CN108147449B - Gold-zinc oxide heterojunction nanoparticle array and preparation method thereof - Google Patents
Gold-zinc oxide heterojunction nanoparticle array and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a gold-zinc oxide heterojunction nanoparticle array and a preparation method thereof. The preparation method comprises the following steps: mixing gold nanospheres, zinc nitrate, sodium hydroxide and sodium borohydride in water to prepare a precursor mixed solution; and then placing the mixture at the temperature of 60-100 ℃ for reaction for 10-60 minutes to prepare gold-zinc oxide heterojunction nanoparticle colloidal solution, then carrying out centrifugal separation, dispersing the colloidal solution into n-butyl alcohol solution, carrying out treatment by adopting a gas-liquid interface self-assembly method, and fishing out the single-layer nanoparticle array floating on the liquid surface by using a substrate. The invention has strong absorption peaks in both ultraviolet and visible light regions, has high catalytic reaction efficiency, simple preparation process, low cost, environmental protection and no pollution, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of zinc oxide composite nano materials, in particular to a gold-zinc oxide heterojunction nano particle array and a preparation method thereof.
Background
Zinc oxide (ZnO) is a wide bandgap semiconductor material with excellent optical, catalytic, electrical, gas sensing, photoelectric conversion, photoelectric and piezo-chemical properties. However, the absorption peak of the existing zinc oxide nanoparticles is mainly concentrated in an ultraviolet region, the absorption strength is weak, and in addition, the photogenerated electrons and holes are easy to recombine in the reaction, so that the catalytic reaction efficiency is greatly reduced.
Disclosure of Invention
The invention provides a gold-zinc oxide heterojunction nanoparticle array and a preparation method thereof, aiming at solving the technical problems that the absorption peak of the existing zinc oxide nanoparticles is mainly concentrated in an ultraviolet region, the absorption strength is weak, the photogenerated electron-hole is easy to recombine in the reaction to cause the great reduction of the catalytic reaction efficiency, and the like.
The purpose of the invention is realized by the following technical scheme:
the gold-zinc oxide heterojunction nanoparticle array is characterized in that gold-zinc oxide heterojunction nanoparticles in the gold-zinc oxide heterojunction nanoparticle array are in hexagonal close arrangement, the shapes of the gold-zinc oxide heterojunction nanoparticles are in a multi-asteroid shape, the multi-asteroid shape takes a gold nanosphere as a center, and zinc oxide nanosheets grow on the periphery of the gold nanosphere in a non-close mode.
Preferably, the gold-zinc oxide heterojunction nanoparticle array is an ordered single-layer array, an ordered double-layer array or an ordered multi-layer array.
Preferably, the gold-zinc oxide heterojunction nanoparticle array is grown on a substrate, and the gold-zinc oxide heterojunction nanoparticles in the gold-zinc oxide heterojunction nanoparticle array are uniform in size.
Preferably, the substrate is a silicon wafer, a quartz wafer or a silicon dioxide wafer.
A preparation method of a gold-zinc oxide heterojunction nanoparticle array comprises the following steps:
step A, mixing gold nanospheres, zinc nitrate, sodium hydroxide and sodium borohydride together in water to ensure that the concentration of the gold nanospheres in the mixed solution is 0.2-0.3 mmol/L, the concentration of the zinc nitrate is 0.001-0.008 mmol/L, the concentration of the sodium hydroxide is 15-30 mmol/L and the concentration of the sodium borohydride is 5-20 mmol/L, so as to prepare a precursor mixed solution;
step B, placing the precursor mixed solution at the temperature of 60-100 ℃ for reaction for 10-60 minutes to prepare a gold-zinc oxide heterojunction nanoparticle colloidal solution;
step C, carrying out centrifugal separation on the gold-zinc oxide heterojunction nanoparticle colloidal solution, and dispersing the precipitate after the centrifugal separation into an n-butyl alcohol solution to prepare an n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction composite nanoparticles;
and D, carrying out self-assembly treatment on the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction nano particles by adopting a gas-liquid interface self-assembly method, taking out the single-layer nano particle array floating on the liquid level by using a substrate, and airing to obtain the ordered single-layer gold-zinc oxide heterojunction nano particle array.
