CN106887295A - A kind of structure and preparation method of magnetic honeysuckle flower nano particle - Google Patents
A kind of structure and preparation method of magnetic honeysuckle flower nano particle Download PDFInfo
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- CN106887295A CN106887295A CN201510932466.XA CN201510932466A CN106887295A CN 106887295 A CN106887295 A CN 106887295A CN 201510932466 A CN201510932466 A CN 201510932466A CN 106887295 A CN106887295 A CN 106887295A
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 48
- 241000205585 Aquilegia canadensis Species 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 23
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 23
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 23
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 239000004332 silver Substances 0.000 claims abstract description 17
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006249 magnetic particle Substances 0.000 claims abstract description 12
- 238000002604 ultrasonography Methods 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 230000012010 growth Effects 0.000 claims abstract description 4
- 238000007747 plating Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 230000004043 responsiveness Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 2
- 239000012263 liquid product Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000011241 protective layer Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 230000035040 seed growth Effects 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 238000001069 Raman spectroscopy Methods 0.000 description 16
- 239000005843 Thiram Substances 0.000 description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 9
- 229960002447 thiram Drugs 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012990 dithiocarbamate Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011806 microball Substances 0.000 description 3
- 239000011807 nanoball Substances 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- ZVAVRBUTFWLEBK-UHFFFAOYSA-N NC1=CC(=C(C=C1)S)C1=CC=CC=C1 Chemical compound NC1=CC(=C(C=C1)S)C1=CC=CC=C1 ZVAVRBUTFWLEBK-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical class [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 235000011091 sodium acetates Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010876 biochemical test Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
- H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
- H01F1/112—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles with a skin
-
- B22F1/0007—
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- 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
- B22F2207/00—Aspects of the compositions, gradients
- B22F2207/01—Composition gradients
- B22F2207/07—Particles with core-rim gradient
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
Abstract
The invention discloses a kind of structure of magnetic honeysuckle flower nano particle and preparation method thereof, the structure is with magnetic nano-particle (Fe3O4) it is core, with silica shell (SiO2) it is Multifunctional layered, and the flower-shaped silver-colored shell that fast-growth goes out similar needle point is reduced by formaldehyde.Preparation method is as follows：In 100-600 nanometer Fes3O4One layer of SiO of magnetic nano-particle Surface coating2Shell, improves the dispersiveness of magnetic nano-particle and provides the site of silver-colored seed growth；Then by the chemical-electrical plating method of ultrasonic wave added in Fe3O4@SiO2Magnetic particle superficial growth goes out the seed that one layer of homogeneous, intensive silver particles grow as flower-shaped silver-colored shell；Finally with formaldehyde as reducing agent, ammoniacal liquor quickly restores magnetic honeysuckle flower nano particle for catalyst under ultrasound condition.The invention also discloses the magnetic honeysuckle flower nano particle prepared by the above method as high performance magnetic SERS substrates, its good dispersion, magnetic induction strong, Stability Analysis of Structures, with a large amount of focuses, can be directly used for the SERS detections of the illegal additive of various small molecule contaminants, residues of pesticides, food etc..
Description
Technical field
The present invention relates to a kind of structure and preparation method for preparing magnetic honeysuckle flower nano particle, belong to photonic material, nano material neck
Domain.
Background technology
Magnetic nanoparticle can in the presence of external magnetic field fast enriching, capture target sample, it is simple to operate, it is easy to modify,
It is widely used in various biochemical tests at present.Exposed magnetic bead is easily oxidized, and is dissolved in sour environment, and
Surface lacks active group.Therefore, multiple material is used to parcel or modifying magnetic nano particle, makes it have preferably stabilization
Property, biocompatibility and multifunctionality, such as SiO2、TiO2、Au、Ag、Al2O3Deng.Wherein, silver have catalysis, it is sterilized and
The properties such as optics, are a kind of ideal materials for modifying magnetic bead.The particularly noble metal such as gold, silver can significantly increase its near surface
The Raman signal of material, this phenomenon be referred to as SERS (Surface Enhanced Raman Scattering,
SERS).This is that, because gold, silver nano-particle has surface plasma resonance property, and surface plasma resonance causes nano-particle
Neighbouring localized electromagnetic field greatly strengthens.Now there are some researches show the surface plasma resonance property of noble metal is big with particle
Small, shape and species are closely related, and wherein nanotip and nano gap can produce the electromagnetic field " focus ", these focuses can to show
Write the analyte signal amplified positioned at nano gap area.The surface enhanced ability of silver is stronger 10-100 times than golden.
