CN110548878A - Preparation method of uniform and ordered platinum cubic or polyhedral nanoparticle array - Google Patents
Preparation method of uniform and ordered platinum cubic or polyhedral nanoparticle array Download PDFInfo
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Abstract
The invention discloses a method for preparing a uniform and ordered platinum cubic or polyhedral nano-particle array, which is characterized in that a hole array obtained after micelle array plasma etching based on a double-block copolymer self-assembly template method is used as a template, an open hole type array template is used for packaging a platinum precursor and an ionic end-capping agent, so that the block copolymer self-assembly template method is compatible with the end-capping agent for controlling the shape of platinum nano-particles, and the non-spherical or linear platinum nano-particles with specific configuration which are difficult to obtain by the traditional block template method are obtained, the problem that the template of the double-block copolymer self-assembly and the organic end-capping agent are incompatible is solved, the problem that the platinum nano-particles with specific configuration which are difficult to obtain by the traditional block template method is solved, the large-scale uniformity and high yield of the cubic or polyhedral platinum nano-particles are ensured, and the technical bottleneck of the preparation technology of the platinum nano-particles with high, the method is favorable for realizing the high-efficiency application of the platinum nanoparticle array with special shape in the aspects of catalysis, photoelectricity and the like.
Description
the technical field is as follows:
the invention relates to the technical field of nanoparticles, in particular to a preparation method of a uniform and ordered platinum cubic or polyhedral nanoparticle array.
Background art:
The platinum nanoparticles have good physical and chemical stability, light-sensitive capacity and electric conductivity, and have excellent oxidation reduction catalytic capacity on energy raw materials such as hydrogen, oxygen, alcohols, organic acid and the like, so the platinum nanoparticles are widely applied to the fields of catalysis, energy conversion, electrons, optics and the like and are used as efficient catalysts or sensitizers in mutual energy conversion processes including chemical energy, light energy, electric energy and the like. In practical applications, the shape of platinum nanoparticles is one of the most important factors affecting the intrinsic properties of each type. The nano particles which are terminated by different platinum crystal faces and have different shapes have the characteristics in the aspects of arrangement of platinum atoms on the surface, an electron cloud structure, an average coordination number and the like, and the development and preparation of the platinum nano particles with various shapes can not only obtain abundant and various catalytic sensitization characteristics and expand the applicable range of the platinum nano particles, but also carry out targeted shape design on the specific application process of the platinum nano particles, and improve the performances of catalytic sensitization and the like by several times to tens of times.
In the existing shape control process, the preparation of different shapes of platinum nanoparticles is mainly realized by adding a blocking agent in the material growth process. The method utilizes different adsorption degrees of different crystal face electronic structures and atomic arrangement on organic matters, and adds the adsorbate to adsorb a specific crystal face to reduce the free energy of the specific crystal face, so as to prevent the specific crystal face from further growing or agglomerating to cause different growth speeds of the crystal faces, thereby obtaining the special particle shape exposing the specific crystal face. Common capping agents include organic amines, alcohols, acids, and macromolecular copolymers. However, for mainstream techniques of growing platinum nanoparticles such as chemical reduction, thermal vacuum evaporation, pulsed laser deposition, buffer layer assisted growth, chemical vapor deposition, gas condensation, electrochemical deposition, ionized cluster beam deposition, sol-gel, impregnation, etc., the specific shape and even large-scale uniformity of the particles cannot be ensured in the process of controlling the shape by using a capping agent, and the repeatability of shape preparation is poor, so that the platinum nanoparticles cannot fully exert the characteristic performance of a special shape. This problem arises from the fact that the capping agent is affected by technically complicated growth environments and is difficult to disperse uniformly around the platinum particles during nucleation growth.
