CN110293231A - A kind of using non-noble metal j element is core and precious metal element as the preparation method of the Core-shell Structure Nanoparticles array of shell - Google Patents
A kind of using non-noble metal j element is core and precious metal element as the preparation method of the Core-shell Structure Nanoparticles array of shell Download PDFInfo
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- CN110293231A CN110293231A CN201910625427.3A CN201910625427A CN110293231A CN 110293231 A CN110293231 A CN 110293231A CN 201910625427 A CN201910625427 A CN 201910625427A CN 110293231 A CN110293231 A CN 110293231A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of preparation methods of the Core-shell Structure Nanoparticles array of base metal@noble metal, the base metal@noble metal Core-shell Structure Nanoparticles array of acquisition can greatly improve the utilization rate of noble metal under the premise of guaranteeing high performance, reduce noble metal dosage, to reduce the application cost of precious metal material, and stability will be much higher than traditional core-shell structure discrete particles, extend the service life of Core-shell Structure Nanoparticles, the prior art is solved since noble metal application cost is high, the problems such as limiting noble metal nano particles applications in various fields.
Description
Technical field:
The present invention relates to nanocomposite technical fields, and in particular to one kind is using non-noble metal j element as core and noble metal
Element is the preparation method of the orderly nuclear shell structure nano array of particles of shell.
Background technique:
Noble metal nano particles itself have excellent redox catalysis performance, photoperceptivity, conductance ability etc. excellent
Characteristic, therefore catalysis, optics, electronics and energy conversion storage etc. fields have important application value and widely answer
Use prospect.And after noble metal nano particles realize uniform sequential arrangement, unique effect on a microscopic scale can be macro
Scale concentrated reflection is seen, and the probability that noble metal nano particles are reunited in application process can be reduced significantly, thus
High-performance is realized to develop simultaneously with high stable.Self-Assembling of Block Copolymer template (BC) may be implemented to prepare noble metal nano particles
Required dispersibility, order and uniformity.The nano-grain array prepared by BC method particle size, grain spacing,
Grain shape etc. levels off to single distribution, there are other technologies can not match in excellence or beauty in the control of uniform sequential property excellent
Gesture.
However, the unfavorable factors such as the reserves of noble metal, cost and price abnormality are limited to, so that noble metal nano particles
Application cost can not have always been high any more, therefore use cost undoubtedly limits noble metal nano particles applications in various fields, this
Considerable hurdle is caused to the large-scale commercial applications for realizing noble metal nano particles.It is therefore desirable to consider how protecting
The usage amount for how further decreasing noble metal under the prerequisite of performance is demonstrate,proved, and then realizes the efficient utilization of noble metal, thus
Reduce the application cost of noble metal nano particles.
Summary of the invention:
It is that core and precious metal element as shell (your non-gold are abbreviated as that the object of the present invention is to provide one kind using non-noble metal j element
Belong to@noble metal) Core-shell Structure Nanoparticles array preparation method, the base metal@noble metal nuclear shell structure nano of acquisition
Array of particles can greatly improve the utilization rate of noble metal under the premise of guaranteeing high performance, noble metal dosage be reduced, to drop
The application cost of low noble metal material, and stability will be much higher than traditional core-shell structure discrete particles, extend core-shell structure and receive
The service life of rice grain solves the prior art since the application cost of noble metal nano particles can not have always been high any more, limits
The problem of noble metal nano particles applications in various fields.
The present invention is achieved by the following technical programs:
One kind is core and precious metal element as the nucleocapsid knot of shell (being abbreviated as base metal@noble metal) using non-noble metal j element
The preparation method of structure nano-grain array, method includes the following steps:
(1) carrier is being dispersed with base metal presoma/diblock copolymer in a manner of Best-Effort request or spin coating spin coating
The load of single layer has the spherical micelle array of templates of base metal presoma/orderly in immersion plating or spin coating in the solution of micelle, then
Cleaning is put into air plasma cleaning machine to completely remove to diblock copolymer template, be initially implanted by hexagonal lattice
The carrier of the orderly non-noble metal oxide nano-grain array of arrangement；
(2) the carrier impregnation reducing solution for being loaded with non-noble metal oxide nano-grain array that obtains step (1) or
It is handled with hydrogen gas plasma, is rinsed, dried with the deionized water for removing oxygen in subsequent inert gas shielding atmosphere, carried
There is the carrier of non-noble metal nanoparticles array；
(3) the certain density noble metal of carrier impregnation for being loaded with non-noble metal nanoparticles array for obtaining step (2)
Precursor solution takes out after a certain period of time, with deionized water cleaning, dries, obtains base metal noble metal nano-particle array.
