Universal plasmon photocatalytic material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of photoelectric materials, and provides a universal plasmon photocatalytic material as well as a preparation method and application thereof. According to the universal plasmon photocatalytic material, not only is a plasmon mode (provided by metal particles in the metal particle layer) introduced, but also an optical cavity mode (provided by the metal film layer and the dielectric film layer, and provided by the metal particles in the metal particle layer) is additionally introduced; the micro-nano porous structure can also provide an optical cavity mode) and a plasmon mirror image mode (provided by the metal film layer / metal particle layer), so that coupling of multiple modes is realized, and a local field is enhanced (namely, three-dimensional densely distributed local field active point locations are provided) and light absorption are enhanced; meanwhile, effective excitation and transportation of plasmonic hot electrons are improved, and the hot electrons generated by plasmon decay can directly participate in photocatalysis, so that the high excitation efficiency of the plasmonic hot electrons greatly improves the probability that the hot electrons directly participate in catalytic reaction, and finally the photocatalytic efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic materials, and in particular to a universal plasmon photocatalytic material and a preparation method and application thereof. Background Art

[0002] Photocatalytic technology has attracted considerable attention from researchers due to its ability to directly harness solar energy and convert it into chemical energy for reactions such as water splitting to produce hydrogen, degrading organic pollutants, and reducing carbon dioxide. However, existing photocatalytic materials still face numerous challenges in terms of performance and practical application, limiting their widespread adoption.

[0003] Traditional semiconductor photocatalysts (such as titanium dioxide, TiO2) have a wide band gap (about 3.2eV) and can only absorb ultraviolet light. Ultraviolet light only accounts for about 5% of the energy in the solar spectrum, which greatly limits the efficiency of solar energy utilization. Plasmonic photocatalytic materials are considered to be an effective means to solve the above dilemma. However, the plasmonic nanomaterials currently in common use are generally single nanoparticles, with low solar energy utilization efficiency. The light absorption efficiency and absorption wavelength range are limited by the plasmon resonance of the nanoparticles themselves. Therefore, it is difficult to meet the photocatalytic efficiency requirements when using plasmonic nanomaterials directly as photocatalytic materials. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a universal plasmon photocatalytic material and its preparation method and application. The universal plasmon photocatalytic material provided by the present invention has high photocatalytic efficiency when used directly as a photocatalytic material and is not limited to different types of reactions.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] A universal plasmon photocatalytic material comprises a substrate, wherein one side surface of the substrate is provided with a micro-nano porous structure; a metal film layer, a dielectric film layer and a metal particle layer are sequentially deposited on the surface of the substrate provided with the micro-nano porous structure;

[0007] The metal particle layer is formed of dispersed metal nanoparticles.

[0008] Preferably, the shape of the pores in the micro-nano porous structure is a cuboid, a cylinder, a cone, a parabola between a cylinder and a cone, or an arc shape, and the diameter of the pores ranges from 20 to 2000 nm;

[0009] The substrate is made of an inorganic material or an organic material. The inorganic material is glass, Si, SiO2, Al or Al2O3; the organic material is polyterephthalate plastic (PET), polydimethylsiloxane (PDMS) or polyimide (PI).

[0010] Preferably, the metal film layer is a single layer or a multi-layer composite;

[0011] The material of each layer in the single-layer or multi-layer composite is independently one or more of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo.

[0012] Preferably, the thickness of the metal film layer is 20 to 300 nanometers.

[0013] Preferably, the dielectric film layer is a single layer or a multi-layer composite;

[0014] The material of each layer in the single-layer or multi-layer composite is independently TiO2, graphene, ZnO, Al2O3, CdS, WO3, MoO3, SrTiO3, BiFeO3, g-C3N4 or MoS2.

[0015] Preferably, the thickness of the dielectric film layer is 1 to 1000 nanometers.

[0016] Preferably, the material of the metal nanoparticles is one or more of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo;

[0017] The particle size of the metal nanoparticles is 1 to 500 nanometers.

[0018] The present invention also provides a method for preparing the universal plasmon photocatalytic material described in the above technical solution, comprising the following steps:

[0019] preparing a micro-nano porous structure on one surface of the substrate;

[0020] A metal film layer, a dielectric film layer and a metal particle layer are sequentially deposited on the surface of a substrate provided with a micro-nano porous structure to obtain the universal plasmon photocatalytic material.