the block copolymer self-assembly template method is a representative technique capable of ensuring large-scale uniformity in the shape and size of the prepared platinum particles and extremely high reproducibility. The nano-scale organic micelle is used as a template for growth and encapsulation of platinum nanoparticles. Nanoscale micelles tend to be composed of two different macromolecular polymers: for a specific selective organic solvent, one polymer is a nanometer soluble micelle capable of forming a corona, the other is a nanometer insoluble micelle capable of forming a core, the two are self-assembled into a micelle with highly uniform morphology and size in the solvent, and a platinum precursor is loaded on the micelle core through complexation or protonation. The micelle templates are loaded on the carrier by spin coating or dipping techniques, and the stable force among the micelles can make the templates highly ordered. And after the precursor is reduced by using the plasma and organic matters are cleaned completely, the uniform and ordered platinum nanoparticle array is obtained. The method not only ensures the uniformity and the repeatability of the prepared platinum nanoparticles, but also enables the characteristic structure and the active sites of the platinum nanoparticles to appear periodically and repeatedly through ordered particle arrangement. For platinum nanoparticles having a specific shape, the above advantages can maximize specific functionality due to the shape.
However, the micelle template used in the block copolymer self-assembly template method is a long-chain organic macromolecular polymer, if the end-capping reagent is encapsulated while the nanoparticle precursor is encapsulated, the template cannot be compatible with the organic end-capping reagent, and the two are either complexed to affect the configuration and uniformity of the template and the loading process of the precursor, or repelled to enable the organic end-capping reagent not to be encapsulated; if the end-capping reagent is added after the precursor is packaged, the end-capping reagent is difficult to contact with the precursor, and the adsorption of a specific crystal face in the growth process cannot be finished. Therefore, the platinum nanoparticles prepared by the method at present do not involve the participation of a blocking agent, and the particle shapes are mostly single spherical or linear, so that other shape types are difficult to realize. The problems not only block the application of the block copolymer self-assembly template method in the preparation of multi-configuration multifunctional platinum nanoparticles, but also limit the development possibility of a preparation technology of high-uniformity high-repeatability special-shape platinum nanoparticles.
The invention content is as follows:
The invention aims to provide a preparation method of a uniform and ordered platinum cubic or polyhedral nano-particle array, which takes a hole array obtained after micelle array plasma etching based on a double-block copolymer self-assembly template method as a template, utilizes an open hole type array template to package a platinum precursor and an ionic end-capping agent, enables the block copolymer self-assembly template method to be compatible with the end-capping agent for controlling the shape of platinum nano-particles, obtains non-spherical or linear platinum nano-particles with specific configuration which are difficult to obtain by the traditional block template method, solves the problem that the template of double-block copolymer self-assembly and the organic end-capping agent are incompatible, solves the problem that the platinum nano-particles with specific configuration which are difficult to obtain by the traditional block template method, utilizes the hole type array template to continue the uniform and ordered properties of the micelle template, ensures that the platinum nano-particles have uniform configuration height and ordered particle arrangement and dispersion, the method ensures the large-scale uniformity and high yield of the cubic or polyhedral platinum nanoparticles, solves the technical bottleneck of the preparation technology of the high-uniformity high-repeatability special-shape platinum nanoparticles, and is beneficial to realizing the high-efficiency application of the special-shape platinum nanoparticle array in the aspects of catalysis, photoelectricity and the like.
The invention is realized by the following technical scheme:
A method for preparing a uniformly ordered platinum cubic or polyhedral nanoparticle array, comprising the steps of:
(1) Preparing a carrier loaded with a porous array template by a diblock copolymer template method: uniformly spreading the organic solution dispersed with the diblock copolymer on the surface of a carrier in a spin coating manner to obtain the carrier loaded with the ordered spherical micelle array self-assembled by the diblock copolymer, then putting the carrier into a plasma cleaning machine for plasma etching, and uniformly etching each spherical micelle in the array to an open part until an ordered hole type array template is obtained on the carrier to obtain the carrier loaded with the ordered hole type array template;
(2) filling the hole array template with the precursor/end-capping reagent solution: uniformly spin-coating a chloroplatinic acid platinum precursor aqueous solution containing a hydrochloric acid end-capping reagent on the surface of the carrier loaded with the ordered hole type array template obtained in the step (1), and filling holes of the template to obtain the carrier loaded with the ordered hole type array template filled with hydrochloric acid/chloroplatinic acid on the surface;
(3) preparing a platinum nanoparticle array by plasma cleaning and reduction: and (3) putting the carrier which is loaded with the ordered hole type array template filled with hydrochloric acid/chloroplatinic acid on the surface and is obtained in the step (2) into a plasma cleaning machine, and reducing the carrier by plasma cleaning until organic matters are completely removed to obtain a uniform and ordered platinum cube or polyhedral nano particle array.
