of the present invention 2
Electron micrograph；
Fig. 8 is to utilize the Silver nanorod prepared in the embodiment of the present invention 2/polymer/silver nanometer sheet core-shell nano material
Raman detection result；
Fig. 9 is the Silver nanorod/polymer/silver nanometer sheet core-shell nano material transmission prepared in the embodiment of the present invention 3
Electron micrograph；
Figure 10 is to utilize the Silver nanorod prepared in the embodiment of the present invention 3/polymer/silver nanometer sheet core-shell nano material
Raman detection result；
Figure 11 is the transmission electron microscope photo of the nucleocapsid silver nanoparticle keeper material prepared in the embodiment of the present invention 4；
Figure 12 is the Raman detection result using the nucleocapsid silver nanoparticle keeper material prepared in the embodiment of the present invention 4；
Figure 13 is the transmission electron microscope photo of the nucleocapsid silver nanoparticle keeper material prepared in the embodiment of the present invention 5；
Figure 14 is the Raman detection result using the nucleocapsid silver nanoparticle keeper material prepared in the embodiment of the present invention 5；
Figure 15 is the transmission electron microscope photo of the nucleocapsid silver nanoparticle keeper material prepared in the embodiment of the present invention 6；
Figure 16 is the Raman detection result using the nucleocapsid silver nanoparticle keeper material prepared in the embodiment of the present invention 6.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Unless otherwise specified, embodiment
Used in the conventional means that are well known to those skilled in the art of technological means, raw materials used is commercial goods.Embodiment
Used in Raman spectrum detector BWS415 be purchased from U.S. Bi Da Imtech (B&W Tek Inc.).
Embodiment 1
Silver nanorod/polymer/silver nanometer sheet core-shell nano material preparation method the following steps are included:
1,0.5 milligram of gold chloride, 0.735 milligram of sodium citrate and 0.0567 milligram of sodium borohydride are dissolved in 9.65 milliliters
In ionized water, standing after ten minutes is mixed and obtains gold seeds aqueous solution within 2 hours；By 2.92 grams of CTAB(cetyl front threes
Base ammonium bromide), 16 milligrams of gold chlorides, 1.36 milligrams of silver nitrates, 11.26 milligrams of ascorbic acid, 1.33 milliliters of hydrochloric acid and 0.4 milliliter
Centrifugation obtains gold nano pair to above-mentioned gold seeds solution after static 12 hours after being mixed 1 minute in 85 ml deionized waters
Cone；By whole gold nano bipyramids obtained above, 6.14 grams of CTAC(hexadecyltrimethylammonium chlorides), 81.6 milligrams of silver nitrates
It is dissolved in 422.4 milligrams of ascorbic acid after being mixed evenly in 400 ml deionized waters, heating reaction 4 hours at 60 DEG C
Precipitating is collected after centrifugation to get Silver nanorod；
2, whole Silver nanorods obtained above is taken to be added to containing 0.05 milligram of Raman molecular 2- thionaphthol and 0.5 milligram
The mixing of polystyrene polyacrylic acid block copolymer being made of 900 microlitres of dimethylformamides and 200 microlitres of deionized waters
It in liquid, and is heated 2 hours at 110 DEG C after being vigorously stirred, is slowly dropped to room temperature later, precipitating is collected after centrifugation and is received to get silver
Rice stick/polymer core shell nanometer material；
3, whole Silver nanorod/polymer core shell nanometer materials obtained above are dissolved in by 2 milligrams of silver nitrates and 6 milligrams
Sodium citrate is dissolved in 9 milliliters of mixed liquors made of water, and the aqueous solution (concentration of 2 milliliters of ascorbic acid is slowly added dropwise while stirring
It is 2 milligrams every milliliter), it reacts at room temperature 1 hour, after reaction, precipitating is collected after centrifugation to get Silver nanorod/polymerization
Object/Nano silver piece core-shell nano material.
Centrifugal speed is 5000 revs/min in above-mentioned steps 1-3, and centrifugation time is 10 minutes.