Recently, the correlative study for carrying out modified magnetic micro-/ nano ball using silver is more and more, but typically just simply by silver parcel with
Nucleocapsid structure is formed on magnetic micro-/ nano ball or Nano silver grain is directly connected to magnetic micro-/ nano ball surface.These silver are repaiied
The magnetic nano-composite particle of decorations can not provide enough focuses for SERS detection fields, and SERS performances are not ideal enough.Than
Surface area is big, and surface extra coarse degree is big and magnetic honeysuckle flower nanostructured of flower-like structure with nanotip is not obtained also.
The content of the invention
Single dispersing, high-performance, the magnetic honeysuckle flower nanometer with flower-shaped silver-colored shell structure are prepared it is an object of the invention to provide a kind of
The method of grain.Wherein, Fe3O4Particle provides very strong magnetic response ability as core, can be quick in the presence of external magnetic field
Enrichment target sample, and flower-shaped silver-colored shell has coarse surface and nano level tip, there is substantial amounts of hotspot architecture.It is this
Magnetic honeysuckle flower nano-particle can be used as a kind of magnetic SERS substrates of excellent performance.
A kind of preparation method of high performance magnetic honeysuckle flower nano-particle, it is characterised in that comprise the following steps：
1) 100-600 nanometer Fes are synthesized3O4Magnetic nano-particle；
2) in step 1) synthesis 100-600 nanometer Fes3O4One layer of thicker SiO of magnetic nano-particle Surface coating2Shell, shape
Into Fe3O4@SiO2Magnetic nano-particle；
3) in step 2) synthesis Fe3O4@SiO2Magnetic nano-particle surface ultrasound assisted chemical galvanoplastic, grow one layer
Ag nanometers of tiny seed, forms Fe3O4@SiO2- Ag seed magnetic nano-particles, preserve in ethanol after magnetic enrichment；
4) step 3) synthesis Fe3O4@SiO2- Ag seed magnetic nano-particles disperse in aqueous, under ultrasound condition according to
Secondary addition silver nitrate, formaldehyde, ammoniacal liquor, reaction add polyvinylpyrrolidone after five minutes, continue to react 5-10 minutes；
5) utilize external magnetic field enriching step 4) synthesis magnetic product, ultrasonic dispersion cycle clean 3 times, removal reaction residual
Thing, that is, obtain high-performance, monodispersed magnetic honeysuckle flower nano-particle.
Step (1) described Fe3O4The preparation method of magnetic nano-particle is as follows：By 1.35g Iron(III) chloride hexahydrates, the poly- second two of 1g
Alcohol 20000,2.7g anhydrous sodium acetates are dissolved in 40mL ethylene glycol solutions, and stirring is until be completely dissolved；By the transfer of above-mentioned solution
To in 50 milliliters of pyroreaction kettles of polytetrafluoroethylliner liner, it is placed in after sealing in air blast constant temperature oven, 6-24 is reacted at 200 DEG C
Hour；Reaction naturally cools to room temperature after terminating, and black precipitate is collected with magnet, and 2 are respectively washed with deionized water and absolute ethyl alcohol
It is secondary, in 60 DEG C of dryings 5 hours in vacuum drying chamber, obtain powdered Fe3O4Magnetic nano-particle is standby.
Step (2) described SiO2Shell cladding uses teos hydrolysis method, concretely comprises the following steps：Take 100 milligrams of Fe3O4Powder
It is dissolved in 150 milliliters of ethanol solutions, adds 10 milliliters of ammoniacal liquor and 10 ml deionized waters, ultrasonic disperse adds one after 10 minutes
Quantitative tetraethyl orthosilicate, continues to react 1 hour.
