CN110252297B - Gold nanoparticle-zinc oxide nano-cap array and preparation method thereof - Google Patents
Gold nanoparticle-zinc oxide nano-cap array and preparation method thereof Download PDFInfo
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- CN110252297B CN110252297B CN201910556142.9A CN201910556142A CN110252297B CN 110252297 B CN110252297 B CN 110252297B CN 201910556142 A CN201910556142 A CN 201910556142A CN 110252297 B CN110252297 B CN 110252297B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 93
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 88
- 239000010931 gold Substances 0.000 title claims abstract description 88
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004793 Polystyrene Substances 0.000 claims abstract description 113
- 229920002223 polystyrene Polymers 0.000 claims abstract description 113
- 239000004005 microsphere Substances 0.000 claims abstract description 112
- 239000000758 substrate Substances 0.000 claims abstract description 64
- 239000002356 single layer Substances 0.000 claims abstract description 52
- 238000000151 deposition Methods 0.000 claims abstract description 40
- 238000004544 sputter deposition Methods 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 24
- 239000010410 layer Substances 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000001338 self-assembly Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 85
- 239000008367 deionised water Substances 0.000 claims description 65
- 229910021641 deionized water Inorganic materials 0.000 claims description 65
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- 239000011521 glass Substances 0.000 claims description 40
- 239000000725 suspension Substances 0.000 claims description 27
- 230000005660 hydrophilic surface Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 238000005477 sputtering target Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003491 array Methods 0.000 claims 2
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 238000001782 photodegradation Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/347—Ionic or cathodic spraying; Electric discharge
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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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- B82—NANOTECHNOLOGY
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- B82—NANOTECHNOLOGY
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- B82Y40/00—Manufacture or treatment of nanostructures
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a gold nanoparticle-zinc oxide nanometer cap array and a preparation method thereof, wherein a gas-liquid interface self-assembly technology is utilized to lay a layer of polystyrene microspheres on a substrate, then a zinc film is deposited on the surface of the substrate, a zinc oxide nanometer cap array with very uniform components and ordered arrangement is prepared on the substrate after annealing treatment, then a layer of monolayer polystyrene microspheres with ordered arrangement is covered on the surface of the zinc oxide nanometer cap array, and then the gold nanoparticle array is prepared on the surface of the zinc oxide nanometer cap array by taking the zinc oxide nanometer cap array as a template and adopting an ion sputtering deposition method and a thermal annealing treatment technology, so that the uniform gold nanoparticle-zinc oxide nanometer cap array is obtained. The composite structure can fully exert the adsorption performance and the unique electronic transmission performance of the zinc oxide nanometer cap on specific harmful organic molecules, and greatly improve the photocatalysis performance of gold nanometer particles on the surface of zinc oxide, thereby greatly improving the photodegradation performance of the harmful organic molecules.
Description
Technical Field
The invention relates to the technical field of harmful organic molecule degradation, in particular to a gold nanoparticle-zinc oxide nano-cap array and a preparation method thereof.
Background
With the progress of scientific technology and the improvement of the living standard of human beings, the demands of various non-renewable resources such as coal, petroleum, natural gas and the like are increased, but the utilization efficiency of the resources is not high in the utilization process, and some wastes are inevitably generated; the waste materials usually contain some organic molecules which are harmful to life bodies and are not easy to naturally degrade, so that the harmful organic molecules are very necessary to be degraded and removed.
