CN107282918A - 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
- Publication number
- CN107282918A CN107282918A CN201710347677.6A CN201710347677A CN107282918A CN 107282918 A CN107282918 A CN 107282918A CN 201710347677 A CN201710347677 A CN 201710347677A CN 107282918 A CN107282918 A CN 107282918A
- Authority
- CN
- China
- Prior art keywords
- silver
- polymer
- nanorod
- nano material
- milligrams
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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 material and its preparation method and application, feature is that the core-shell nano material is made up of Silver nanorod kernel, polymer covering layer and the part of Nano silver piece outer layer three, and wherein polymer covering layer is the polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness；The length of Silver nanorod kernel is 400 nanometers 1.3 microns, and corresponding Nano silver piece outer layer is the irregular sheet of 120 320 nanometers of the length of side；Or the length of Silver nanorod kernel is 175 310 nanometers, corresponding Nano silver piece outer layer is the keeper shape of 510 780 nanometers of bottom side length and its half parcel Silver nanorod kernel, Silver nanorod/polymer/silver nanometer sheet core-shell nano material that the present invention is prepared using Seed inducement method, advantage is to produce the SERS signal with very high strength to export, its preparation technology is simple, cycle is short, and yield is high, it is easy to promotes and mass produces.
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 technology
In past 20 years, due to the sensitivity with unimolecule rank, SERS（SERS）Technology
Have been developed as life health care, the efficient analysis detection means in the field such as environmental monitoring and food security.In various SERS materials
In material, the advantage of noble metal nanometer material is its surface plasma body resonant vibration（LSPR）It can induce and produce extremely strong local electricity
Magnetic field, shows excellent enhancing characteristic.In these noble metal nanometer materials, silver is with its preferably enhancing characteristic and simply system
Standby technique is shown one's talent.By using polytype surfactant, people have been prepared for receiving with diversified silver
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, single silver nano-grain, its SERS signal is in general too weak to be used for Single Molecule Detection.Meanwhile,
The efficiency and reliability of SERS nano-probes are frequently subjected to the infringement of dissociation of ligand or exchange.In addition, except the output of high intensity
Signal, the uniformity and stability of other performances such as signal is also most important for the practical application of SERS substrates.Therefore, use
Advanced nano-fabrication technique makes novel Silver nanorod/polymer/silver nanometer sheet core-shell nano material, to obtain preferably
SERS performances are the technical problems of current detection field urgent need to resolve.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of silver nanoparticle of the SERS signal output with very high strength
Rod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：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
Constituted positioned at the part of Nano silver piece outer layer three of cover surface, wherein described polymer covering layer is the poly- of 10 nanometers of thickness
Styrene polyacrylic acid block copolymer layer；The length of described Silver nanorod kernel is 400 nanometers -1.3 microns, corresponding institute
The Nano silver piece outer layer stated is the irregular sheet of 120-320 nanometers of the length of side；Or the length of described Silver nanorod kernel is
175-310 nanometers, corresponding described Nano silver piece outer layer is the keeper shape of 510-780 nanometers of bottom side length and its half parcel is described
Silver nanorod kernel.
The preparation method of above-mentioned Silver nanorod/polymer/silver nanometer sheet core-shell nano material, comprises the following steps：
1）The preparation of Silver nanorod：Gold chloride, sodium citrate and sodium borohydride are dissolved in deionized water, mixed 10 minutes
Stand afterwards and obtain the gold seeds aqueous solution in 2 hours；CTAB, gold chloride, silver nitrate, ascorbic acid, hydrochloric acid and gold seeds solution is molten
In deionized water, after mixing 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, in heating response 4 hours at 60 DEG C, centrifugation
Precipitation is collected afterwards, produces Silver nanorod；
2）The preparation of Silver nanorod/polymer core shell nanometer material：Take step 1）Obtained Silver nanorod is added to containing Raman
In the dimethylformamide deionized water mixed solution of molecule 2- thionaphthols and polystyrene polyacrylic acid block copolymer, and it is acute
Strong stirring is slowly dropped to room temperature afterwards after being heated 2 hours at 110 DEG C, and collected after centrifugation precipitation produces Silver nanorod/polymerization
Thing core-shell nano material；
3）The preparation of Silver nanorod/polymer/silver nanometer sheet core-shell nano material：By step 2）Obtained Silver nanorod/polymerization
Thing core-shell nano material is dissolved in silver nitrate and sodium citrate are dissolved in the mixed liquor that water is made, and is slowly added dropwise while stirring anti-bad
The hematic acid aqueous solution, reacts 1 hour at room temperature, after reaction terminates, collected after centrifugation precipitation, produces Silver nanorod/polymer/silver
Nanometer sheet core-shell nano material；
Or by step 2）Obtained Silver nanorod/polymer core shell material is dissolved in by sodium citrate, ascorbic acid and hydrogen peroxide
It is dissolved in the mixed liquor that water is made, silver nitrate aqueous solution is slowly added dropwise while stirring, after reaction terminates for 1 hour at room temperature, from
Precipitation is collected after the heart, Silver nanorod/polymer/silver nanometer sheet core-shell nano material is produced.