Preferably, in the step C, the gold-zinc oxide heterojunction nanoparticle colloidal solution is subjected to centrifugal separation at a centrifugal separation rotation speed of 4000-7000 rpm for 10-30 minutes, colorless liquid in a centrifugal tube is removed, centrifugal separation is repeatedly performed for three times, and then the precipitate after centrifugal separation is dispersed in an n-butanol solution.
Preferably, the gold nanospheres are prepared by the following preparation method: adding chloroauric acid, phthalic acid diethylene glycol diacrylate and hydrochloric acid into an ethylene glycol solvent, heating to 195 ℃ by adopting an oil bath, preserving heat for 30 minutes, and then carrying out wet chemical etching by adopting hydrochloric acid to prepare a monodisperse gold nanosphere colloidal solution; and then carrying out centrifugal treatment on the gold nanosphere colloidal solution to obtain the gold nanospheres.
Preferably, the substrate is a silicon wafer, a quartz wafer or a silicon dioxide wafer.
Preferably, the steps A, B, C and D are repeatedly executed, and when the step D is executed, the single-layer nanoparticle array floating on the liquid surface is fished up by the substrate loaded with the gold-zinc oxide heterojunction nanoparticle array and dried in the air, so that the ordered double-layer or ordered multi-layer gold-zinc oxide heterojunction nanoparticle array is prepared.
According to the technical scheme provided by the invention, the gold-zinc oxide heterojunction nanoparticle array provided by the invention is prepared by taking gold nanospheres, zinc nitrate, sodium hydroxide and sodium borohydride as raw materials and adopting a hydrothermal method to prepare gold-zinc oxide heterojunction nanoparticles with the shape of a polyhedron star, and then adopting a gas-liquid interface self-assembly method to prepare the gold-zinc oxide heterojunction nanoparticle array; the gold-zinc oxide heterojunction nano-particles prepared by the method have the shape of a polygonal star, the multi-angular star is that the gold nanosphere is taken as the center, the zinc oxide nanosheet grows around the gold nanosphere non-tightly, the heterojunction nano-particle formed by compounding the gold nano-particle with a strong absorption peak in a visible light range and the zinc oxide nano-sheet can regulate and control the absorption peak position of the zinc oxide nano-sheet so that the zinc oxide nano-sheet has strong absorption peaks in an ultraviolet light region and a visible light region, and has good stability and high catalytic reaction efficiency, is expected to obtain more novel performances, can promote the application of the nano-structure unit in the assembly of nano devices, is favorable for further device formation, therefore, the gold-zinc oxide heterojunction nanoparticle array provided by the invention has better application prospects in the aspects of optics, photocatalysis, photoelectrocatalysis, electricity, gas sensing, photoelectric conversion, piezoelectric chemistry and the like. The method can control the morphology of the gold-zinc oxide heterojunction nano-particles by adjusting the dosage of each raw material in the precursor mixed solution, has the advantages of simple preparation process, low reaction temperature, rapidness, high efficiency, low cost, environmental protection, no pollution and suitability for large-scale industrial production.
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 Field Emission Scanning Electron Microscope (FESEM) photograph and an X-ray diffraction (XRD) pattern of gold nanospheres used in example 1 of the present invention, gold-zinc oxide heterojunction nanoparticles prepared in example 1 of the present invention, and gold-zinc oxide heterojunction nanoparticles prepared in example 2 of the present invention.
FIG. 2 is an element distribution diagram of the gold-zinc oxide heterojunction nanoparticles prepared in example 1 of the present invention.
FIG. 3 is an element distribution diagram of the gold-zinc oxide heterojunction nanoparticles prepared in example 2 of the present invention.
Fig. 4 is a scanning electron micrograph of the gold-zinc oxide heterojunction nanoparticle array prepared in example 1 of the present invention.