[0021] Preferably, the preparation method of the micro-nano porous structure is photolithography, electron beam etching, ion beam etching, electrochemical anodization, laser etching, chemical wet etching or nanoimprinting;

[0022] The metal film layer is deposited by thermal evaporation, magnetron sputtering, physical vapor deposition, chemical vapor deposition, atomic layer deposition or electroplating;

[0023] The dielectric film layer is deposited by magnetron sputtering, electron beam evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, solvent thermal reaction or sol-gel method;

[0024] The metal particle layer is deposited by thermal evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, electroplating, solvent thermal reaction, cluster beam deposition, gas aggregation or nanoimprinting.

[0025] The present invention also provides the use of the universal plasmon photocatalytic material described in the above technical solution or the universal plasmon photocatalytic material prepared by the preparation method described in the above technical solution in photocatalysis, electrocatalysis, photoelectric detection, photoelectric conversion or surface enhanced spectroscopy.

[0026] The present invention provides a universal plasmon photocatalytic material.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. The universal plasmon photocatalytic material of the present invention not only introduces a plasmon mode (provided by the metal particles in the metal particle layer), but also additionally introduces an optical cavity mode (provided by the metal film layer and the dielectric film layer, and at the same time, the micro-nano porous structure can also provide an optical cavity mode) and a plasmon mirror mode (provided by the metal film layer / metal particle layer), thereby achieving synergistic coupling of multiple modes, including plasmon mode-plasmon mode coupling, plasmon mode-plasmon mirror mode coupling, and plasmon mode-optical cavity mode coupling. The coupling of multiple modes achieves local field enhancement (i.e., providing a three-dimensional dense distribution of local field active sites) and enhanced light absorption. At the same time, it improves the excitation efficiency of plasmon hot electrons, that is, improves the effective excitation and transport of plasmon hot electrons. Since the hot electrons generated by plasmon decay can directly participate in photocatalysis, the high excitation efficiency of plasmon hot electrons greatly increases the probability of hot electrons directly participating in the catalytic reaction, ultimately improving the photocatalytic efficiency of the universal plasmon photocatalytic material. In addition, due to multi-mode coupling, universal plasmonic photocatalytic materials also have the characteristics of broadband response and can absorb a wider wavelength range, overcoming the problem of limited absorption wavelength range of single nanoparticles as plasmonic materials, thereby improving light absorption efficiency and sunlight utilization efficiency, and ultimately improving photocatalytic efficiency.

[0029] 2. The universal plasmonic photocatalytic material of the present invention has a micro-nano porous structure set on the surface of one side of the substrate. The micro-nano porous structure supports a gradient change in the dielectric constant, which can effectively achieve broadband absorption of light, and is more conducive to the utilization of solar energy in photocatalysis, that is, it improves the utilization rate of sunlight.

[0030] In summary, the universal plasmon photocatalytic material provided by the present invention has high photocatalytic efficiency when directly used as a photocatalytic material and is not limited to different types of reactions.

[0031] The present invention also provides a method for preparing the universal plasmonic photocatalytic material described in the above technical solution. The preparation method provided by the present invention has a simple process and the prepared universal plasmonic photocatalytic material has good uniformity. In addition, the preparation method provided by the present invention has high controllability, can be easily prepared on a large area, and is not dependent on the type of substrate material.

[0032] The present invention also provides the use of the universal plasmonic photocatalytic material described in the above technical solution, or the universal plasmonic photocatalytic material prepared by the preparation method described in the above technical solution, in photocatalysis, electrocatalysis, photodetection, photoelectric conversion, or surface-enhanced spectroscopy. The universal plasmonic photocatalytic material of the present invention is a plasmonic material with high efficiency and broadband light absorption. It is highly versatile and can be used in a variety of photocatalytic reactions, such as photocatalytic decomposition of water to produce hydrogen, photocatalytic CO2 reduction, and photocatalytic degradation of pollutants. Furthermore, the metamaterial can also be used in the fields of electrocatalysis, photodetection, photoelectric conversion, and surface-enhanced spectroscopy. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 A schematic structural diagram of the universal plasmon photocatalytic material provided by the present invention;

[0034] Figure 2 A flow chart of the preparation method of the universal plasmon photocatalytic material provided by the present invention;

[0035] Figure 3 This is a surface SEM morphology image of the universal plasmon photocatalytic material obtained in Example 1;