The present invention can regulate and control the size of nano particle by the regulation to base metal precursor concentration, by your gold
The regulation of displaced noble metal amount may be implemented in the adjusting for belonging to the concentration or time swap length of precursor solution.
Best-Effort request mode described in step (1) specifically: carrier merging is dispersed with base metal presoma/bis- embedding
30s or more is impregnated in the solution of section copolymer micelle, carrier is at the uniform velocity then lifted out by solution with the speed of 2~5mm/min, it is quiet
It sets, obtains load base metal presoma/orderly spherical micelle array of templates carrier of single layer.
The mode of spin coating spin coating described in step (1) specifically: carrier is placed at desk-top sol evenning machine suction piece, presses suction
Spin coating time and spin coating revolving speed are adjusted after piece, spin coating duration is arranged generally according to actual demand in 10s~60s, spin coating revolving speed
Generally according to demand setting in 500rpm~5000rpm, with glass dropper be added dropwise described in be dispersed with base metal presoma/bis- embedding
The solution of section copolymer micelle then stands and dries, obtain the load base metal forerunner of single layer on carrier, starting spin coating
Body/orderly spherical micelle array of templates carrier.
Preferably, the carrier includes but is not limited to one of carriers such as semiconductor, electro-conductive glass.
Preferably, the diblock copolymer is Polystyrene-Polyethylene yl pyridines, is dispersed with described in step (1) non-
It is spherical with pyridine to be added to PS-b-P4VP by base metal presoma for noble metal precursor body/diblock copolymer micelle solution
In micelle solution, 50 DEG C of constant temperature are at the uniform velocity stirred 8 hours and are formulated, right using selective deliquescent organic solvent as solvent
The dissolubility of polystyrene PS is more preferable with respect to polyvinylpyridine PVP, therefore can be self-assembly of spherical micelle structure.
Particularly, the molar ratio of the acid group of base metal presoma and pyridine is 1:8~2:1.
The selective deliquescent organic solvent includes but is not limited in the PS selective solvent such as tetrahydrofuran, toluene
One kind.
Preferably, the base metal presoma includes but is not limited to ferric nitrate, cobalt nitrate, nickel nitrate, chromic nitrate, nitre
One or more of base metals salt such as sour copper, iron chloride, cobalt chloride.
Preferably, the noble metal precursor body includes but is not limited to gold chloride, chloroplatinic acid, chloro-iridic acid, ruthenium hydrochloride, chlorine rhodium
One of the noble metals chlorine complex acid and various salt such as acid, chlorine palladium acid, chlorine osmic acid, sodium chloroplatinate, Tetrachloroplatinate sodium, silver nitrate
Or it is several.
The diblock copolymer is polystyrene -- when polyvinylpyridine, step (1) is described to be dispersed with your non-gold
Belong to the centre that base metal presoma is supported on spherical micelle by presoma/diblock copolymer micelle solution, passes through
Best-Effort request or the mode of spin coating spin coating will be spread evenly across load according to the spherical micelle of molar ratio load base metal presoma
On body, the orderly spherical micelle array of templates that load has base metal presoma is obtained, when going micella peripheral with plasma cleaning
PS and inside PVP, and decompose the base metal presoma that is supported on internal PVP, obtain base metal presoma point
Solve product, that is, non-noble metal oxide oldered array.Then to base metal presoma decomposition product, that is, base metal of acquisition
The oldered array of oxide is restored, acquisition base metal oldered array, the subsequent type by changing noble metal precursor body,
Concentration and displaced time span, which can obtain displacement, variety classes noble metal, and displacement has the non-of different noble metal amounts
Noble metal@noble metal Core-shell Structure Nanoparticles array.
Particularly, step (2) reducing solution is sodium borohydride solution.
Beneficial effects of the present invention are as follows:
1) the base metal@noble metal Core-shell Structure Nanoparticles array that the present invention obtains is under the premise of guaranteeing high performance
The utilization rate of noble metal can be greatly improved, noble metal dosage is reduced, to reduce the application cost of precious metal material.
2) the base metal@noble metal Core-shell Structure Nanoparticles array that the present invention obtains is compared to traditional core-shell structure point
Scattered seed is not susceptible to the advantages of reuniting, therefore stability will be much higher than traditional core-shell structure discrete particles, keep
Also have the advantages that high stability under the premise of high performance, the service life of Core-shell Structure Nanoparticles can be extended, this is quite
In further reducing costs.
