WO2017080495A1 - 一种复合材料器件 - Google Patents

一种复合材料器件 Download PDF

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Publication number
WO2017080495A1
WO2017080495A1 PCT/CN2016/105410 CN2016105410W WO2017080495A1 WO 2017080495 A1 WO2017080495 A1 WO 2017080495A1 CN 2016105410 W CN2016105410 W CN 2016105410W WO 2017080495 A1 WO2017080495 A1 WO 2017080495A1
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Prior art keywords
composite device
metal particles
pores
metal
npt
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PCT/CN2016/105410
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English (en)
French (fr)
Inventor
朱嘉
周林
谭颖玲
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南京大学
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Priority to EP16863671.0A priority Critical patent/EP3375912B1/en
Priority to US15/775,767 priority patent/US10974971B2/en
Publication of WO2017080495A1 publication Critical patent/WO2017080495A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/14—Treatment of water, waste water, or sewage by heating by distillation or evaporation using solar energy
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/46—Sputtering by ion beam produced by an external ion source
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • the invention belongs to the field of composite materials, and in particular relates to a composite material device.
  • Light absorbers are widely used in light/thermal detection, solar energy conversion, infrared imaging and other fields.
  • the range of light absorption and absorption spectra of a light absorber is a key factor in determining its performance.
  • An ideal light absorber should have a higher light absorption over a wider spectral range, that is, a lower light transmission and a lower light reflectance over a wider spectral range.
  • a light absorber having a metallic super-surface structure and a light absorber having a tapered structure
  • the two types of light absorbers broaden the bandwidth of the light absorber by a composite resonance mode.
  • a plasmon light absorber with a crossed trapezoidal grating array that has an absorption efficiency of 71% for light having a wavelength of 400-700 nm.
  • a metal light absorber having an ultra-tip concave-convex groove structure which has an absorption efficiency of 96% for light of a wavelength of 450-850 nm.
  • high temperature resistant materials such as tantalum nitride and vanadium dioxide are also applied to the light absorber.
  • the preparation process of most of the light absorbers in the prior art is mainly a top-down method such as a focused ion beam or electron beam etching.
  • the high manufacturing costs limit the yield of the light absorber and the potential for wide application.
  • the prior art light absorbers also have the disadvantages of a narrow range of absorption spectra and low absorption efficiency of light.
  • a first aspect of the present invention provides a composite device, the device comprising a substrate having a plurality of holes, the inner wall of the hole being attached with a plurality of metal particles, the particle size of the metal particles being 1 to 200 nm, the plurality of metal particles have at least x different particle diameters d, and x is greater than or equal to 2.
  • a second aspect of the present invention provides a composite material device, the device comprising a substrate having a plurality of holes, the inner wall of the hole being attached with a plurality of metal particles, the plurality of holes including at least z kinds of apertures f , z is greater than or equal to 2.
  • a third aspect of the invention provides a method of preparing a composite device according to any of the invention, comprising the step of depositing metal particles on a surface of the substrate and an inner wall of the pore by a physical vapor deposition method, the physical gas phase
  • the parameters of the deposition include: vacuum degree: 4 to 5 ⁇ 10 -4 Pa.
  • a fourth aspect of the invention provides the use of a composite device according to any of the inventions for absorbing light.
  • a fifth aspect of the invention provides the use of the composite device of any of the inventions for photothermal conversion.
  • a sixth aspect of the invention provides the use of the composite device of any of the inventions for desalinating seawater.
  • the matrix of the invention may be a porous alumina template.
  • the porous alumina template of the present invention can be a porous alumina template that is common in the art.
  • the porous alumina template may be referred to as AAO (Anodic Aluminum Oxide).
  • AAO Anadic Aluminum Oxide
  • it may be a single pass AAO template, a two-pass AAO template or a V-type AAO template produced by Hefei Microcrystalline Materials Technology Co., Ltd.
  • it can be a controlled multi-branched anodized aluminum prepared by Chen Shuoshu in "Controllable Multi-branched Anode Alumina: Preparation and Application" / South China University of Technology / 2010.
  • it may be an anodized aluminum template having a gradient nanopore as disclosed in CN102925947A.
  • it may be a porous alumina template having a Y-type structure as disclosed in CN101451260.
  • the metal particles of the present invention include all particles containing a simple substance of a metal, including simple metal particles, and metal particles combined with other materials, such as chemically modified metal particles, such as surface coating. Metal particles coated with an oxide layer.
  • the particle diameter of the metal particles refers to the diameter of the circumscribed circle of the metal particles in the scanning electron micrograph of the cross section of the composite device.
  • the aspect ratio of the metal particles means that in the scanning electron micrograph of the cross section of the composite device, the smallest area of the metal particles circumscribes the aspect ratio of the rectangle.
  • the shape of the metal particles means the shape of the metal particles in the scanning electron micrograph of the cross section of the composite device.
  • the pore size, porosity, pore spacing, pore shape, and degree of disorder of the pores of the template can be controlled by parameters of anodization.
  • the particle size, shape or distribution of the metal particles can be controlled by the degree of vacuum of physical vapor deposition and/or the time of deposition.
  • ⁇ means greater than or equal to, and ⁇ means less than or equal to.
  • the composite device of the present invention has a high light absorption rate
  • the composite device of the present invention has a high light absorption rate over a wide range of light wavelengths
  • the composite device of the present invention has a low reflectance
  • the composite device of the present invention converts absorbed light energy into heat energy.
  • the composite device of the present invention can utilize the absorbed light energy to generate heat, which is used for evaporation of the liquid.
  • the composite device of the present invention is a porous material which facilitates the effective escape of vapor of the liquid when the composite device of the present invention is used to evaporate a liquid.
  • the composite device of the present invention can be used for evaporation and purification of liquids, and is particularly suitable for evaporation and purification of water, particularly seawater desalination.
  • the composite device of the present invention has one or more advantages such as environmental friendliness, low cost, easy preparation, and mass production.
  • Example 1 is a scanning electron micrograph of Au/NPT of Example 1;
  • Example 2 is a scanning electron micrograph of the ordered surface of the Au/NPT of Example 1;
  • Example 3 is a scanning electron micrograph of the disordered surface of the Au/D-NPT of Example 2;
  • Figure 4 is a Fourier transform diagram of Figure 2;
  • Figure 5 is a Fourier transform diagram of Figure 3.
  • Figure 7 is a scanning electron micrograph of a partial region of the Au/D-NPT of Example 2.
  • Figure 8 is a scanning electron micrograph of the Au/NPT of Example 1.
  • Figure 9 is a scanning electron micrograph of Al/D-NPT of Example 5.
  • Figure 10 is a schematic view of a composite device of the present invention.
  • Figure 11 is a graph showing the light absorption rate of Au/NPT, Au/D-NPT, and D-NPT as a function of light wavelength;
  • Figure 12 is a graph showing the light absorption rate of Al/D-NPT as a function of light wavelength
  • Figure 13 is a graph showing the amount of water vapor generation as a function of time when using Au/D-NPT and not using Au/D-NPT;
  • the invention provides the following specific embodiments and all possible combinations between them.
  • the present application does not describe various specific combinations of the embodiments one by one, but it should be considered that the present application specifically recites and discloses all possible combinations of the specific embodiments.
  • An aspect of the invention provides a composite device, the device comprising a substrate having a plurality of holes, the inner wall of the hole being attached with a plurality of metal particles, the metal particles having a particle diameter of 1 to 200 nm
  • the plurality of metal particles have at least x different particle sizes d, x being greater than or equal to two.
  • the composite device according to any of the preceding claims, wherein the metal particles have a particle size of from 1 to 150 nm.
  • the composite device according to any of the preceding claims, wherein the metal particles have a particle size of from 1 to 100 nm.
  • x is equal to 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the x different particle diameters d are selected from any of the following d 1 to d 10 : 1 nm ⁇ d 1 ⁇ 10 nm 10 nm ⁇ d 2 ⁇ 20 nm, 20 nm ⁇ d 3 ⁇ 30 nm, 30 nm ⁇ d 4 ⁇ 40 nm, 40 nm ⁇ d 5 ⁇ 50 nm, 50 nm ⁇ d 6 ⁇ 60 nm, 60 nm ⁇ d 7 ⁇ 70 nm, 70 nm ⁇ d 8 ⁇ 80 nm, 80 nm ⁇ d 9 ⁇ 90 nm, 90 nm ⁇ d 10 ⁇ 100 nm.
  • the x different particle diameters d are selected from any of the following d 11 to d 15 : 1 nm ⁇ d 11 ⁇ 20 nm 20 nm ⁇ d 12 ⁇ 40 nm, 40 nm ⁇ d 13 ⁇ 60 nm, 60 nm ⁇ d 14 ⁇ 80 nm; 80 nm ⁇ d 15 ⁇ 100 nm; x is equal to 2, 3 or 4 or 5.
  • the composite device of any one of the present invention the plurality of metal particles
  • the granules have at least y aspect ratio e, y greater than or equal to two.
  • y is equal to 2, 3, 4, 5, 6, 7, or 8.
  • the composite device according to any one of the present invention, wherein the aspect ratio e is selected from any of the following e 1 to e 8 : 1 ⁇ e 1 ⁇ 1.2, 1.2 ⁇ e 2 ⁇ 1.5, 1.5 ⁇ e 3 ⁇ 2, 2 ⁇ e 4 ⁇ 3, 3 ⁇ e 5 ⁇ 4, 4 ⁇ e 6 ⁇ 6, 6 ⁇ e 7 ⁇ 8, 8 ⁇ e 8 ⁇ 10.