At present, a technology which is more environment-friendly and convenient is to use noble metal nanoparticles (such as Pt, Au, Ag) to realize photodegradation of harmful organic molecules under light irradiation, but for some harmful organic molecules which are not basically adsorbed by noble metal nanoparticles, pure noble metal nanoparticles cannot exert better catalytic performance, and the degradation rate of harmful organic molecules is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a gold nanoparticle-zinc oxide nano-cap array and a preparation method thereof, which can give full play to the adsorption performance and the unique electronic transmission performance of the zinc oxide nano-cap on specific molecules and greatly improve the photodegradation performance of the gold nanoparticles on the surface of zinc oxide on specific harmful organic molecules.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a gold nanoparticle-zinc oxide nanometer cap array comprises the following steps:
step A, preparing a single-layer polystyrene microsphere array on a substrate by adopting a gas-liquid interface self-assembly method;
step B, taking the single-layer polystyrene microsphere array as a template, depositing a layer of zinc film on the surface of the template by adopting a magnetron sputtering deposition method, and then annealing the template deposited with the zinc film to prepare a zinc oxide nano cap array;
step C, preparing a single-layer polystyrene microsphere on the water surface of the deionized water, and then fishing the single-layer polystyrene microsphere from the water surface of the deionized water by adopting a substrate loaded with the zinc oxide nano-cap array, thereby preparing the zinc oxide nano-cap array covered with the single-layer polystyrene microsphere;
and D, taking the zinc oxide nanometer cap array covered with the single-layer polystyrene microspheres as a template, depositing a layer of gold film on the surface of the template by adopting an ion sputtering deposition method, and then annealing the template deposited with the gold film to prepare the gold nanoparticle-zinc oxide nanometer cap array.
Preferably, the preparation of the monolayer polystyrene microsphere array on the substrate by the gas-liquid interface self-assembly method comprises the following steps:
a1, placing the clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 10-40 min to obtain a glass substrate with a hydrophilic surface; then, sucking deionized water by using a pipette, and injecting the deionized water onto a glass substrate with a hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film;
step A2, taking a polystyrene microsphere suspension with a polystyrene sphere diameter of 1000nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to the ethanol of 1.5:1, and performing ultrasonic oscillation treatment for 40min to prepare a uniformly dispersed polystyrene microsphere ethanol solution;
step A3, injecting the polystyrene microsphere ethanol solution onto the glass substrate with the surface covered with the deionized water film, adding a surfactant, and transferring the solution onto the water surface of deionized water to prepare a single-layer polystyrene microsphere on the water surface of the deionized water;
and A4, fishing the monolayer polystyrene microsphere from the deionized water surface by using the substrate, thereby preparing the monolayer polystyrene microsphere array on the substrate.
Preferably, the preparation of the monolayer polystyrene microspheres on the deionized water surface comprises the following steps:
step C1, placing the clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 10-40 min, thereby obtaining the glass substrate with a hydrophilic surface; then, sucking deionized water by using a pipette, and injecting the deionized water onto a glass substrate with a hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film;
step C2, taking a polystyrene microsphere suspension with the polystyrene microsphere diameter of 150nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to the ethanol of 1:1.5, and performing ultrasonic oscillation treatment for 40min to prepare a uniformly dispersed ethanol solution of the polystyrene microsphere;
and step C3, injecting the polystyrene microsphere ethanol diluent onto the glass substrate with the surface covered with the deionized water film, adding a surfactant, and transferring the mixture onto the water surface of deionized water to prepare the single-layer polystyrene microsphere on the water surface of the deionized water.
Preferably, the depositing a zinc film on the surface of the template by magnetron sputtering deposition comprises: and putting the template into a magnetron sputtering instrument, selecting a zinc target as a sputtering target material, setting the vacuum degree to be 30mtor, the sputtering current to be 30mA and the sputtering time to be 6min, and depositing a layer of zinc film on the surface of the template.
Preferably, the annealing the template on which the zinc film is deposited includes: and (3) placing the template deposited with the zinc film into a crucible of a muffle furnace, setting the heating rate to be increased from room temperature to 800 ℃ for two hours, then preserving the heat for two hours, and naturally annealing to obtain the zinc oxide nano cap array.
Preferably, the depositing a gold film on the surface of the template by using an ion sputtering deposition method comprises: and placing the template into an ion sputtering instrument, selecting a gold target as a sputtering target material, setting the vacuum degree to be 0.1mbar, the sputtering current to be 30mA and the sputtering time to be 45-90 s, and depositing a layer of gold film on the surface of the template.