3) type, concentration and displaced time that the present invention passes through change base metal presoma and noble metal precursor body
Length, can obtain different core element species, different shell element species, variable grain size, different shell thicknesses core
Shell structural nano array of particles, therefore there is wide applicability, it can be catalysis, optics, electronics and energy conversion storage
The developing material research in equal fields provides new mentality of designing.
Detailed description of the invention:
Fig. 1 a is the shape appearance figure that the ITO electro-conductive glass that 1 step of embodiment (1) obtains carries Ni oxide nano particles array；
Fig. 1 b is the shape appearance figure for the Ni@Pt nano-grain array that 1 step of embodiment (2) obtains；
Fig. 1 c is that the Ni@Pt nano-grain array that 1 step of embodiment (2) obtains passes through the cyclic voltammetric under three-electrode system
Scanning carries out testing resulting cyclic voltammetry curve；
Fig. 2 is the shape appearance figure that ITO electro-conductive glass prepared by embodiment 2 carries Ni@Pt nano-grain array；
Fig. 3 a is the shape appearance figure that ITO electro-conductive glass prepared by embodiment 3 carries Co@Pt nano-grain array；
Fig. 3 b is that Co Pt nano-grain array prepared by embodiment 3 passes through the cyclic voltammetry scan under three-electrode system
It carries out testing resulting cyclic voltammetry curve；
Fig. 4 a is the shape appearance figure that ITO electro-conductive glass prepared by embodiment 4 carries Cr@Pt nano-grain array；
Fig. 4 b is that Cr Pt nano-grain array prepared by embodiment 4 passes through the cyclic voltammetry scan under three-electrode system
It carries out testing resulting cyclic voltammetry curve；
Fig. 5 is the shape appearance figure that Si piece prepared by embodiment 5 carries Ni@Pt nano-grain array；
Fig. 6 is the shape appearance figure that Si piece prepared by embodiment 6 carries Ni@Pt nano-grain array；
Fig. 7 is the shape appearance figure that Si piece prepared by embodiment 7 carries Co@Au nano-grain array；
Fig. 8 is that FTO electro-conductive glass prepared by embodiment 8 carries Cr@Pt nano-grain array shape appearance figure.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1:
A kind of preparation method of base metal@noble metal Core-shell Structure Nanoparticles array, includes the following steps:
1) diblock copolymer template prepares Ni oxide nano particles oldered array
Make the spherical micelle/tetrahydrofuran solution of PS-b-P4VP that solvent prepares 4m/mL with tetrahydrofuran, by base metal
Presoma solid Nickelous nitrate hexahydrate and pyridine are added in the micelle solution according to molar ratio for 1:4, at room temperature with 400rpm's
Rotor speed magnetic agitation 6h obtains being dispersed with nickel nitrate/diblock copolymer micelle tetrahydrofuran solution.
It selects carrier for ITO electro-conductive glass, dehydrated alcohol is carried out to the carrier and deionized water is respectively cleaned by ultrasonic 10min's
Pre-treatment is then dried stand-by.Using prepared nickel nitrate/diblock copolymer micelle tetrahydrofuran solution as maceration extract,
The ITO electro-conductive glass dried is immersed and stands 30s, is then at the uniform velocity mentioned ITO electro-conductive glass with the pull rate of 2mm/min
It pulls out maceration extract and horizontal rest for 24 hours, is then placed in air plasma cleaning machine and cleans 5min in air, obtained after cleaning
The carrier for being loaded with Ni oxide nano particles array, pattern photo is as shown in Figure 1a.