[0036] Figure 4 This is a cross-sectional SEM image of the universal plasmon photocatalytic material obtained in Example 1;

[0037] Figure 5 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Example 1 under simulated sunlight irradiation for 60 minutes;

[0038] Figure 6 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Example 2 under simulated sunlight irradiation for 60 minutes;

[0039] Figure 7 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Example 3 under simulated sunlight irradiation for 60 minutes is as follows:

[0040] Figure 8 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Comparative Example 1 under simulated sunlight irradiation for 60 minutes;

[0041] Figure 9The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Comparative Example 2 under simulated sunlight irradiation for 60 minutes;

[0042] Figure 10 This is a cycle test stability diagram of the universal plasmon photocatalytic material obtained in Example 1;

[0043] Reference numerals: 1 is a substrate, 2 is a micro-nano porous structure, 3 is a metal film layer, 4 is a dielectric film layer, and 5 is a metal particle layer. DETAILED DESCRIPTION

[0044] Figure 1 Schematic diagram of the structure of the universal plasmon photocatalytic material provided by the present invention, 1 is the substrate, 2 is the micro-nano porous structure, 3 is the metal film layer, 4 is the dielectric film layer, and 5 is the metal particle layer; Figure 1 The technical solution of the present invention is described in detail.

[0045] The present invention provides a universal plasmon photocatalytic material, comprising a substrate, wherein one side surface of the substrate is provided with a micro-nano porous structure; a metal film layer, a dielectric film layer and a metal particle layer are sequentially deposited on the surface of the substrate provided with the micro-nano porous structure;

[0046] The metal particle layer is formed of dispersed metal nanoparticles.

[0047] Unless otherwise specified, the raw materials used in the present invention are preferably commercially available products.

[0048] The universal plasmonic photocatalytic material provided by the present invention includes a substrate, and a micro-nano porous structure is provided on one side surface of the substrate. In the present invention, the shape of the pores in the micro-nano porous structure is preferably a cuboid, a cylinder, a cone, a parabola between a cylinder and a cone, or a circular arc. The diameter of the pores is preferably in the range of 20 to 2000 nm, and specifically can be 20 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 1000 nm, 1500 nm, 1600 nm, or 2000 nm. In the present invention, the material of the substrate is preferably an inorganic material or an organic material. The inorganic material is preferably glass, Si, SiO2, Al, or Al2O3; the organic material is preferably polyethylene terephthalate (PET), polydimethylsiloxane (PDMS), or polyimide (PI). In the present invention, the micro-nano porous structure can provide an optical cavity mode; at the same time, the micro-nano porous structure supports a gradient change in dielectric constant, which can effectively achieve broadband absorption of light, and is more conducive to the utilization of solar energy in photocatalysis, that is, it is conducive to improving the utilization rate of sunlight for general-purpose plasmonic photocatalytic materials.

[0049] The universal plasmonic photocatalytic material provided by the present invention includes a metal film layer deposited on the side of a substrate provided with a micro-nano porous structure. Specifically, the metal film layer is disposed on the side having the micro-nano porous structure. In the present invention, the metal film layer is preferably a single layer or a multilayer composite. Each layer of the single layer or multilayer composite is preferably independently made of one or more of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W, and Mo. In the present invention, when the material of each layer in a single layer or multilayer composite is independently preferably multiple of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W, and Mo, each layer in the single layer or multilayer composite is an alloy, that is, the material of the metal film layer is an alloy; when the material of each layer in a multilayer composite is one of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W, and Mo, but the materials of each layer in the multilayer composite are not completely the same, the material of the metal film layer composed of the multilayer composite can also be called an alloy; when the material of a single layer is one of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W, and Mo, the material of the metal film layer can also be called a metal element. In the present invention, the thickness of the metal film layer is preferably 20 to 300 nanometers, specifically 20 nanometers, 30 nanometers, 50 nanometers, 100 nanometers, 150 nanometers, 200 nanometers, 250 nanometers, or 300 nanometers.