The core-shell nano material prepared in the present embodiment by Silver nanorod kernel, be wrapped in the polymer on Silver nanorod surface
Clad and positioned at cover surface Nano silver piece outer layer three parts form, wherein kernel be 500 nanometers to 1 micron of length
Silver nanorod, clad is 10 nanometers of thickness of polystyrene polyacrylic acid block copolymer layer, and outermost layer is side length 130-
250 nanometers of Nano silver piece.
Fig. 1 shows the transmission electron microscope photo of the Silver nanorod kernel prepared in the present embodiment.Fig. 2 shows this
The larger range of transmission electron microscope photo of Silver nanorod kernel prepared in embodiment, the as seen from the figure size of Silver nanorod
Very inconsistent, silver nanoparticle keeper material is the selective smaller Silver nanorod that coated, and another structure due to
It is not formed and is effectively coated, so to Silver nanorod without selectivity.
Fig. 3 shows the Silver nanorod/polymer core shell material transmission electron microscope photo prepared in the present embodiment,
From figure 3, it can be seen that prepared silver nanoparticle core is wrapped up by one layer of almost transparent polymeric shell layer.Fig. 4 shows this implementation
Silver nanorod/larger range of transmission electron microscope photo of polymer core shell material for preparing in example, as seen from the figure silver nanoparticle
The size of stick is very inconsistent, and Fig. 5 shows the transmission electron microscope photo of the Silver nanorod prepared in the present embodiment, from figure
5 as can be seen that prepared nano material is three-layer nuclear shell structure.
Fig. 6 is to be prepared using the above method with the active Silver nanorod of SERS/polymer/silver nanometer sheet nucleocapsid
The Raman spectrogram of nano material.From fig. 6, it can be seen that the SERS active material has good SERS signal enhancement effect,
It is in 1382 cm-1The Raman signal intensity at place reaches 25000.
Embodiment 2
Silver nanorod/polymer/silver nanometer sheet core-shell nano material preparation method the following steps are included:
1, by 1 milligram of gold chloride, 1.47 milligrams of sodium citrates and 0.1134 milligram of sodium borohydride in 19.3 milliliters of deionizations
Standing after ten minutes is mixed in water and obtains gold seeds aqueous solution within 2 hours；By 5.84 grams of CTAB, 32 milligrams of gold chlorides, 2.72
Milligram silver nitrate, 22.52 milligrams of ascorbic acid, 2.66 milliliters of hydrochloric acid and 0.8 milliliter of above-mentioned gold seeds solution gone in 170 milliliters from
In sub- water, centrifugation obtains gold nano bipyramid after static 12 hours after being mixed 1 minute；Whole gold nanos obtained above are double
Cone, 12.28 grams of CTAC, 163.2 milligrams of silver nitrates and 844.8 milligrams of ascorbic acid are dissolved in mixing in 800 ml deionized waters and stir
Precipitating is collected after centrifugation for 4 hours to get Silver nanorod in heating reaction at 60 DEG C after mixing uniformly；
2, whole Silver nanorods obtained above are taken to be added to poly- containing 0.1 milligram of Raman molecular 2- thionaphthol and 1 milligram
The mixed liquor of styrene polyacrylic acid block copolymer being made of 1800 microlitres of dimethylformamides and 400 microlitres of deionized waters
In, and heated 2 hours at 110 DEG C after being vigorously stirred, it is slowly dropped to room temperature later, is centrifuged, collects precipitating to get silver nanoparticle
Stick/polymer core shell nanometer material；
3, whole Silver nanorod/polymer core shell nanometer materials obtained above are dissolved in by 4 milligrams of silver nitrates and 12 millis
Gram sodium citrate is dissolved in 18 milliliters of mixed liquors made of water, and the aqueous solution that 4 milliliters of ascorbic acid are slowly added dropwise while stirring is (dense
Degree is 2 milligrams every milliliter), it reacts 1 hour at room temperature, after reaction, precipitating is collected after centrifugation to get Silver nanorod/poly-
Close object/Nano silver piece core-shell nano material.
Centrifugal speed is 8000 revs/min in above-mentioned steps 1-3, and centrifugation time is 7 minutes.