2) it restores, replacement process
The ITO electro-conductive glass carrier impregnation of Ni oxide nano particles array largely excessive sodium borohydride solution will be loaded with
Ni oxide is reverted to elemental stage with a large amount of excessive sodium borohydrides, then with nitrogen as inert gas shielding by 5min
Atmosphere is rinsed with the deionized water for removing oxygen by high pure nitrogen purging 15min, is dried, and acquisition is loaded with Ni nano particle battle array
The carrier of column.It will take out, spend after 6min in the chloroplatinic acid aqueous solution for the carrier impregnation 1mg/mL for being loaded with Ni nano-grain array
Ionized water cleaning is dried, and Ni@Pt nano-grain array is obtained.Pattern photo such as Fig. 1 b of resulting Ni@Pt nano-grain array
Shown, Ni@Pt nano-grain array is arranged by hexagonal lattice form, it can be seen that grain before Ni@Pt nano-particle diameter is relatively replaced
Diameter size is without significant changes.The test of electro-chemical activity is carried out to Ni@Pt nano particle, electro-chemical activity passes through three electrode bodies
Cyclic voltammetry scan under system is analyzed, scanning speed 100mV/s, tests the H that electrolyte used is 0.5M2SO4It is water-soluble
Liquid is saturated mercury/mercuric sulfate (Hg/HgSO4- 0.7V vs.RHE) it is reference electrode.First lead into electrolyte before electro-chemical test
Enter 15min high pure nitrogen to remove the oxygen wherein dissolved, all electrode potentials can be converted into phase in analysis discusses
For the electrode potential V (vs.RHE) of reversible hydrogen electrode, test gained cyclic voltammetry curve as illustrated in figure 1 c, is computed and learns institute
The electrochemical surface area of the Ni@Pt nano particle of preparation are as follows: ECSANi@Pt=85.1m2/ g learns business Pt/ after consulting literatures
The electrochemical surface area of C is about in 55m2/ g or so, therefore it can be seen that the electro-chemical activity of prepared Ni@Pt nano particle is wanted
It is apparently higher than the electro-chemical activity of business Pt/C.Your gold realizes reduces under conditions of guaranteeing or even improving electro-chemical activity
The usage amount of category has achieved the purpose that reduce noble metal consuming cost.
Embodiment 2:
The specific implementation step of the present embodiment is substantially the same manner as Example 1, and difference is only that: the first step in embodiment 1,
Diblock copolymer template is prepared in Ni oxide nano particles oldered array, changes the mode of Best-Effort request into spin coating spin coating
Mode, specific implementation step are as follows:
1) diblock copolymer template prepares Ni oxide nano particles oldered array
Make the spherical micelle/tetrahydrofuran solution of PS-b-P4VP that solvent prepares 4m/mL with tetrahydrofuran, by six water of solid
It is during 1:8 is added in the micelle solution, at room temperature with the rotor speed magnetic force of 400rpm that nickel nitrate and pyridine, which are closed, according to molar ratio
6h is stirred, is that presoma/copolymer tetrahydrofuran that non-noble metal j element nickel is loaded into spherical micelle by 1:8 is molten according to molar ratio
Liquid obtains being dispersed with nickel nitrate/diblock copolymer micelle tetrahydrofuran solution.
It selects carrier for ITO electro-conductive glass, dehydrated alcohol is carried out to the carrier and deionized water is respectively cleaned by ultrasonic 10min's
Pre-treatment is then dried stand-by.The ITO electro-conductive glass that processing terminate and dries is placed at desk-top sol evenning machine suction piece, suction is pressed
60s is set by spin coating duration after piece, the setting of spin coating revolving speed is being 2000rpm, the nickel nitrate prepared with glass dropper dropwise addition/
Block copolymer tetrahydrofuran solution then stands and dries for 24 hours on carrier, starting spin coating.Subsequent operation and 1 phase of embodiment
Together, Ni@Pt nano-grain array may finally be obtained.The pattern photo of resulting Ni@Pt nano-grain array as shown in Fig. 2,
Ni@Pt nano-grain array is arranged by hexagonal lattice form.
Embodiment 3:
The specific implementation step of the present embodiment is substantially the same manner as Example 1, and difference is only that: by base metal presoma by
Nickelous nitrate hexahydrate changes cabaltous nitrate hexahydrate into, and noble metal precursor body still selects chloroplatinic acid.By with the identical place of embodiment 1
Step is managed, Co@Pt nano-grain array can be obtained.The pattern photo of resulting Co@Pt nano-grain array is as shown in Figure 3a,
Co@Pt nano-grain array is arranged by hexagonal lattice form.The test of electro-chemical activity, electricity are carried out to Co@Pt nano particle
Chemical activity is analyzed by the cyclic voltammetry scan under three-electrode system, scanning speed 100mV/s, tests electricity used
The H2SO4 aqueous solution of Xie Zhiwei 0.5M, saturation mercury/mercuric sulfate (Hg/HgSO4, -0.7V vs.RHE) are reference electrode.In electrification
First it is passed through 15min high pure nitrogen into electrolyte before learning test to remove the oxygen wherein dissolved, it is all in analysis discusses
Electrode potential can be converted into the electrode potential V (vs.RHE) relative to reversible hydrogen electrode, test gained cyclic voltammetry curve
As shown in Figure 3b, it is computed the electrochemical surface area for learning prepared Co@Pt nano particle are as follows: ECSACo@Pt=
154.2m2/ g is still higher than the electro-chemical activity of general commercial Pt/C.