Preferably, the annealing the template on which the gold film is deposited includes: and (3) placing the template deposited with the gold film into a crucible of a muffle furnace, setting the heating rate to be two hours, heating from room temperature to 800 ℃, then preserving the heat for two hours, and naturally annealing to obtain the gold nanoparticle-zinc oxide nano cap array.
A gold nanoparticle-zinc oxide nano-cap array is prepared by adopting the preparation method of the gold nanoparticle-zinc oxide nano-cap array.
According to the technical scheme provided by the invention, the preparation method of the gold nanoparticle-zinc oxide nanometer cap array comprises the steps of firstly paving a layer of polystyrene microspheres on a substrate by using a gas-liquid interface self-assembly technology, then depositing a layer of zinc film on the surface, carrying out annealing treatment to prepare the zinc oxide nanometer cap array with very uniform components and ordered arrangement on the substrate, then covering a layer of ordered single-layer polystyrene microspheres on the surface of the zinc oxide nanometer cap array, and then preparing the gold nanoparticle array on the surface of the zinc oxide nanometer cap array by using the zinc oxide nanometer cap array as a template by using an ion sputtering deposition method and an annealing treatment technology, thereby obtaining the extremely uniform gold nanoparticle-zinc oxide nanometer cap array; the composite structure can fully exert the adsorption performance and the unique electronic transmission performance of the zinc oxide nanometer cap on specific harmful organic molecules, and greatly improve the photocatalysis performance of gold nanometer particles on the surface of zinc oxide, thereby greatly improving the photodegradation performance of the harmful organic molecules.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a scanning electron microscope photograph of the gold nanoparticle-zinc oxide nano cap array provided in example 1 of the present invention.
FIG. 2 is a schematic flow diagram of a preparation method of a gold nanoparticle-zinc oxide nanocap array in an embodiment of the present disclosure.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The gold nanoparticle-zinc oxide nano cap array and the preparation method thereof provided by the present invention are described in detail below. Details which are not described in detail in the embodiments of the invention belong to the prior art which is known to the person skilled in the art.
As shown in fig. 2, a preparation method of a gold nanoparticle-zinc oxide nano cap array may include the following steps:
step a, preparing a monolayer polystyrene microsphere array on a substrate by using a gas-liquid interface self-assembly method (as shown in fig. 2 a), wherein the diameter of the polystyrene microsphere is at least 1000nm, and the diameter of each polystyrene microsphere is consistent, for example: the diameter size of each polystyrene microsphere is 1000nm, the diameter size of each polystyrene microsphere is 2000nm, and so on.
And step B, taking the single-layer polystyrene microsphere array as a template, depositing a layer of zinc film on the surface of the template by adopting a magnetron sputtering deposition method (as shown in figure 2B), and then annealing the template deposited with the zinc film to remove the single-layer polystyrene microsphere, thereby preparing the zinc oxide nanometer cap array (as shown in figure 2 c) with uniform components and orderly arrangement.
Step C, preparing single-layer polystyrene microspheres on the deionized water surface, wherein the diameters of the polystyrene microspheres are 150-600 nm, and the diameters of the polystyrene microspheres are consistent; then, the substrate carrying the zinc oxide nano-cap array is adopted to fish up the single-layer polystyrene microspheres from the water surface of the deionized water, so as to prepare the zinc oxide nano-cap array covered with the single-layer polystyrene microspheres (as shown in figure 2 d).
And step D, taking the zinc oxide nanometer cap array covered with the single-layer polystyrene microspheres as a template, depositing a layer of gold film on the surface of the template by adopting an ion sputtering deposition method (as shown in figure 2 e), then annealing the template deposited with the gold film to remove the single-layer polystyrene microspheres and form gold nanoparticles on the surface of the zinc oxide, thereby preparing the extremely uniform gold nanoparticle-zinc oxide nanometer cap array (as shown in figure 2 f).