[0050] The universal plasmonic photocatalytic material provided by the present invention includes a dielectric film layer deposited on a metal film layer, wherein the dielectric film layer is preferably a single layer or a multi-layer composite; the material of each layer in the single layer or multi-layer composite is preferably TiO2, graphene, ZnO, Al2O3, CdS, WO3, MoO3, SrTiO3, BiFeO3, g-C3N4, or MoS2, specifically TiO2, graphene, or ZnO. In the present invention, the thickness of the dielectric film layer is preferably 1 to 1000 nanometers, specifically 1 nanometer, 5 nanometers, 10 nanometers, 20 nanometers, 30 nanometers, 50 nanometers, 100 nanometers, 150 nanometers, 200 nanometers, 250 nanometers, 300 nanometers, 350 nanometers, 400 nanometers, 450 nanometers, 500 nanometers, 550 nanometers, 600 nanometers, 700 nanometers, 750 nanometers, 800 nanometers, 850 nanometers, 900 nanometers, 950 nanometers, or 1000 nanometers. In the present invention, the metal film layer and the dielectric film layer jointly provide an optical cavity mode.

[0051] The universal plasmonic photocatalytic material provided by the present invention includes a metal particle layer deposited on the dielectric film layer, and the metal particle layer is formed by dispersed metal nanoparticles. In the present invention, the material of the metal nanoparticles is preferably one or more of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo. In the present invention, when the material of each metal nanoparticle in the metal nanoparticles is preferably multiple of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo, the material of the metal nanoparticles is preferably called an alloy, that is, the material of the metal particle layer is preferably an alloy. In the present invention, when the material of each metal nanoparticle in the metal nanoparticles is preferably one of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo, but the materials of different metal nanoparticles are different, the material of the metal nanoparticles can be said to be a metal mixture, that is, the material of the metal particle layer is preferably a metal mixture. In the present invention, when the material of each metal nanoparticle in the metal nanoparticles is preferably one of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo, and the different metal nanoparticles are made of the same material, the material of the metal nanoparticles can be referred to as a metal element, that is, the material of the metal particle layer is preferably a metal element. In the present invention, the particle size of the metal nanoparticles is preferably 1 to 500 nanometers, specifically 1 nanometer, 5 nanometers, 10 nanometers, 12 nanometers, 15 nanometers, 20 nanometers, 25 nanometers, 30 nanometers, 35 nanometers, 40 nanometers, 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers, 95 nanometers, 100 nanometers, 150 nanometers, 200 nanometers, 250 nanometers, 300 nanometers, 350 nanometers, 400 nanometers, 450 nanometers or 500 nanometers. In the present invention, the metal particle layer can provide a plasmon mode; at the same time, the metal film layer and the metal particle layer jointly provide a plasmon mirror mode.

[0052] Figure 2 The flow chart of the preparation method of the universal plasmon photocatalytic material provided by the present invention is as follows: Figure 2 The preparation method provided by the present invention is described in detail.

[0053] The present invention also provides a method for preparing the universal plasmon photocatalytic material described in the above technical solution, comprising the following steps:

[0054] preparing a micro-nano porous structure on one surface of the substrate;

[0055] A metal film layer, a dielectric film layer and a metal particle layer are sequentially deposited on the surface of a substrate provided with a micro-nano porous structure to obtain the universal plasmon photocatalytic material.

[0056] The present invention prepares a micro-nano porous structure on one side surface of a substrate.

[0057] In the present invention, the substrate is preferably cleaned before use. The cleaning method and operation are not particularly limited, as long as the impurities and oxide film on the substrate can be completely removed.

[0058] In the present invention, the method for preparing the micro-nano porous structure is preferably photolithography, electron beam etching, ion beam etching, electrochemical anodization, laser etching, chemical wet etching, or nanoimprinting, specifically electrochemical anodization, chemical wet etching, or nanoimprinting. The present invention does not specifically limit the process and parameters of the photolithography, electron beam etching, ion beam etching, electrochemical anodization, laser etching, chemical wet etching, or nanoimprinting, as long as a micro-nano porous structure of a specified shape and diameter range can be obtained.

[0059] After preparing a micro-nano porous structure on one side of the substrate, the present invention sequentially deposits a metal film layer, a dielectric film layer and a metal particle layer on the surface of the substrate provided with the micro-nano porous structure to obtain the universal plasmon photocatalytic material.