Preferably, the spin coating method in step (1) specifically comprises: dropping an organic solution containing a diblock copolymer on the surface of the carrier, spin-coating the organic solution on a spin-coating spin coater at a speed of 2000-6000 rpm for more than 1min, and standing to obtain the carrier loaded with the single-layer ordered spherical micelle array template.
Preferably, the diblock copolymer in step (1) is polystyrene-block-polyvinylpyridine PS-block-PVP, also denoted as PS (m) -b-PVP (n), and the numbers m, n in the parenthesis indicate the number of monomers contained in the block.
preferably, the solvent of the organic solution in step (1) causes the diblock copolymer to self-assemble into spherical micelles having the structure polystyrene shell/polyvinylpyridine core.
Preferably, the support is selected from one of a metal, an alloy, carbon, a semiconductor and a conductive glass.
the hole type array template in the step (1) is a uniform and ordered array with the top of each spherical micelle particle open.
And (1) treating the carrier loaded with the diblock copolymer self-assembled ordered spherical micelle array through plasma etching, and uniformly etching each spherical micelle in the array to be open, thereby obtaining the ordered hole type array template. The template not only inherits the uniform order of the ordered micelle template, but also can directly load the liquid drop of the platinum precursor and the end-capping reagent which are uniformly mixed, thereby being unnecessary to relate to the encapsulation of the micelle template to the end-capping reagent.
Preferably, the carrier loaded with the diblock copolymer self-assembled ordered spherical micelle array is treated by plasma etching in the step (1), and the method comprises the following steps: and (3) standing the carrier loaded with the diblock copolymer self-assembled ordered spherical micelle array for more than 24h, then putting the carrier into an air plasma cleaning machine, bombarding the micelle array within 150s under a vacuum environment by using air plasma, and uniformly etching each spherical micelle in the array until the spherical micelle array is open, thereby obtaining the single-layer hole type array template on the carrier.
In order to further avoid the problem that the organic end-capping reagent is compatible with the organic micelle, the invention selects hydrochloric acid as the ionic end-capping reagent. The hydrogen ions and the chloride ions of the hydrochloric acid have stronger synergistic adsorption on the (100) plane and weaker adsorption on the (111) plane in the platinum basic crystal plane. Therefore, hydrochloric acid is used as an end-capping reagent to slow down the growth rate of the (100) surface in the nucleation process, so that the shape of the hemispherical platinum particles formed by the (111) and (100) steps, which are naturally formed in the spherical micelle, is changed. Different hydrochloric acid/platinum precursor ratios can result in different platinum (111) face and (100) face ratios, resulting in cubic platinum particles that are all end-capped with (100) faces, or polyhedral particles between spherical and cubic that are end-capped with different ratios of (111) and (100) faces.
Preferably, in the step (2), the mass ratio of the hydrochloric acid to the chloroplatinic acid in the aqueous solution is 0-0.3, so that the platinum nanoparticle array particles are uniform in shape and size and highly ordered in particle arrangement.
And if the mass ratio of the hydrochloric acid to the chloroplatinic acid in the aqueous solution is more than 0.3, the shape of the platinum nanoparticle array particles is indefinite, and the particles are disordered in arrangement.
further, the control of the shape of the uniform ordered platinum nanoparticle array particles is realized by controlling the mass ratio of hydrochloric acid to chloroplatinic acid in a chloroplatinic acid platinum precursor aqueous solution containing a hydrochloric acid end-capping agent.