Fig. 5 is a scanning electron micrograph of the gold-zinc oxide heterojunction nanoparticle array prepared in example 2 of the present invention.
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-zinc oxide heterojunction nanoparticle array and the preparation method thereof provided by the 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.
The gold-zinc oxide heterojunction nanoparticle array is characterized in that gold-zinc oxide heterojunction nanoparticles in the gold-zinc oxide heterojunction nanoparticle array are in hexagonal close arrangement, the shapes of the gold-zinc oxide heterojunction nanoparticles are in a multi-asteroid shape, the multi-asteroid shape takes a gold nanosphere as a center, and zinc oxide nanosheets grow on the periphery of the gold nanosphere in a non-close mode.
The gold-zinc oxide heterojunction nanoparticle array is an ordered single-layer array, an ordered double-layer array or an ordered multi-layer array. The gold-zinc oxide heterojunction nanoparticle array grows on a substrate, and the gold-zinc oxide heterojunction nanoparticle in the gold-zinc oxide heterojunction nanoparticle array is uniform in size. In practical application, the substrate for growing the gold-zinc oxide heterojunction nanoparticle array can be a substrate with any shape or material commonly used in the field, such as a silicon wafer, a quartz plate, a silicon dioxide plate and the like, and the gold-zinc oxide heterojunction nanoparticle array can be transferred between different substrates at will.
Specifically, the preparation method of the gold-zinc oxide heterojunction nanoparticle array can comprise the following steps:
and step A, mixing gold nanospheres, zinc nitrate, sodium hydroxide and sodium borohydride together in water to ensure that the concentration of the gold nanospheres in the mixed solution is 0.2-0.3 mmol/L, the concentration of the zinc nitrate is 0.001-0.008 mmol/L, the concentration of the sodium hydroxide is 15-30 mmol/L and the concentration of the sodium borohydride is 5-20 mmol/L, and preparing a precursor mixed solution. In practical application, the gold nanospheres are prepared by adopting the following preparation method: adding chloroauric acid, phthalic acid diethylene glycol diacrylate (PDDA, used as a surfactant) and hydrochloric acid into an ethylene glycol solvent, heating to 195 ℃ by adopting an oil bath, preserving heat for 30 minutes, and then carrying out wet chemical etching by adopting a small amount of hydrochloric acid to prepare a monodisperse gold nanoparticle colloidal solution; and then carrying out centrifugal treatment on the gold nanosphere colloidal solution to obtain the gold nanospheres.
And step B, placing the precursor mixed solution at the temperature of 60-100 ℃ for reaction for 10-60 minutes to prepare a light purple red gold-zinc oxide heterojunction nanoparticle colloidal solution.
And C, carrying out centrifugal separation on the gold-zinc oxide heterojunction nanoparticle colloidal solution, wherein the centrifugal separation rotating speed is 4000-7000 revolutions per minute, the centrifugal separation processing time is 10-30 minutes, removing colorless liquid in a centrifugal tube, repeatedly carrying out centrifugal separation for three times, and dispersing the precipitate after centrifugal separation into a n-butyl alcohol solution, thereby preparing the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction composite nanoparticle.
And D, carrying out self-assembly treatment on the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction nano particles by adopting a gas-liquid interface self-assembly method, and fishing out the single-layer nano particle array floating on the liquid level by using the substrate, and airing to obtain the ordered single-layer gold-zinc oxide heterojunction nano particle array.