  • the composite device according to any one of the present invention, wherein the aspect ratio e is selected from any of the following e 9 to e 12 : 1 ⁇ e 9 ⁇ 2, 2 ⁇ e 10 ⁇ 3, 3 ⁇ e 11 ⁇ 4, 4 ⁇ e 12 ⁇ 6; y is equal to 2, 3 or 4.
  • the metal nanoparticle has a shape selected from the group consisting of one, two or three of the following: a rod shape, an ellipsoid shape, and a spherical shape.
  • the composite device of any of the present invention has a spacing between adjacent metal nanoparticles of from 1 to 50 nanometers, such as from 1 to 30 nanometers, such as from 1 to 15 nanometers.
  • the composite device according to any of the preceding claims wherein the metal particles have a distribution density of about 10 2 to 10 4 / ⁇ 2 in the inner wall of the pores, for example, about 10 3 to 10 4 /
  • the micron 2 is , for example, about 2 ⁇ 10 3 to 5 ⁇ 10 3 / ⁇ 2 .
  • the composite device of claim 1 according to any of the preceding claims, wherein the gold particles are distributed in a range from the surface of the substrate to a depth in the range of g to h micrometers, g ⁇ h ;
  • G preferably 0-5, preferably about 0, 1, 2, 3, 4 or 5;
  • h ⁇ 0, preferably 0 to 10, preferably about 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the composite device of any of the present invention has a gradient in particle size of the metal particles from one side of the substrate to the other.
  • the composite device of any of the present invention has a gradient in the aspect ratio of the metal particles from one side of the substrate to the other.
  • the shape of the metal particles changes from one side of the substrate to the other.
  • the composite device according to any one of the present invention, wherein the shape of the metal particles is changed from a rod shape to an elliptical shape, and then changes to a spheroidal shape.
  • the composite device of any of the present invention the plurality of metal particles are disorderly distributed on an inner wall of the pore.
  • the composite device according to any one of the invention, wherein the material of the metal particles is selected from one or more of the following: a noble metal (such as gold, silver or platinum), a transition metal (for example) Copper) and light Metal (such as aluminum).
  • a noble metal such as gold, silver or platinum
  • a transition metal for example
  • copper copper
  • light Metal such as aluminum
  • the composite device according to any of the preceding claims, wherein the metal particles are made of gold or aluminum.
  • the composite device of any of the present invention comprising at least z species of apertures f, z greater than or equal to two.
  • a composite device includes a substrate having a plurality of holes, and a plurality of metal particles are attached to an inner wall of the hole, the plurality of holes including at least z kinds of apertures f , z is greater than or equal to 2.
  • the composite device of any of the inventions, z is equal to 3, 4, 5, 6, 7, or 8.
  • the z different pore diameters f are selected from any of the following f 1 to f 8 : 100 ⁇ f 1 ⁇ 150, 150 ⁇ f 2 ⁇ 200,200 ⁇ f 3 ⁇ 250,250 ⁇ f 4 ⁇ 300,300 ⁇ f 5 ⁇ 350,350 ⁇ f 6 ⁇ 400,400 ⁇ f 7 ⁇ 450,450 ⁇ f 8 ⁇ 500, z is equal to 2, 3, 4, 5, 6, 7 or 8.
  • the composite device of any one of the present invention wherein the z different pore diameters f are selected from any of the following f 9 to f 13 : 160 ⁇ f 9 ⁇ 200, 200 ⁇ f 10 ⁇ 250, 250 ⁇ f 11 ⁇ 300, 300 ⁇ f 12 ⁇ 350, 350 ⁇ f 13 ⁇ 380; z is equal to 2, 3, 4 or 5.
  • the composite device of any of the present invention wherein the pores have an average pore diameter of from 200 to 1000 nm.
  • the composite device of any of the inventions, wherein the pores have an average pore diameter of from 300 to 600 nanometers.
  • the composite device of any of the inventions, wherein the pores have an average pore diameter of from 300 to 500 nanometers.
  • the composite device of any of the present invention wherein the pores have an average pore diameter of from 350 to 500 nanometers.
  • the composite device of any of the inventions, wherein the pores have an average pore diameter of from 350 to 400 nanometers.
  • the composite device according to any one of the present invention, wherein the aspect ratio of the pores is in the range of 1 to 3, for example, in the range of 1 to 2, and further, for example, in the range of 1 to 1.5. Distribution within the range.
  • the composite device of any of the invention wherein the pores comprise pores having an aspect ratio of about 1, 1.1, 1.2, 1.3, 1.4 and 1.5.
  • the composite device of any of the invention comprising pores having an aspect ratio of about 1, 1.2, 1.4, 1.5, 1.8 and 2.
  • the composite device of any of the inventions, wherein the pores have an average pore spacing of from 300 to 600 nanometers, preferably from 400 to 500 nanometers.
  • the composite device according to any of the preceding claims, wherein the shape of the pores is selected from the following two, three, four, five or six: triangular, quadrangular, and five-sided Shape, hexagon, circle, ellipse.
  • the composite device according to any one of the present invention wherein the pores have a porosity of 20 to 80%, preferably 40 to 70%, on at least one surface of the substrate. It is preferably 50 to 60%.
  • the composite device of any of the present invention the distribution of the pores on the surface of the substrate is disordered.
  • the composite device of any one of the present invention performs a Fourier transform on a scanning electron micrograph of a side surface of the substrate adjacent to the metal particle, and the obtained Fourier transform image
  • the ratio of the outer diameter to the inner diameter of the ring is 2 or more, preferably 2.5 or more, more preferably 2.5 to 5, still more preferably 2.5 to 3.5, still more preferably 2.8 to 3.2.
  • the path of the aperture is a straight line or a curve.
  • the pores may have a path at 90 degrees or other angles to the surface of the substrate.
  • the hole is a through hole or a non-through hole.
  • the composite device of any of the present invention is in the form of a flat plate or a curved plate.
  • the composite device of any of the present invention has a total thickness of from 20 to 200 microns, preferably from 50 to 100 microns.
  • the composite device of any one of the present invention the surface of the substrate adjacent to one side of the metal particles is covered with a metal layer.
  • the composite device of claim 40 said metal layer only covering a non-porous region of said surface.
  • the composite device according to any of the preceding claims, wherein the metal layer has a thickness of 50 to 100 nm, preferably 60 to 90 nm.
  • the composite device of any one of the present invention wherein the hole is a non-through hole
  • the metal layer covers the surface on one side without the holes.
  • the pores are through holes, and a metal layer is deposited on a surface adjacent to one side of the gold particles.
  • the composite device of any one of the present invention wherein the material of the metal layer is selected from one or more of the following: a noble metal (such as gold, silver or platinum), a transition metal (for example) Copper) or light metal (such as aluminum).
  • a noble metal such as gold, silver or platinum
  • a transition metal for example
  • copper copper
  • light metal such as aluminum
  • the substrate is made of a dielectric.
  • the substrate is made of a metal oxide.
  • the substrate is made of alumina or titania.
  • the composite device of any of the inventions is prepared by anodizing.
  • the composite device of any of the inventions obtains the metal particles by physical vapor deposition.
  • the composite device according to any one of the present invention, wherein the physical vapor deposition parameters include: a degree of vacuum: 4 ⁇ 10 -4 to 6 ⁇ 10 -4 Pa.
  • the composite device of any one of the present invention the physical vapor deposition method is selected from one or more of sputtering and evaporation.
  • the composite device of any of the present invention the physical vapor deposition method is ion beam sputtering.
  • the composite device of any one of the present invention wherein the ion beam sputtering parameter is selected from one or more of the following (i) to (iv):
  • Vacuum degree 4 ⁇ 10 -4 to 6 ⁇ 10 -4 Pa, for example, about 5 ⁇ 10 -4 Pa;
  • Ion gun voltage 6 ⁇ 8keV, for example about 7keV;
  • Ion current 200 ⁇ 400 ⁇ A, for example about 300 ⁇ A;
  • Sputtering time 5 to 20 minutes, for example 8 to 16 minutes.
  • the composite device of any of the present invention the physical vapor deposition method is electron beam evaporation.
  • the composite device of any of the present invention the electron beam steaming
  • the parameters of the condition of the hair are selected from one or more of the following (i) to (ii):
  • the composite device of any one of the present invention has an average light absorption efficiency of greater than 85%, preferably greater than 90%, and more preferably greater than 95%. More preferably, it is higher than 99%.
  • the composite device of any of the present invention wherein the light has a wavelength in the range of from 1 nanometer to 50 micrometers, such as from 200 nanometers to 25 micrometers, such as from 200 nanometers to 20 micrometers, for example.
  • From 200 nanometers to 10 micrometers for example from 400 nanometers to 20 micrometers, and further, for example, from 400 nanometers to 10 micrometers, and further, for example, from 400 nanometers to 5 micrometers, and further, for example, from 400 nanometers to 2.5 micrometers.
  • the composite device according to any one of the present invention when exposed to light, uses the absorbed light to convert liquid water into water vapor, and the energy conversion efficiency of the conversion is higher than 80%. It is preferably higher than 90%, and more preferably higher than 95%.
  • the composite device according to any one of the invention has an optical power density of 1 kWm -2 or more, preferably 2 to 6 kWm -2 , more preferably 3 to 4 kWm -2 .
  • the material capable of improving the properties of the metal particles is capable of improving the oxidation resistance and/or corrosion resistance of the metal particles.
  • the material capable of improving the properties of the metal particles is an oxidation resistant material and/or a corrosion resistant material.
