CN116623133A - Preparation method of metal needle point array type plasma photocatalyst - Google Patents
Preparation method of metal needle point array type plasma photocatalyst Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 60
- 239000002184 metal Substances 0.000 title claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002923 metal particle Substances 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 26
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- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005498 polishing Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 230000008021 deposition Effects 0.000 claims abstract description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
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- 238000005406 washing Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
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- 238000001179 sorption measurement Methods 0.000 description 2
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- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
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Classifications
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J35/39—
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- B01J35/50—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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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
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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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
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0005—Separation of the coating from the substrate
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention discloses a preparation method of a metal needle point array type plasma photocatalyst, which relates to the technical field of catalytic materials and has the technical scheme that: the method comprises the following steps: s1: preparing a long-range ordered porous alumina template; s2: ultrasonically cleaning and drying the porous alumina template; s3: electrochemical polishing is carried out on the metal particles; s4: placing the metal particles subjected to electrochemical polishing in a position corresponding to an evaporation source of a deposition chamber for vacuum thermal evaporation to form an alumina-coated needle point array; stopping evaporation when the thickness of the metal layer reaches 2-5 mu m; s5: demolding; s6: cleaning; s7: and (5) drying. And generating a uniform metal layer on the surface of the customized alumina template by utilizing a vacuum thermal evaporation instrument, and obtaining the metal nano needle tip array with controllable curvature and controllable orientation as a plasma photocatalyst by changing the aperture depth and the aperture density of the customized porous alumina.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a preparation method of a metal needle point array type plasma photocatalyst.
Background
Most of the currently known photocatalytic materials are semiconductor materials, and in order to solve the problems that the traditional semiconductor photocatalyst is low in sunlight utilization rate and photo-generated electrons and holes are easy to compound, nano particles with surface plasmon resonance activity are compounded with the semiconductor photocatalytic materials to improve the photocatalytic performance of the semiconductor catalyst, so that the photocatalyst is one of the most studied material systems at present. However, due to the schottky barrier between the interface of the semiconductor and the metal nanomaterial, the transfer efficiency of the plasma metal hot electrons to the semiconductor is often low, which limits the application of the plasma metal. The metal plasma photocatalysis is photochemical reaction directly taking a plasma nanostructure as a photocatalyst, and can be understood as plasma resonance-assisted hot electron photocatalysis, and the reaction mechanism is essentially different from that of metal plasma composite semiconductor photocatalysis. However, plasma photocatalysts have the same problems as semiconductor photocatalysts: how efficiently the photogenerated electrons and holes are separated. Meanwhile, most of plasma photocatalysts are noble metals such as Ag, au and the like at present, the combination energy of reactant intermediates and the surfaces of the noble metals is not ideal due to the low surface activity, and a great reaction energy barrier often exists in the reaction process. In the previous research, the morphology and structure of the nano material can effectively adjust the adsorption energy of the intermediate product, thereby reducing the energy barrier of the reaction. For example, in the field of electrocatalytic carbon dioxide reduction, a metal catalyst with a nano-needle-point structure can form a needle-point electric field on the surface of the metal catalyst, so that the adsorption energy of a metal intermediate product can be regulated, and the reaction energy barrier is reduced. In the traditional nanoparticle metal plasma catalyst, the curvature of the periphery of the nanoparticle cannot collect photo-generated electrons, and a huge electric field effect cannot be generated around the catalyst. The needle tip has a unique structure, and the tip end of the needle tip has a great curvature, so that electrons are induced to gather at the tip end of the needle tip to form a needle tip electric field. The characteristic can effectively gather photo-generated electrons in photocatalysis, so that holes and photo-generated electrons are separated, and the service life of carriers in the photocatalyst is prolonged. Therefore, the synthesis of the nanometer needle tip type plasma photocatalyst has important significance.
However, the traditional nano needle point size and structure regulation method is complex, the synthesis period is long, the synthesis conditions are harsh, and complicated steps and various chemical processes are often involved, so that the problems of unstable synthesis effect, difficulty in repeating too many impurities and the like are caused, and the control of the needle point and the preparation of the catalyst with the nano structure are greatly limited. The traditional method for synthesizing the nanometer needle point cannot determine the needle point orientation, electric fields among the disordered nanometer needle points counteract each other, and the advantages of the needle point electric field cannot be exerted to the greatest extent. Therefore, the development of a controllable synthesis method which is simple and easy to implement, high in repetition rate, few in impurities and capable of uniformly facing the plasma photocatalysis of the nanometer needle tip array is necessary.