Further, the substrate used in step D may be a silicon wafer, a quartz wafer, a silicon dioxide wafer, or any other substrate with any shape or material commonly used in the art, and the gold-zinc oxide heterojunction nanoparticle array may be transferred between different substrates at will. Repeatedly executing the step A, the step B, the step C and the step D, and fishing up the single-layer nanoparticle array floating on the liquid surface by using the substrate loaded with the gold-zinc oxide heterojunction nanoparticle array when executing the step D, and airing to prepare the ordered double-layer or ordered multi-layer gold-zinc oxide heterojunction nanoparticle array; for example: repeatedly executing the step A, the step B, the step C and the step D, and fishing up the single-layer nano particle array floating on the liquid surface by using the substrate loaded with the single-layer gold-zinc oxide heterojunction nano particle array and airing to prepare the ordered double-layer gold-zinc oxide heterojunction nano particle array when the step D is executed; repeatedly executing the step A, the step B, the step C and the step D, and fishing up the single-layer nanoparticle array floating on the liquid surface by using the substrate loaded with the double-layer gold-zinc oxide heterojunction nanoparticle array and airing to prepare the ordered three-layer gold-zinc oxide heterojunction nanoparticle array when executing the step D; and so on.
Compared with the prior art, the gold-zinc oxide heterojunction nanoparticle array and the preparation method thereof provided by the invention have the following advantages:
(1) the gold-zinc oxide heterojunction nanoparticle array provided by the invention presents large-area compact hexagonal arrangement and is formed by gold-zinc oxide heterojunction nanoparticles with uniform size, the shapes of the gold-zinc oxide heterojunction nanoparticles are in a multi-angular star shape, the multi-angular star shape takes a gold nanosphere as a center, and a zinc oxide nanosheet grows around the gold nanosphere in a non-compact manner; the heterojunction nano-particle formed by compounding the gold nano-particle with a strong absorption peak in a visible light range and the zinc oxide nano-sheet can regulate and control the absorption peak position of the zinc oxide nano-sheet, so that the zinc oxide nano-sheet has strong absorption peaks in an ultraviolet light region and a visible light region, has good stability and high catalytic reaction efficiency, is expected to obtain more novel performances, can promote the application of a nano-structure unit in the assembly of nano-devices, and is favorable for further device formation, so that the gold-zinc oxide heterojunction nano-particle array provided by the invention has better application prospects in the aspects of optics, photocatalysis, photoelectrocatalysis, electricity, gas sensing, photoelectric conversion, piezoelectric chemistry and the like.
(2) The gold-zinc oxide heterojunction nanoparticle array provided by the invention has good strength when combined with a substrate, and can be transferred to substrates of any shape and material, so that high stability in various application fields can be ensured.
(3) The morphology of the gold-zinc oxide heterojunction nano particles in the gold-zinc oxide heterojunction nano particle array provided by the invention can be controlled by adjusting the using amount of each raw material in the precursor mixed solution, and the preparation process is simple, the using amount of the raw materials in the preparation process is small, no pollution is caused, the gold-zinc oxide heterojunction nano particle array belongs to a green synthesis technology, the production efficiency is high, and the gold-zinc oxide heterojunction nano particle array is suitable for large-scale industrial production.
In conclusion, the invention has strong absorption peaks in both ultraviolet and visible light regions, has high catalytic reaction efficiency, simple preparation process, high speed and high efficiency, low cost, environmental protection and no pollution, and is suitable for large-scale industrial production.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the following detailed description of the gold-zinc oxide heterojunction nanoparticle array and the preparation method thereof in the embodiments of the present invention is provided in specific embodiments.
Example 1
A preparation method of a gold-zinc oxide heterojunction nanoparticle array comprises the following steps:
step a 1: adding chloroauric acid, phthalic acid diethylene glycol diacrylate (PDDA, used as a surfactant) and hydrochloric acid into an ethylene glycol solvent, heating to 195 ℃ by adopting an oil bath, preserving heat for 30 minutes, and then carrying out wet chemical etching by adopting a small amount of hydrochloric acid to prepare a monodisperse gold nanoparticle colloidal solution; and then carrying out centrifugal treatment on the gold nanosphere colloidal solution to obtain the gold nanospheres.
Step b 1: mixing gold nanospheres, zinc nitrate, sodium hydroxide and sodium borohydride together in water to ensure that the concentration of the gold nanospheres in the mixed solution is 0.25 millimole/liter, the concentration of the zinc nitrate is 0.002 millimole/liter, the concentration of the sodium hydroxide is 30 millimole/liter and the concentration of the sodium borohydride is 10 millimole/liter, thus preparing a precursor mixed solution.