Step 1）Specially：
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 waters, is stood after mixing 10 minutes and obtain the gold seeds aqueous solution in 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 waters
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 waters, after being mixed evenly, at 60 DEG C plus
Thermal response 4 hours, collected after centrifugation precipitation, produces Silver nanorod.
Step 2）Specially：Take step 1）Obtained Silver nanorod is 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
In the mixed liquor of 200-600 microlitres of deionized water composition, and it is stirred vigorously after being heated 2 hours at 110 DEG C, is slowly dropped to afterwards
Room temperature, collected after centrifugation precipitation, produces Silver nanorod/polymer core shell nanometer material.
Step 3）Specially：Take step 2）Obtained Silver nanorod/polymer core shell nanometer material is dissolved in by 2-6 milligrams of nitre
Sour silver and 6-18 milligrams of sodium citrates are dissolved in the 9-27 milliliter mixed liquors that water is made, and 2-6 milliliters are slowly added dropwise while stirring
Concentration is 2 milligrams every milliliter of aqueous ascorbic acid, is reacted 1 hour at room temperature, after reaction terminates, and collected after centrifugation sinks
Form sediment, produce Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
Step 1）-3）Middle centrifugal speed is 5000-10000 revs/min, and centrifugation time is 5-10 minutes.
Step 3）Specially：Take step 2）Obtained Silver nanorod/polymer core shell nanometer material is 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 the 9-27 milliliter mixed liquors that water is made, and are delayed while stirring
The slow concentration for being added dropwise 3-9 milliliters is 2 milligrams every milliliter of silver nitrate aqueous solution, is reacted at room temperature after terminating within 1 hour, after centrifugation
Precipitation is collected, Silver nanorod/polymer/silver nanometer sheet core-shell nano material is produced.
Rapid 1）-3）Middle centrifugal speed is 8000-16000 revs/min, and centrifugation time is 10-20 minutes.
The application of above-mentioned Silver nanorod/polymer/silver nanometer sheet core-shell nano material, described core-shell nano material is increasing
The purposes of strong SERS signal output facet.
Compared with prior art, the advantage of the invention is that：Present invention firstly discloses a kind of silver with SERS activity
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 polymer covering layer positioned at Silver nanorod surface and the part of Nano silver piece outer layer three composition on Silver nanorod,
The Silver nanorod for being coated with Raman molecular is wrapped up using polystyrene acrylic acid block copolymer, and it is former in shell copolymers layer surface
Position reduction silver nitrate formation Nano silver piece outer layer, obtains a kind of novel three-decker wherein two with excellent SERS characteristics
The block copolymer of parent's property, particularly polystyrene acrylic acid block copolymer are due to good translucency, without influenceing
The output of SERS signal.In addition, it, which forms exposed hydrophilic functional group after clad, can adsorb silver ion and also
Outside silver-colored shell is formed in the presence of former agent, by very thin polymer shell, the plasmon coupling of inside and outside silver layer will cause
Strong electromagnetic hotspot, causing the extreme of SERS signal strengthens.Particularly in core-shell nano keeper material, outside silver-colored shell
Half parcel is formd to Silver nanorod kernel, more preferably, obtained SERS signal intensity is higher for electromagnetic coupled effect therebetween.
Silver nanorod/polymer/silver nanometer sheet core-shell nano material that the present invention is prepared using Seed inducement method has phase
Two layers of noble silver nanometer layer away from only 10nm or so, in the presence of external exciting light, the surface local electricity that they are produced
The effect of intercoupling more by force can occur between magnetic field, hot spot region is produced, so that this material has very high strength
SERS signal is exported.The preparation technology that the present invention is used is simple, any toxic reagent is not used, green high-efficient, the cycle is short, yield
It is high, it is easy to promote and mass produce.