Step (3) ultrasound assisted chemical galvanoplastic are concretely comprised the following steps：Fe3O4@SiO2Add in the magnetic nano-particle aqueous solution
Enter 10 milliliters of dilute hydrochloric acid solutions of stannous chloride, ultrasonic reaction 30 minutes, stannous ion is adsorbed in Fe3O4@SiO2Magnetic nano particle
The SiO of son2Case surface.Washed 5 times after magnetic enrichment product, add 10 milliliters 20-40 mM/ls of silver ammino solution, surpassed
Phonoresponse 20-30 minutes, it is dispersed in ethanol solution after magnetic enrichment cleaning.
Silver nitrate addition described in step (4) is 0.03-0.1 mg/mls, and formaldehyde addition is overall solution volume
0.03%-0.05%, ammoniacal liquor addition is the 0.05%-0.1% of solution weight volume, addition 5-10 milligrams of polyvinylpyrrolidone
/ milliliter.
Beneficial effect
The method of the present invention can simply efficient preparation structure be homogeneous, good dispersion, the magnetic with magnetic responsiveness and a large amount of focuses
Property honeysuckle flower nano-particle.In the building block of the magnetic honeysuckle flower nano-particle, Fe3O4Magnetic nano-particle is provided as core
Enough magnetic, preparing, washing when, in that context it may be convenient to collected using additional magnet, it is to avoid numerous using centrifugation, filtering etc.
Trivial time-consuming method.
The method of the present invention is first using the chemical-electrical plating method of stannous chloride mediation in Fe3O4@SiO2Surface form homogeneous, intensive silver
Nanometer seed, the growth of follow-up flower-shaped silver-colored shell is preferentially carried out on these silver nanoparticle seeds.Simultaneously thicker SiO2Shell causes magnetic
Particle has dispersiveness well, and the reunion of magnetic particle occurs in ensure that building-up process under ultrasound condition, finally determines
The dispersiveness and structural homogeneity of magnetic honeysuckle flower nano-particle.
The present invention is by controlling the addition of silver nitrate can be with the length of precise control magnetic honeysuckle flower nano-particle honeysuckle flower shell.It is existing
Research shows that nano level tip can produce very strong surface Raman enhancement effect, while the surface of flower-shaped silver-colored shell is very coarse
Further increase the quantity that focus is emerged.
The magnetic honeysuckle flower nano-particle of present invention synthesis had both had the characteristic of enrichment with magnetic bead concentrating sample, and with silver nano material light
Learn and chemical characteristic, and flower-shaped silver-colored shell is easy to chemical modification, is a kind of effective multifunctional nanocomposites.
The simple synthetic method of magnetic honeysuckle flower nano-particle of the present invention, material requested is common medicine, reagent, required
Instrument is common test instrument, and cost is relatively low.
The present invention prepares magnetic honeysuckle flower nano-particle can be dirty in identification and the environment of different material as a kind of effective SERS substrates
Superpower sensitivity is shown in the detection for contaminating thing, there is very big application potential in the detection of the harmful substances such as chemistry, biology,
Field of fast detection has broad application prospects at the scene especially to coordinate Portable Raman spectrometer.
Brief description of the drawings
Fig. 1 is the experiment flow figure that embodiment 1 prepares magnetic honeysuckle flower nano-particle.
Fig. 2 is transmission electron microscope (TEM) photo of magnetic honeysuckle flower nano-particle prepared by embodiment 1.
Fig. 3 is field emission scanning electron microscope (SEM) photo of magnetic honeysuckle flower nano-particle prepared by embodiment 1.
Fig. 4 is X-ray diffraction (XRD) result of magnetic honeysuckle flower nano-particle prepared by embodiment 1.
Fig. 5 is the B-H loop result of magnetic honeysuckle flower nano-particle prepared by embodiment 1.
Fig. 6 is the SERS collection of illustrative plates of Raman labels molecule p-aminophenyl thiophenol (PATP) detection of the magnetic honeysuckle flower nano-particle to commonly using.