Step c 1: and (3) placing the precursor mixed solution at the temperature of 60-100 ℃ for reaction for 10-60 minutes to prepare a light purple red gold-zinc oxide heterojunction nanoparticle colloidal solution.
And d1, performing centrifugal separation on the gold-zinc oxide heterojunction nanoparticle colloidal solution, wherein the centrifugal separation rotation speed is 4000-7000 r/min, the centrifugal separation treatment time is 10-30 min, removing colorless liquid in a centrifugal tube, performing centrifugal separation for three times repeatedly, and dispersing the precipitate after centrifugal separation into n-butyl alcohol solution to obtain the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction composite nanoparticle.
And e1, carrying out self-assembly treatment on the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction nano particles by adopting a gas-liquid interface self-assembly method, taking out the single-layer nano particle array floating on the liquid surface by using the substrate, and airing to obtain the ordered single-layer gold-zinc oxide heterojunction nano particle array.
Example 2
A preparation method of a gold-zinc oxide heterojunction nanoparticle array comprises the following steps:
step a 2: adding chloroauric acid, phthalic acid diethylene glycol diacrylate (PDDA, used as a surfactant) and hydrochloric acid into an ethylene glycol solvent, heating to 195 ℃ by adopting an oil bath, preserving heat for 30 minutes, and then carrying out wet chemical etching by adopting a small amount of hydrochloric acid to prepare a monodisperse gold nanoparticle colloidal solution; and then carrying out centrifugal treatment on the gold nanosphere colloidal solution to obtain the gold nanospheres.
Step b 2: mixing gold nanospheres, zinc nitrate, sodium hydroxide and sodium borohydride together in water to ensure that the concentration of the gold nanospheres in the mixed solution is 0.25 millimole/liter, the concentration of the zinc nitrate is 0.004 millimole/liter, the concentration of the sodium hydroxide is 15 millimole/liter and the concentration of the sodium borohydride is 10 millimole/liter, thus preparing a precursor mixed solution.
Step c 2: and (3) placing the precursor mixed solution at the temperature of 60-100 ℃ for reaction for 10-60 minutes to prepare a light purple red gold-zinc oxide heterojunction nanoparticle colloidal solution.
And d2, performing centrifugal separation on the gold-zinc oxide heterojunction nanoparticle colloidal solution, wherein the centrifugal separation rotation speed is 4000-7000 r/min, the centrifugal separation treatment time is 10-30 min, removing colorless liquid in a centrifugal tube, performing centrifugal separation for three times repeatedly, and dispersing the precipitate after centrifugal separation into n-butyl alcohol solution to obtain the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction composite nanoparticle.
And e2, carrying out self-assembly treatment on the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction nano particles by adopting a gas-liquid interface self-assembly method, taking out the single-layer nano particle array floating on the liquid surface by using the substrate, and airing to obtain the ordered single-layer gold-zinc oxide heterojunction nano particle array.
Morphology and Performance detection
The following topography observations, composition analyses and performance tests were performed during the above-described implementation of examples 1 and 2 of the invention:
(1) respectively observing the shapes of the gold nanospheres used in the embodiments 1 and 2 of the present invention, the gold-zinc oxide heterojunction nanoparticles prepared in the embodiment 1 of the present invention, and the gold-zinc oxide heterojunction nanoparticles prepared in the embodiment 2 of the present invention by using a scanning electron microscope, and performing composition characterization on the gold-zinc oxide heterojunction nanoparticles prepared in the embodiment 2 of the present invention by using an X-ray diffractometer, thereby obtaining a Field Emission Scanning Electron Microscope (FESEM) photograph and an X-ray diffraction (XRD) pattern as shown in fig. 1; wherein, fig. 1a is an XRD spectrum of the gold-zinc oxide heterojunction nanoparticles prepared in example 2 of the present invention, fig. 1b is gold nanospheres used in example 1 of the present invention, fig. 1c is a FESEM photograph of the gold-zinc oxide heterojunction nanoparticles prepared in example 1 of the present invention, fig. 1d is a TEM photograph of the gold-zinc oxide heterojunction nanoparticle array prepared in example 1 of the present invention, fig. 1e is a FESEM photograph of the gold-zinc oxide heterojunction nanoparticles prepared in example 2 of the present invention, and fig. 1f is a TEM photograph of the gold-zinc oxide heterojunction nanoparticles prepared in example 2 of the present invention. As can be seen from fig. 1: the gold-zinc oxide heterojunction nanoparticles prepared in the embodiments 1 and 2 of the present invention have uniform morphology and uniform size, and are symmetrically and non-closely arranged, and each of the gold-zinc oxide heterojunction nanoparticles has a shape of a polygon (the polygon is centered on a gold nanosphere, and a zinc oxide nanosheet is not closely grown around the gold nanosphere), except that the number, position and size of the polygon middle corners are different.
