CN116288295A - Au nail with adjustable length and surface roughness and preparation method thereof - Google Patents
Au nail with adjustable length and surface roughness and preparation method thereof Download PDFInfo
- Publication number
- CN116288295A CN116288295A CN202310290929.1A CN202310290929A CN116288295A CN 116288295 A CN116288295 A CN 116288295A CN 202310290929 A CN202310290929 A CN 202310290929A CN 116288295 A CN116288295 A CN 116288295A
- Authority
- CN
- China
- Prior art keywords
- nail
- surface roughness
- chloroauric acid
- aniline
- reaction
- 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.)
- Pending
Links
- 230000003746 surface roughness Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000010931 gold Substances 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000012071 phase Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052737 gold Inorganic materials 0.000 claims abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 10
- 241000587161 Gomphocarpus Species 0.000 claims abstract description 6
- 238000004458 analytical method Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 57
- 239000011521 glass Substances 0.000 claims description 56
- 239000010408 film Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000005520 cutting process Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000008346 aqueous phase Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002070 nanowire Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- ULHFFAFDSSHFDA-UHFFFAOYSA-N 1-amino-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1N ULHFFAFDSSHFDA-UHFFFAOYSA-N 0.000 description 1
- -1 1-octyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- FIMJSWFMQJGVAM-UHFFFAOYSA-N chloroform;hydrate Chemical compound O.ClC(Cl)Cl FIMJSWFMQJGVAM-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to an Au nail with adjustable length and surface roughness and a preparation method thereof, wherein aniline is added into chloroform to form a solution with certain concentration as an organic phase, the organic phase is added into a reaction vessel with a carrier at the bottom, then chloroauric acid solution with certain concentration is added to form a liquid/liquid two-phase interface reaction system, after standing reaction at room temperature, gold films are grown at the two-phase interface, the organic phase and the water phase in the solution system after standing reaction are respectively extracted, the films are deposited on the carrier, and the gold films with the nail morphology are obtained by purifying the films. The preparation method is simple and easy to implement, and can prepare the composite material in one step at room temperature without a hard template, seeds and the like. The prepared gold film has a nail-shaped structure, a larger nail head and a slender nail body, is rough in surface, can realize the regulation and control of the surface roughness and the length of the nail body by adjusting the concentration of reactants, has sensitive SERS reaction, and can be used in SERS analysis.
Description
Technical Field
The invention relates to the field of preparation of precious metal Au micro-nano materials, in particular to an Au nail with adjustable length and surface roughness and a preparation method thereof.
Background
The liquid/liquid interface is used as a special place, has special properties different from the organic phase and the water phase, such as higher viscosity, density, dielectric constant with wider gradient and the like, can effectively assemble nano materials with ordered structures, and can also be used as a reaction place for preparing micro-nano materials and film materials.
The chinese patent application No. 201010558973.9 devised a special reaction apparatus for obtaining different conductive polymer films, such as polymer films of thiophene, pyrrole, indole and derivatives thereof, by polymerizing monomers at an organic-water interface using an electrochemical method. The invention is as follows: 201911244484.3 at chloroform-water interface, chloroplatinic acid is taken as an electron acceptor and an acidic environment is provided, and the poly-o-ethoxyaniline micro-nano structural material with a large number of burrs at the two sides of the strip is obtained through interfacial polymerization. The Chinese patent application No. 202110454844.3 prepares the one-dimensional nano fibrous Au nanoparticle composite material with the particle size of 8nm loaded by the poly 3, 4-ethylenedioxythiophene by dissolving the 3, 4-ethylenedioxythiophene in dichloromethane, dissolving chloroauric acid in water phase and performing liquid/liquid interface reaction.