Disclosure of Invention
The invention aims to provide a preparation method of a metal needle point array type plasma photocatalyst, which is characterized in that a vacuum thermal evaporation instrument is utilized to generate a uniform metal layer on the surface of a customized alumina template, and the curvature can be controlled by changing the aperture depth and the aperture density of customized porous alumina, so that the metal nanometer needle point array with controllable orientation can be obtained as the plasma photocatalyst.
The technical aim of the invention is realized by the following technical scheme: the preparation method of the metal needle tip array type plasma photocatalyst specifically comprises the following steps:
s1: preparing a long-range ordered porous alumina template by a nano-imprinting auxiliary method;
s2: ultrasonically cleaning a porous alumina template by using a template cleaning liquid, and then washing with deionized water and ethanol to remove residual ions on the surface of the template and drying;
s3: carrying out electrochemical polishing on the metal particles to remove impurities and pollutants on the surfaces of the metal particles;
s4: taking the prepared porous alumina template as a base material, placing metal particles subjected to electrochemical polishing in a position corresponding to an evaporation source of a deposition chamber for vacuum thermal evaporation, vaporizing the metal particles into metal particles, uniformly depositing the metal particles on the surface of a substrate material, and filling uniform holes in porous alumina to form an alumina-coated needle tip array; stopping evaporation when the thickness of the metal layer reaches 2-5 mu m;
s5: demolding: soaking the deposited aluminum oxide template in a release agent, and exposing the orderly arranged metal needle tip array after the aluminum oxide is corroded;
s6: cleaning: soaking in deionized water and performing ultrasonic treatment for 5min, taking out, soaking and washing with deionized water for multiple times, and washing to remove the residual release agent on the surface;
s7: and (3) drying: and S5, soaking and washing with deionized water, immersing the needle tip array into ethanol for ultrasonic treatment, and then drying to obtain the metal needle tip array.
Further, the pore depth of the porous alumina template can be adjusted to 400-1500nm, and the size is 2cm multiplied by 6cm.
Further, the S2 template cleaning liquid comprises 36-38% of concentrated hydrochloric acid, 95-99% of acetone and deionized water; the ratio of the components is 1:20:30.
Further, the drying temperature in S2 is 50 ℃, and the drying time is 2h.
Further, the specific step of S3 is:
s3-1: respectively and uniformly mixing 80-85% of phosphoric acid solution, 90-95% of sulfuric acid solution and 95-99% of acetone according to a volume ratio of 7:2:1 to prepare an electrochemical polishing solution;
s3-2: metal particles are placed in electrochemical polishing solution and used as a working electrode, and a carbon rod is used as a counter electrode;
s3-3: electrochemical polishing is carried out for 60-90s at constant pressure of 4-5V and temperature of 50-70 ℃. .
Further, the metal particles are one of Ag, au, ru, rh, pt, bi.
Further, the vacuum pressure of the vacuum evaporation in the step S4 is 1×10 -5 Pa-2×10 -5 Pa, the substrate rotation speed is 20-30rpm, the substrate temperature is 10-30deg.C, and the evaporation speed is/s。
Further, the release agent in the step S5 is FeCl 3 The concentration of one of the solution, hydrochloric acid, sodium hydroxide solution and potassium hydroxide solution is 1-10M.
Further, the types of the metal nano needle tip arrays in the step S5 correspond to the types of the metals placed in the evaporation source in the step S4; the curvature and the size of the prepared metal nano needle point array are regulated and controlled by changing the aperture of the porous alumina template prepared in the step S1.