Fig. 7 is the SERS collection of illustrative plates that magnetic honeysuckle flower nano-particle is detected to dithiocarbamate agricultural chemicals thiram (thiram).
Specific embodiment
Hereinafter implementation will the present invention will be further described with reference to accompanying drawing.
Embodiment 1
A kind of preparation of high performance magnetic honeysuckle flower nano-particle：
Fig. 1 provides the preparation flow schematic diagram of magnetic honeysuckle flower nano-particle.Its specific preparation method is divided into following five step：First
Step, 100-600 nanometers of Fe is synthesized using solvent-thermal process method3O4Magnetic nano-particle.Take 1.35g Iron(III) chloride hexahydrates molten
Solution in 40ml ethylene glycol, magnetic agitation 30 minutes.Then, 2.7g sodium acetates and 1g PEG 20000s are added to this
In solution and stir until reactant be completely dissolved, then, by mixture be transferred to polytetrafluoroethylliner liner autoclave (50 milli
Rise capacity) in and be heated to 200 degrees Celsius react 6-24 hours.Product is collected with magnet, respectively with deionized water and ethanol
Each washing 2 times, finally by the vacuum drying 5 hours of 60 degrees Celsius of product, obtains powdered Fe3O4Magnetic particle is standby.
Second step, using SiO2Shell coats Fe3O4Magnetic particle, SiO2Shell cladding uses teos hydrolysis method, specific steps
For：Take 100 milligrams of Fe3O4Powder is dissolved in 150 milliliters of ethanol solutions, adds 10 milliliters of ammoniacal liquor and 10 ml deionized waters,
Ultrasonic disperse adds a certain amount of tetraethyl orthosilicate after 10 minutes, continue to react 1 hour.
3rd step, using stannous chloride to Fe3O4@SiO2Magnetic particle is sensitized, and is concretely comprised the following steps：Fe3O4@SiO2Magnetic is received
10 milliliters of dilute hydrochloric acid solutions of stannous chloride are added in the rice corpuscles aqueous solution, ultrasonic reaction 30 minutes, stannous ion absorption exists
Fe3O4@SiO2The SiO of magnetic nano-particle2Case surface.Washed 5 times after magnetic enrichment product.
4th step, using the chemical-electrical plating method of ultrasonic wave added in SiO2Shell superficial growth goes out a large amount of silver nanoparticle seed (Fe3O4@SiO2-Ag
Seed), concretely comprise the following steps：The Fe that stannous ion is sensitized3O4@SiO2Magnetic particle is added in 10 milliliters of saturation silver ammino solutions,
Ultrasonic reaction 20 minutes so that Ag nanometers of seed it is uniform, intensive be grown on Fe3O4@SiO2Magnetic particle surface.Magnetic enrichment is sunk
It is washed with deionized water behind shallow lake 2 times, is stored in ethanol.
Finally, Fe is added in 200 milliliters of aqueous solution3O4@SiO20.1 milliliter of-Ag seed magnetic nano-particles, under ultrasound condition
Silver nitrate, formaldehyde, ammoniacal liquor and polyvinylpyrrolidone are sequentially added, continues to react obtaining within 5-10 minutes monodispersed magnetic honeysuckle flower
Nano-particle.
The transmission electron microscope picture of sample forms a large amount of as shown in Fig. 2 magnetic honeysuckle flower nanoparticle surface has the projection of many columns
Nanoscale tip.Scale is respectively 100 nanometers with 500 nanometers.
Fig. 3 is shown the field emission scanning electron microscope picture of magnetic honeysuckle flower nano-particle, it can be seen that petal-like prominent from picture
The surface for being uniformly distributed in magnetic honeysuckle flower nano-particle is acted, and with preferable structural integrity.Scale is respectively 100 nanometers
With 500 nanometers.
Fig. 4 is shown the X-ray diffraction result of magnetic honeysuckle flower nano-particle, it was demonstrated that the crystalline structure of sample is by Fe3O4
Constituted with Ag.