  • the material capable of improving the properties of the metal particles comprises a metallic material, an inorganic non-metallic material, and/or an organic material.
  • the material capable of improving the properties of the metal particles comprises an oxide, such as a metal oxide, such as alumina.
  • the composite device of any of the present invention the material capable of improving the properties of the metal particles is different from the material of the metal particles.
  • the metal particles have a material capable of improving the properties of the metal particles, for example, a material capable of improving the oxidation resistance or corrosion resistance of the metal particles, which can improve the properties of the metal particles, thereby improving the performance of the composite device, for example, Improve the life and reliability of composite devices.
  • a further aspect of the invention provides a method of making a composite device according to any of the inventions, comprising Metal particles are deposited on the surface of the substrate and the inner wall of the pore by physical vapor deposition.
  • a further aspect of the invention provides a method of making a composite device according to any of the inventions, the physical vapor deposition being ion beam sputtering.
  • a further aspect of the invention provides a method of preparing a composite device according to any of the preceding claims, wherein the ion beam sputtering parameter is selected from one or more of the following (i) to (iv):
  • ion gun voltage 6-8 keV, for example about 7 keV;
  • a further aspect of the invention provides a method of making a composite device according to any of the inventions, the physical vapor deposition being electron beam evaporation.
  • a further aspect of the invention provides a method of preparing a composite device according to any of the preceding claims, wherein the parameter of the condition of electron beam evaporation is selected from one or more of the following (i) to (ii):
  • a further aspect of the invention provides a method of making a composite device according to any of the inventions, further comprising applying a material on the metal particles that is capable of improving the properties of the metal particles.
  • a further aspect of the invention provides a method of preparing a composite device according to any of the invention, wherein the application of the metal particles by means of oxidation, growth, deposition, sputtering and/or plating can improve the A material for the properties of metal particles.
  • a further aspect of the invention provides the use of a composite device according to any of the inventions for absorbing light.
  • a further aspect of the invention provides the use of the composite device of any of the inventions for photothermal conversion.
  • a further aspect of the invention provides the use of the composite device of any of the inventions for desalinating seawater.
  • Step 1 A porous alumina template (hereinafter referred to as NPT) was prepared by a two-step anodization method.
  • the preparation method comprises: anodizing the aluminum foil in 0.3 M phosphoric acid at 5 ° C, the oxidation voltage starts from 50 V, increases 10 V to 150 V every 2 min, and then holds for 24 hours to complete the first oxidation. Then, the aluminum oxide film formed by the first oxidation is dissolved, and the second oxidation is performed under the same conditions as the first oxidation conditions. After the second oxidation and secondary oxidation, an aluminum foil having a porous alumina film was placed in a mixed solution containing 1 M CuCl2 and 0.1 M HCl to dissolve the aluminum substrate. Finally, the porous alumina film film was transferred into 5 wt% of H 3 PO 4 and expanded at 30 ° C for about 1 hour to obtain NPT of Example 1.
  • Figure 1 is a scanning electron micrograph of Au/NPT.
  • the thickness of the NPT was measured to be about 60 microns.
  • the NPT has a through hole that is perpendicular to the surface.
  • the pores of the two surfaces of the NPT are different in morphology.
  • the morphology of the pores of the surface is more orderly, and the surface is an ordered surface of NPT; and for the anodization, the surface of the surface is close to the surface of the aluminum foil.
  • the morphology is relatively disordered, and the surface is a disordered surface of NPT.
  • Step 2 Depositing gold (Au) into the ordered surface of the above NPT and the pores of the surface using an ion beam coater Gatan Model 682.
  • the deposition conditions were: a vacuum of 5 ⁇ 10 -4 Pa, an electron gun voltage of 7 keV, a current of 300 uA, and a deposition time of 16 min.
  • the obtained product was the composite device of Example 1, hereinafter referred to as Au/NPT.
  • the Au/NPT includes NPT and gold particles attached to the inner wall of the pore of the NPT.
  • the gold particles are distributed in a range from 0 to 2 microns in depth from the surface of the ordered surface of the NPT.
  • the Au/NPT may also include a gold layer overlying the ordered surface of the NPT, which may cover only areas of the ordered surface that have no holes.
  • the thickness of the gold layer is about 60 to 90 nm.
  • the total thickness of the Au/NPT is about 60 microns.
  • Figure 2 is a high resolution scanning electron micrograph of the ordered surface of Au/NPT.
  • the ordered surface of the Au/NPT has a plurality of pores having different pore sizes, and the pore diameter is distributed in the range of 250 to 360 nm.
  • the average pore diameter is about 300 nm
  • the average pore spacing is about 450 nm
  • the porosity is about 40%.
  • the pore diameters of the respective pores are relatively close, and the length and width of the pores are relatively close, and the shapes of the pores are relatively similar.
  • the figure has, for example, a pore having a pore diameter of 250 nm, for example, a pore having a pore diameter of 280 nm, for example, a pore having a pore diameter of 290 nm, for example, a pore having a pore diameter of 300 nm, for example, a pore having a pore diameter of 310 nm.
  • there are pores having a pore diameter of 330 nm for example, pores having a pore diameter of 350 nm, for example, pores having a pore diameter of 360 nm.
  • the apertures of the holes in the figure have different aspect ratios, and the aspect ratios are distributed in the range of 1 to 1.44.
  • the aspect ratios are distributed in the range of 1 to 1.44.
  • the hole for example, has a hole having an aspect ratio of 1.19, for example, a hole having an aspect ratio of 1.21, for example, a hole having an aspect ratio of 1.25, for example, a hole having an aspect ratio of 1.28, for example, having an aspect ratio of 1.31.
  • the hole for example, has a hole having an aspect ratio of 1.44.
  • the shape of the hole is substantially elliptical or circular.
  • the Au/D-NPT includes NPT and gold particles attached to the inner wall of the pore of the NPT, and the gold particles are distributed in a range from 0 to 2 ⁇ m from the surface to the inside of the disordered surface of the NPT.
  • the Au/D-NPT may also include a gold layer overlying the NPT disordered surface, the gold layer may cover only areas of the disordered surface that have no pores, and the gold layer has a thickness of about 60-90 nm.
  • the Au/D-NPT has a thickness of about 60 microns. After depositing gold onto the disordered surface of NPT, a disordered surface of Au/D-NPT was obtained.
  • Figure 3 is a high resolution scanning electron micrograph of the Au/D-NPT disordered surface. As shown in FIG. 3, the Au/D-NPT has a plurality of pores having different pore sizes, and the pore diameter is distributed in the range of 160 to 370 nm.
  • pores having a pore diameter of 160 to 200 nm for example, pores having a pore diameter of 160 nm, for example, pores having a pore diameter of 180 nm, for example, pores having a pore diameter of 200 nm; for example, pores having a pore diameter of 200 to 250 nm, for example, a pore having a pore diameter of 240 nm; for example, a pore having a pore diameter of 250 to 300 nm, for example, a pore having a pore diameter of 260 nm, for example, a pore having a pore diameter of 280 nm, for example, a pore having a pore diameter of 300 nm; for example, having a pore diameter A pore of 300 to 350 nm, for example, a pore having a pore diameter of 320 nm, for example, a pore having a pore diameter of 340 nm, for example, a pore having
  • the pores of the Au/D-NPT have different aspect ratios, and the aspect ratio is distributed in the range of 1 to 2.
  • a hole having an aspect ratio of 1.38 for example, a hole having an aspect ratio of 1.41, for example, a hole having an aspect ratio of 1.54, for example, a hole having an aspect ratio of 1.67, for example, a hole having an aspect ratio of 1.91.
  • the shapes of the respective holes are largely different, for example, a triangle, a quadrangle, a pentagon, a hexagon, an n-gon (n is greater than or equal to 7), a circle, an ellipse, and the like. Or a variety of shapes of holes.
  • FIG. 4 and FIG. 5 are the Fourier transform diagrams of FIGS. 2 and 3, respectively.
  • the dot matrix inverted lattice vector is more in FIG. 5, and the lattice inverted lattice vector is also discretely dispersed, which illustrates FIG.
  • the hole shape is more disordered and irregular than Figure 2.
  • the ratio of the outer diameter to the inner diameter of the ring in the Fourier transform diagram of Figure 4 is about 2.16
  • the ratio of the outer diameter to the inner diameter of the ring in the Fourier transform of Figure 5 is about 2.92.
  • FIG. 6 is a high resolution scanning electron micrograph of a cross section of the composite device (Au/D-NPT) of Example 2. As shown in Fig. 6, the inner walls of the pores of the Au/D-NPT are attached with a plurality of metal particles having different particle diameters, aspect ratios or shapes.
  • FIG. 7 is a partial enlarged view of a cross section of the composite device (Au/D-NPT) of Example 2, as shown in FIG. 7, the inner wall of the hole of the Au/D-NPT is deposited with a plurality of metal particles, metal particles
  • the distribution density is from about 10 3 to 10 4 /m 2 , and may be, for example, from about 2.67 to 4.86*10 3 /micron 2 .
  • the metal particles have particle sizes of different sizes ranging from 1 to 100 nm.
  • there are metal particles of 1 to 20 nm for example, metal particles having a particle diameter of 5.44 nm, for example, metal particles having a particle diameter of 9.07 nm, for example, metal particles having a particle diameter of 11.47 nm, for example, having a particle diameter of 14.95 nm.
  • the metal particles for example, have metal particles having a particle diameter of 17.20 nm.