Brief description of the drawings
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 for preparing in the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope photo of the Silver nanorod/polymer core shell material prepared in the embodiment of the present invention 1；
Fig. 4 is Silver nanorod/larger range of transmission electron microscopy of polymer core shell material for preparing in the embodiment of the present invention 1
Mirror photo；
Fig. 5 is the transmitted electron of the Silver nanorod/polymer/silver nanometer sheet core-shell nano material prepared in the embodiment of the present invention 1
Microphotograph；
Fig. 6 is the drawing using the silver-colored Silver nanorod prepared in the embodiment of the present invention 1/polymer/silver nanometer sheet core-shell nano material
Graceful testing result；
Fig. 7 is the transmitted electron of the Silver nanorod/polymer/silver nanometer sheet core-shell nano material prepared in the embodiment of the present invention 2
Microphotograph；
Fig. 8 is the Raman using the Silver nanorod prepared in the embodiment of the present invention 2/polymer/silver nanometer sheet core-shell nano material
Testing result；
Fig. 9 is the transmitted electron of the Silver nanorod/polymer/silver nanometer sheet core-shell nano material prepared in the embodiment of the present invention 3
Microphotograph；
Figure 10 is the Raman using the Silver nanorod prepared in the embodiment of the present invention 3/polymer/silver nanometer sheet core-shell nano material
Testing 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.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.Unless otherwise specified, embodiment
In the conventional meanses that are well known to those skilled in the art of used technological means, raw materials used is commercial goods.Embodiment
The middle Raman spectrum detector BWS415 used is purchased from Bi Da Imtech of the U.S.（B&W Tek Inc.）.
Embodiment 1
The preparation method of Silver nanorod/polymer/silver nanometer sheet core-shell nano material comprises the following steps：
1st, 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 of deionizations
In water, stood after mixing 10 minutes and obtain the gold seeds aqueous solution in 2 hours；By 2.92 grams of CTAB（Cetyl trimethyl bromine
Change ammonium）, 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 it is above-mentioned
Centrifugation obtains gold nano bipyramid to gold seeds solution after static 12 hours after being mixed 1 minute in 85 ml deionized waters；Will
Whole gold nano bipyramids obtained above, 6.14 grams of CTAC（Hexadecyltrimethylammonium chloride）, 81.6 milligrams of silver nitrates and
422.4 milligrams of ascorbic acid are dissolved in be mixed evenly in 400 ml deionized waters after, in heating response at 60 DEG C 4 hours from
Precipitation is collected after the heart, Silver nanorod is produced；
2nd, whole Silver nanorods obtained above are taken to be added to containing 0.05 milligram of Raman molecular 2- thionaphthol and 0.5 milligram of polyphenyl
In the mixed liquor being made up of 900 microlitres of dimethylformamides and 200 microlitres of deionized waters of ethylene polypropylene acid block copolymer,
And be stirred vigorously after being heated 2 hours at 110 DEG C, be slowly dropped to room temperature afterwards, collected after centrifugation precipitation, produce Silver nanorod/
Polymer core shell nanometer material；
3rd, whole Silver nanorods/polymer core shell nanometer material obtained above is dissolved in by 2 milligrams of silver nitrates and 6 milligrams of lemons
Sour sodium is dissolved in 9 milliliters of mixed liquors that water is made, and the aqueous solution of 2 milliliters of ascorbic acid is slowly added dropwise while stirring（Concentration is 2 millis
Gram every milliliter）, react 1 hour at room temperature, after reaction terminates, collected after centrifugation precipitation produces Silver nanorod/polymer/silver
Nanometer sheet 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 the part of Nano silver piece outer layer three composition positioned at cover surface, wherein, kernel is 500 nanometers to 1 micron of length
Silver nanorod, clad be 10 nanometers of thickness polystyrene polyacrylic acid block copolymer layer, outermost layer be length of side 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
Do not formed and effectively coated, so to Silver nanorod without selectivity.
Fig. 3 shows the transmission electron microscope photo of the Silver nanorod/polymer core shell material prepared in the present embodiment,
From figure 3, it can be seen that prepared silver nanoparticle core is wrapped up by one layer of intimate transparent polymeric shell layer.Fig. 4 shows this implementation
The larger range of transmission electron microscope photo of Silver nanorod/polymer core shell material for preparing in example, as seen from the figure silver nanoparticle
The size of rod 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 the Silver nanorod/polymer/silver nanometer sheet nucleocapsid with SERS activity prepared using the above method
The Raman spectrogram of nano material.From fig. 6, it can be seen that the SERS active materials have good SERS signal enhancement effect,
It is in 1382 cm-1The Raman signal intensity at place reaches 25000.