The core-shell nano material prepared in the present embodiment by it is interior by Silver nanorod kernel, be wrapped in the poly- of Silver nanorod surface
It closes object clad and is formed positioned at the Nano silver piece outer layer three parts of cover surface, wherein kernel is 700 nanometers of length and arrives
1.3 microns of Silver nanorods, the polystyrene polyacrylic acid block copolymer layer that clad is 10 nanometers of thickness, outermost layer is side length
130-320 nanometers of Nano silver piece.
Fig. 7 shows that is prepared in the present embodiment there is the active Silver nanorod of SERS/polymer/silver nanometer sheet nucleocapsid to receive
The transmission electron microscope photo of rice material, from figure 7 it can be seen that prepared nano material is three-layer nuclear shell structure.
Fig. 8 is to be prepared using the above method with the active Silver nanorod of SERS/polymer/silver nanometer sheet nucleocapsid
The Raman spectrogram of nano material.From figure 8, it is seen that the SERS active material has good SERS signal enhancement effect,
It is in 1382 cm-1 The Raman signal intensity at place reaches 20000.
Embodiment 3
Silver nanorod/polymer/silver nanometer sheet core-shell nano material preparation method the following steps are included:
1,1.5 milligrams of gold chlorides, 2.205 milligrams of sodium citrates and 0.1701 milligram of sodium borohydride are gone in 28.95 milliliters
In ionized water, standing after ten minutes is mixed and obtains gold seeds aqueous solution within 2 hours；By 8.76 grams of CTAB, 48 milligrams of gold chlorides,
4.08 milligrams of silver nitrates, 33.78 milligrams of ascorbic acid, 3.99 milliliters of hydrochloric acid and 1.2 milliliters of above-mentioned gold seeds solution are in 255 milliliters
Centrifugation obtains gold nano bipyramid after static 12 hours after being mixed 1 minute in deionized water；By whole Jenners obtained above
Rice bipyramid, 18.42 grams of CTAC, 244.8 milligrams of silver nitrates and 1267.2 milligrams of ascorbic acid are dissolved in 1200 ml deionized waters
After being mixed evenly, precipitating is collected after centrifugation for 4 hours to get Silver nanorod in heating reaction at 60 DEG C；
2, whole Silver nanorods obtained above are taken to be added poly- containing 0.15 milligram of Raman molecular 2- thionaphthol and 1.5 milligrams
The mixed liquor of styrene polyacrylic acid block copolymer being made of 2700 microlitres of dimethylformamides and 600 microlitres of deionized waters
In, and heated 2 hours at 110 DEG C after being vigorously stirred, it is slowly dropped to room temperature later, precipitating is collected after centrifugation to get silver nanoparticle
Stick/polymer core shell nanometer material；
3, whole Silver nanorod/polymer core shell nanometer materials obtained above are dissolved in by 6 milligrams of silver nitrates and 18 millis
Gram sodium citrate is dissolved in 27 milliliters of mixed liquors made of water, and the aqueous solution that 6 milliliters of ascorbic acid are slowly added dropwise while stirring is (dense
Degree is 2 milligrams every milliliter), it reacts 1 hour at room temperature, after reaction, precipitating is collected after centrifugation to get Silver nanorod/poly-
Close object/Nano silver piece core-shell nano material.
Centrifugal speed is 10000 revs/min in above-mentioned steps 1-3, and centrifugation time is 5 minutes.
The core-shell nano material prepared in the present embodiment by Silver nanorod kernel, be wrapped in the polymer on Silver nanorod surface
Clad and positioned at cover surface Nano silver piece outer layer three parts form, wherein kernel be 400 nanometers of length received to 480
The Silver nanorod of rice, the polystyrene polyacrylic acid block copolymer layer that clad is 10 nanometers of thickness, outermost layer is side length
130-140 nanometers of Nano silver piece.
Fig. 9 shows that is prepared in the present embodiment there is the active Silver nanorod of SERS/polymer/silver nanometer sheet nucleocapsid to receive
The transmission electron microscope photo of rice material, from fig. 9, it can be seen that prepared nano material is three-layer nuclear shell structure.