The liquid/liquid interface not only consists of an organic phase-water phase, but also can form a liquid/liquid two-phase reaction system by hydrophobic ionic liquid and water, and the invention patent 201810674134.X is a hydrophobic ionic liquid 1-octyl-3-methylimidazole hexafluorophosphate ([ C) 8 mim][PF 6 ]) And the Ag-polypyrrole or Ag-poly 3, 4-ethylenedioxythiophene composite film material is prepared by successful polymerization at the liquid/liquid interface formed by water. Although the methods adopt liquid/liquid interfaces to prepare different materials, complex electrochemical devices or expensive ionic liquids are used, or the prepared materials are polymers or metal-polymer composite materials, and the metal materials have no special morphology or structure.
The Au nano-material has good biocompatibility, adjustable matrix characteristics, higher catalytic activity and the like, and is widely applied to the fields of medical treatment, cosmetics, catalysis and the like. The preparation method of the Au nano-material is roughly divided into the following steps: gas-liquid-solid (VLS) growth methods, vapor phase growth methods (non-VLS mechanisms), seed methods, template methods, and the like. For example, the Chinese patent with publication number of CN 107322007A uses Au salt as a precursor, 1-naphthol as a reducing agent and a structure directing agent, and the Au nanowire is obtained by reaction at 60 ℃. The Chinese patent publication No. CN105675688A provides a technical route for preparing the ultra-long Au nanowire by adopting a hard template method, and the method firstly needs to synthesize the Te ultra-long nanowire, prepares the Au ultra-long nanowire by taking the Te ultra-long nanowire as a template, and the like.
Because the performance of the Au nano-material is closely related to the shape, size and structure of the Au nano-material and the wide application of the Au nano-material, researchers are still enthusiastic to develop a new synthetic technology route so as to prepare the Au micro-nano-material with special shape and excellent performance.
Disclosure of Invention
The invention provides an Au nail with adjustable length and surface roughness and a preparation method thereof, and aims to provide a gold micro-nano material with a novel morphology structure and a preparation method thereof, so that a gold film with a nail morphology is prepared by a one-step method at room temperature, the preparation difficulty of the gold micro-nano material is reduced, the surface roughness and the length of a nail body of the gold film are adjustable, and the performance of the gold film in the application fields of optics, surface enhanced Raman scattering, catalysis and the like is controllable.
The invention is realized by the following technical scheme, and the Au nail with adjustable length and surface roughness and the preparation method thereof provided by the invention comprise the following steps:
(1) Cutting the glass slide, soaking the glass slide in a mixed solution of hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 2 hours to remove surface impurities, and then cleaning the glass slide with absolute ethyl alcohol for later use;
(2) Weighing a certain amount of aniline, adding the aniline into chloroform, and preparing aniline solution with a certain concentration as an organic phase for later use;
(3) Weighing a certain amount of chloroauric acid, adding the chloroauric acid into distilled water, and preparing a chloroauric acid solution with a certain concentration as a water phase for later use;
(4) Placing the glass slide cleaned in the step (1) into the bottom of a transparent glass reaction container, adding a certain volume of the aniline solution prepared in the step (2) into the transparent glass reaction container, then adding an equal volume of the chloroauric acid solution prepared in the step (3) to form a liquid/liquid two-phase interface reaction system, standing at room temperature for reaction for 12-36 hours, and generating a film at the two-phase interface;
(5) After the reaction is finished, extracting an organic phase, depositing a film on a glass slide which is placed at the bottom of a transparent glass reaction container in advance, extracting a water phase, soaking and cleaning the film with absolute ethyl alcohol for 5 times, and naturally airing to prepare the purified gold film with nail morphology loaded on the glass slide.
Preferably, the molar concentration of the aniline solution prepared in step (2) is 25-150 mM.
Preferably, the chloroauric acid solution prepared in the step (3) has a molar concentration of 5-10 mM.
In the preparation method of the Au nail with adjustable length and surface roughness, the organic phase and the water phase in the step (5) can be extracted by a syringe.
Further, the gold film prepared by the method has a nail-shaped structure, is of a face-centered cubic structure, has a rough surface, is provided with a large nail head and a slender nail body, the diameter of the nail head is about 3-5 mu m, the diameter of the nail body is about 1-3 mu m, and the surface roughness and the length of the nail body can be regulated and controlled by changing the concentration of aniline solution and chloroauric acid solution, so that the performance of the gold film is controllable.