When the mass ratio of the hydrochloric acid to the chloroplatinic acid in the aqueous solution is between 0.2 and 0.3, the particle shape of the uniform and ordered platinum nanoparticle array is cubic; when the mass ratio of the hydrochloric acid to the chloroplatinic acid is less than 0.2 and more than 0, the particle shape of the uniform and ordered platinum nanoparticle array is a polyhedron between a hemisphere and a cube; when the mass ratio of the hydrochloric acid to the chloroplatinic acid is 0, the shape of the uniform ordered platinum nanoparticle array particles is hemispherical.
Compared with the prior art, the invention has the following advantages:
1, a diblock copolymer template method is used as a key preparation technology, so that large-scale uniformity of platinum nanoparticles and long-range order of platinum nanoparticle arrangement can be guaranteed, and the repeatability of a platinum nanoparticle growth process is high;
2, loading a platinum precursor and a capping agent by using an ordered hole type array template obtained after the carrier carrying the ordered spherical micelle array is subjected to plasma etching, wherein the packaging process of the capping agent is not involved, the capping agent can be ensured to uniformly and fully contact the precursor, the adsorption capping effect can be effectively exerted, and the uniformity and high yield of the specific configuration of the platinum nanoparticles are ensured;
And 3, selecting an ionic end-capping reagent hydrochloric acid, so that the problem that the organic template is incompatible with the organic end-capping reagent can be solved. The invention realizes the application of the block copolymer self-assembly template method in the preparation of multi-configuration platinum nanoparticles, provides a preparation method and a preparation process for developing platinum nanoparticles with high uniformity, high order, high repeatability and special shapes, and has important significance for the application of platinum nanoparticle arrays in the aspects of catalysis, photoelectric energy conversion and the like.
4. the control of the shape of the uniform ordered platinum nanoparticle array particles is realized by controlling the mass ratio of hydrochloric acid to chloroplatinic acid in a chloroplatinic acid platinum precursor aqueous solution containing a hydrochloric acid end-capping reagent.
In conclusion, the invention uses the hole array obtained after the micelle array plasma etching based on the double-block copolymer self-assembly template method as the template, uses the open hole array template to package the platinum precursor and the ionic end-capping agent, leads the block copolymer self-assembly template method to be compatible with the end-capping agent for controlling the shape of the platinum nano-particles, obtains the non-spherical or linear platinum nano-particles with specific configuration which is difficult to obtain by the traditional block template method, realizes the control of the shape of the uniform ordered platinum nano-particle array particles by controlling the mass ratio of hydrochloric acid and chloroplatinic acid in the chloroplatinic acid platinum precursor aqueous solution containing the hydrochloric acid end-capping agent, solves the problem that the template of the double-block copolymer self-assembly cannot be compatible with the organic end-capping agent, solves the problem that the platinum nano-particles with specific configuration which are difficult to obtain by the traditional block template method, and uses the hole array template to carry on the uniformity and the orderliness, the method has the advantages of ensuring that the platinum nano-particle configuration is highly uniform and the platinum nano-particles are distributed and dispersed orderly, ensuring the large-scale uniformity and high yield of cubic or polyhedral nano-particles, solving the technical bottleneck of the preparation technology of the high-uniformity high-repeatability platinum nano-particles with special shapes, and being beneficial to realizing the high-efficiency application of the platinum nano-particle array with special shapes in the aspects of catalysis, photoelectricity and the like.
Description of the drawings:
FIG. 1 is an SEM image of a uniformly ordered pore-type array template prepared based on a PS (27000) -b-P4VP (17000) block copolymer micelle array prepared in example 1.
Fig. 2(a) is a top and side SEM image of a uniform ordered array of carbon-supported platinum cubic nanoparticles prepared from the PS (27000) -b-P4VP (17000) pore grid of example 1 at a hydrochloric acid to chloroplatinic acid mass ratio of 0.25. Fig. 2 (b) is a schematic diagram of the shape of the platinum cubic nanoparticles corresponding to the sample of fig. 2(a), wherein the gray plane is the Pt (100) crystal plane.
Fig. 2(c) is a statistical distribution of particle shapes for a uniform ordered array of carbon-supported platinum cubic nanoparticles prepared with a PS (27000) -b-P4VP (17000) pore grid at a hydrochloric acid to chloroplatinic acid mass ratio of 0.25.