(2) Elemental analysis was performed on the gold-zinc oxide heterojunction nanoparticles prepared in example 1 of the present invention with elemental mapping (element mapping), so as to obtain an elemental distribution diagram as shown in fig. 2; wherein, fig. 2a is an element distribution diagram of all elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 1 of the present invention, fig. 2b is an element distribution diagram of Au elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 1 of the present invention, fig. 2c is an element distribution diagram of Zn elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 1 of the present invention, and fig. 2d is an element distribution diagram of O elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 1 of the present invention. As can be seen from fig. 2: the three elements of Au, Zn and O are uniformly distributed on the gold-zinc oxide heterojunction nano-particles prepared in the embodiment 1 of the invention.
(3) Elemental analysis was performed on the gold-zinc oxide heterojunction nanoparticles prepared in example 2 of the present invention with elemental mapping (element mapping), so as to obtain an elemental distribution map as shown in fig. 3; wherein, fig. 3a is an element distribution diagram of all elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 2 of the present invention, fig. 3b is an element distribution diagram of Au elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 2 of the present invention, fig. 3c is an element distribution diagram of Zn elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 2 of the present invention, and fig. 3d is an element distribution diagram of O elements of the Au-zno heterojunction nanoparticles prepared in the embodiment 2 of the present invention. As can be seen from fig. 3: the three elements of Au, Zn and O are uniformly distributed on the gold-zinc oxide heterojunction nano-particles prepared in the embodiment 2 of the invention.
(4) Detecting the gold-zinc oxide heterojunction nanoparticle array prepared in the embodiment 1 of the invention by using a scanning electron microscope, so as to obtain a scanning electron microscope photo as shown in fig. 4; fig. 4a is a low power FESEM image of the gold-zinc oxide heterojunction nanoparticle array prepared in example 1 of the present invention, and fig. 4b is a high power FESEM image of the gold-zinc oxide heterojunction nanoparticle array prepared in example 1 of the present invention. As can be seen from fig. 4: the gold-zinc oxide heterojunction nanoparticle array prepared in the embodiment 1 of the invention is uniform in size, large in area and tightly tiled on a silicon wafer substrate.
(5) Detecting the gold-zinc oxide heterojunction nanoparticle array prepared in the embodiment 2 of the invention by using a scanning electron microscope, so as to obtain a scanning electron microscope photo as shown in fig. 5; fig. 5a is a low power FESEM image of the au-zno heterojunction nanoparticle array prepared in example 2 of the present invention, and fig. 5b is a high power FESEM image of the au-zno heterojunction nanoparticle array prepared in example 2 of the present invention. As can be seen from fig. 5: the gold-zinc oxide heterojunction nanoparticle array prepared in the embodiment 2 of the invention is uniform in size, large in area and tightly tiled on a silicon wafer substrate.
In conclusion, the embodiment of the invention has strong absorption peaks in both the ultraviolet region and the visible region, has high catalytic reaction efficiency, simple preparation process, high speed and high efficiency, low cost, environmental protection and no pollution, and is suitable for large-scale industrial production.