The gold film prepared by the method can be used as an active substrate for SERS analysis, and has sensitive SERS response.
Compared with the prior art, the invention has obvious advantages and beneficial effects. By means of the technical scheme, the invention can achieve quite technical progress and practicability, has wide utilization value, and has at least the following advantages:
(1) The preparation method of the invention carries out reaction at the liquid/liquid two-phase interface, the product grows into a film with a golden nail shape at the interface, the whole process is simple to operate, seed solution, soft template and hard template are not needed, and complex processes such as high temperature, stirring and the like are not needed. The reaction condition is simple and mild, and the gold nail with stable structure and adjustable length and surface roughness can be synthesized in one step by standing reaction at room temperature.
(2) From Scanning Electron Microscope (SEM) images of the product, it can be seen that the gold film produced has a typical nail-like structure with a large head and an elongated shank. The diameter of the head is about 3-5 mu m, the diameter of the shank is about 1-3 mu m, the length of the shank is adjustable, the surface is rough, and the shank has an obvious hierarchical structure. Under the condition that the concentration of the chloroauric acid solution is unchanged, the length of the gold nail body can be increased by properly increasing the concentration of the aniline solution. In a certain range, the smaller the concentration ratio of the aniline solution to the chloroauric acid solution is, the larger the surface roughness of the product is, so that the length and the surface roughness of the final product can be adjusted by regulating the concentration of the reactant. Therefore, the optical, surface enhanced Raman scattering, catalysis and other properties of the prepared gold nails can be changed.
(3) The film prepared by the invention can be conveniently transferred to any carrier (such as a silicon chip, a glass slide and the like) and used as an active substrate for SERS test, and no complex post-treatment process is needed. The prepared gold nails with adjustable surface roughness have sensitive SERS reaction, and can be used for analysis and research related to SERS.
Drawings
FIG. 1 is an SEM image at a magnification of 5000 times of an Au nail prepared in example 1;
FIG. 2 is an XRD pattern of the Au nail prepared in example 1;
FIG. 3 is an SEM image at a magnification of 5000 times of Au nails prepared in example 2;
FIG. 4 is an SEM image at a magnification of 5000 times of Au nails prepared in example 3;
FIG. 5 is an SEM image at a magnification of 5000 times of an Au nail prepared in example 4;
fig. 6 is an SEM image of the Au nail prepared in example 5 at 5000 x magnification.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
(1) Cutting a glass slide into square blocks with the size of 1cm multiplied by 1cm, soaking the square blocks in a mixed solution of hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 2 hours to remove surface impurities, and cleaning the square blocks with absolute ethyl alcohol for later use;
(2) Weighing a certain amount of aniline, adding the aniline into chloroform, and preparing an aniline solution with the molar concentration of 25.5mM as an organic phase for later use;
(3) Weighing a certain amount of chloroauric acid, adding the chloroauric acid into distilled water to prepare a chloroauric acid solution with a molar concentration of 5.0mM, and taking the chloroauric acid solution as a water phase for later use;
(4) Placing the glass slide cleaned in the step (1) into a cylindrical glass bottle bottom with the diameter of about 2.2cm, adding 4mL of the aniline solution prepared in the step (2) into the cylindrical glass bottle, then adding 4mL of the chloroauric acid solution prepared in the step (3) to form a liquid/liquid two-phase interface reaction system, standing at room temperature for reaction for 36h, and generating a film at the two-phase interface;
(5) After the reaction is finished, the lower organic phase is pumped out by a syringe, the film is deposited on a glass slide which is placed at the bottom of the glass bottle in advance, the water phase is pumped out by the syringe, the film is soaked and washed for 5 times by absolute ethyl alcohol, and the Au nail loaded on the glass slide is prepared by naturally airing.