Embodiment 2
The preparation method of Silver nanorod/polymer/silver nanometer sheet core-shell nano material comprises the following steps：
1st, by 1 milligram of gold chloride, 1.47 milligrams of sodium citrates and 0.1134 milligram of sodium borohydride in 19.3 ml deionized waters
Stood after mixing 10 minutes and obtain the gold seeds aqueous solution in 2 hours；By 5.84 grams of CTAB, 32 milligrams of gold chlorides, 2.72 milligrams
Silver nitrate, 22.52 milligrams of ascorbic acid, 2.66 milliliters of hydrochloric acid and 0.8 milliliter of above-mentioned gold seeds solution are in 170 ml deionized waters
In, centrifugation obtains gold nano bipyramid after static 12 hours after mixing 1 minute；By whole gold nano bipyramids obtained above,
12.28 grams of CTAC, 163.2 milligrams of silver nitrates and 844.8 milligrams of ascorbic acid, which are dissolved in 800 ml deionized waters, to be mixed
It is even to be precipitated after 4 hours collected after centrifugation of heating response at 60 DEG C, produce Silver nanorod；
2nd, whole Silver nanorods obtained above are taken to be added to containing 0.1 milligram of Raman molecular 2- thionaphthol and 1 milligram of polyphenyl second
In the mixed liquor being made up of 1800 microlitres of dimethylformamides and 400 microlitres of deionized waters of alkene polyacrylic acid block copolymer,
And be stirred vigorously after being heated 2 hours at 110 DEG C, room temperature is slowly dropped to afterwards, is centrifuged, precipitation is collected, and produces Silver nanorod/poly-
Compound core-shell nano material；
3rd, whole Silver nanorods/polymer core shell nanometer material obtained above is dissolved in by 4 milligrams of silver nitrates and 12 milligrams of lemons
Lemon acid sodium is dissolved in 18 milliliters of mixed liquors that water is made, and the aqueous solution of 4 milliliters of ascorbic acid is slowly added dropwise while stirring（Concentration is
2 milligrams every milliliter）, at room temperature react 1 hour, reaction terminate after, collected after centrifugation precipitation, produce Silver nanorod/polymer/
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
Compound clad and the part of Nano silver piece outer layer three composition positioned at cover surface, wherein, kernel is that 700 nanometers of length is arrived
1.3 microns of Silver nanorods, clad is the polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness, and outermost layer is the length of side
130-320 nanometers of Nano silver piece.
Fig. 7 shows that the Silver nanorod/polymer/silver nanometer sheet nucleocapsid with SERS activity prepared in the present embodiment is received
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 the Silver nanorod/polymer/silver nanometer sheet nucleocapsid with SERS activity prepared using the above method
The Raman spectrogram of nano material.From figure 8, it is seen that the SERS active materials have good SERS signal enhancement effect,
It is in 1382 cm-1 The Raman signal intensity at place reaches 20000.
Embodiment 3
The preparation method of Silver nanorod/polymer/silver nanometer sheet core-shell nano material comprises the following steps：
1st, by 1.5 milligrams of gold chlorides, 2.205 milligrams of sodium citrates and 0.1701 milligram of sodium borohydride in 28.95 milliliters of deionizations
In water, stood after mixing 10 minutes and obtain the gold seeds aqueous solution in 2 hours；By 8.76 grams of CTAB, 48 milligrams of gold chlorides, 4.08
Milligram silver nitrate, 33.78 milligrams of ascorbic acid, 3.99 milliliters of hydrochloric acid and 1.2 milliliters of above-mentioned gold seeds solution gone in 255 milliliters from
Centrifugation obtains gold nano bipyramid after static 12 hours after being mixed 1 minute in sub- water；Whole gold nanos obtained above are double
Cone, 18.42 grams of CTAC, 244.8 milligrams of silver nitrates and 1267.2 milligrams of ascorbic acid, which are dissolved in 1200 ml deionized waters, to be mixed
After stirring, in 4 hours collected after centrifugation precipitations of heating response at 60 DEG C, Silver nanorod is produced；
2nd, take whole Silver nanorods obtained above to add and contain 0.15 milligram of Raman molecular 2- thionaphthol and 1.5 milligrams of polyphenyl second
In the mixed liquor being made up of 2700 microlitres of dimethylformamides and 600 microlitres of deionized waters of alkene polyacrylic acid block copolymer,
And be stirred vigorously after being heated 2 hours at 110 DEG C, be slowly dropped to room temperature afterwards, collected after centrifugation precipitation, produce Silver nanorod/
Polymer core shell nanometer material；
3rd, whole Silver nanorods/polymer core shell nanometer material obtained above is dissolved in by 6 milligrams of silver nitrates and 18 milligrams of lemons
Lemon acid sodium is dissolved in 27 milliliters of mixed liquors that water is made, and the aqueous solution of 6 milliliters of ascorbic acid is slowly added dropwise while stirring（Concentration is
2 milligrams every milliliter）, at room temperature react 1 hour, reaction terminate after, collected after centrifugation precipitation, produce Silver nanorod/polymer/
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 the part of Nano silver piece outer layer three composition positioned at cover surface, wherein, kernel is that 400 nanometers of length is received to 480
The Silver nanorod of rice, clad is the polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness, and outermost layer is the length of side
130-140 nanometers of Nano silver piece.