  • metal particles of 20 to 40 nm for example, metal particles having a particle diameter of 21.91 nm, for example, metal particles having a particle diameter of 26.96 nm, for example, metal particles having a particle diameter of 31.64 nm, for example, having a particle diameter of 36.69 nm.
  • the metal particles are, for example, metal particles having a particle diameter of 38.04 nm.
  • metal particles of 40 to 60 nm for example, metal particles having a particle diameter of 83.14 nm, for example, metal particles having a particle diameter of 41.67 nm, for example, metal particles having a particle diameter of 43.87 nm, for example, having a particle diameter of 51.33 nm.
  • the metal particles for example, have metal particles having a particle diameter of 57.59 nm.
  • metal particles having a particle diameter of 60 to 80 nm for example, metal particles having a particle diameter of 62.58 nm, for example, metal particles having a particle diameter of 68.20 nm, for example, metal particles having a particle diameter of 71.51 nm, for example, having a particle diameter It is a metal particle of 76.59 nm, for example, a metal particle having a particle diameter of 79.24 nm.
  • metal particles of 80 to 100 nm for example, metal particles having a particle diameter of 82.04 nm, for example, metal particles having a particle diameter of 83.14 nm, for example, metal particles having a particle diameter of 92.30 nm, for example, having a particle diameter of 94.52 nm.
  • the metal particles for example, have metal particles having a particle diameter of 97.33 nm.
  • the metal particles have different aspect ratios in the range of 1 to 6.
  • there are metal particles having an aspect ratio of 1 to 2 for example, metal particles having an aspect ratio of 1.06, for example, metal particles having an aspect ratio of 1.18, for example, metal particles having an aspect ratio of 1.37, for example, length and width.
  • the metal particles having a ratio of 1.64 for example, metal particles having an aspect ratio of 1.83; the metal particles having different aspect ratios in the range of 2 to 3, for example, metal particles having an aspect ratio of 2.05, for example, having an aspect ratio of
  • the metal particles of 2.14 for example, metal particles having an aspect ratio of 2.40, for example, metal particles having an aspect ratio of 2.52, for example, metal particles having an aspect ratio of 2.72; metal particles having different lengths in the range of 3 to 4
  • the width ratio for example, metal particles having an aspect ratio of 3.05, for example, metal particles having an aspect ratio of 3.58, for example, metal particles having an aspect ratio of 3.86; metal particles having different aspect ratios in the range of 4 to 6.
  • there are metal particles having an aspect ratio of 4.69 for example, metal particles having an aspect ratio of 4.81, for example, metal particles having an aspect ratio of 5.03, for example, metal particles having an aspect ratio of 5.63.
  • the plurality of metal particles have different shapes, for example, rod-shaped metal particles, for example, elliptical metal particles, for example, circular-like metal particles.
  • the particle size of the gold particles has a gradient.
  • the particle size gradually changes from about 100 nanometers to 1 nanometer.
  • the aspect ratio of the particles has a gradient as the depth of the pores increases.
  • the aspect ratio is gradually changed from about 6 to about 1.
  • the shape of the particles gradually changes as the depth of the pores increases.
  • the shape of the particles gradually changes from a rod shape to an ellipse shape, and then gradually changes from an elliptical shape to a circular shape.
  • Example 8 is a high resolution scanning electron micrograph of a cross section of the composite device (Au/NPT) of Example 1. As shown in FIG. 8, the metal particles in the Au/NPT of Example 1 were substantially the same as those of the metal particles of Au/D-NPT of Example 2.
  • Step 1 Prepare an NPT method with an average pore diameter of about 200 nm as follows:
  • a porous alumina template (hereinafter referred to as NPT) was prepared by a two-step anodization method.
  • the preparation method comprises: anodizing the aluminum foil in 0.5 M phosphoric acid at 5 ° C, the oxidation voltage starts from 50 V, increases 10 V to 150 V every 2 min, and then holds for 24 hours to complete the first oxidation. Then, the aluminum oxide film formed by the first oxidation is dissolved, and the second oxidation is performed under the same conditions as the first oxidation conditions. After the second oxidation, the aluminum foil having the porous alumina film was placed in a mixture of 1 M CuCl 2 and 0.1 M HCl, and the aluminum substrate was dissolved. Finally, the porous alumina film film was transferred into 5 wt% of H 3 PO 4 and expanded at 30 ° C for about 1 hour to obtain NPT of Example 1.
  • Step 2 Same as Example 1, except that the deposition time was adjusted to 12 minutes.
  • the composite device Au/NPT-200 of Example 3 was obtained.
  • Step 1 NPT was prepared as in Example 1.
  • Step 2 In the same manner as in Example 3, except that the deposition time was adjusted to 8 minutes, 12 minutes, and 16 minutes, respectively, the composite devices of Example 4 were obtained Au/D-NPT-8, Au/D-NPT-12, Au/D. -NPT-16.
  • NPT was prepared in the same manner as in Example 1.
  • Al/D-NPT Aluminum (Al) was deposited into the disordered surface of the above NPT and the pores of the surface using electron beam evaporation (device FU-20PEB-RH). Electron beam evaporation condition vacuum degree 6 ⁇ 10 -4 Pa, coating speed The obtained product was the composite device of Example 3 (hereinafter referred to as Al/D-NPT).
  • Figure 9 is a scanning electron micrograph of Al/D-NPT.
  • the Al/D-NPT includes NPT and aluminum particles attached to the inner wall of the pore of the NPT.
  • the aluminum particles are distributed from the disordered surface of the NPT.
  • the depth inward is in the range of 0 to 4 microns.
  • the Al/D-NPT may also include an aluminum layer overlying the NPT disordered surface, which may cover only areas of the disordered surface that are free of pores, the aluminum layer having a thickness of about 85 nanometers.
  • the thickness of the Al/D-NPT is about 60 microns.
  • Figure 14 is a transmission electron microscope (TEM) photograph of Al/D-NPT in which an oxide layer of about 2 nm thick is observed on the surface of the Al metal particles.
  • the oxide layer (alumina layer) on the surface of the Al metal particles can function to protect the Al metal particles, prevent the Al metal particles from being oxidized or corroded, and improve the life and stability of the composite device.
  • Figure 10 is a schematic illustration of a composite device of the present invention.
  • the composite device includes a substrate 1 having a plurality of apertures with a plurality of metal particles 2 attached to the inner wall of the aperture.
  • a layer of metal 3 is also covered.
  • the topographical features of the holes and metal particles in the figures are merely illustrative and not actual.
  • the light absorption experiment was performed on the disordered surface of Au/NPT of Example 1, Au/D-NPT of Example 2, Al/D-NPT of Example 3, and NPT (hereinafter referred to as D-NPT, respectively) as a comparative example. .
  • UV-VIS-NIR UV-VIS-NIR
  • ISR-3100 integrating sphere
  • the transmittance and reflectance of Au/NPT, Au/D-NPT and NPT in the mid-infrared region were measured using a PerkinElmer GX-Fourier transform infrared spectrometer. Measuring wavenumber range 400-4000cm -1, with a resolution of 4cm -1. At this time, the absorption rate - 1 - the transmittance - the reflectance.
  • Figure 11 shows the absorbance of Au/NPT, Au/D-NPT, and D-NPT measured in the visible to near-infrared region (400 nm - 2.5 ⁇ m) and the mid-infrared region (2.5 ⁇ m - 10 ⁇ m). The curve of the change in wavelength of light.
  • Figure 12 is a graph showing the light absorption rate of Al/D-NPT measured in the visible to near-infrared region (400 nm - 2.5 ⁇ m) as a function of wavelength of light.
  • a solar water vapor generation experiment was conducted on the composite device (Au/D-NPT) of Example 2 and the composite device (Al/D-NPT) of Example 5.
  • the water vapor generating device comprises:
  • Light source Solar simulator (Newport94043A, ClassAAA), dual lens focusing system (Beijing Beiguang Century Instrument Co., Ltd.; convex lens #1 with focal length of 200mm, diameter of 100mm; convex lens #2 with focal length of 50mm and diameter of 30mm);
  • Container Dewar (Shanghai Glass Factory), 28mm inner diameter, 38mm outer diameter, height 96mm;
  • thermocouple thermocouple probe deposited by atomic layer deposition method with high reflectivity Titanium oxide suppresses the heat generated by direct light on the probe, serial communication components (RS232), and computers.
  • Au/D-NPT and pure water control group ambient temperature 24 ° C, humidity 42%;
  • Al/D-NPT and pure water control group ambient temperature 24 ° C, humidity 48%.
  • the experimental steps include:
  • the porous composite device of the present invention (Au/D-NPT; Al/D-NPT) is capable of naturally floating on the water surface.
  • the porous structure with through holes provides a convenient passage for the emission of a continuously generated stream of water vapor.
  • a pure water control group was also set up, that is, only water was contained in the Dewar, and no composite device was placed.
  • the light generated by the solar simulator (Newport 94043A) is filtered through a filter to obtain solar radiation in accordance with the AM 1.5G spectral standard.
  • the solar radiation was focused by a two-lens system and incident on a composite device in a Dewar (for contrast experiments, the light was focused and incident on the water surface).
  • the incident optical power density C opt P 0 is measured and set in advance by a power meter, and the unit is kW ⁇ m -2 .
  • the analytical balance can measure the reduced quality of the water, and then calculate the mass loss rate of the water, that is, the water vapor generation rate by mass, in units of kg/m 2 /h.
  • the water vapor generation rate (m) of the present invention is the measured average water vapor generation rate of 2600 to 3600 seconds after the start of illumination.