Specifically, the preparation method of the gold nanoparticle-zinc oxide nanometer cap array comprises the following steps:
(1) in step a, the preparation of the monolayer polystyrene microsphere array on the substrate by the gas-liquid interface self-assembly method comprises the following steps (taking the polystyrene microsphere with a diameter of 1000nm as an example):
a1, placing the clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 10-40 min to obtain a glass substrate with a hydrophilic surface; and sucking deionized water by using a pipette, and injecting the deionized water onto the glass substrate with the hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film.
Step A2, taking a polystyrene microsphere suspension with the polystyrene microsphere diameter of 1000nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to the ethanol of 1.5:1, and performing ultrasonic oscillation treatment for 40min to obtain the uniformly dispersed polystyrene microsphere ethanol diluent. The polystyrene microsphere suspension can be a commercially available polystyrene microsphere suspension.
Step A3, injecting the polystyrene microsphere ethanol solution onto the glass substrate with the surface covered with the deionized water film, adding a surfactant into a beaker filled with deionized water, and then transferring the beaker onto the water surface of the deionized water, thereby preparing the single-layer polystyrene microsphere on the water surface of the deionized water.
And A4, fishing the monolayer polystyrene microsphere from the deionized water surface by using the substrate, thereby preparing the monolayer polystyrene microsphere array on the substrate.
(2) In step B, depositing a zinc film on the surface of the template by magnetron sputtering deposition comprises: and (3) putting the template into a magnetron sputtering instrument, selecting a zinc target as a sputtering target material, setting the vacuum degree to be 30mtor, the sputtering current to be 30mA and the sputtering time to be 6min, and depositing a layer of zinc film on the surface of the template.
(3) In step B, the heat-treating the template on which the zinc film is deposited includes: and (3) placing the template deposited with the zinc film into a crucible of a muffle furnace, setting the heating rate to be two hours, heating from room temperature to 800 ℃, then preserving the heat for two hours, and naturally annealing to remove the single-layer polystyrene microspheres to form the zinc oxide nano cap array.
(4) In step C, the step of preparing the monolayer polystyrene microspheres on the deionized water surface comprises the following steps (taking the polystyrene microspheres with the diameter of 150nm as an example):
step C1, placing the clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 10-40 min, thereby obtaining the glass substrate with a hydrophilic surface; and sucking deionized water by using a pipette, and injecting the deionized water onto the glass substrate with the hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film.
And step C2, taking the polystyrene microsphere suspension with the polystyrene microsphere diameter of 150nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to the ethanol of 1:1.5, and performing ultrasonic oscillation treatment for 40min to obtain the uniformly dispersed polystyrene microsphere ethanol solution. The polystyrene microsphere suspension may be commercially available.
And step C3, injecting the polystyrene microsphere ethanol solution onto the glass substrate with the surface covered with the deionized water film, adding a surfactant into a beaker filled with deionized water, and transferring the beaker onto the water surface of the deionized water, so as to prepare the single-layer polystyrene microsphere on the water surface of the deionized water.
(5) In step D, the depositing a gold film on the surface of the template by using an ion sputtering deposition method includes: and placing the template into an ion sputtering instrument, selecting a gold target as a sputtering target material, setting the vacuum degree to be 0.1mbar, the sputtering current to be 30mA and the sputtering time to be 45-90 s, and depositing a layer of gold film on the surface of the template.
(6) In step D, the heat-treating the template on which the gold film is deposited includes: and (3) placing the template deposited with the gold film into a crucible of a muffle furnace, setting the heating rate to be two hours, heating from room temperature to 800 ℃, then preserving the heat for two hours, and naturally annealing to finish removing the single-layer polystyrene microspheres to obtain the gold nanoparticle-zinc oxide nano cap array.
Further, compared with the prior art, the preparation method of the gold nanoparticle-zinc oxide nano cap array provided by the invention at least has the following advantages:
(1) in the preparation method of the gold nanoparticle-zinc oxide nano-cap array, firstly, a gas-liquid interface self-assembly method, a magnetron sputtering deposition method and a thermal annealing treatment technology are adopted to prepare the zinc oxide nano-cap array with very uniform components and regular and ordered arrangement on a substrate; the zinc oxide nanometer cap array has unique electronic transmission performance, surface cutting performance and larger specific surface area, and can fully exert specificity to adsorb some harmful organic molecules.