[0060] In the present invention, the deposition method of the metal film layer is preferably thermal evaporation, magnetron sputtering, physical vapor deposition, chemical vapor deposition, atomic layer deposition or electroplating, specifically thermal evaporation or magnetron sputtering. The present invention does not specifically limit the parameters of the thermal evaporation, magnetron sputtering, physical vapor deposition, chemical vapor deposition, atomic layer deposition or electroplating, as long as a metal film layer of the required material and thickness can be obtained. In the present invention, the metal film layer will be deposited on the surface of the substrate provided with the micro-nano porous structure. If the micro-nano porous structure is exposed, a metal film layer will also be deposited on the surface of the micro-nano porous structure.

[0061] In the present invention, the dielectric film layer is preferably deposited by magnetron sputtering, electron beam evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, a solvothermal reaction method, or a sol-gel method, more specifically magnetron sputtering, electron beam evaporation, or chemical vapor deposition. The present invention does not impose specific limitations on the parameters of the magnetron sputtering, electron beam evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, solvothermal reaction method, or sol-gel method, as long as a dielectric film layer of the desired material and thickness can be obtained.

[0062] In the present invention, the deposition method of the metal particle layer is preferably thermal evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, electroplating, solvent thermal reaction, cluster beam deposition, gas aggregation method or nanoimprinting, specifically magnetron sputtering, thermal evaporation or gas aggregation method. The present invention does not specifically limit the parameters of the thermal evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, electroplating, solvent thermal reaction, cluster beam deposition, gas aggregation method or nanoimprinting, as long as a metal particle layer of the required material and particle size can be obtained. In the present invention, when the deposition time of the thermal evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, electroplating and solvent thermal reaction is short, a dispersed metal particle layer is obtained. In the present invention, when the deposition time of thermal evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, electroplating, and solvothermal reaction is long, a continuous film layer is obtained. The present invention preferably also includes heat treating the obtained continuous film layer to obtain a metal particle layer. The present invention does not specifically limit the parameters and process of the heat treatment, and operations familiar to those skilled in the art can be used. In the present invention, the cluster beam deposition, gas aggregation method, or nanoimprinting method can directly deposit a metal particle layer.

[0063] The present invention also provides the use of the universal plasmon photocatalytic material described in the above technical solution or the universal plasmon photocatalytic material prepared by the preparation method described in the above technical solution in photocatalysis, electrocatalysis, photoelectric detection, photoelectric conversion or surface enhanced spectroscopy.

[0064] In the present invention, the photocatalysis preferably includes photocatalytic decomposition of water to produce hydrogen, photocatalytic CO2 reduction or photocatalytic degradation of pollutants.

[0065] The present invention does not specifically limit the application mode of the universal plasmon photocatalytic material, and those skilled in the art can configure it according to actual needs.

[0066] The general plasmon photocatalytic material provided by the present invention, its preparation method and application are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0067] Example 1

[0068] A method for preparing a universal plasmon photocatalytic material comprises the following steps:

[0069] (1) Al was selected as the substrate material, and a micro-nano porous structure was prepared on one side of the substrate by anodization (at this time, the Al in the micro-nano porous structure was oxidized to Al2O3). The cross-sectional shape of the pores was parabolic close to a cone, and the maximum diameter of the pores was 400 nanometers.

[0070] (2) A thermal evaporation method is used to deposit an Au metal film layer on the surface of the substrate provided with the micro-nano porous structure, and the thickness of the metal film layer is 100 nanometers.

[0071] (3) A TiO2 dielectric film layer is prepared on the surface of the metal film layer by magnetron sputtering, and the thickness of the dielectric film layer is 20 nanometers.

[0072] (4) Cluster beam deposition is used to prepare an Au metal nanoparticle layer on the surface of the dielectric film layer. The average size of the nanoparticles in the metal nanoparticle layer is 20 nanometers.

[0073] Example 2

[0074] A method for preparing a universal plasmon photocatalytic material comprises the following steps:

[0075] (1) Si was selected as the substrate material, and a micro-nano porous structure was prepared on one side of the substrate by chemical wet etching. The shape of the pores was cylindrical, and the diameter of the pores was 1600 nanometers.

[0076] (2) A Ag metal film layer is deposited on the surface of the substrate provided with the micro-nano porous structure by thermal evaporation method, and the thickness of the metal film layer is 300 nanometers.

[0077] (3) A ZnO dielectric film layer is prepared on the surface of the metal film layer by electron beam evaporation, and the thickness of the dielectric film layer is 200 nanometers.