  • the experiment used the use of serial communication systems and computers to record data.
  • the solar water vapor generation experiments were carried out for the Au/D-NPT of the composite device of Example 2 and the Al/D-NPT of Example 3, respectively, and the water without the composite device.
  • the water vapor generation rate (m) was measured at different optical power densities (C opt P 0 ), and the energy conversion efficiency ( ⁇ ) was calculated.
  • Tables 5 and 6 show the water vapor generation rate (m) and energy conversion efficiency at different optical power densities (C opt P 0 ) for the Au/D-NPT and pure water control groups (without Au/D-NPT).
  • Tables 7 and 8 show the water vapor generation rate (m) and energy conversion at different optical power densities (C opt P 0 ) for Al/D-NPT and pure water control (no Al/D-NPT). Efficiency ( ⁇ ).
  • the water vapor generation rate is the evaporation rate of pure water without Au/D-NPT after using the composite device Au/D-NPT. 2.1 and 3.6 times.
  • the above beneficial effects are mainly attributed to the composite material device of the invention having a broad absorption spectrum and a high light absorption rate, which can be further attributed to the morphology characteristics of the metal particles of the composite device of the invention, which can be further attributed to the composite material of the invention.
  • Al/D-NPT of Example 5 its cycle performance at different optical power densities was tested.
  • the specific steps are as follows: The Al/D-NPT is subjected to a light cycle test in the order of illumination power of 1-2-3-4-6-1 kW ⁇ m -2 , and is cycled 4 times for each optical power.
  • One cycle means that the Al/D-NPT is illuminated for 1 hour and then the illumination is stopped for 20 minutes.
  • the average water vapor generation rate (m) for each cycle is shown in Table 10.
  • the cycle stability of the composite device Al/D-NPT of the present invention was measured under conditions of optical power densities of 2 kW ⁇ m -2 and 4 kW ⁇ m -2 , respectively, and the number of cycles was 25 weeks.
  • One cycle means that the Al/D-NPT is illuminated for 1 hour and then the illumination is stopped for 20 minutes.
  • the water vapor generation rate (m) per cycle is shown in Table 11 and Table 12, respectively.
  • the composite device of the present invention has excellent cycle stability and thermal stability, and has a relatively smooth output at different illumination powers. After 25 weeks of circulation, the water vapor generation rate m (kg/m 2 /h) remained substantially stable without attenuation.
  • the seawater desalination experiment was carried out on the composite device Al/D-NPT of the present invention.
  • the above aqueous NaCl solution was evaporated, and the water vapor was condensed and collected to obtain dehydrated water.
  • the NaCl concentration (C1 mg/L) of the NaCl aqueous solution and the NaCl concentration (C2 mg/L) in the desalinated water are shown in Table 13 below.
  • the composite device of the present invention can utilize light energy to desalinate seawater, and effectively reduce the content of one or more ions of Na + , Mg 2+ , Ca 2+ , K + and B 3+ in seawater. .

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Abstract

本发明提供一种复合材料器件，所述器件包括基体，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒，所述金属颗粒的粒径为1～200纳米，所述多个金属颗粒具有至少x种不同的颗粒粒径d，x大于或等于2。本发明复合材料器件具有较高的光吸收率，和较宽的光吸收带宽。

Description

一种复合材料器件 技术领域
本发明属于复合材料领域，具体涉及一种复合材料器件。
背景技术
光吸收器在光/热探测、太阳能转换、红外成像等领域均有广泛的应用。光吸收器的光吸收率和吸收光谱的范围是决定其性能优劣的关键因素。理想的光吸收器应该在较宽的光谱范围内具有较高的光吸收率，也就是说，在较宽的光谱范围内具有较低的光透射率和较低的光反射率。
现有技术中存在多种光吸收器，尤其是纳米等离激元光吸收器。例如，具有金属超表面结构的光吸收器，以及具有锥形结构的光吸收器，这两种光吸收器通过复合共振模式扩宽了光吸收器的带宽。还有一种具有交叉梯形光栅阵列的等离激元光吸收器，其对400-700纳米波长的光的吸收效率达到71％。还有一种具有超尖端凹凸槽结构的金属光吸收器，其对450-850纳米波长的光的吸收效率达到96％。另外，氮化钽和二氧化钒等耐高温材料也被运用到光吸收器上。
现有技术中的大部分的光吸收器的制备工艺主要是由上而下的方法，例如聚焦离子束或电子束刻蚀等方法。高昂的制备成本限制了光吸收器的产量和可广泛应用的可能。同时，现有技术的光吸收器还存在吸收光谱的范围较窄，以及光的吸收效率较低等缺点。
利用光能直接蒸发海水，实现海水淡化的方法是一种低成本、环境友好的方式。然而，传统的蒸发淡化海水器件和方法存在低能量转换效率、可重复性差和制作成本高等一系列不足。
发明内容
为了解决现有技术中的一个或多个问题。本发明的一个目的是提供一种复合材料器件。本发明的再一个目的是提供一种可用于光吸收的复合材料器件。本发明的再一个目的是提供一种吸光效率高的复合材料器件。本发明的再一个目的是提供一种光吸收带宽较宽的复合材料器件。本发明的再一个目的是提供一种成本低的复合材料器件。本发明的再一个目的是提供一种可用于淡化海水的复合材料器件。本发明再一个目的 是提供一种海水淡化效率高的复合材料器件。
为此，本发明第一方面提供一种复合材料器件，所述器件包括基体，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒，所述金属颗粒的粒径为1～200纳米，所述多个金属颗粒具有至少x种不同的颗粒粒径d，x大于或等于2。
本发明第二方面提供一种复合材料器件，所述器件包括基体，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒，所述多个孔至少包括z种孔径f，z大于或等于2。
本发明第三方面提供一种制备本发明任一项所述的复合材料器件的方法，其包括采用物理气相沉积的方法在所述基体的表面及孔内壁沉积金属颗粒的步骤，所述物理气相沉积的参数包括：真空度：4～5×10-4Pa。
本发明第四方面提供本发明任一项所述的复合材料器件用于吸收光的用途。
本发明第五方面提供本发明任一项所述的复合材料器件用于光热转换的用途。
本发明第六方面提供本发明任一项所述的复合材料器件用于淡化海水的用途。
本发明基体可以是多孔氧化铝模板。本发明的多孔氧化铝模板可以是本领域常见的多孔氧化铝模板。多孔氧化铝模板可以简称AAO(Anodic Aluminum Oxide)。例如可以是合肥微晶材料科技有限公司生产的单通AAO模板、双通AAO模板或V型AAO模板。例如可以是陈烁烁在《可控多分枝管道阳极氧化铝：制备和应用》/华南理工大学/2010中制备的可控多分枝管道阳极氧化铝。例如可以是CN102925947A公开的具有梯度纳米孔径的阳极氧化铝模板。例如可以是CN101451260公开的具有Y型结构的多孔氧化铝模板。
在一个实施方案中，本发明的金属颗粒包括一切含有金属单质的颗粒，既包括单纯的金属颗粒，也包括与其它材料相复合的金属颗粒，例如表面经化学修饰的金属颗粒，再例如表面包覆了氧化层的金属颗粒。
本发明中，金属颗粒的粒径指：复合材料器件横截面的扫描电子显微镜照片中，金属颗粒的外接圆的直径。
本发明中，金属颗粒的长宽比是指：在复合材料器件横截面的扫描电子显微镜照片中，金属颗粒的最小面积外接矩形的长宽比。