Fig. 9 shows that the Silver nanorod/polymer/silver nanometer sheet nucleocapsid with SERS activity prepared in the present embodiment is received
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 the Silver nanorod/polymer/silver nanometer sheet core with SERS activity prepared using the above method
The Raman spectrogram of shell nanometer material.From fig. 10 it can be seen that the SERS active materials have good SERS signal enhancing effect
Should, it is in 1382 cm-1The Raman signal intensity at place reaches 15000.
Embodiment 4
With above-mentioned specific embodiment 1, its difference is：
Whole Silver nanorod/polymer core shell materials made from step 2 are dissolved in by 2 milligrams of sodium citrates, 4 milligrams of ascorbic acid
It is dissolved in 12 microlitres of hydrogen peroxide in 9 milliliters of mixed liquors that water is made, the aqueous solution of 3 milliliters of silver nitrates is slowly added dropwise while stirring
（Concentration is 2 milligrams every milliliter）, react 1 hour at room temperature, after reaction terminates, precipitation be collected by centrifugation, produces in bolt structure
Silver nanorod/polymer/silver nanometer sheet core-shell nano material.Wherein rapid 1）-3）Middle centrifugal speed is 12000 revs/min, from
The heart 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 is constituted, and wherein kernel is the Silver nanorod of 230 nanometers of length, and intermediate layer is the polystyrene polypropylene of 10 nanometers of thickness
Sour block copolymer layer, shell is the Nano silver piece in 780 nanometers of keeper shape and bottom side length.It is actual when making keeper material
The upper only less nanometer rods of size are wrapped, and the larger longer nanometer rods of size can not be wrapped, what is subsequently centrifuged
During, not wrapped 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.Can be with from Figure 12
Find out, the SERS active materials have good SERS signal enhancement effect, its Raman signal intensity at 1382 cm-1
Reach 50000.
Embodiment 5
With above-mentioned specific embodiment 1, its difference is：
Whole Silver nanorod/polymer core shell materials made from step 2 are dissolved in by 4 milligrams of sodium citrates, 8 milligrams of ascorbic acid
It is dissolved in 24 microlitres of hydrogen peroxide in 18 milliliters of mixed liquors that water is made, the aqueous solution of 6 milliliters of silver nitrates is slowly added dropwise while stirring
（Concentration is 2 milligrams every milliliter）, react 1 hour at room temperature, after reaction terminates, collected after centrifugation precipitation is produced in keeper knot
The Silver nanorod of structure/polymer/silver nanometer sheet core-shell nano material.Rapid 1）-3）Middle centrifugal speed is 8000 revs/min, 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 is constituted, and wherein kernel is the Silver nanorod of 175 nanometers of length, and intermediate layer is the polystyrene polypropylene of 10 nanometers of thickness
Sour block copolymer layer, shell is the Nano silver piece in 510 nanometers of keeper shape and bottom side length.
Figure 14 shows the Raman spectrogram of the nucleocapsid silver nanoparticle keeper material prepared in the present embodiment.Can be with from Figure 14
Find out, the SERS active materials have good SERS signal enhancement effect, and it is in 1382 cm-1 The Raman signal intensity at place
Reach 40000.
Embodiment 6
With above-mentioned specific embodiment 1, its difference is：
By whole nanometer rods/polymer core shell material made from above-mentioned steps 2 be dissolved in by 6 milligrams of sodium citrates, 12 milligrams it is anti-bad
Hematic acid and 36 microlitres of hydrogen peroxide are dissolved in 27 milliliters of mixed liquors that water is made, and the water of 9 milliliters of silver nitrates is slowly added dropwise while stirring
Solution（Concentration is 2 milligrams every milliliter）, react 1 hour at room temperature, after reaction terminates, precipitation be collected by centrifugation, produces in keeper
The Silver nanorod of structure/polymer/silver nanometer sheet core-shell nano material.Rapid 1）-3）Middle centrifugal speed is 16000 revs/min, from
The heart time is 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, wherein kernel are the Silver nanorod of 310 nanometers of length, and intermediate layer is embedding for the polystyrene polyacrylic acid of 10 nanometers of thickness
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.Can be with from Figure 16
Find out, the SERS active materials have good SERS signal enhancement effect, and it is 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, belong to the scope of protection of present 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 the Nano silver piece outer layer three positioned at cover surface
It is grouped into, wherein described polymer covering layer is the polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness；It is described
The length of Silver nanorod kernel be 400 nanometers -1.3 microns, corresponding described Nano silver piece outer layer is received for length of side 120-320
The irregular sheet of rice；Or the length of described Silver nanorod kernel is 175-310 nanometers, corresponding described Nano silver piece
Outer layer is the keeper shape of 510-780 nanometers of bottom side length and the described Silver nanorod kernel of its half parcel.