Fig. 2(d) is a statistical distribution of particle sizes for a uniform ordered array of carbon-supported platinum cubic nanoparticles prepared with a PS (27000) -b-P4VP (17000) pore grid at a hydrochloric acid to chloroplatinic acid mass ratio of 0.25.
fig. 3(a) is an SEM photograph of a uniformly ordered array of carbon-supported platinum polyhedral nanoparticles prepared with a PS (27000) -b-P4VP (17000) pore grid at a hydrochloric acid to chloroplatinic acid mass ratio of 0.18 in example 2.
Fig. 3(b) is a schematic diagram showing an approximate shape of the platinum polyhedral nanoparticles corresponding to the sample of fig. 3(a), in which the gray surface is a Pt (100) crystal surface, and the white region is a step surface formed by Pt (100) and Pt (111).
Fig. 4(a) is an SEM photograph of a uniformly ordered array of carbon-supported platinum polyhedral nanoparticles prepared with a PS (27000) -b-P4VP (17000) pore grid at a hydrochloric acid to chloroplatinic acid mass ratio of 0.1 in example 3.
Fig. 4(b) is a schematic diagram showing an approximate shape of the platinum polyhedral nanoparticles corresponding to the sample of fig. 4(a), in which the gray surface is a Pt (100) crystal surface, and the white region is a step surface formed by Pt (100) and Pt (111).
FIG. 5 is top and side SEM photographs of a uniformly ordered array of hemispherical carbon-supported platinum nanoparticles prepared according to example 4 using a PS (27000) -b-P4VP (17000) pore grid at a hydrochloric acid to chloroplatinic acid mass ratio of 0.
FIG. 6 is an SEM photograph of disordered carbon-supported platinum nanoparticle arrays prepared with a PS (27000) -b-P4VP (17000) pore grid at a hydrochloric acid to chloroplatinic acid mass ratio of 0.32 in example 5, with platinum particles of variable shape.
FIG. 7 is an SEM photograph of a uniformly ordered array of titanium platinum-loaded cubic nanoparticles prepared according to example 6 using a PS (27000) -b-P4VP (17000) pore grid at a hydrochloric acid to chloroplatinic acid mass ratio of 0.25.
FIG. 8 is an SEM photograph of a uniformly ordered array of carbon-supported platinum cubic nanoparticles prepared from the PS (81000) -b-P2VP (24000) hole grid of example 7 at a hydrochloric acid to chloroplatinic acid mass ratio of 0.25.
The specific implementation mode is as follows:
The following is a further description of the invention and is not intended to be limiting.
example 1:
(1) Method for preparing carrier loaded with porous array template by using diblock copolymer template method
a polystyrene-block-polyvinylpyridine (PS (27000) -b-P4VP (17000)) block copolymer with a pyridine concentration of 5.1 mM. L -1 was added to a tetrahydrofuran organic solution, sealed, and stirred at 50 ℃ and 400rpm on a magnetic stirrer until the solution was transparent, to obtain an organic solution self-assembled into spherical micelles having a polystyrene shell/polyvinylpyridine core structure.
Carbon paper with a size of 10mm x 10mm and a thickness of 0.2mm was surface-purged with high-purity nitrogen gas for 5min, and placed on a spin-on spin coater as a carrier. 0.2mL of spherical micelle organic solution which is self-assembled into a structure of a polystyrene shell/polyvinyl pyridine core is dripped on the surface of carbon paper, and is firstly homogenized for 5s at the rotating speed of 1000rpm at room temperature, and then homogenized for 60s at the rotating speed of 4000 rpm. And standing the sample subjected to spin coating in air for 24 hours, and then putting the sample into an air plasma cleaning machine to clean for 100 seconds to obtain the carbon paper loaded with the uniform and ordered hole type array template. The array topography is shown in FIG. 1.