本发明中，金属颗粒的形状是指：在复合材料器件横截面的扫描电子显微镜照片中，金属颗粒的形状。
本发明中，模板的孔径、孔隙率、孔间距、孔形状和孔的无序程度可以通过阳极氧化的参数控制。
本发明中，金属颗粒的粒径、形状或分布可以通过物理气相沉积的真空度和/或沉积的时间控制。
本发明中≥表示大于或等于，≤表示小于或等于。
本发明的有益效果
(1)本发明复合材料器件具有较高的光吸收率；
(2)本发明复合材料器件在较宽的光波长范围具有较高的光吸收率；
(3)本发明复合材料器件具有较低的反射率；
(4)本发明复合材料器件可将吸收的光能转变为热能。
(5)本发明复合材料器件可利用吸收的光能产生热量，进而用于液体的蒸发。
(6)本发明复合材料器件是多孔材料，当本发明的复合材料器件用于蒸发液体时，这些孔有利于液体的蒸汽有效逸出。
(7)本发明复合材料器件可用于液体的蒸发和提纯，尤其适用于水的蒸发和提纯，特别是海水淡化。
(8)本发明复合材料器件具有环境友好、成本低、容易制备、可批量化生产等一种或多种优点。
本发明的上述一项或多项有益效果可以归功于本发明复合材料器件的金属颗粒的形貌特性，进一步可以归功于本发明复合材料器件的孔的形貌特征，进一步还可以归功于本发明复合材料器件的前述任一项特征。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本申请的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的限定。在附图中：
图1为实施例1的Au/NPT的扫描电子显微镜照片；
图2为实施例1的Au/NPT的有序表面的扫描电子显微镜照片；
图3为实施例2的Au/D-NPT的无序表面的扫描电子显微镜照片；
图4为图2的傅里叶转换图；
图5为图3的傅里叶转换图；
图6为实施例2的Au/D-NPT的扫描电子显微镜照片；
图7为实施例2的Au/D-NPT的部分区域的扫描电子显微镜照片；
图8为实施例1的Au/NPT的扫描电子显微镜照片；
图9为实施例5的Al/D-NPT的扫描电子显微镜照片；
图10为本发明一个复合材料器件的示意图；
图11为Au/NPT、Au/D-NPT和D-NPT的光吸收率随光波长变化的曲线；
图12为Al/D-NPT的光吸收率随光波长变化的曲线；
图13为使用Au/D-NPT和不使用Au/D-NPT时，水蒸气产生量随时间变化曲线；
图14是实施例5的Al/D-NPT的透射电子显微镜(TEM)照片。
具体实施方案
本发明提供了如下的具体实施方案以及他们之间的所有可能的组合。出于简洁的目的，本申请没有逐一记载实施方案的各种具体组合方式，但应当认为本申请具体记载并公开了所述具体实施方案的所有可能的组合方式。
本发明一方面提供一种复合材料器件，所述器件包括基体，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒，所述金属颗粒的粒径为1～200纳米，所述多个金属颗粒具有至少x种不同的颗粒粒径d，x大于或等于2。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属颗粒的粒径为1～150纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属颗粒的粒径为1～100纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，x等于2、3、4、5、6、7、8、9或10。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，x种不同的颗粒粒径d选自以下d1至d10中的任意x种：1纳米≤d1＜10纳米、10纳米≤d2＜20纳米、20纳米≤d3＜30纳米、30纳米≤d4＜40纳米、40纳米≤d5＜50纳米、50纳米≤d6＜60纳米、60纳米≤d7＜70纳米、70纳米≤d8≤80纳米、80纳米≤d9≤90纳米、90纳米≤d10≤100纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，x种不同的颗粒粒径d选自以下d11至d15中的任意x种：1纳米≤d11＜20纳米、20纳米≤d12＜40纳米、40纳米≤d13＜60纳米、60纳米≤d14≤80纳米；80纳米≤d15≤100纳米；x等于2、3或4或5。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属颗粒的长宽比为1～10(例如1～8，再例如1～6)。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述多个金属颗 粒的具有至少y种长宽比e，y大于或等于2。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，y等于2、3、4、5、6、7或8。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，y种长宽比e选自以下e1至e8中任意y种：1≤e1＜1.2、1.2≤e2＜1.5、1.5≤e3＜2、2≤e4＜3、3≤e5＜4、4≤e6＜6、6≤e7≤8、8≤e8≤10。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，y种长宽比e选自以下e9至e12中任意y种：1≤e9＜2、2≤e10＜3、3≤e11＜4、4≤e12≤6；y等于2、3或4。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属纳米颗粒的形状选自以下的1种、2种或3种：棒状、椭球状、球状。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，相邻金属纳米颗粒之间的间距为1～50纳米，例如1～30纳米，例如1～15纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，金属颗粒在孔内壁的分布密度为约102～104个/微米2，例如为约103～104个/微米2，例如为约2×103～5×103个/微米2。
在一个优选的实施方案中，本发明任一项所述的权利要求1的复合材料器件，金颗粒分布在从基体的一侧表面自表向里深度为g～h微米的范围，g＜h；
g≥0，优选为0～5，优选为约0、1、2、3、4或5；
h≥0，优选为0～10，优选为约1、2、3、4、5、6、7、8、9或10。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，从所述基体的一侧到另一侧，金属颗粒的粒径存在梯度。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，从所述基体的一侧到另一侧，金属颗粒的长宽比存在梯度。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，从所述基体一侧到另一侧，金属颗粒的形状发生变化。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属颗粒的形状由棒状变化为椭圆状，再变化为类球状。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述多个金属颗粒在所述孔的内壁上无序分布。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属颗粒的材质选自以下的一种或多种：贵金属(例如金、银或铂)、过渡金属(例如铜)和轻 金属(例如铝)。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属颗粒的材质为金或铝。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述多个孔至少包括z种孔径f，z大于或等于2。
本发明又一方面提供一种复合材料器件，所述器件包括基体，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒，所述多个孔至少包括z种孔径f，z大于或等于2。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，z等于3、4、5、6、7或8。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述z种不同的孔径f选自以下f1至f8中的任意z种：100≤f1＜150、150≤f2＜200、200≤f3＜250、250≤f4＜300、300≤f5＜350、350≤f6＜400，400≤f7＜450，450≤f8≤500，z等于2、3、4、5、6、7或8。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述z种不同的孔径f选自以下f9至f13中的任意z种：160≤f9＜200、200≤f10＜250、250≤f11＜300、300≤f12＜350、350≤f13≤380；z等于2、3、4或5。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的平均孔径为200～1000纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的平均孔径为300～600纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的平均孔径为300～500纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的平均孔径为350～500纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的平均孔径为350～400纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的长宽比在1～3范围内分布，例如在1～2范围内分布，再例如在1～1.5范围内分布。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔包括长宽比为约1、1.1、1.2、1.3、1.4和1.5的孔。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔包括长宽比为约1、1.2、1.4、1.5、1.8和2的孔。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的平均孔间距为300～600纳米，优选为400～500纳米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的形状选自以下的2种、3种、4种、5种或6种：三角形、四边形、五边形、六边形、圆形、椭圆形。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，在所述基体的至少一个表面上，所述孔的孔隙率为20～80％，优选为40～70％，再优选为50～60％。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔在所述基体的表面的分布是无序的。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，对基体靠近金属颗粒的一侧表面的扫描电子显微镜照片的进行傅里叶变换，获得的傅里叶变换图中的圆环的外径和内径之比为2以上，优选为2.5以上，再优选为2.5～5，再优选为2.5～3.5，再优选为2.8～3.2。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的路径为直线或者曲线。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔的路径可以与基体表面呈90度或其它角度。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔为通孔或非通孔。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述复合材料器件的形状为平面板状或曲面板状。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述复合材料器件的总厚度为20～200微米，优选为50～100微米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述基体靠近金属颗粒的的一侧的表面覆盖有金属层。