2. a kind of preparation method of Silver nanorod according to claim 1/polymer/silver nanometer sheet core-shell nano material,
It is characterized in that comprising the following steps：
1）The preparation of Silver nanorod：Gold chloride, sodium citrate and sodium borohydride are dissolved in deionized water, mixed 10 minutes
Stand afterwards and obtain the gold seeds aqueous solution in 2 hours；CTAB, gold chloride, silver nitrate, ascorbic acid, hydrochloric acid and gold seeds solution is molten
In deionized water, after mixing 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, in heating response 4 hours at 60 DEG C, centrifugation
Precipitation is collected afterwards, produces Silver nanorod；
2）The preparation of Silver nanorod/polymer core shell nanometer material：Take step 1）Obtained Silver nanorod is added to containing Raman
In the dimethylformamide deionized water mixed solution of molecule 2- thionaphthols and polystyrene polyacrylic acid block copolymer, and it is acute
Strong stirring is slowly dropped to room temperature afterwards after being heated 2 hours at 110 DEG C, and collected after centrifugation precipitation produces Silver nanorod/polymerization
Thing core-shell nano material；
3）The preparation of Silver nanorod/polymer/silver nanometer sheet core-shell nano material：By step 2）Obtained Silver nanorod/polymerization
Thing core-shell nano material is dissolved in silver nitrate and sodium citrate are dissolved in the mixed liquor that water is made, and is slowly added dropwise while stirring anti-bad
The hematic acid aqueous solution, reacts 1 hour at room temperature, after reaction terminates, collected after centrifugation precipitation, produces Silver nanorod/polymer/silver
Nanometer sheet core-shell nano material；
Or by step 2）Obtained Silver nanorod/polymer core shell material is dissolved in by sodium citrate, ascorbic acid and hydrogen peroxide
It is dissolved in the mixed liquor that water is made, silver nitrate aqueous solution is slowly added dropwise while stirring, after reaction terminates for 1 hour at room temperature, from
Precipitation is collected after the heart, Silver nanorod/polymer/silver nanometer sheet core-shell nano material is produced.
3. a kind of preparation method of Silver nanorod according to claim 2/polymer/silver nanometer sheet core-shell nano material,
It is characterized in that step 1）Specially：
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 waters, is stood after mixing 10 minutes and obtain the gold seeds aqueous solution in 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 waters
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 waters, after being mixed evenly, at 60 DEG C plus
Thermal response 4 hours, collected after centrifugation precipitation, produces Silver nanorod.
4. a kind of preparation method of Silver nanorod according to claim 3/polymer/silver nanometer sheet core-shell nano material,
It is characterized in that step 2）Specially：Take step 1）Obtained Silver nanorod is added to containing 0.05-0.15 milligrams of Raman moleculars
2- thionaphthols and 0.5-1.5 milligrams of polystyrene polyacrylic acid block copolymers by 900-2700 microlitres of dimethylformamide and
In the mixed liquor of 200-600 microlitres of deionized water composition, and it is stirred vigorously after being heated 2 hours at 110 DEG C, is slowly dropped to afterwards
Room temperature, collected after centrifugation precipitation, produces Silver nanorod/polymer core shell nanometer material.
5. a kind of preparation method of Silver nanorod according to claim 4/polymer/silver nanometer sheet core-shell nano material,
It is characterized in that step 3）Specially：Take step 2）Obtained Silver nanorod/polymer core shell nanometer material is dissolved in by 2-6 milligrams
Silver nitrate and 6-18 milligrams of sodium citrates are dissolved in the 9-27 milliliter mixed liquors that water is made, 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 terminates, collected after centrifugation sinks
Form sediment, produce Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
6. a kind of preparation method of Silver nanorod according to claim 5/polymer/silver nanometer sheet core-shell nano material,
It is characterized in that：Step 1）-3）Middle centrifugal speed is 5000-10000 revs/min, and centrifugation time is 5-10 minutes.
7. a kind of preparation method of Silver nanorod according to claim 4/polymer/silver nanometer sheet core-shell nano material,
It is characterized in that step 3）Specially：Take step 2）Obtained Silver nanorod/polymer core shell nanometer material is dissolved in by 2-4 milligrams
Silver nitrate, 4-8 milligram ascorbic acid and 12-36 microlitres of hydrogen peroxide are dissolved in the 9-27 milliliter mixed liquors that water is made, while stirring
The concentration for being slowly added dropwise 3-9 milliliters is 2 milligrams every milliliter of silver nitrate aqueous solution, after reaction terminates for 1 hour at room temperature, centrifugation
Precipitation is collected afterwards, produces Silver nanorod/polymer/silver nanometer sheet core-shell nano material.
8. a kind of preparation method of Silver nanorod according to claim 7/polymer/silver nanometer sheet core-shell nano material,
It is characterized in that：Rapid 1）-3）Middle centrifugal speed is 8000-16000 revs/min, and centrifugation time is 10-20 minutes.