In summary, the invention has the following beneficial effects:
1. the preparation method is simple, and the curvature and the size of the formed needle point array only need to be regulated and controlled, so that the porous alumina template is not influenced by external environment;
2. compared with the nanoparticle type plasma catalyst, the nanoparticle type plasma catalyst prepared by the invention is more beneficial to collecting photo-generated electrons and generating larger field effect;
3. the metal needle tip array prepared by the preparation method has adjustable curvature, and can effectively separate photogenerated electrons and holes according to the characteristic that free charges of metal tend to positions with large curvature, so that the service life of carriers is prolonged;
4. the preparation method of the invention has universality, not only can prepare any metal needle tip array, but also can prepare any element type needle tip array by adopting different evaporation equipment, such as SiO x ，TiO 2 An isopmetal oxide;
5. compared with the common randomly oriented needlepoint catalyst, the needlepoint orientation of the prepared metal needlepoint array is uniform, and the uniform orientation can effectively promote the needlepoint electric field;
6. the invention realizes the convenient and controllable preparation method of the metal needle point array type plasma photocatalyst, and the obtained nano material can be applied to the field of electro-catalysis, has excellent catalytic activity and maximum atom use efficiency, has extremely strong universality, and can be popularized to other fields such as photocatalysis, thermocatalysis, fuel cells, electrochemical ammonia synthesis and the like.
Drawings
FIG. 1 is a morphology diagram of a scanning electron microscope of the silver nanoneedle tip array prepared in the embodiment 1;
FIG. 2 is a graph showing light absorption properties of the silver nanotip array prepared in example 1 of the present invention;
FIG. 3 is a graph of photocurrent versus time for the silver nanotip array prepared in example 1 of the invention;
fig. 4 is a graph showing the photocatalytic carbon dioxide reduction performance of the silver nanotip array prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to fig. 1-4.
The basic idea of the invention is as follows: the metal source particles are gasified into nano metal particles by a simple and easy vacuum thermal evaporation technology, then the particles fly to the surface of the alumina template, and then holes on the surface of the alumina are filled up to form metal needle points buried in the alumina. The porous alumina prepared by the nano-imprinting auxiliary method has uniform surface pores, uniform orientation and adjustable size. Therefore, the size and the curvature of the metal nano needle tip array formed after the holes are filled with the metal particles are uniform and same in orientation, and are determined by the alumina template. The size of deposited particles of the nano needle point array prepared by the template-assisted electrodeposition method is limited by the concentration of a solution and the ambient temperature, and the condition is difficult to regulate and control, so that a metal cluster is easy to form, and the complete nano needle point is difficult to obtain. The concentration of the solution changes in the deposition process, so that the size of deposited particles changes, and a nano needle tip array with uniform surface is difficult to obtain. The embodiment of the invention adopts a vacuum thermal evaporation method to prepare the nano needle tip array, the film deposition speed, the size of deposited metal particles is only influenced by the passing current of an evaporation source, and the metal nano needle tip array with uniform surface can be obtained by designating the evaporation current in the deposition process.
Example 1: the preparation method of the metal needle tip array type plasma photocatalyst specifically comprises the following steps:
s1: preparing a long-range ordered porous alumina template with the aperture depth of 900nm and the size of 2cm multiplied by 6cm by a nano imprinting auxiliary method;
s2: uniformly mixing 1mL of hydrochloric acid with the mass fraction of 36.5%, 20mL of acetone with the mass fraction of 99.7% and 30mL of deionized water to prepare a template cleaning solution, soaking an alumina template in the template cleaning solution, and ultrasonically cleaning for 2min; taking out the cleaning solution, soaking and washing the cleaning solution with deionized water, washing the cleaning solution with ethanol, and then putting the cleaning solution into an oven for drying at 50 ℃ for 2 hours;
s3: respectively taking 70mL of 80% phosphoric acid solution, 20mL of 95% sulfuric acid solution and 10mL of 99% acetone, and uniformly mixing; taking 24 (0.2 g/grain) silver metal particles with the purity of 99.999%, connecting a conductive adhesive tape with the metal source particles, taking the conductive adhesive tape as a working electrode, taking a carbon rod as a counter electrode, and carrying out electrochemical polishing for 90s under the conditions of constant voltage of 5V and temperature of 70 ℃;
s4: placing the prepared porous alumina template with the pore depth of 900nm on a substrate to be fixed as a base material, placing the electrochemically polished metal particles at the corresponding position of an evaporation source of a deposition chamber, and vacuumizing the deposition chamber to the pressure of 2X 10 -5 Pa, setting evaporation parameter density=10.5, z-ratio=0.529; setting the rotation speed of the substrate to 20rpm, setting the temperature of the substrate to 30 ℃, and opening the steamingThe power generation source selects an A evaporation source, the evaporation current is slowly regulated, the instrument starts to heat, the metal source is gasified into metal particles, the metal particles fly to the surface of the substrate material to be condensed, the surface of the anodized aluminum is filled, a needle point array buried in the anodized aluminum is formed, and the evaporation speed is equal toS; stopping evaporation when the deposition thickness reaches 2 mu m, and taking out three porous alumina filled with metal silver;
s5: demolding: soaking the deposited alumina template in KOH solution with the concentration of 5M, and exposing an ordered metal needle tip array after the alumina is corroded;
s6: cleaning: soaking in deionized water and performing ultrasonic treatment for 5min, taking out, soaking and washing with deionized water for multiple times, and washing to remove the residual release agent on the surface;
s7: and (3) drying: and S5, soaking and washing with deionized water, immersing the needle tip array in ethanol for 5min, putting into an oven, and after the needle tip array is completely dried, obtaining the metal needle tip array with the needle height of 900 nm.