权利要求40的复合材料器件，所述金属层仅覆盖所述表面的没有孔的区域。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属层的厚度为50～100nm，优选为60～90纳米
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔为非通孔， 所述金属层覆盖在没有孔的的一侧的表面。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述孔为通孔，靠近金颗粒一侧的表面沉积有金属层。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属层的材质选自以下的一种或多种：贵金属(例如金、银或铂)、过渡金属(例如铜)或轻金属(例如铝)。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述基体的材质是电介质。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述基体的材质是金属氧化物。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述基体的材质是氧化铝或二氧化钛。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，采用阳极氧化法制备得到所述基体。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，采用物理气相沉积的方法获得所述金属颗粒。
在一个优选的实施方案中，本发明任一项所述的的复合材料器件，所述物理气相沉积的参数包括：真空度：4×10-4～6×10-4Pa。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述物理气相沉积的方法选自溅射、蒸镀的一种或多种。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述物理气相沉积的方法为离子束溅射。
在一个优选的实施方案中，本发明任一项所述的的复合材料器件，所述离子束溅射的参数选自以下(i)～(iv)的一项或多项：
真空度：4×10-4～6×10-4Pa，例如约5×10-4Pa；
离子枪电压：6～8keV，例如约7keV；
离子电流：200～400μA，例如约300μA；
溅射时间：5～20分钟，例如8～16min。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述物理气相沉积的方法为电子束蒸发。
在一个优选的实施方案中，本发明任一项所述的的复合材料器件，所述电子束蒸 发的条件的参数选自以下(i)～(ii)的一项或多项：
(i)真空度：4×10-4～6×10-4Pa，例如6×10-4Pa；
(ii)镀膜速度：
Figure PCTCN2016105410-appb-000001
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述复合材料器件的对光的平均吸收效率高于85％，优选高于90％，再优选高于95％，再优选高于99％。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述光的波长范围为1纳米～50微米，例如200纳米～25微米，例如从200纳米～20微米，再例如从200纳米～10微米，再例如从400纳米～20微米，再例如从400纳米～10微米，再例如从400纳米～5微米，再例如400纳米～2.5微米。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，其受光照时，将吸收的光用于将液态水转化为水蒸气，该转化的能量转化效率高于80％，优选高于90％，再优选高于95％。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述光照的光功率密度为1kWm-2以上，优选为2～6kWm-2，再优选为3～4kWm-2。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述金属颗粒上有能够改善所述金属颗粒的性能的材料。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料能够改善所述金属颗粒的抗氧化性能和/或耐腐蚀性能。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料为抗氧化材料和/或耐腐蚀材料。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料包括金属材料、无机非金属材料和/或有机物。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料包括氧化物，例如金属氧化物，再例如氧化铝。
在一个优选的实施方案中，本发明任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料与所述金属颗粒的材质不同。
所述金属颗粒上有能够改善所述金属颗粒的性能的材料，例如有能够提高金属颗粒康氧化性或耐腐性性的材料，能够改善金属颗粒的性能，进而改善复合材料器件的性能，例如改善复合材料器件的寿命和可靠性。
本发明又一方面提供一种制备本发明任一项所述的复合材料器件的方法，其包括 采用物理气相沉积的方法在所述基体的表面及孔内壁沉积金属颗粒。
本发明又一方面提供一种制备本发明任一项所述的复合材料器件的方法，所述物理气相沉积是离子束溅射。
本发明又一方面提供一种制备本发明任一项所述的复合材料器件的方法，所述离子束溅射的参数选自以下(i)～(iv)的一项或多项：
(i)真空度：4×10-4～6×10-4Pa，例如约5×10-4Pa；
(ii)离子枪电压：6～8keV，例如约7keV；
(iii)离子电流：200～400μA，例如约300μA；
(iv)溅射时间：5～20分钟，例如8～16min。
本发明又一方面提供一种制备本发明任一项所述的复合材料器件的方法，所述物理气相沉积是电子束蒸发。
本发明又一方面提供一种制备本发明任一项所述的复合材料器件的方法，所述电子束蒸发的条件的参数选自以下(i)～(ii)的一项或多项：
(i)真空度：4×10-4～6×10-4Pa，例如6×10-4Pa；
(ii)镀膜速度
Figure PCTCN2016105410-appb-000002
本发明又一方面提供一种制备本发明任一项所述的复合材料器件的方法，还包括在所述金属颗粒上施加能够改善所述金属颗粒的性能的材料。
本发明又一方面提供一种制备本发明任一项所述的复合材料器件的方法，采用氧化、生长、沉积、溅射和/或镀覆的手段在所述金属颗粒上施加能够改善所述金属颗粒的性能的材料。
本发明又一方面提供本发明任一项所述的复合材料器件用于吸收光的用途。
本发明又一方面提供本发明任一项所述的复合材料器件用于光热转换的用途。
本发明又一方面提供本发明任一项所述的复合材料器件用于淡化海水的用途。
具体实施方式
下面通过附图和实施例，对本发明的技术方案做进一步的详细描述。
实施例1
步骤1：采用两步阳极氧化法制备得到多孔氧化铝模板(以下简称NPT)。制备方法包括：将铝箔置于5℃的0.3M的磷酸中进行阳极氧化，氧化电压从50V开始，每隔2min增加10V直至150V，然后保持24小时，完成第一次氧化。然后溶去第一次氧化形成的氧化铝膜，在与第一次氧化条件完全相同的条件下，进行第二次氧化。第二次氧化后二次氧化后将长有多孔氧化铝膜的铝箔放入含1M CuCl2和0.1M HCl的混 合液中，溶去铝基底。最后将多孔氧化铝薄膜膜移入5wt％的H3PO4中，在30℃扩孔约1小时，获得实施例1的NPT。
图1是Au/NPT的扫描电子显微镜照片。经测量，NPT的厚度为约60微米。NPT具有垂直于表面的通孔。特别地，NPT的两个表面的孔的形貌不同。对于阳极氧化时NPT远离铝箔的一侧表面，该表面的孔的形貌较为有序，该表面为NPT的有序表面；而对于阳极氧化时NPT靠近铝箔的一侧表面，该表面的孔的形貌较为无序，该表面为NPT的无序表面。
步骤2：使用离子束镀膜仪Gatan Model 682向上述NPT的有序表面及该表面的孔内沉积金(Au)。具体地，沉积条件为：真空度为5×10-4Pa，电子枪电压为7kev，电流为300uA，沉积时间为16min。获得产品为实施例1的复合材料器件，以下简称Au/NPT。
Au/NPT包括NPT和附着在NPT的孔的内壁的金颗粒。金颗粒分布在从NPT的有序表面自表向里深度为0～2微米的范围。Au/NPT还可以包括覆盖在NPT有序表面上的金层，金层可以仅覆盖有序表面上没有孔的区域。金层的厚度为约60～90纳米。Au/NPT的总厚度为约60微米。向NPT的有序表面沉积了金之后，就得到了Au/NPT的有序表面。
图2是Au/NPT的有序表面的高分辨扫描电子显微镜照片。如图2所示，Au/NPT的有序表面上有多个孔径大小不同的孔，孔径在250～360纳米范围内分布。平均孔径为约300纳米，平均孔间距为约450nm，孔隙率为约40％。各个孔的孔径较为接近，孔的长宽比较为接近，孔的形状较为相似。具体地，图中例如有孔径为250纳米的孔，例如有孔径为280纳米的孔，例如有孔径为290纳米的孔，例如有孔径为300纳米的孔，例如有孔径为310纳米的孔，例如有孔径为330纳米的孔，例如有孔径为350纳米的孔，例如有孔径为360纳米的孔。
随机测量图2中50个孔的孔径，不同孔径的分布频率如下表1所示：
表1
孔径(纳米) 250-300 300-360
分布频率％ 84％ 16％
进一步，如图2所示，图中孔的孔径具有不同的长宽比，长宽比在1～1.44范围内分布。例如有长宽比为1.00的孔，例如有长宽比为1.04的孔，例如有长宽比为1.07的孔，例如有长宽比为1.08的孔，例如有长宽比为1.11的孔，例如有长宽比为1.15 的孔，例如有长宽比为1.19的孔，例如有长宽比为1.21的孔，例如有长宽比为1.25的孔，例如有长宽比为1.28的孔，例如有长宽比为1.31的孔，例如有长宽比为1.44的孔。
进一步，如图2所示，孔的形状基本为椭圆形或圆形。
实施例2
(1)按实施例1的方法，获得NPT。
(2)使用离子束镀膜仪Gatan Model 682向上述NPT的无序表面及该表面的孔内壁沉积金(Au)。具体地，沉积真空度为5×10-4Pa，电子枪电压为7Kev，电流为300uA，沉积时间为16min。获得产品为实施例2的复合材料器件(以下简称Au/D-NPT)。
Au/D-NPT包括NPT和附着在NPT的孔的内壁的金颗粒，金颗粒分布在从NPT的无序表面自表向里深度为0～2微米的范围。Au/D-NPT还可以包括覆盖在NPT无序表面上的金层，金层可以仅覆盖无序表面上没有孔的区域，金层的厚度为约60～90纳米。Au/D-NPT的厚度为约60微米。向NPT的无序表面沉积了金之后，就得到了Au/D-NPT的无序表面。