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-zinc oxide heterojunction nanoparticle array is characterized by comprising the following steps:
step A, mixing gold nanospheres, zinc nitrate, sodium hydroxide and sodium borohydride together in water to ensure that the concentration of the gold nanospheres in the mixed solution is 0.2-0.3 mmol/L, the concentration of the zinc nitrate is 0.001-0.008 mmol/L, the concentration of the sodium hydroxide is 15-30 mmol/L and the concentration of the sodium borohydride is 5-20 mmol/L, so as to prepare a precursor mixed solution;
step B, placing the precursor mixed solution at the temperature of 60-100 ℃ for reaction for 10-60 minutes to prepare a gold-zinc oxide heterojunction nanoparticle colloidal solution;
step C, carrying out centrifugal separation on the gold-zinc oxide heterojunction nanoparticle colloidal solution, and dispersing the precipitate after the centrifugal separation into an n-butyl alcohol solution to prepare an n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction composite nanoparticles;
d, self-assembling the n-butyl alcohol dispersion liquid of the gold-zinc oxide heterojunction nano-particles by adopting a gas-liquid interface self-assembly method, taking out the single-layer nano-particle array floating on the liquid level by using a substrate, and airing to obtain an ordered single-layer gold-zinc oxide heterojunction nano-particle array;
the gold-zinc oxide heterojunction nano particles in the gold-zinc oxide heterojunction nano particle array are arranged in a hexagonal close manner, the shape of the gold-zinc oxide heterojunction nano particles is in a multi-angular star shape, the multi-angular star shape takes a gold nanosphere as a center, and a zinc oxide nano sheet grows around the gold nanosphere in a non-close manner.
2. The method for preparing a gold-zinc oxide heterojunction nanoparticle array according to claim 1, wherein in the step C, the gold-zinc oxide heterojunction nanoparticle colloidal solution is subjected to centrifugal separation at a centrifugal separation rotation speed of 4000 to 7000 rpm for 10 to 30 minutes, colorless liquid in a centrifugal tube is removed, centrifugal separation is repeated for three times, and the precipitate after centrifugal separation is dispersed in an n-butanol solution.
3. The method for preparing gold-zinc oxide heterojunction nanoparticle array according to claim 1 or 2, wherein the gold nanospheres are prepared by the following preparation method: adding chloroauric acid, phthalic acid diethylene glycol diacrylate and hydrochloric acid into an ethylene glycol solvent, heating to 195 ℃ by adopting an oil bath, preserving heat for 30 minutes, and then carrying out wet chemical etching by adopting hydrochloric acid to prepare a monodisperse gold nanosphere colloidal solution; and then carrying out centrifugal treatment on the gold nanosphere colloidal solution to obtain the gold nanospheres.
4. The method for preparing gold-zinc oxide heterojunction nanoparticle array according to claim 1 or 2, wherein the substrate is a silicon wafer, a quartz wafer or a silicon dioxide wafer.
5. The method for preparing gold-zinc oxide heterojunction nanoparticle array according to claim 1 or 2, wherein the steps A, B, C and D are repeatedly performed, and when the step D is performed, the single-layer nanoparticle array floating on the liquid surface is fished up by the substrate loaded with the gold-zinc oxide heterojunction nanoparticle array and dried in the air, so that the ordered double-layer or ordered multi-layer gold-zinc oxide heterojunction nanoparticle array is prepared.
6. The method of claim 1 or 2, wherein the gold-zinc oxide heterojunction nanoparticle array is grown on a substrate, and the gold-zinc oxide heterojunction nanoparticles in the gold-zinc oxide heterojunction nanoparticle array are uniform in size.
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| "Rapid and Efficient Self-Assembly of Au@ZnO Core−Shell Nanoparticle Arrays with an Enhanced and Tunable Plasmonic Absorption for Photoelectrochemical Hydrogen Generation";Yiqiang Sun et al.;《ACS Appl. Mater. Interfaces》;20170830;第9卷;第31898页右栏第1段至第31890页右栏第1段，Scheme 1和图7 * |
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