[0078] (4) A Ag metal nanoparticle layer is prepared on the surface of the dielectric film layer by thermal evaporation. The average size of the nanoparticles in the metal nanoparticle layer is 200 nanometers.

[0079] Example 3

[0080] A method for preparing a universal plasmon photocatalytic material comprises the following steps:

[0081] (1) PDMS was selected as the substrate material, and a micro-nano porous structure was prepared on one side of the substrate by nanoimprinting. The shape of the pores was cylindrical and the diameter of the pores was 2000 nanometers.

[0082] (2) A Cu metal film layer is deposited on the surface of the substrate provided with the micro-nano porous structure by magnetron sputtering, and the thickness of the metal film layer is 200 nanometers.

[0083] (3) A graphene film layer is prepared on the surface of the metal film layer by chemical vapor deposition, and the thickness of the graphene film is 1 nanometer.

[0084] (4) A Ag / Au / Cu / Ru / Pt / Pd alloy metal nanoparticle layer was prepared on the surface of the graphene film layer by a gas aggregation method. The average size of the metal nanoparticles in the metal particle layer was 5 nm.

[0085] Comparative Example 1

[0086] The difference from Example 1 is that the micro-nano porous structure is not prepared on one side of the surface of the alumina substrate, and the rest is the same as Example 1.

[0087] Comparative Example 2

[0088] The Au metal nanoparticle layer is directly prepared on the alumina substrate using a cluster beam, and the average size of the nanoparticles in the metal nanoparticle layer is 20 nanometers.

[0089] Figure 3 This is a surface SEM morphology image of the universal plasmon photocatalytic material obtained in Example 1; Figure 4 This is a cross-sectional SEM morphology of the universal plasmon photocatalytic material obtained in Example 1.

[0090] from Figure 3 It can be seen that the universal plasmon photocatalytic material has porous characteristics as a whole, with a maximum pore size of about 400 nanometers, and metal nanoparticles are evenly distributed on the surface of the material and the inner wall of the pores.

[0091] from Figure 4 It can be seen that the cross-sectional shape of the pores in the universal plasmonic photocatalytic material is parabolic, and the pore depth is about 300 nanometers.

[0092] The universal plasmon photocatalytic materials obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were placed in 100 mL of water and irradiated with simulated sunlight of 300 W intensity. The hydrogen production after 60 minutes of irradiation was measured. The results are as follows: Figures 5 to 9 As shown, Figure 5 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Example 1 under simulated sunlight irradiation for 60 minutes; Figure 6 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Example 2 under simulated sunlight irradiation for 60 minutes; Figure 7 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Example 3 under simulated sunlight irradiation for 60 minutes is as follows: Figure 8 The photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Comparative Example 1 under simulated sunlight irradiation for 60 minutes is shown in FIG. Figure 9 This is the photocatalytic hydrogen production of the universal plasmon photocatalytic material obtained in Comparative Example 2 under simulated sunlight irradiation for 60 minutes. The above hydrogen production was measured using gas chromatography.

[0093] from Figure 5 It can be seen that an obvious hydrogen peak appears in the gas chromatogram, and the integrated area of ​​the peak is 99320, indicating that the universal plasmon photocatalytic material prepared in Example 1 can effectively catalyze water decomposition to produce hydrogen.

[0094] from Figure 6 It can be seen that an obvious hydrogen peak also appears in the gas chromatogram, and the integrated area of ​​the peak is 46183, which also shows that the universal plasmonic photocatalytic material can effectively catalyze water decomposition to produce hydrogen. Compared with Example 1, the hydrogen production of the universal plasmonic photocatalytic material in Example 2 is slightly lower.

[0095] from Figure 7 It can be seen that a clear hydrogen peak also appears in the gas chromatogram, and the integrated area of ​​the peak is 77512, which also shows that the universal plasmonic photocatalytic material can effectively catalyze water decomposition to produce hydrogen. Compared with Examples 1 and 2, the hydrogen production of the universal plasmonic photocatalytic material in Example 3 is between the hydrogen production of Examples 1 and 2. However, the universal plasmonic photocatalytic materials in the three examples all have obvious photocatalytic hydrogen production activity.

[0096] from Figure 8 It can be seen that a hydrogen peak appears in the gas chromatogram, indicating that the material prepared in Comparative Example 1 has a certain photocatalytic hydrolysis hydrogen production activity, but compared with Examples 1 to 3, the photocatalytic activity of the material in Comparative Example 1 is very low.