9. a kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material any one of claim 1-8 should
With, it is characterised in that：Described Silver nanorod/polymer/silver nanometer sheet nucleocapsid receives material in enhancing SERS signal output facet
Purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347677.6A CN107282918B (en) | 2017-05-17 | 2017-05-17 | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710347677.6A CN107282918B (en) | 2017-05-17 | 2017-05-17 | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107282918A true CN107282918A (en) | 2017-10-24 |
| CN107282918B CN107282918B (en) | 2019-01-22 |
Family
ID=60094348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710347677.6A Active CN107282918B (en) | 2017-05-17 | 2017-05-17 | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107282918B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108746595A (en) * | 2018-06-22 | 2018-11-06 | 黄河科技学院 | A kind of different-shape gold nano bipyramid-gold and silver nanocomposite and preparation method thereof |
| CN109232863A (en) * | 2018-07-19 | 2019-01-18 | 华侨大学 | A kind of preparation method of Silver nanorod/poly- (3,4- ethylenedioxy thiophene) core-shell nano material |
| CN109270046A (en) * | 2018-08-30 | 2019-01-25 | 东南大学 | A kind of construction method of the controllable micro-nano array based on gold and silver nano brick and its application |
| CN110899720A (en) * | 2018-09-18 | 2020-03-24 | 东南大学 | Two-dimensional flexible noble metal nanoparticle superlattice film and construction method and application thereof |
| CN114990494A (en) * | 2022-05-27 | 2022-09-02 | 江苏师范大学 | Gold nano-layer-coated silver nano-rod array-based surface-enhanced Raman scattering (SERS) substrate with pine cone structure and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060053971A1 (en) * | 2004-09-10 | 2006-03-16 | Shouheng Sun | Dumbbell-like nanoparticles and a process of forming the same |
| CN101306468A (en) * | 2007-05-19 | 2008-11-19 | 浙江师范大学 | Preparation method of conductive silver composite nano particles coated by polypyrrole |
| WO2013052541A2 (en) * | 2011-10-04 | 2013-04-11 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Quantum dots, rods, wires, sheets, and ribbons, and uses thereof |
| CN103394704A (en) * | 2013-08-20 | 2013-11-20 | 纳米籽有限公司 | Method for preparing high-purity gold nanoparticle bipyramid and composite nanomaterial of gold nanoparticle bipyramid |
| CN104162665A (en) * | 2014-08-29 | 2014-11-26 | 华东理工大学 | Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof |
| CN104308184A (en) * | 2014-10-24 | 2015-01-28 | 武汉理工大学 | Method for preparing Au-Ag (gold-silver) nuclear shell nano particles by visible light |
| CN104607654A (en) * | 2015-02-10 | 2015-05-13 | 济南大学 | Self-assembly material based on silver nanoparticles and preparation method thereof |
| CN106041352A (en) * | 2016-08-17 | 2016-10-26 | 武汉工程大学 | Silver nano-particle coated by organic acid silver, method for preparing silver nano-particle and application thereof |
-
2017
- 2017-05-17 CN CN201710347677.6A patent/CN107282918B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060053971A1 (en) * | 2004-09-10 | 2006-03-16 | Shouheng Sun | Dumbbell-like nanoparticles and a process of forming the same |
| CN101306468A (en) * | 2007-05-19 | 2008-11-19 | 浙江师范大学 | Preparation method of conductive silver composite nano particles coated by polypyrrole |
| WO2013052541A2 (en) * | 2011-10-04 | 2013-04-11 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For And On Behalf Of Arizona State University | Quantum dots, rods, wires, sheets, and ribbons, and uses thereof |
| CN103394704A (en) * | 2013-08-20 | 2013-11-20 | 纳米籽有限公司 | Method for preparing high-purity gold nanoparticle bipyramid and composite nanomaterial of gold nanoparticle bipyramid |
| CN104162665A (en) * | 2014-08-29 | 2014-11-26 | 华东理工大学 | Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof |
| CN104308184A (en) * | 2014-10-24 | 2015-01-28 | 武汉理工大学 | Method for preparing Au-Ag (gold-silver) nuclear shell nano particles by visible light |
| CN104607654A (en) * | 2015-02-10 | 2015-05-13 | 济南大学 | Self-assembly material based on silver nanoparticles and preparation method thereof |
| CN106041352A (en) * | 2016-08-17 | 2016-10-26 | 武汉工程大学 | Silver nano-particle coated by organic acid silver, method for preparing silver nano-particle and application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108746595A (en) * | 2018-06-22 | 2018-11-06 | 黄河科技学院 | A kind of different-shape gold nano bipyramid-gold and silver nanocomposite and preparation method thereof |
| CN109232863A (en) * | 2018-07-19 | 2019-01-18 | 华侨大学 | A kind of preparation method of Silver nanorod/poly- (3,4- ethylenedioxy thiophene) core-shell nano material |