(2) Precursor/end-capping agent solution filled hole array template
and (2) placing the carbon paper loaded with the uniform and ordered hole array template obtained in the step (1) on a spin-coating spin coater again, dripping 0.2mL of chloroplatinic acid aqueous solution containing a hydrochloric acid end-capping agent on the surface of the carbon paper, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 0.25, and homogenizing at the rotation speed of 4000rpm for 60s to obtain the carbon paper loaded with the ordered hole array template filled with hydrochloric acid/chloroplatinic acid on the surface.
(3) preparation of cubic platinum nanoparticle array by plasma cleaning reduction
And (3) putting the carbon paper loaded with the ordered hole array filled with hydrochloric acid/chloroplatinic acid on the surface obtained in the step (2) into an air plasma cleaning machine for cleaning for 20min to obtain a uniform and ordered carbon-loaded cubic platinum nanoparticle array. In fig. 2, (a), (b), (c), and (d) show top and side view morphology photographs, schematic particle shape diagrams, statistical particle shape distributions, and statistical particle size distributions, respectively, of the platinum cubic nanoparticle array. The grey side of the diagram represents the Pt (100) side.
Example 2:
Referring to example 1, the only difference is that in the chloroplatinic acid aqueous solution containing the hydrochloric acid capping agent in step (2), the mass ratio of hydrochloric acid to chloroplatinic acid is 0.18, and in the uniformly ordered platinum nanoparticle array finally obtained, the particles are polyhedrons between hemispheres and cubes. Fig. 3(a) and (b) respectively show the morphology photograph and the approximate shape schematic diagram of the obtained polyhedral platinum nanoparticle array, wherein the gray surface represents the crystal surface of Pt (100), and the white area represents the step surface formed by Pt (100) and Pt (111).
Example 3:
Referring to example 1, the only difference is that in the chloroplatinic acid aqueous solution containing the hydrochloric acid capping agent in step (2), the mass ratio of hydrochloric acid to chloroplatinic acid is 0.1, and in the uniformly ordered platinum nanoparticle array finally obtained, the particles are polyhedrons between hemispheres and cubes. Fig. 4(a) and (b) respectively show the morphology photograph and the approximate shape schematic diagram of the obtained polyhedral platinum nanoparticle array, wherein the gray surface represents the crystal surface of Pt (100), and the white area represents the step surface formed by Pt (100) and Pt (111).
Example 4:
Referring to example 1, the only difference is that in the aqueous chloroplatinic acid solution containing the hydrochloric acid blocking agent in step (2), the mass ratio of hydrochloric acid to chloroplatinic acid is 0, i.e., no hydrochloric acid is added. In the final uniform and ordered platinum nanoparticle array, the particles are hemispherical. Fig. 5 shows top and side view morphology photographs of the resulting hemispherical platinum nanoparticle array.
Example 5:
Referring to example 1, the only difference is that in the chloroplatinic acid aqueous solution containing the hydrochloric acid capping agent in step (2), the mass ratio of hydrochloric acid to chloroplatinic acid is 0.32, and the platinum nanoparticle array finally obtained has an indefinite shape and disordered arrangement. Fig. 6 shows a morphology photograph of the resulting platinum nanoparticle array.
example 6:
With reference to example 1, the only difference is that the support used is a titanium sheet, the titanium sheet having a size of 10mm x 10mm and a thickness of 0.2mm is pickled in 10% by mass hydrochloric acid at 80 ℃ for 10min, followed by rinsing several times with deionized water. And (3) polishing the titanium sheet after acid washing by using No. 600, No. 1000, No. 2000 and No. 3000 metallographic abrasive paper in sequence, and ultrasonically washing the titanium sheet in absolute ethyl alcohol and deionized water for 10min in sequence. Figure 7 gives a photograph of the morphology of the resulting uniformly ordered titanium supported cubic platinum nanoparticle array.
Example 7:
referring to example 1, the only difference is that the diblock copolymer used is PS (81000) -b-P2VP (24000). Fig. 8 shows a photograph of the morphology of the resulting uniformly ordered array of cubic platinum nanoparticles.