Fig. 1 is an SEM image of the product of this example at 5000 x magnification, as can be seen to have a typical nail-like structure with a large head and an elongated shank. The head diameter is about 3.5 μm, the shank diameter is about 2.5 μm, and the shank length is about 9.5 μm. The surface is rough and has obvious hierarchical structure.
Fig. 2 is an XRD pattern of the product of this example, which can be seen to be a face-centered cubic structure.
Example 2
(1) Cutting a glass slide into square blocks with the size of 1cm multiplied by 1cm, soaking the square blocks in a mixed solution of hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 2 hours to remove surface impurities, and cleaning the square blocks with absolute ethyl alcohol for later use;
(2) Weighing a certain amount of aniline, adding the aniline into chloroform, and preparing an aniline solution with the molar concentration of 98.8mM as an organic phase for later use;
(3) Weighing a certain amount of chloroauric acid, adding the chloroauric acid into distilled water to prepare a chloroauric acid solution with a molar concentration of 5.0mM, and taking the chloroauric acid solution as a water phase for later use;
(4) Placing the glass slide cleaned in the step (1) into a cylindrical glass bottle bottom with the diameter of about 2.2cm, adding 4mL of the aniline solution prepared in the step (2) into the cylindrical glass bottle, then adding 4mL of the chloroauric acid solution prepared in the step (3) to form a liquid/liquid two-phase interface reaction system, standing at room temperature for reaction for 20 hours, and generating a film at the two-phase interface;
(5) After the reaction is finished, the lower organic phase is pumped out by a syringe, the film is deposited on a glass slide which is placed at the bottom of the glass bottle in advance, the water phase is pumped out by the syringe, the film is soaked and washed for 5 times by absolute ethyl alcohol, and the Au nail loaded on the glass slide is prepared by naturally airing.
FIG. 3 is an SEM image at 5000 Xmagnification of the product of this example, and it can be seen that the Au nail prepared is significantly longer, becomes bent, and has a length of about 34.4. Mu.m. The diameter of the nail head hardly changed, and the diameter of the shank became smaller, about 1.5 μm. The surface was also rougher, but less rough than the sample obtained in example 1.
Example 3
(1) Cutting a glass slide into square blocks with the size of 1cm multiplied by 1cm, soaking the square blocks in a mixed solution of hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 2 hours to remove surface impurities, and cleaning the square blocks with absolute ethyl alcohol for later use;
(2) Weighing a certain amount of aniline, adding the aniline into chloroform, and preparing an aniline solution with the molar concentration of 97.4mM as an organic phase for later use;
(3) Weighing a certain amount of chloroauric acid, adding the chloroauric acid into distilled water to prepare a chloroauric acid solution with the molar concentration of 10.0mM, and taking the chloroauric acid solution as a water phase for later use;
(4) Placing the glass slide cleaned in the step (1) into a cylindrical glass bottle bottom with the diameter of about 2.2cm, adding 4mL of the aniline solution prepared in the step (2) into the cylindrical glass bottle, then adding 4mL of the chloroauric acid solution prepared in the step (3) to form a liquid/liquid two-phase interface reaction system, standing at room temperature for reaction for 36h, and generating a film at the two-phase interface;
(5) After the reaction is finished, the lower organic phase is pumped out by a syringe, the film is deposited on a glass slide which is placed at the bottom of the glass bottle in advance, the water phase is pumped out by the syringe, the film is soaked and washed for 5 times by absolute ethyl alcohol, and the Au nail loaded on the glass slide is prepared by naturally airing.
Fig. 4 is an SEM image of the gold nail prepared in this example at 5000 x magnification, and it can be seen that the Au nail length is still longer, beyond the shooting range of the SEM image, the surface is slightly roughened, and the roughness is lower than that of the samples obtained in examples 1 and 2.