Figure 10 is to be prepared using the above method with the active Silver nanorod of SERS/polymer/silver nanometer sheet core
The Raman spectrogram of shell nanometer material.From fig. 10 it can be seen that the SERS active material has good SERS signal enhancing effect
It answers, in 1382 cm-1The Raman signal intensity at place reaches 15000.
Embodiment 4
With above-mentioned specific embodiment 1, difference is:
By the Silver nanorod of whole made from step 2/polymer core shell material be dissolved in by 2 milligrams of sodium citrates, 4 milligrams it is anti-bad
Hematic acid and 12 microlitres of hydrogen peroxide are dissolved in 9 milliliters of mixed liquors made of water, and the water-soluble of 3 milliliters of silver nitrates is slowly added dropwise while stirring
Liquid (concentration is 2 milligrams every milliliter) reacts 1 hour at room temperature, after reaction, precipitating is collected by centrifugation to get in keeper knot
The Silver nanorod of structure/polymer/silver nanometer sheet core-shell nano material.Wherein rapid 1) -3) centrifugal speed is 12000 revs/min in,
Centrifugation time is 15 minutes.
Figure 11 shows the transmission electron microscope photo of the nucleocapsid silver nanoparticle keeper material prepared in the present embodiment, from figure
11 as can be seen that prepared nano material is three-layer nuclear shell structure, by Silver nanorod kernel, Polymer interlayers and silver nanoparticle
Piece shell composition, the Silver nanorod that wherein kernel is 230 nanometers of length, the polystyrene polypropylene that middle layer is 10 nanometers of thickness
Sour block copolymer layer, shell are in keeper shape and 780 nanometers of bottom side length of Nano silver piece.It is practical when making keeper material
The upper only lesser nanometer rods of size are wrapped, and the larger longer nanometer rods of size cannot be wrapped up, in subsequent centrifugation
In the process, that is not wrapped up is just fallen by differential centrifugation.And irregular Nano silver piece shell is to the inside in above-described embodiment 1-3
Nanometer rods just without this selectivity.
Figure 12 shows the Raman spectrogram of the nucleocapsid silver nanoparticle keeper material prepared in the present embodiment.It can be with from Figure 12
Find out, which has good SERS signal enhancement effect, the Raman signal intensity at 1382 cm-1
Reach 50000.
Embodiment 5
With above-mentioned specific embodiment 1, difference is:
By the Silver nanorod of whole made from step 2/polymer core shell material be dissolved in by 4 milligrams of sodium citrates, 8 milligrams it is anti-bad
Hematic acid and 24 microlitres of hydrogen peroxide are dissolved in 18 milliliters of mixed liquors made of water, and the water of 6 milliliters of silver nitrates is slowly added dropwise while stirring
Solution (concentration is 2 milligrams every milliliter) reacts 1 hour at room temperature, after reaction, precipitating is collected after centrifugation to get in door
The Silver nanorod of stud structure/polymer/silver nanometer sheet core-shell nano material.Rapid 1) -3) centrifugal speed is 8000 revs/min in,
Centrifugation time is 20 minutes.
Figure 13 shows the transmission electron microscope photo of the nucleocapsid silver nanoparticle keeper material prepared in the present embodiment, from figure
13 as can be seen that prepared nano material is three-layer nuclear shell structure, by Silver nanorod kernel, Polymer interlayers and silver nanoparticle
Piece shell composition, the Silver nanorod that wherein kernel is 175 nanometers of length, the polystyrene polypropylene that middle layer is 10 nanometers of thickness
Sour block copolymer layer, shell are in keeper shape and 510 nanometers of bottom side length of Nano silver piece.
Figure 14 shows the Raman spectrogram of the nucleocapsid silver nanoparticle keeper material prepared in the present embodiment.It can be with from Figure 14
Find out, which has good SERS signal enhancement effect, in 1382 cm-1 The Raman signal intensity at place
Reach 40000.