(2) According to the preparation method of the gold nanoparticle-zinc oxide nanometer cap array, a layer of orderly-arranged single-layer polystyrene microspheres covers the surface of the zinc oxide nanometer cap array, and then a layer of gold nanoparticles is prepared on the surface of the zinc oxide nanometer cap array by taking the single-layer polystyrene microspheres as a template and adopting an ion sputtering deposition method and a thermal annealing treatment technology, so that an extremely uniform gold nanoparticle-zinc oxide nanometer cap array is obtained; the composite structure can fully exert the adsorption performance and the unique electronic transmission performance of the zinc oxide nanometer cap on specific harmful organic molecules, and greatly improve the photocatalysis performance of gold nanometer particles on the surface of zinc oxide, thereby greatly improving the photodegradation performance of the harmful organic molecules.
(3) In the preparation method of the gold nanoparticle-zinc oxide nanometer cap array, the diameter of the polystyrene microsphere and the sputtering deposition time of the gold film determine the number and the size of the gold nanoparticles on the surface of the zinc oxide nanometer cap, so that the number and the size of the gold nanoparticles are controllable, the SPR (surface plasmon resonance) on the surface of the material can be adjusted, and various optical properties (such as photocatalysis, light absorption, reflection and the like) of the material can be adjusted.
In conclusion, the embodiment of the invention can fully exert the adsorption performance and the unique electronic transmission performance of the zinc oxide nanometer cap on the specific molecules, and greatly improve the photodegradation performance of the gold nanometer particles on the surface of the zinc oxide on the specific harmful organic molecules.
In order to show the technical scheme and the technical effects provided by the present invention more clearly, the gold nanoparticle-zinc oxide nano cap array and the preparation method thereof provided by the present invention are described in detail with specific embodiments below.
Example 1
A gold nanoparticle-zinc oxide nano cap array and a preparation method thereof can comprise the following steps:
step a, placing a clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 30min to obtain a glass substrate with a hydrophilic surface; and sucking deionized water by using a pipette, and injecting the deionized water onto the glass substrate with the hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film. Taking a polystyrene microsphere suspension with the diameter of 1000nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to ethanol of 1.5:1, and performing ultrasonic oscillation treatment for 40min to prepare the uniformly dispersed polystyrene microsphere ethanol diluent. Injecting the polystyrene microsphere ethanol diluent to the glass substrate with the surface covered with the deionized water film, adding a surfactant into a beaker filled with deionized water, and transferring the polystyrene microspheres to the deionized water surface in the beaker, thereby preparing the single-layer polystyrene microspheres on the deionized water surface. And fishing the single-layer polystyrene microspheres from the deionized water surface by using the silicon wafer substrate, thereby preparing the single-layer polystyrene microsphere array on the substrate.
And b, taking the single-layer polystyrene microsphere array as a template, putting the template into a magnetron sputtering instrument, selecting a zinc target as a sputtering target material, setting the vacuum degree to be 30mtor, the sputtering current to be 30mA and the sputtering time to be 6min, and depositing a layer of zinc film on the surface of the template. And (3) placing the template with the zinc film deposited on the surface into a crucible of a muffle furnace, setting the heating rate to be two hours, heating from room temperature to 800 ℃, then preserving the heat for two hours, and naturally annealing to obtain the zinc oxide nano cap array with uniform components and orderly arrangement.