Fig. 5 is shown the B-H loop result of magnetic honeysuckle flower nano-particle, and saturation magnetization is 23.1emu/g, shows sample
Product have preferable magnetic response ability.
Embodiment 2
The SERS for characterizing magnetic honeysuckle flower nano-particle using Raman labels molecule p-aminophenyl thiophenol (PATP) strengthens ability：
PATP is conventional sulfydryl Raman mark, and significant Chemical enhancement raman characteristic peak can be produced when being combined with gold or silver.Match somebody with somebody
Put the PATP ethanol solutions (10 of various concentrations-5-10-12Mole), every 1 milliliter of pipe.Magnetic honeysuckle flower nano-particle is added above-mentioned
In solution, ultrasonic reaction 30 minutes makes PATP fully be incorporated into the surface of magnetic honeysuckle flower nano-particle, by particle after Magneto separate
Concentrate is added drop-wise on clean silicon chip, and Raman detection is carried out after drying.
Fig. 6 is the experimental result of embodiment 2.Fig. 6 is shown the Raman collection of illustrative plates of the PATP that magnetic honeysuckle flower nano-particle is excited,
Abscissa is Raman shift, wherein 1078,1576cm-1Peak is the main peak in PATP characteristic peaks.The experimental result shows, magnetic
The detection of honeysuckle flower detection PATP is limited to 1 × 10-11Mole.Raman detection condition is firing time 5 seconds, 20% exciting power.
Embodiment 3
Dithiocarbamate agricultural chemicals thiram (thiram) is detected using magnetic honeysuckle flower nano-particle：
Thiram is a kind of conventional dithiocarbamate agricultural chemicals, with stronger raman characteristic peak.Magnetic honeysuckle flower is received
Rice corpuscles is added in the thiram aqueous solution of various concentrations, and ultrasound is incubated 15 minutes, and portable drawing is directly used after magnetic enrichment particle
Graceful spectrometer is detected.
Fig. 7 is the experimental result of embodiment 3.Fig. 7 is shown the Raman of the thiram molecule that magnetic honeysuckle flower nano-particle is excited
Collection of illustrative plates, abscissa is Raman shift, wherein 561,1385cm-1Peak is the main peak in thiram characterization of molecules peak.Raman detection bar
Part is firing time 5 seconds, 20% exciting power.The experimental result shows that magnetic honeysuckle flower nano-particle detects the test limit of thiram
It is 1 × 10-10Mole, with very effective surface-enhanced Raman performance.
Above-described embodiment only technology design and feature to illustrate the invention, its object is to allow the person skilled in the art can
Understand present disclosure and implement according to this, can not limit the scope of the invention according to this.It is all according to spirit of the invention
The equivalent change or modification made, should all be included within the scope of the present invention.
Claims (5)
1. a kind of structure and preparation method of magnetic honeysuckle flower nano particle, it is characterised in that following steps：
1) in 100-600 nanometers of Fe3O4The method of magnetic particle surface teos hydrolysis, it is quick under ultrasound condition
One layer of SiO of cladding2Shell, forms Fe3O4@SiO2Magnetic nano-particle.
2) under ultrasound condition, using the method for chemical plating in Fe3O4@SiO2The superficial growth of magnetic nano-particle goes out intensive, equal
One silver-colored seed, forms Fe3O4@SiO2- Ag seed magnetic particles.It is stored in ethanol solution after magnetic enrichment cleaning.
3) by Fe3O4@SiO2- Ag seed magnetic particles disperse in aqueous, under ultrasound condition, to be sequentially added into silver nitrate,
Formaldehyde, is subsequently adding ammoniacal liquor.Ultrasonic temperature is controlled for 20-40 degrees Celsius, it is ultrasonic 10-30 minutes, treat flower-shaped magnetic silver nanoparticle
Toward PVP is added in solution after the completion of granular grows, continue to react more than 10 minutes.Cleaned with water after magnetic enrichment
3 times, obtain monodispersed magnetic honeysuckle flower nano particle.