Embodiment 6
With above-mentioned specific embodiment 1, difference is:
The nanometer rods of whole made from above-mentioned steps 2/polymer core shell material is dissolved in by 6 milligrams of sodium citrates, 12 milligrams
Ascorbic acid and 36 microlitres of hydrogen peroxide are dissolved in 27 milliliters of mixed liquors made of water, and 9 milliliters of silver nitrates are slowly added dropwise while stirring
Aqueous solution (concentration be 2 milligrams every milliliter), react at room temperature 1 hour, after reaction, precipitating be collected by centrifugation to get being in
The Silver nanorod of bolt structure/polymer/silver nanometer sheet core-shell nano material.Rapid 1) -3) centrifugal speed is 16000 revs/min in
Clock, centrifugation time are 10 minutes.
Figure 15 shows the transmission electron microscope photo of the nucleocapsid silver nanoparticle keeper material prepared in the present embodiment, from figure
15 as can be seen that prepared nano material is core-shell structure, by Silver nanorod kernel, Polymer interlayers and Nano silver piece shell
Layer composition, the Silver nanorod that wherein kernel is 310 nanometers of length, middle layer are that 10 nanometers of thickness of polystyrene polyacrylic acid is embedding
Section copolymer layer, shell be in keeper shape and be 520 nanometers of bottom side length Nano silver piece.
Figure 16 shows the Raman spectrogram of the nucleocapsid silver nanoparticle keeper material prepared in the present embodiment.It can be with from Figure 16
Find out, which has good SERS signal enhancement effect, in 1382 cm-1 The Raman signal intensity at place
Reach 33000.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material, it is characterised in that: the core-shell nano material is by silver
Nanometer rods kernel, the polymer covering layer for being wrapped in Silver nanorod surface and Nano silver piece outer layer three positioned at cover surface
It is grouped as, wherein the polystyrene polyacrylic acid block copolymer layer that the polymer covering layer is 10 nanometers of thickness；It is described
The length of Silver nanorod kernel be 400 nanometers -1.3 microns, the Nano silver piece outer layer is that side length 120-320 receives
The irregular sheet of rice；Or the length of the Silver nanorod kernel is 175-310 nanometers, the corresponding Nano silver piece
The keeper shape and its half package that outer layer is bottom side length 510-780 nanometers the Silver nanorod kernel.
2. a kind of Silver nanorod according to claim 1/polymer/silver nanometer sheet core-shell nano material preparation method,
Characterized by the following steps:
1) preparation of Silver nanorod: gold chloride, sodium citrate and sodium borohydride are dissolved in deionized water, are mixed 10 minutes
It stands 2 hours afterwards and obtains gold seeds aqueous solution；CTAB, gold chloride, silver nitrate, ascorbic acid, hydrochloric acid and gold seeds solution is molten
In deionized water, after being mixed 1 minute after static 12 hours, centrifugation obtains gold nano bipyramid；By gold nano bipyramid,
CTAC, silver nitrate and ascorbic acid are dissolved in be mixed evenly in deionized water after, at 60 DEG C heating reaction 4 hours, centrifugation
Collect precipitating afterwards to get Silver nanorod；
2) Silver nanorod/polymer core shell nanometer material preparation: Silver nanorod made from step 1) is taken to be added to containing Raman
In the dimethylformamide deionized water mixed solution of molecule 2- thionaphthol and polystyrene polyacrylic acid block copolymer, and it is acute
It is heated 2 hours at 110 DEG C after strong stirring, is slowly dropped to room temperature later, precipitating is collected after centrifugation to get Silver nanorod/polymerization
Object core-shell nano material；
3) Silver nanorod/polymer/silver nanometer sheet core-shell nano material preparation: by Silver nanorod/polymerization made from step 2)
Object core-shell nano material is dissolved in be dissolved in mixed liquor made of water silver nitrate and sodium citrate, is slowly added dropwise while stirring anti-bad
Hematic acid aqueous solution reacts 1 hour at room temperature, after reaction, precipitating is collected after centrifugation to get Silver nanorod/polymer/silver
Nanometer sheet core-shell nano material；
Or Silver nanorod made from step 2)/polymer core shell material is dissolved in by sodium citrate, ascorbic acid and hydrogen peroxide