C, placing the clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 30min to obtain the glass substrate with a hydrophilic surface; and sucking deionized water by using a pipette, and injecting the deionized water onto the glass substrate with the hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film. Taking a polystyrene microsphere suspension with the diameter of 150nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to ethanol of 1:1.5, and performing ultrasonic oscillation treatment for 40min to prepare the uniformly dispersed polystyrene microsphere ethanol diluent. And injecting the polystyrene microsphere ethanol solution onto the glass substrate with the surface covered with the deionized water film, adding a surfactant, and transferring to the water surface of deionized water to prepare the single-layer polystyrene microsphere on the water surface of the deionized water. The substrate carrying the zinc oxide nanometer cap array is adopted to fish up the single-layer polystyrene microsphere from the water surface of the deionized water, thereby preparing the zinc oxide nanometer cap array covered with the single-layer polystyrene microsphere
And d, taking the zinc oxide nanometer cap array covered with the single-layer polystyrene microspheres as a template, putting the template into an ion sputtering instrument, selecting a gold target as a sputtering target material, setting the vacuum degree to be 0.1mbar, the sputtering current to be 30mA and the sputtering time to be 45-90 s, and depositing a layer of gold film on the surface of the template. And (3) placing the template deposited with the gold film into a crucible of a muffle furnace, setting the heating rate to be two hours, heating from room temperature to 800 ℃, then preserving the heat for two hours, and naturally annealing to obtain the gold nanoparticle-zinc oxide nano cap array.
Specifically, the gold nanoparticle-zinc oxide nanocap array prepared in example 1 of the present invention was observed with a scanning electron microscope, so as to obtain a scanning electron microscope photograph as shown in fig. 1. FIG. 1a is a top view of an array of gold nanoparticles-zinc oxide nano-caps prepared in example 1 of the present invention; FIG. 1b is a perspective view of the gold nanoparticle-zinc oxide nanocap array prepared in example 1 of the present invention; FIG. 1c is a scanning electron microscope photograph of the gold nanoparticle-zinc oxide nanocap array prepared in step d of example 1 according to the present invention, using a sputtering time of 45 s; FIG. 1d is a scanning electron microscope photograph of the gold nanoparticle-zinc oxide nanocap array prepared in step d of example 1 according to the present invention, using a sputtering time of 60 s; FIG. 1e is a scanning electron microscope photograph of the gold nanoparticle-zinc oxide nanocap array prepared in step d of example 1 according to the present invention, using a sputtering time of 75 s; fig. 1f is a scanning electron microscope photograph of the gold nanoparticle-zinc oxide nanocap array prepared in step d of example 1 according to the present invention, using a sputtering time of 90 s. As can be seen from fig. 1: the gold nanoparticle-zinc oxide nano-cap array prepared in the embodiment 1 of the invention is a gold nanoparticle-zinc oxide nano-cap array which is extremely ordered, the sputtering deposition time of the gold film determines the size of the gold nanoparticles on the surface of the zinc oxide nano-cap, and the longer the sputtering deposition time of the gold film, the larger the size of the gold nanoparticles on the surface of the zinc oxide nano-cap.
In conclusion, the embodiment of the invention can fully exert the adsorption performance and the unique electronic transmission performance of the zinc oxide nanometer cap on the specific molecules, and greatly improve the photodegradation performance of the gold nanometer particles on the surface of the zinc oxide on the specific harmful organic molecules.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. A preparation method of a gold nanoparticle-zinc oxide nanometer cap array is characterized by comprising the following steps:
step A, preparing a single-layer polystyrene microsphere array on a substrate by adopting a gas-liquid interface self-assembly method;
step B, taking the single-layer polystyrene microsphere array as a template, depositing a layer of zinc film on the surface of the template by adopting a magnetron sputtering deposition method, and then annealing the template deposited with the zinc film to prepare a zinc oxide nano cap array;
step C, preparing a single-layer polystyrene microsphere on the water surface of the deionized water, and then fishing the single-layer polystyrene microsphere from the water surface of the deionized water by adopting a substrate loaded with the zinc oxide nano-cap array, thereby preparing the zinc oxide nano-cap array covered with the single-layer polystyrene microsphere;
step D, taking the zinc oxide nanometer cap array covered with the single-layer polystyrene microspheres as a template, depositing a layer of gold film on the surface of the template by adopting an ion sputtering deposition method, and then annealing the template deposited with the gold film to prepare the gold nanoparticle-zinc oxide nanometer cap array;
wherein the annealing treatment of the template on which the zinc film is deposited comprises: placing the template deposited with the zinc film into a crucible of a muffle furnace, setting the heating rate to be two hours, heating from room temperature to 800 ℃, then preserving the heat for two hours, and naturally annealing to obtain a zinc oxide nano cap array;
the annealing treatment of the template deposited with the gold film comprises the following steps: and (3) placing the template deposited with the gold film into a crucible of a muffle furnace, heating the template from room temperature to 800 ℃ at a heating rate of two hours, then preserving the heat for two hours, and naturally annealing to obtain the gold nanoparticle-zinc oxide nano cap array.