[0097] from Figure 9 It can be seen that no obvious hydrogen peak appears in the gas chromatogram, indicating that the material prepared in Comparative Example 2 has no photocatalytic activity.

[0098] The universal plasmon photocatalytic material obtained in Example 1 was placed in 100 mL of water and irradiated with simulated sunlight of 300 W intensity, and the hydrogen production after 4 h of irradiation was measured; then the universal plasmon photocatalytic material was taken out and placed in 100 mL of water again, and irradiated with simulated sunlight of 300 W intensity, and the hydrogen production after 4 h of irradiation was measured; the above process was repeated for 7 cycles, and the hydrogen production in each cycle was as follows: Figure 10 shown. Figure 10 The cyclic test stability diagram of the universal plasmon photocatalytic material obtained in Example 1; Figure 10 It can be seen that the photocatalytic hydrogen production activity of plasmons remains stable, and the hydrogen production amount hardly decays in the 7 cycles of the test.

[0099] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A universal plasmon photocatalytic material, characterized in that: The invention comprises a substrate, wherein a micro-nano porous structure is arranged on one side surface of the substrate; a metal film layer, a dielectric film layer and a metal particle layer are sequentially deposited on the surface of the substrate provided with the micro-nano porous structure; The metal particle layer is formed of dispersed metal nanoparticles.

2. The universal plasmon photocatalytic material according to claim 1, characterized in that: The shape of the pores in the micro-nano porous structure is a cuboid, a cylinder, a cone, a parabola or an arc between a cylinder and a cone, and the diameter of the pores ranges from 20 to 2000 nm; The substrate is made of inorganic material or organic material. The inorganic material is glass, Si, SiO2, Al or Al2O3. The organic material is polyterephthalate plastic, polydimethylsiloxane or polyimide.

3. The universal plasmon photocatalytic material according to claim 1, characterized in that: The metal film layer is a single layer or a multi-layer composite; The material of each layer in the single-layer or multi-layer composite is independently one or more of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo.

4. The universal plasmon photocatalytic material according to claim 1 or 3, characterized in that: The thickness of the metal film layer is 20 to 300 nanometers.

5. The universal plasmon photocatalytic material according to claim 1, characterized in that: The dielectric film layer is a single layer or a multi-layer composite; The material of each layer in the single-layer or multi-layer composite is independently TiO2, graphene, ZnO, Al2O3, CdS, WO3, MoO3, SrTiO3, BiFeO3, g-C3N4 or MoS2.

6. The universal plasmon photocatalytic material according to claim 1 or 5, characterized in that: The thickness of the dielectric film layer is 1 to 1000 nanometers.

7. The universal plasmon photocatalytic material according to claim 1, characterized in that: The material of the metal nanoparticles is one or more of Au, Ag, Cu, Al, Ni, Co, Fe, Ru, Rh, Pt, W and Mo; The particle size of the metal nanoparticles is 1 to 500 nanometers.

8. The method for preparing a universal plasmon photocatalytic material according to any one of claims 1 to 7, characterized in that: The following steps are involved: A micro-nano porous structure is prepared on one surface of the substrate; A metal film layer, a dielectric film layer and a metal particle layer are sequentially deposited on the surface of a substrate provided with a micro-nano porous structure to obtain the universal plasmon photocatalytic material.

9. The preparation method according to claim 8, characterized in that: The preparation method of the micro-nano porous structure is photolithography, electron beam etching, ion beam etching, electrochemical anodization, laser etching, chemical wet etching or nanoimprinting; The deposition method of the metal film layer is thermal evaporation, magnetron sputtering, physical vapor deposition, chemical vapor deposition, atomic layer deposition or electroplating; The dielectric film layer is deposited by magnetron sputtering, electron beam evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, solvent thermal reaction or sol-gel method; The metal particle layer is deposited by thermal evaporation, physical vapor deposition, chemical vapor deposition, atomic layer deposition, electroplating, solvent thermal reaction, cluster beam deposition, gas aggregation or nanoimprinting.

10. Use of the universal plasmon photocatalyst material according to any one of claims 1 to 7 or the universal plasmon photocatalyst material prepared by the preparation method according to any one of claims 8 to 9 in photocatalysis, electrocatalysis, photoelectric detection, photoelectric conversion or surface enhanced spectroscopy.

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