As shown in FIG. 1, which is a scanning electron microscope topography diagram of a 900nm Ag nanoneedle tip prepared in example 1, it can be seen that the prepared nanoneedle tip array is uniform in orientation and ordered.
As shown in FIG. 2, for comparison of the light absorption spectrum of the needle length 900nm of the needle tip array type plasma catalyst prepared in example 1, the light absorption performance of the Ag film with the same thickness was tested, and it can be seen from the figure that the light absorption performance of the nano needle tip array type plasma catalyst is higher than that of the Ag film with the same thickness.
As shown in fig. 3, the graph of the photocurrent versus time for the needle length of 900nm prepared in example 1 shows that the Ag needle tip array with a height of 900nm has a longer carrier lifetime, which proves that the needle tip array is favorable for separating the photo-generated electrons from the holes.
Example 2: the preparation method of the metal needle tip array type plasma photocatalyst is different from the preparation method of the embodiment 1 in that concentrated hydrochloric acid, acetone and deionized water of a template cleaning liquid in S2 are not mixed according to the volume ratio of 1:20:30, other steps are the same as the embodiment 1, the inside of the aperture of an alumina template is not cleaned, and a complete needle tip array cannot be formed by evaporation.
Example 3: the preparation method of the metal needle tip array type plasma photocatalyst is different from the preparation method of the embodiment 1 in that the surface moisture is not removed in ethanol for 5min in S7, and is directly dried, and other steps are the same as the embodiment 1; the morphology of the needle tip array is severely damaged due to the huge surface tension of water.
Working principle: the preparation method of the invention ensures the uniform deposition of the thermal evaporation metal particles by controlling the substrate treatment mode and the evaporation process (substrate temperature, evaporation current, substrate rotation speed, metal source polishing mode and the like), can realize the regulation and control of the thickness, particle spacing, pore size, compactness, multi-layer core-shell structure and the like of the evaporation shell, can not only regulate the thickness of the shell, but also control the particle size of the formed shell, the spacing between the metal particles and the pore of the core-shell structure, and can increase the stability of the electrode material, promote charge transfer and facilitate various catalytic reactions. Specifically, the evaporation rate is controlled by controlling the size of evaporation current, so that the size of the metal particle size of evaporation is changed; the surface coverage densification degree and the inter-particle distance can be changed by changing the rotation speed of the substrate; the substrate is heated during vapor plating, a porous loose structure can be realized, and the compactness of the material is further changed. The thickness of the vapor deposition can be detected through a quartz crystal microbalance, so that the thickness of the vapor deposition can be accurately controlled.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.