2. The method for preparing a gold nanoparticle-zinc oxide nano cap array according to claim 1, wherein the step of preparing a monolayer polystyrene microsphere array on a substrate by a gas-liquid interface self-assembly method comprises the following steps:
a1, placing the clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 10-40 min to obtain a glass substrate with a hydrophilic surface; then sucking deionized water by using a liquid transfer gun, and injecting the deionized water onto a glass substrate with a hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film;
step A2, taking a polystyrene microsphere suspension with the polystyrene microsphere diameter of 1000nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to the ethanol =1.5:1, and then carrying out ultrasonic oscillation treatment for 40min to prepare a uniformly dispersed polystyrene microsphere ethanol solution;
step A3, injecting the polystyrene microsphere ethanol solution onto the glass substrate with the surface covered with the deionized water film, adding a surfactant, and transferring the solution onto the water surface of deionized water to prepare a single-layer polystyrene microsphere on the water surface of the deionized water;
and A4, fishing the monolayer polystyrene microsphere from the deionized water surface by using the substrate, thereby preparing the monolayer polystyrene microsphere array on the substrate.
3. The method for preparing gold nanoparticle-zinc oxide nano cap array according to claim 1 or 2, wherein the step C of preparing the single-layer polystyrene microsphere on the deionized water surface comprises the following steps:
step C1, placing the clean glass substrate in an ultraviolet ozone cleaning machine for irradiation for 10-40 min, thereby obtaining the glass substrate with a hydrophilic surface; then sucking deionized water by using a liquid transfer gun, and injecting the deionized water onto a glass substrate with a hydrophilic surface to prepare the glass substrate with the surface covered with the deionized water film;
step C2, taking a polystyrene microsphere suspension with the polystyrene microsphere diameter of 150nm, mixing the polystyrene microsphere suspension with ethanol according to the volume ratio of the polystyrene microsphere suspension to the ethanol =1:1.5, and then carrying out ultrasonic oscillation treatment for 40min to prepare a uniformly dispersed polystyrene microsphere ethanol solution;
and step C3, injecting the polystyrene microsphere ethanol diluent onto the glass substrate with the surface covered with the deionized water film, adding a surfactant, and transferring the mixture onto the water surface of deionized water to prepare the single-layer polystyrene microsphere on the water surface of the deionized water.
4. The method for preparing gold nanoparticle-zinc oxide nanocap arrays according to claim 1 or 2, wherein depositing a zinc film on the surface of the template by magnetron sputtering deposition comprises: and (3) putting the template into a magnetron sputtering instrument, selecting a zinc target as a sputtering target material, setting the vacuum degree to be 30mtor, the sputtering current to be 30mA and the sputtering time to be 6min, and depositing a layer of zinc film on the surface of the template.
5. The method for preparing gold nanoparticle-zinc oxide nanocap arrays according to claim 1 or 2, wherein depositing a gold film on the surface of the template by ion sputtering deposition comprises: and placing the template into an ion sputtering instrument, selecting a gold target as a sputtering target material, setting the vacuum degree to be 0.1mbar, the sputtering current to be 30mA and the sputtering time to be 45-90 s, and depositing a layer of gold film on the surface of the template.
6. A gold nanoparticle-zinc oxide nano cap array, characterized by being prepared by the preparation method of the gold nanoparticle-zinc oxide nano cap array according to any one of claims 1 to 5.
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