| CN109232863B (en) * | 2018-07-19 | 2021-04-30 | 华侨大学 | Preparation method of silver nanorod/poly (3, 4-ethylenedioxythiophene) core-shell nano material |
| CN109270046A (en) * | 2018-08-30 | 2019-01-25 | 东南大学 | A kind of construction method of the controllable micro-nano array based on gold and silver nano brick and its application |
| CN110899720A (en) * | 2018-09-18 | 2020-03-24 | 东南大学 | Two-dimensional flexible noble metal nanoparticle superlattice film and construction method and application thereof |
| CN114990494A (en) * | 2022-05-27 | 2022-09-02 | 江苏师范大学 | Gold nano-layer-coated silver nano-rod array-based surface-enhanced Raman scattering (SERS) substrate with pine cone structure and preparation method thereof |
| CN114990494B (en) * | 2022-05-27 | 2024-02-09 | 江苏师范大学 | Pine cone structure SERS substrate with gold nano layer coated with silver nano rod array and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107282918B (en) | 2019-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107282918A (en) | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application | |
| Brinson et al. | Nanoshells made easy: improving Au layer growth on nanoparticle surfaces | |
| CN107189317B (en) | A kind of silver/polymer/silver/graphene core-shell nano mushroom material and its preparation method and application | |
| Bonacchi et al. | Luminescent chemosensors based on silica nanoparticles | |
| Kim et al. | Facile method to prepare surface-enhanced-Raman-scattering-active Ag nanostructures on silica spheres | |
| CN104741603B (en) | A kind of dissymmetrical structure Tri-metal nanoparticle, preparation method and applications | |
| CN107418124B (en) | A kind of dendritic nucleocapsid Silver nanodisks material and its preparation method and application | |
| Huang et al. | Trapping iron oxide into hollow gold nanoparticles | |
| CN102094246A (en) | Gold nucleus and silver shell double-metal nanocrystal and preparation method thereof | |
| CN110735131A (en) | Bionic SERS substrate with metal-based compound eye bowl structures, construction method and application | |
| CN106623979A (en) | Preparation method of gold-silver alloy nanoparticles | |
| CN107186210B (en) | A kind of gold/silver/polymer/silver nanometer sheet core-shell material and preparation method thereof | |
| CN107225235B (en) | One kind having the active gold/silver of SERS/polymer/silver core-shell nano mushroom material and its preparation method and application | |
| CN109128210A (en) | A kind of dumbbell shaped gold nano bipyramid/argentum nano composite material and preparation method thereof | |
| CN107189314A (en) | A kind of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material and its preparation method and application | |
| CN109295716A (en) | A kind of preparation method of magnetic, temperature collaboration stimuli responsive hydrogel | |
| CN103198913B (en) | Silver-tri-iron tetroxide core shell nanoparticles and preparation method thereof | |
| CN109807323B (en) | Silver cube/flower-shaped silicon dioxide core-shell nano material and preparation method and application thereof | |
| CN107322005A (en) | A kind of SERS substrate fabrication method based on nano-Ag particles | |
| CN108152266B (en) | Core-shell material based on polydopamine, and preparation method and application thereof | |
| CN108202140A (en) | The seed mediated growth method of polyethyleneimine prepares silicon core silver core-shell nanoparticles | |
| CN113084192A (en) | Method for synthesizing gold nano-star at normal temperature by one step | |
| CN107189315A (en) | A kind of nucleocapsid silver nanoparticle triangular plate material and preparation method thereof | |
| CN109187482A (en) | A kind of preparation method and application of the nanocomposite with core-shell structure | |
| CN107189316B (en) | A kind of nucleocapsid silver nanoparticle hexagonal disk material and its preparation method and application with longer nano gap |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220714 Address after: Room 2202, 22 / F, Wantong building, No. 3002, Sungang East Road, Sungang street, Luohu District, Shenzhen City, Guangdong Province Patentee after: Shenzhen dragon totem technology achievement transformation Co.,Ltd. Address before: 315211, Fenghua Road, Jiangbei District, Zhejiang, Ningbo 818 Patentee before: Ningbo University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221104 Address after: No. 99, Gangcheng Road, Dongying Port Economic Development Zone, Dongying City, Shandong Province 257237 Patentee after: Dongying Ruigang Investment Service Co.,Ltd. Address before: Room 2202, 22 / F, Wantong building, No. 3002, Sungang East Road, Sungang street, Luohu District, Shenzhen City, Guangdong Province Patentee before: Shenzhen dragon totem technology achievement transformation Co.,Ltd. |