Claims (9)
1. A preparation method of a metal needle tip array type plasma photocatalyst is characterized by comprising the following steps: the method specifically comprises the following steps:
s1: preparing a long-range ordered porous alumina template by a nano-imprinting auxiliary method;
s2: ultrasonically cleaning a porous alumina template by using a template cleaning liquid, and then washing with deionized water and ethanol to remove residual ions on the surface of the template and drying;
s3: carrying out electrochemical polishing on the metal particles to remove impurities and pollutants on the surfaces of the metal particles;
s4: taking the prepared porous alumina template as a base material, placing metal particles subjected to electrochemical polishing in a position corresponding to an evaporation source of a deposition chamber for vacuum thermal evaporation, vaporizing the metal particles into metal particles, uniformly depositing the metal particles on the surface of a substrate material, and filling uniform holes in porous alumina to form an alumina-coated needle tip array; stopping evaporation when the thickness of the metal layer reaches 2-5 mu m;
s5: demolding: soaking the deposited aluminum oxide template in a release agent, and exposing the orderly arranged metal needle tip array after the aluminum oxide is corroded;
s6: cleaning: soaking in deionized water and performing ultrasonic treatment for 5min, taking out, soaking and washing with deionized water for multiple times, and washing to remove the residual release agent on the surface;
s7: and (3) drying: and S5, soaking and washing with deionized water, immersing the needle tip array into ethanol for ultrasonic treatment, and then drying to obtain the metal needle tip array.
2. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 1, which is characterized in that: the pore depth of the porous alumina template can be adjusted to 400-1500nm, and the size is 2cm multiplied by 6cm.
3. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 1, which is characterized in that: the S2 template cleaning liquid comprises 36-38% of concentrated hydrochloric acid, 95-99% of acetone and deionized water; the ratio of the components is 1:20:30.
4. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 1, which is characterized in that: the drying temperature in the step S2 is 50 ℃, and the drying time is 2 hours.
5. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 1, which is characterized in that: the specific steps of the S3 are as follows:
s3-1: respectively and uniformly mixing 80-85% of phosphoric acid solution, 90-95% of sulfuric acid solution and 95-99% of acetone according to a volume ratio of 7:2:1 to prepare an electrochemical polishing solution;
s3-2: metal particles are placed in electrochemical polishing solution and used as a working electrode, and a carbon rod is used as a counter electrode;
s3-3: electrochemical polishing is carried out for 60-90s at constant pressure of 4-5V and temperature of 50-70 ℃. .
6. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 5, wherein the method comprises the following steps: the metal particles are one of Ag, au, ru, rh, pt, cu, bi.
7. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 1, which is characterized in that: the vacuum pressure of the vacuum evaporation in the S4 is 1 multiplied by 10 -5 Pa-2×10 -5 Pa, the substrate rotation speed is 20-30rpm, the substrate temperature is 10-30deg.C, and the evaporation speed is
8. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 1, which is characterized in that: the release agent in the S5 is FeCl 3 The concentration of one of the solution, hydrochloric acid, sodium hydroxide solution and potassium hydroxide solution is 1-10M.
9. The method for preparing the metal needle tip array type plasma photocatalyst according to claim 1, which is characterized in that: the types of the metal nano needle tip arrays in the S5 correspond to the types of the metals placed in the evaporation source in the S4; the curvature and the size of the prepared metal nano needle point array are regulated and controlled by changing the aperture of the porous alumina template prepared in the step S1.
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| JP2006326723A (en) * | 2005-05-24 | 2006-12-07 | Canon Inc | Method for manufacturing nano-structure and nano-structure |
| CN102431962A (en) * | 2011-12-07 | 2012-05-02 | 北京航空航天大学 | Preparation method and application of nanoimprint template |
| CN108344725A (en) * | 2018-03-15 | 2018-07-31 | 南通大学 | Top coats the flexible nano column array and its preparation method and application of noble metal |
| CN112479154A (en) * | 2020-11-13 | 2021-03-12 | 中南大学深圳研究院 | Preparation method of ordered metal nano needle tip array |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006326723A (en) * | 2005-05-24 | 2006-12-07 | Canon Inc | Method for manufacturing nano-structure and nano-structure |
| CN102431962A (en) * | 2011-12-07 | 2012-05-02 | 北京航空航天大学 | Preparation method and application of nanoimprint template |
| CN108344725A (en) * | 2018-03-15 | 2018-07-31 | 南通大学 | Top coats the flexible nano column array and its preparation method and application of noble metal |
| CN112479154A (en) * | 2020-11-13 | 2021-03-12 | 中南大学深圳研究院 | Preparation method of ordered metal nano needle tip array |
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