Example 4
(1) Cutting a glass slide into square blocks with the size of 1cm multiplied by 1cm, soaking the square blocks in a mixed solution of hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 2 hours to remove surface impurities, and cleaning the square blocks with absolute ethyl alcohol for later use;
(2) Weighing a certain amount of aniline, adding the aniline into chloroform, and preparing aniline solution with the molar concentration of 199.7mM as an organic phase for later use;
(3) Weighing a certain amount of chloroauric acid, adding the chloroauric acid into distilled water to prepare a chloroauric acid solution with a molar concentration of 5.0mM, and taking the chloroauric acid solution as a water phase for later use;
(4) Placing the glass slide cleaned in the step (1) into a cylindrical glass bottle bottom with the diameter of about 2.2cm, adding 4mL of the aniline solution prepared in the step (2) into the cylindrical glass bottle, then adding 4mL of the chloroauric acid solution prepared in the step (3) to form a liquid/liquid two-phase interface reaction system, standing at room temperature for reaction for 12 hours, and generating a film at the two-phase interface;
(5) After the reaction is finished, the lower organic phase is pumped out by a syringe, the film is deposited on a glass slide which is placed at the bottom of the glass bottle in advance, the water phase is pumped out by the syringe, the film is soaked and washed for 5 times by absolute ethyl alcohol, and the Au nail loaded on the glass slide is prepared by naturally airing.
Fig. 5 is an SEM image of the Au nail prepared in this example at 5000 x magnification, and it can be seen that the Au nail is still long and curved, the head is also significantly changed, the head diameter is slightly larger, and the taper transitions to the shank, rather than the several sample heads and shanks of examples 1-3 having a significant demarcation. In addition, the sample prepared in this example had a smoother surface.
Example 5
(1) Cutting a glass slide into square blocks with the size of 1cm multiplied by 1cm, soaking the square blocks in a mixed solution of hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 2 hours to remove surface impurities, and cleaning the square blocks with absolute ethyl alcohol for later use;
(2) Weighing a certain amount of aniline, adding the aniline into chloroform, and preparing an aniline solution with the molar concentration of 25.2mM as an organic phase for later use;
(3) Weighing a certain amount of chloroauric acid, adding the chloroauric acid into distilled water to prepare a chloroauric acid solution with the molar concentration of 2.5mM, and taking the chloroauric acid solution as a water phase for later use;
(4) Placing the glass slide cleaned in the step (1) into a cylindrical glass bottle bottom with the diameter of about 2.2cm, adding 4mL of the aniline solution prepared in the step (2) into the cylindrical glass bottle, then adding 4mL of the chloroauric acid solution prepared in the step (3) to form a liquid/liquid two-phase interface reaction system, standing at room temperature for reaction for 12 hours, and generating a film at the two-phase interface;
(5) After the reaction is finished, the lower organic phase is pumped out by a syringe, the film is deposited on a glass slide which is placed at the bottom of the glass bottle in advance, the water phase is pumped out by the syringe, the film is soaked and washed for 5 times by absolute ethyl alcohol, and the Au nail loaded on the glass slide is prepared by naturally airing.
Fig. 6 is an SEM image of a gold nail prepared in this example at 5000 x magnification, and it can be seen that this sample only left a rough head, without growing a shank, with the surface of the head being the most rough.
As is clear from the comparison of the above examples, in order to prepare a gold thin film having a gold nail morphology, the optimum molar concentration of the aniline solution is 25 to 150mM, the optimum molar concentration of the chloroauric acid solution is 5 to 10mM, and the ratio of the molar concentration of the aniline solution to the molar concentration of the chloroauric acid solution is preferably (5 to 20): 1.
In the above embodiments. The addition amount of the aniline solution and the chloroauric acid solution is 4mL. However, the present invention is not limited to the specific addition amount of the aniline solution, and the same scale up or down can be performed according to the above method.