Claims (7)
1. A method for preparing a uniform ordered platinum cubic or polyhedral nanoparticle array, comprising the steps of:
(1) Uniformly spreading the organic solution dispersed with the diblock copolymer on the surface of a carrier in a spin coating manner to obtain the carrier loaded with the ordered spherical micelle array self-assembled by the diblock copolymer, then putting the carrier into a plasma cleaning machine for plasma etching, and uniformly etching each spherical micelle in the array to an open part until an ordered hole type array template is obtained on the carrier to obtain the carrier loaded with the ordered hole type array template;
(2) uniformly spin-coating a chloroplatinic acid platinum precursor aqueous solution containing a hydrochloric acid end-capping reagent on the surface of the carrier loaded with the ordered hole type array template obtained in the step (1), and filling holes of the template to obtain the carrier loaded with the ordered hole type array template filled with hydrochloric acid/chloroplatinic acid on the surface;
(3) And (3) putting the carrier which is loaded with the ordered hole type array template filled with hydrochloric acid/chloroplatinic acid on the surface and is obtained in the step (2) into a plasma cleaning machine, and reducing the carrier by plasma cleaning until organic matters are completely removed to obtain a uniform and ordered platinum cube or polyhedral nano particle array.
2. The method for preparing a uniformly ordered platinum cubic or polyhedral nanoparticle array according to claim 1, wherein the spin coating in step (1) is specifically: dropping an organic solution containing a diblock copolymer on the surface of the carrier, spin-coating the organic solution on a spin-coating spin coater at a speed of 2000-6000 rpm for more than 1min, and standing to obtain the carrier loaded with the single-layer ordered spherical micelle array template.
3. The method for preparing a homogeneously ordered platinum cubic or polyhedral nanoparticle array as claimed in claim 1 or 2, wherein the diblock copolymer in step (1) is polystyrene-block-polyvinylpyridine.
4. The method for preparing a uniformly ordered platinum cubic or polyhedral nanoparticle array as claimed in claim 1 or 2, wherein the solvent of the organic solution in the step (1) allows the diblock copolymer to self-assemble into spherical micelles having a structure of polystyrene shell/polyvinylpyridine core; the hole type array template in the step (1) is a uniform and ordered array with the top of each spherical micelle particle open; the carrier is selected from one of metal, alloy, carbon, semiconductor and conductive glass.
5. the method for preparing a uniformly ordered platinum cubic or polyhedral nanoparticle array as claimed in claim 1 or 2, wherein the carrier loaded with the diblock copolymer self-assembled ordered spherical micelle array is treated by plasma etching in step (1) by: and (3) standing the carrier loaded with the diblock copolymer self-assembled ordered spherical micelle array for more than 24h, then putting the carrier into an air plasma cleaning machine, bombarding the micelle array within 150s under a vacuum environment by using air plasma, and uniformly etching each spherical micelle in the array until the spherical micelle array is open, thereby obtaining the single-layer hole type array template on the carrier.
6. The method of claim 1 or 2, wherein the shape of the particles of the uniformly ordered platinum nanoparticle array is controlled by controlling the mass ratio of hydrochloric acid to chloroplatinic acid in an aqueous solution of a chloroplatinic acid platinum precursor containing a hydrochloric acid capping agent.
7. The method for preparing a uniformly ordered platinum cubic or polyhedral nanoparticle array as claimed in claim 6, wherein when the mass ratio of hydrochloric acid to chloroplatinic acid in the aqueous solution is in the range of 0.2 to 0.3, the particle shape of the uniformly ordered platinum nanoparticle array is cubic; when the mass ratio of the hydrochloric acid to the chloroplatinic acid is less than 0.2 and more than 0, the particle shape of the uniform and ordered platinum nanoparticle array is a polyhedron between a hemisphere and a cube; when the mass ratio of the hydrochloric acid to the chloroplatinic acid is 0, the shape of the uniform ordered platinum nanoparticle array particles is hemispherical.
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| CN111607786A (en) * | 2020-05-26 | 2020-09-01 | 复旦大学 | Material surface metal nano array patterning modification method |
| CN115672320A (en) * | 2022-11-04 | 2023-02-03 | 上海交通大学 | In WO 3 Method for loading noble metal catalyst nanoparticles on film |
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