It is dissolved in mixed liquor made of water, silver nitrate aqueous solution is slowly added dropwise while stirring, after reacting 1 hour at room temperature, from
Precipitating is collected after the heart to get Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
3. a kind of Silver nanorod according to claim 2/polymer/silver nanometer sheet core-shell nano material preparation method,
It is characterized in that step 1) specifically:
A. by 0.5-1.5 milligrams of gold chlorides, 0.735-2.205 milligrams of sodium citrates and 0.0567-0.1701 milligrams of sodium borohydrides
It is dissolved in 9.65-28.95 ml deionized water, standing after ten minutes is mixed and obtains gold seeds aqueous solution within 2 hours；
B. 2.92-8.76 grams of CTAB, 16-48 milligram gold chloride, 1.36-4.08 milligrams of silver nitrates, 11.26-33.78 milligrams are resisted
Bad hematic acid, 1.33-3.99 milliliter hydrochloric acid and 0.4-1.2 milliliters of gold seeds solution are mixed in 85-255 ml deionized water
Centrifugation obtains gold nano bipyramid after static 12 hours after 1 minute；
C. take above-mentioned steps prepare whole gold nano bipyramids, 6.14-18.42 grams of CTAC, 81.6-244.8 milligrams of silver nitrates and
422.4-1267.2 milligrams of ascorbic acid are dissolved in 400-1200 ml deionized water, after being mixed evenly, are added at 60 DEG C
Thermal response 4 hours, precipitating is collected after centrifugation to get Silver nanorod.
4. a kind of Silver nanorod according to claim 3/polymer/silver nanometer sheet core-shell nano material preparation method,
It is characterized in that step 2) specifically: Silver nanorod made from step 1) is taken to be added to containing 0.05-0.15 milligrams of Raman moleculars
2- thionaphthol and 0.5-1.5 milligrams of polystyrene polyacrylic acid block copolymers by 900-2700 microlitres of dimethylformamide and
It in the mixed liquor of 200-600 microlitres of deionized water composition, and heats 2 hours at 110 DEG C after being vigorously stirred, is slowly dropped to later
Precipitating is collected after centrifugation to get Silver nanorod/polymer core shell nanometer material in room temperature.
5. a kind of Silver nanorod according to claim 4/polymer/silver nanometer sheet core-shell nano material preparation method,
It is characterized in that step 3) specifically: Silver nanorod made from step 2)/polymer core shell nanometer material is taken to be dissolved in by 2-6 milligrams
Silver nitrate and 6-18 milligrams of sodium citrates are dissolved in 9-27 made of water milliliters of mixed liquor, and 2-6 milliliters are slowly added dropwise while stirring
Concentration be 2 milligrams every milliliter of aqueous ascorbic acid, react 1 hour at room temperature, after reaction, it is heavy to be collected after centrifugation
It forms sediment to get Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
6. a kind of Silver nanorod according to claim 5/polymer/silver nanometer sheet core-shell nano material preparation method,
It is characterized by: step 1) -3) in centrifugal speed be 5000-10000 revs/min, centrifugation time be 5-10 minutes.
7. a kind of Silver nanorod according to claim 4/polymer/silver nanometer sheet core-shell nano material preparation method,
It is characterized in that step 3) specifically: Silver nanorod made from step 2)/polymer core shell nanometer material is taken to be dissolved in by 2-4 milligrams
Sodium citrate, 4-8 milligram ascorbic acid and 12-36 microlitres of hydrogen peroxide are dissolved in 9-27 made of water milliliters of mixed liquor, side stirring
While the silver nitrate aqueous solution that the concentration for being slowly added dropwise 3-9 milliliters is 2 milligrams every milliliter, after reacting 1 hour at room temperature, from
Precipitating is collected after the heart to get Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
8. a kind of Silver nanorod according to claim 7/polymer/silver nanometer sheet core-shell nano material preparation method,
It is characterized by: rapid 1) -3) in centrifugal speed be 8000-16000 revs/min, centrifugation time is 10-20 minutes.
9. a kind of Silver nanorod of any of claims 1-8/polymer/silver nanometer sheet core-shell nano material is answered
With, it is characterised in that: the Silver nanorod/polymer/silver nanometer sheet nucleocapsid receives material in enhancing SERS signal output facet
Purposes.
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