Embodiment 4:
The specific implementation step of the present embodiment is substantially the same manner as Example 1, and difference is only that: by base metal presoma by
Nickelous nitrate hexahydrate changes Chromium nitrate (Cr(NO3)3),nonahydrate into, and the molar ratio of solid Chromium nitrate (Cr(NO3)3),nonahydrate and pyridine is changed to as 1:8 addition
In micelle solution, noble metal precursor body still selects chloroplatinic acid.By with the identical processing step of embodiment 1, Cr@can be obtained
Pt nano-grain array.The pattern photo of resulting Cr@Pt nano-grain array as shown in fig. 4 a, Cr@Pt nano-grain array
It arranges by hexagonal lattice form.The test of electro-chemical activity is carried out to Cr@Pt nano particle, electro-chemical activity passes through three electrodes
Cyclic voltammetry scan under system is analyzed, scanning speed 100mV/s, tests the H2SO4 that electrolyte used is 0.5M
Aqueous solution, saturation mercury/mercuric sulfate (Hg/HgSO4, -0.7V vs.RHE) are reference electrode.First to electrolysis before electro-chemical test
15min high pure nitrogen is passed through in matter to remove the oxygen wherein dissolved, all electrode potentials can turn in analysis discusses
The electrode potential V (vs.RHE) relative to reversible hydrogen electrode is turned to, test gained cyclic voltammetry curve is as shown in Figure 4 b, is computed
Learn the electrochemical surface area of prepared Cr@Pt nano particle are as follows: ECSACr@Pt=164.3m2/ g is still higher than commercialization
The electro-chemical activity of Pt/C.
Embodiment 5:
The specific implementation step of the present embodiment is substantially the same manner as Example 1, and difference is only that: by solid Nickelous nitrate hexahydrate
1:8 is changed to the molar ratio of pyridine to be added in micelle solution, and carrier is changed by ITO electro-conductive glass and makees Si piece, Si piece used
Processing step is as follows:
Concentration is mixed for 20% aqueous hydrogen peroxide solution and the concentrated sulfuric acid according to the ratio of 3:7, the Si that will then cut out
Piece is immersed, and is heated to 200 degrees Celsius of constant temperature, is needed to be stirred continuously silicon wafer in treatment process, make silicon chip surface with mix it is molten
Liquid comes into full contact with and is activated, to increase the compatibility of Si piece and solvent, is cooled to room temperature after three hours, takes out silicon wafer,
It is rinsed well and is dried stand-by with its ionized water.Others operation is same as Example 1, may finally obtain and be supported on Si on piece
Ni@Pt nano-grain array.The pattern photo of resulting Ni@Pt nano-grain array is as shown in figure 5, Pt nanometers of gained Ni@
Array of particles is arranged by hexagonal lattice form.
Embodiment 6:
The specific implementation step of the present embodiment is substantially the same manner as Example 2, and difference is only that: by solid Nickelous nitrate hexahydrate
It is changed to be added in micelle solution for 1:8 with the molar ratio of pyridine, and the organic solvent with selective dissolution used is first
Benzene, and used carrier is Si piece, others operation is same as Example 2, may finally obtain and be supported on the Ni@Pt of Si on piece and receive
Rice grain array.The pattern photo of resulting Ni@Pt nano-grain array is as shown in fig. 6, gained Ni@Pt nano-grain array is pressed
The arrangement of hexagonal lattice form.
Embodiment 7:
The specific implementation step of the present embodiment is substantially the same manner as Example 3, and difference is only that: by noble metal precursor body by chlorine
Platinic acid changes gold chloride into, and used carrier is Si piece.By with the identical processing step of embodiment 2, Au nanometers of Co@can be obtained
Array of particles.The pattern photo of resulting Co@Au nano-grain array is as shown in fig. 7, Co@Au nano-grain array presses hexagonal point
The arrangement of formation formula.
Embodiment 8:
The specific implementation step of the present embodiment is substantially the same manner as Example 3, and difference is only that: base metal presoma is nitre
Sour chromium, the acid group of base metal presoma and the molar ratio of pyridine are 2:1.Noble metal precursor body is chloro-iridic acid, and used carrier
For FTO glass.Pattern photo such as Fig. 8 depicted of resulting Cr@Ir nano-grain array.