4) magnetic honeysuckle flower nano particle has the Fe of strong magnetic response ability3O4The flower-shaped silver-colored shell of core and similar needle point, with multiple heat
Point effect, is a kind of high performance magnetic SERS substrates.
2. preparation method according to claim 1, it is characterised in that：With in step (3), the Fe of input3O4@SiO2-Ag seed
Particle concentration is 0.1-0.2 mg/mls, and the silver nitrate concentration of addition is 0.03-0.1 mg/mls, and the addition of formaldehyde is molten
The 0.03%-0.05% of liquid product, the addition of ammoniacal liquor is the 0.05%-0.1% of liquor capacity, and the concentration of PVP is
5-10 mg/mls.Reaction condition is ultrasonic reaction.
3. preparation method according to claim 1, it is characterised in that：The specific method of the step (1) is：Superparamagnetic
The Fe of property3O4Nano particle is synthesized using solvent-thermal process method, is distributed to ethanol/water/ammoniacal liquor=180: in 10: 8 mixed solution, plus
Enter 200 microlitres of tetraethyl orthosilicate, ultrasonic reaction 1 hour.
4. preparation method according to claim 1, it is characterised in that：The specific method of the step (2) is：By single point
Scattered Fe3O4@SiO2Magnetic nano-particle is distributed in 10 milliliters of water, adds 30 points of the dilute hydrochloric acid solution ultrasonic reaction of stannous chloride
Clock, centrifugal enrichment particle is simultaneously washed 5 times, is disperseed in backwater solution again.Stannous ion was sensitized under ultrasound condition
Fe3O4@SiO2Magnetic nano-particle is added in the saturation silver ammino solution of 0.1 mol/L, and reaction is cleaned after 20 minutes with water.
5. magnetic honeysuckle flower nano particle according to claim 1, its architectural feature is：Kernel is strong magnetic responsiveness
Fe3O4 magnetic particles, protective layer is water miscible SiO2 shells, and outermost layer is the flower-shaped silver-colored shell of similar needle point.
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| CN108411285A (en) * | 2018-04-24 | 2018-08-17 | 合肥工业大学 | A kind of quick green syt of the flower-shaped silver SERS composite constructions of rice krispies of graphene oxide modification |
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| CN110243801A (en) * | 2019-05-31 | 2019-09-17 | 深圳市农产品质量安全检验检测中心(深圳市动物疾病预防控制中心) | A kind of preparation method of the magnetic composite nano particle of modification and its application in Pesticides Testing |
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| CN113249114A (en) * | 2021-04-30 | 2021-08-13 | 盐城工学院 | Method for enhancing luminescent property of fluorescent material by utilizing magnetization of ferrimagnetic composite particles |
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| CN108411285A (en) * | 2018-04-24 | 2018-08-17 | 合肥工业大学 | A kind of quick green syt of the flower-shaped silver SERS composite constructions of rice krispies of graphene oxide modification |
| CN108837694A (en) * | 2018-07-02 | 2018-11-20 | 宁夏大学 | A method of removing nonvalent mercury and fixed ion mercury from flue gas |
| CN108837694B (en) * | 2018-07-02 | 2021-04-02 | 宁夏大学 | Method for removing zero-valent mercury and fixing ionic mercury from flue gas |
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| CN110243801B (en) * | 2019-05-31 | 2021-08-24 | 深圳市农产品质量安全检验检测中心(深圳市动物疾病预防控制中心) | Preparation method of modified magnetic composite nano-particles and application of modified magnetic composite nano-particles in pesticide detection |
| CN111085181A (en) * | 2019-11-20 | 2020-05-01 | 辽宁石油化工大学 | Preparation method and application of magnetic composite material with porous structure |
| CN111085181B (en) * | 2019-11-20 | 2023-01-13 | 辽宁石油化工大学 | Preparation method and application of magnetic composite material with porous structure |
| CN113249114A (en) * | 2021-04-30 | 2021-08-13 | 盐城工学院 | Method for enhancing luminescent property of fluorescent material by utilizing magnetization of ferrimagnetic composite particles |
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