Meanwhile, the invention is not limited to a cylindrical glass bottle with the diameter of about 2.2cm, other reaction containers, preferably a transparent glass reaction container, can be used, and the generation condition of an interface reaction product is convenient to observe. The invention is not limited to having to cut the slide to the dimensions described, but may be cut to other dimensions in other applications.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, without departing from the scope of the technical solution of the present invention, will still fall within the scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the Au nail with adjustable length and surface roughness is characterized by comprising the following steps of:
(1) Cutting the glass slide, soaking the glass slide in a mixed solution of hydrogen peroxide and concentrated sulfuric acid in a volume ratio of 1:1 for 2 hours to remove surface impurities, and then cleaning the glass slide with absolute ethyl alcohol for later use;
(2) Weighing a certain amount of aniline, adding the aniline into chloroform, and preparing aniline solution with a certain concentration as an organic phase for later use;
(3) Weighing a certain amount of chloroauric acid, adding the chloroauric acid into distilled water, and preparing a chloroauric acid solution with a certain concentration as a water phase for later use;
(4) Placing the glass slide cleaned in the step (1) into the bottom of a transparent glass reaction container, adding a certain volume of the aniline solution prepared in the step (2) into the transparent glass reaction container, then adding an equal volume of the chloroauric acid solution prepared in the step (3) to form a liquid/liquid two-phase interface reaction system, standing at room temperature for reaction for 12-36 hours, and generating a film at the two-phase interface;
(5) After the reaction is finished, extracting an organic phase, depositing a film on a glass slide which is placed at the bottom of a transparent glass reaction container in advance, extracting a water phase, soaking and cleaning the film with absolute ethyl alcohol for 5 times, and naturally airing to prepare the gold film with the nail morphology loaded on the glass slide.
2. The method for producing Au nails with adjustable length and surface roughness as claimed in claim 1, wherein the molar concentration of the aniline solution prepared in the step (2) is 25 to 150mM.
3. The method for producing Au nails with adjustable length and surface roughness as claimed in claim 1 or 2, wherein the chloroauric acid solution prepared in step (3) has a molar concentration of 5 to 10mM.
4. The method of producing Au nails of adjustable length and surface roughness as claimed in claim 1, wherein both the organic phase and the aqueous phase in step (5) are extracted by syringe.
5. The method of manufacturing Au nails with adjustable length and surface roughness as claimed in claim 1, wherein the prepared Au thin film has a nail-like structure with a rough surface, a large nail head and a long and thin shank, the diameter of the nail head is about 3 to 5 μm, the diameter of the shank is about 1 to 3 μm, and the surface roughness and the shank length are adjustable.
6. The method for manufacturing an Au nail with adjustable length and surface roughness as claimed in claim 1 or 5, wherein the surface roughness and the length of the shank of the gold thin film having the morphology of the nail are controlled by changing the concentrations of the aniline solution and the chloroauric acid solution.
7. The method for producing Au nails with adjustable length and surface roughness as claimed in claim 1 or 5, wherein the produced gold thin film is used as an active substrate for SERS analysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310290929.1A CN116288295A (en) | 2023-03-23 | 2023-03-23 | Au nail with adjustable length and surface roughness and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310290929.1A CN116288295A (en) | 2023-03-23 | 2023-03-23 | Au nail with adjustable length and surface roughness and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116288295A true CN116288295A (en) | 2023-06-23 |
Family
ID=86834068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310290929.1A Pending CN116288295A (en) | 2023-03-23 | 2023-03-23 | Au nail with adjustable length and surface roughness and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116288295A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104122244A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Application of Au-polyaniline nano-composite particle in surface enhanced Raman spectrum |