Claims (10)
- It using non-noble metal j element is core and precious metal element as the preparation method of the Core-shell Structure Nanoparticles array of shell 1. a kind of, It is characterized in that, method includes the following steps:(1) carrier is being dispersed with base metal presoma/diblock copolymer micelle in a manner of Best-Effort request or spin coating spin coating Solution in immersion plating or spin coating the load of single layer have the spherical micelle array of templates of base metal presoma/orderly, be then placed in Cleaning is completely removed to diblock copolymer template in air plasma cleaning machine, and what is be initially implanted into arranges by hexagonal lattice Orderly non-noble metal oxide nano-grain array carrier；(2) by the carrier impregnation reducing solution for being loaded with non-noble metal oxide nano-grain array that step (1) obtains or hydrogen is used Gas corona treatment is rinsed in subsequent inert gas shielding atmosphere with the deionized water for removing oxygen, is dried, and acquisition is loaded with non- The carrier of noble metal nano-particle array；(3) the certain density noble metal precursor of carrier impregnation for being loaded with non-noble metal nanoparticles array for obtaining step (2) Liquid solution takes out after a certain period of time, with deionized water cleaning, dries, obtains base metal noble metal nano-particle array.
- 2. preparation method according to claim 1, which is characterized in that by the regulation to base metal precursor concentration come The size for regulating and controlling nano particle realizes displacement by the adjusting of concentration or time swap length to noble metal precursor liquid solution The regulation of noble metal amount.
- 3. preparation method according to claim 1, which is characterized in that Best-Effort request mode described in step (1) is specific Are as follows: carrier merging is dispersed with dipping 30s or more in base metal presoma/diblock copolymer micelle solution, then with 2 Carrier is at the uniform velocity lifted out solution by the speed of~5mm/min, is stood, is obtained load base metal presoma/orderly ball of single layer The carrier of shape micelle array of templates.
- 4. preparation method according to claim 1, which is characterized in that the mode of spin coating spin coating described in step (1) has Body are as follows: carrier is placed at desk-top sol evenning machine suction piece, presses and adjusts spin coating time and spin coating revolving speed after suction piece, spin coating duration according to Actual demand is arranged in 10s~60s, and 500rpm~5000rpm is arranged in as desired, is added dropwise with glass dropper for spin coating revolving speed Base metal presoma/diblock copolymer micelle solution that is dispersed with then stands and dries in the air on carrier, starting spin coating It is dry, obtain load base metal presoma/orderly spherical micelle array of templates carrier of single layer.
- 5. preparation method according to claim 1, which is characterized in that the carrier includes semiconductor, in electro-conductive glass One kind.
- 6. preparation method according to claim 1, which is characterized in that the diblock copolymer is polystyrene-poly Vinylpyridine.
- 7. preparation method according to claim 1, which is characterized in that step (1) is described be dispersed with base metal presoma/ The solution of diblock copolymer micelle is added in the spherical micelle solution of PS-b-P4VP, 50 by base metal presoma and pyridine DEG C constant temperature, which at the uniform velocity stirs 8 hours, to be formulated, using selective deliquescent organic solvent as solvent.
- 8. preparation method according to claim 7, which is characterized in that the acid group of base metal presoma and mole of pyridine Than for 1:8~2:1；The selective deliquescent organic solvent includes one of tetrahydrofuran, toluene.
- 9. preparation method according to claim 1, which is characterized in that the base metal presoma include ferric nitrate, One or more of cobalt nitrate, nickel nitrate, chromic nitrate, copper nitrate, iron chloride, cobalt chloride；The noble metal precursor body packet Include gold chloride, chloroplatinic acid, chloro-iridic acid, ruthenium hydrochloride, chlorine rhodium acid, chlorine palladium acid, chlorine osmic acid, sodium chloroplatinate, Tetrachloroplatinate sodium, nitric acid One or more of silver.
- 10. preparation method according to claim 1, which is characterized in that step (2) reducing solution is that sodium borohydride is molten Liquid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111029443A (en) * | 2019-12-06 | 2020-04-17 | 松山湖材料实验室 | Method for enhancing luminous efficiency of nitride-based LED by using metal nanoparticles |
| CN111690917A (en) * | 2020-05-26 | 2020-09-22 | 复旦大学 | Method for preparing material surface metal nano array by stable block copolymer micelle template method |
| CN112705722A (en) * | 2019-10-25 | 2021-04-27 | 中国科学院广州能源研究所 | Method for controlling size of platinum nano-particles with ordered structures |
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