| CN104119527A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Au-polyaniline nano-composite particle and preparation method thereof |
| CN107840957A (en) * | 2017-11-23 | 2018-03-27 | 华南理工大学 | The gold nano grain@polyaniline nano-composite materials of dandelion shape prepared by one kettle way and its preparation method and application |
| CN108817414A (en) * | 2018-06-27 | 2018-11-16 | 河南科技大学 | The preparation method of Jenner's popped rice in a kind of ionic liquid aqueous solution |
| WO2021057513A1 (en) * | 2019-09-25 | 2021-04-01 | 暨南大学 | Phenol recognition sers probe, preparation thereof, use thereof, and sers-based universal ultrasensitive immunoassay method |
| CN112980019A (en) * | 2021-03-25 | 2021-06-18 | 西安文理学院 | Method for preparing polyaniline-nanogold film through self-assembly regulation and control on liquid-liquid two-phase interface |
-
2023
- 2023-03-23 CN CN202310290929.1A patent/CN116288295A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104122244A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Application of Au-polyaniline nano-composite particle in surface enhanced Raman spectrum |
| CN104119527A (en) * | 2013-04-25 | 2014-10-29 | 天津大学 | Au-polyaniline nano-composite particle and preparation method thereof |
| CN107840957A (en) * | 2017-11-23 | 2018-03-27 | 华南理工大学 | The gold nano grain@polyaniline nano-composite materials of dandelion shape prepared by one kettle way and its preparation method and application |
| CN108817414A (en) * | 2018-06-27 | 2018-11-16 | 河南科技大学 | The preparation method of Jenner's popped rice in a kind of ionic liquid aqueous solution |
| WO2021057513A1 (en) * | 2019-09-25 | 2021-04-01 | 暨南大学 | Phenol recognition sers probe, preparation thereof, use thereof, and sers-based universal ultrasensitive immunoassay method |
| CN112980019A (en) * | 2021-03-25 | 2021-06-18 | 西安文理学院 | Method for preparing polyaniline-nanogold film through self-assembly regulation and control on liquid-liquid two-phase interface |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fu et al. | Aligned polythiophene micro‐and nanotubules | |
| Chen et al. | Electrospun polymer nanofibers decorated with noble metal nanoparticles for chemical sensing | |
| Heli et al. | Synthesis and applications of nanoflowers | |
| CN1740405A (en) | Silver nanometer wire synthesizing process | |
| CN106865537A (en) | A kind of preparation method of high strength graphite alkenyl extrusion coating paper | |
| CN102936795A (en) | Drug-loading nano-fiber membrane and preparation method thereof | |
| Bahadori et al. | New insight into single-crystal silver dendrite formation and growth mechanisms | |
| US7381240B2 (en) | Platinum particles with varying morphology | |
| CN116288295A (en) | Au nail with adjustable length and surface roughness and preparation method thereof | |
| CN107828032A (en) | A kind of hyperbranched starlike poly ion liquid and its preparation method and application | |
| CN108620602B (en) | Nano dendritic Pt, preparation method and application in electrocatalytic methanol oxidation | |
| Sepulveda et al. | Effect of Porous and Nonporous Polycaprolactone Fiber Meshes on CaCO3 Crystallization Through a Gas Diffusion Method | |
| CN113340961A (en) | Flexible enzyme-free glucose sensor electrode and preparation method thereof | |
| CN100475886C (en) | Method for preparing polymer material with gradient distributed surface biomacromolecule | |
| JP2002518570A (en) | Method for preparing gel from polyvinyl alcohol, and mechanically highly stable gel prepared by this method | |
| MXPA00012227A (en) | Process for preparing a polyvinyl alcohol gel and mechanically highly stable gel produced by this process | |
| CN107474225A (en) | A kind of method that chemical vapour deposition technique prepares Parylene nanofiber | |
| Rahman et al. | Ordered Langmuir-Blodgett films of polypyrrole and analogs | |
| CN113629183B (en) | Phenylalanine dipeptidyl co-self-assembled product and preparation method and application thereof | |
| CN109202064A (en) | A kind of short-cut method characterizing gold nanocrystals lattice structure and purity | |
| CN112919543B (en) | Preparation and use method of molybdenum disulfide quantum dots | |
| Gao et al. | ZnO submicron structures of controlled morphology synthesized in zinc-hexamethylenetetramine-ethylenediamine aqueous system | |
| CN102031539B (en) | Method for preparing metallic silver nano particles with controllable shapes in batch | |
| CN101912756B (en) | 1,4-cyclohexane diformyl based preparation method of transparent hydrogel | |
| CN111266598B (en) | Preparation method of chiral metal nano spiral fiber array |
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 |