图3是Au/D-NPT无序表面的高分辨扫描电子显微镜照片。如图3所示，Au/D-NPT具有多个孔径大小不同的孔，孔径在160～370纳米范围内分布。例如有孔径为160～200纳米的孔，例如由孔径为160纳米的孔，例如有孔径为180纳米的孔，例如有孔径为200纳米的孔；例如由孔径为200～250纳米的孔，例如有孔径为240纳米的孔；例如有孔径为250～300纳米的孔，例如有孔径为260纳米的孔，例如有孔径为280纳米的孔，例如有孔径为300纳米的孔；例如有孔径为300～350纳米的孔，例如有孔径为320纳米的孔，例如有孔径为340纳米的孔，例如有孔径为350纳米的孔；例如有孔径为350～380纳米的孔，例如有孔径为370纳米的孔，例如有孔径为380纳米的孔。孔的平均孔径为约360纳米，平均孔间距为约450nm，孔隙率为约59％。
随机测量图3中50个孔的孔径，不同孔径的分布频率如下表2所示：
表2
孔径(纳米) 100-200 200-300 300-400
分布频率％ 33％ 42％ 25％
进一步，如图3所示，Au/D-NPT的孔具有不同的长宽比，长宽比在1～2范围内分布。例如有长宽比为1的孔，例如有长宽比为1.03的孔，例如有长宽比为1.07的孔， 例如有长宽比为1.13的孔，例如有长宽比为1.16的孔，例如有长宽比为1.22的孔，例如有长宽比为1.29的孔，例如有长宽比为1.33的孔，例如有长宽比为1.38的孔，例如有长宽比为1.41的孔，例如有长宽比为1.54的孔，例如有长宽比为1.67的孔，例如有长宽比为1.91的孔。
进一步，如图3所示，各个孔的形状有较大差异，例如有三角形、四边形、五边形、六边形、n边形(n大于或等于7)、圆形、椭圆形等一种或多种形状的孔。
图4和图5分别是图2和3的傅里叶转换图，与图4相比，图5中点阵倒格矢更多，点阵倒格矢也分散地更离散，这说明图3的孔形貌比图2更为无序、无规则。具体地，图4的傅里叶转化图中圆环的外径与内径之比为约2.16，图5的傅里叶转化图中圆环的外径与内径之比为约2.92。
图6是实施例2的复合材料器件(Au/D-NPT)的截面的高分辨扫描电子显微镜照片。如图6所示，Au/D-NPT的孔的内壁都附着有多个金属颗粒，这些金属颗粒具有不同的粒径、长宽比或形状。
图7为实施例2的复合材料器件(Au/D-NPT)的截面的局域放大图，如图7所示，Au/D-NPT的孔的内壁沉积有多个金属颗粒，金属颗粒的分布密度为约103～104个/微米2，例如可以为约2.67～4.86＊103个/微米2。
进一步，金属颗粒具有在1～100纳米范围内不同大小的粒径。例如有1～20纳米的金属颗粒，例如有粒径为5.44纳米的金属颗粒，例如有粒径为9.07纳米的金属颗粒，例如有粒径为11.47纳米的金属颗粒，例如有粒径为14.95纳米的金属颗粒，例如有粒径为17.20纳米的金属颗粒。例如有20～40纳米的金属颗粒，例如有粒径为21.91纳米的金属颗粒，例如有粒径为26.96纳米的金属颗粒，例如有粒径为31.64纳米的金属颗粒，例如有粒径为36.69纳米的金属颗粒，例如有粒径为38.04纳米的金属颗粒。例如有40～60纳米的金属颗粒，例如有粒径为83.14纳米的金属颗粒，例如有粒径为41.67纳米的金属颗粒，例如有粒径为43.87纳米的金属颗粒，例如有粒径为51.33纳米的金属颗粒，例如有粒径为57.59纳米的金属颗粒。例如有粒径为60～80纳米的金属颗粒，例如有粒径为62.58纳米的金属颗粒，例如有粒径为68.20纳米的金属颗粒，例如有粒径为71.51纳米的金属颗粒，例如有粒径为76.59纳米的金属颗粒，例如有粒径为79.24纳米的金属颗粒。例如有80～100纳米的金属颗粒，例如有粒径为82.04纳米的金属颗粒，例如有粒径为83.14纳米的金属颗粒，例如有粒径为92.30纳米的金属颗粒，例如有粒径为94.52纳米的金属颗粒，例如有粒径为97.33纳米的金属颗粒。
随机测量图7中金颗粒的粒径，不同粒径的分布频率如下表3所示：
表3
粒径(纳米) 1～13.8 13.8～35.4 35.4～78.6 78.6～100
分布频率％ 37.5％ 33.3％ 22.5％ 6.7％
进一步，如图7所示，金属颗粒具有在1～6范围内不同的长宽比。例如有长宽比为1～2的金属颗粒，例如有长宽比为1.06的金属颗粒，例如有长宽比为1.18的金属颗粒，例如有长宽比为1.37的金属颗粒，例如有长宽比为1.64的金属颗粒，例如有长宽比为1.83的金属颗粒；金属颗粒具有在2～3范围内不同的长宽比，例如有长宽比为2.05的金属颗粒，例如有长宽比为2.14的金属颗粒，例如有长宽比为2.40的金属颗粒，例如有长宽比为2.52的金属颗粒，例如有长宽比为2.72的金属颗粒；金属颗粒具有在3～4范围内不同的长宽比，例如有长宽比为3.05的金属颗粒，例如有长宽比为3.58的金属颗粒，例如有长宽比为3.86的金属颗粒；金属颗粒具有在4～6范围内不同的长宽比，例如有长宽比为4.69的金属颗粒，例如有长宽比为4.81的金属颗粒，例如有长宽比为5.03的金属颗粒，例如有长宽比为5.63的金属颗粒。
进一步，如图7所示，多个金属颗粒具有不同的形状，例如有棒状的金属颗粒，例如有椭圆形的金属颗粒，例如有类圆形的金属颗粒。
进一步，如图7所示，从Au/D-NPT的无序表面由表及里，随着孔的深度增加，金颗粒的粒径具有梯度。例如粒径由约100纳米逐渐变化到1纳米。
进一步，如图7所示，从Au/D-NPT的无序表面由表及里，随着孔的深度增加，颗粒的长宽比具有梯度。例如长宽比由约6逐渐变化到约1。
进一步，如图7所示，从Au/D-NPT的无序表面由表及里，随着孔的深度增加，颗粒的形状逐渐变化。例如颗粒形状由棒状逐渐变化为椭圆形，再由椭圆形逐渐变化到圆形。
图8是实施例1的复合材料器件(Au/NPT)的截面的高分辨扫描电子显微镜照片。如图8所示，实施例1的Au/NPT中的金属颗粒与实施例2的Au/D-NPT的金属颗粒的各项特征基本相同。
实施例3
步骤1：制备平均孔径为约200nm的NPT方法如下：
采用两步阳极氧化法制备得到多孔氧化铝模板(以下简称NPT)。制备方法包括：将铝箔置于5℃的0.5M的磷酸中进行阳极氧化，氧化电压从50V开始，每隔2min增加10V直至150V，然后保持24小时，完成第一次氧化。然后溶去第一次氧化形成的 氧化铝膜，在与第一次氧化条件完全相同的条件下，进行第二次氧化。第二次氧化后二次氧化后将长有多孔氧化铝膜的铝箔放入1M CuCl2和0.1M HCl混合液中，溶去铝基底。最后将多孔氧化铝薄膜膜移入5wt％的H3PO4中，在30℃扩孔约1小时，获得实施例1的NPT。
步骤2：同实施例1，除了调整沉积时间为12分钟。获得实施例3的复合材料器件Au/NPT-200。
实施例4
步骤1：按实施例1的方法制备NPT。
步骤2：同实施例3，除了调整沉积时间分别为8分钟，12分钟和16分钟，获得实施例4的复合材料器件Au/D-NPT-8、Au/D-NPT-12、Au/D-NPT-16。
实施例5
(1)按实施例1的方法制备NPT。
(2)使用电子束蒸发(设备FU-20PEB-RH)向上述NPT的无序表面及该表面的孔内沉积铝(Al)。电子束蒸发条件真空度6×10-4Pa，镀膜速度
Figure PCTCN2016105410-appb-000003
获得产品为实施例3的复合材料器件(以下简称Al/D-NPT)。
图9是Al/D-NPT的扫描电子显微镜照片，如图所示，Al/D-NPT包括NPT和附着在NPT的孔的内壁的铝颗粒，铝颗粒分布在从NPT的无序表面自表向里深度0～4微米的范围内。Al/D-NPT还可以包括覆盖在NPT无序表面上的铝层，铝层可以仅覆盖无序表面上没有孔的区域，铝层的厚度为约85纳米。Al/D-NPT的厚度为约60微米。
图14是Al/D-NPT的透射电子显微镜(TEM)照片，图中可以观察到Al金属颗粒表面上有一层大约2nm厚的氧化物层。Al金属颗粒表面的氧化物层(氧化铝层)能够起到保护Al金属颗粒的作用，阻止Al金属颗粒被氧化或被腐蚀，改善复合材料器件的寿命和稳定性。
图10为本发明一个复合材料器件的示意图，如图所示，该复合材料器件包括基体1，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒2。在复合材料器件的一侧表面，还覆盖有一层金属层3。图中孔和金属颗粒的形貌特征仅仅是示意，并非实际情况。
分别对实施例1的Au/NPT、实施例2的Au/D-NPT、实施例3的Al/D-NPT和NPT的无序表面(以下简称D-NPT，作为对比例)进行光吸收实验。
采用Shimadzu-UV3600(UV-VIS-NIR)分光光度计，配备积分球(ISR-3100)，测量了Au/NPT、Au/D-NPT和NPT在UV-VIS-NIR光(波长400纳米～2.5微米)的半球反射率。由于光入射后只能在积分球中反射，此时，吸收率＝1-反射率。
采用PerkinElmer GX-傅里叶变换红外光谱仪测量了Au/NPT、Au/D-NPT和NPT在中红外区域(波长2.5μm-10μm)的透射率和反射率。测量波数范围为400-4000cm-1，分辨率为4cm-1。此时，吸收率-＝1-透射率-反射率。
图11示出Au/NPT、Au/D-NPT和D-NPT在可见光到近红外光区域(400纳米-2.5微米)和中红外光区域(2.5微米-10微米)测得的光吸收率随光波长变化的曲线。
图12示出Al/D-NPT在可见光到近红外光区域(400纳米-2.5微米)测得的光吸收率随光波长变化的曲线。
实施例1～5的复合材料器件以及对比例D-NPT在400纳米～2.5微米以及2.5微米到10微米区间，它们的平均光吸收率(％)如表4所示：
表4
Figure PCTCN2016105410-appb-000004
对实施例2的复合材料器件(Au/D-NPT)和实施例5的复合材料器件(Al/D-NPT)进行了太阳能水蒸气产生实验。
水蒸气产生装置包括：
(1)光源：太阳光模拟器(Newport94043A，ClassAAA)、双透镜聚焦系统(北京北光世纪仪器有限公司；焦距200mm，直径100mm的凸透镜#1；焦距50mm，直径30mm的凸透镜#2)；
(2)容器：为杜瓦瓶(上海玻璃厂)，28mm内径，38mm外径，高度96mm；
(3)测量装置：功率计(Coherent#1097901，10W，19mm直径探头)、分析天平(FA2004，0.1mg精度)、热电偶(热电偶的探头经原子层沉积法沉积了一层高反射率的氧化钛，抑制了光直接照在探头上产生的热)、串行通信组件(RS232)、电脑。
实验环境参数包括：
Au/D-NPT及纯水对照组：环境温度24℃，湿度42％；
Al/D-NPT及纯水对照组：环境温度24℃，湿度48％。
实验步骤包括：
(1)在杜瓦瓶中盛水，将复合材料器件(Au/D-NPT；Al/D-NPT)平行置于水面上，沉积了金属颗粒(或金属层)的一侧表面方向朝下，接触水面，部分复合材料器件被水浸没。本发明多孔的复合材料器件(Au/D-NPT；Al/D-NPT)能够自然地漂浮在水面上。具有通孔的多孔结构为连续产生的水蒸气气流的散发提供了方便的通道。还设置纯水对照组，即杜瓦瓶中仅盛水，不放置复合材料器件。
(2)太阳光模拟器(Newport94043A)产生的光经滤光片过滤后，获得符合AM1.5G光谱标准的太阳光辐射。将该太阳光辐射通过双透镜系统聚焦后入射在杜瓦瓶中的复合材料器件上(对于对比实验，则将光聚焦后入射在水面上)。
(3)实验开始前，用功率计预先测量并设定入射光功率密度CoptP0，单位为kW·m-2。同时，在蒸汽的产生过程中，分析天平可测得水的减少质量，进而计算出水的质量损失速率，也即以质量计的水蒸汽产生速率，单位为kg/m2/h。为了得到稳定的蒸汽产生速率，本发明的水蒸气产生速率(m)为使用光照开始后2600～3600秒的测得的平均水蒸气产生速率。实验中使用使用用串行通信系统和电脑记录数据。
为了计算太阳能转化为水蒸气的能量效率(η)，此处引入公式，其中m为水蒸汽产生速率，hLV为液汽相变热，CoptP0为样品表面的光功率密度。
分别针对本发明复合材料器件实施例2的Au/D-NPT和实施例3的Al/D-NPT，以及不使用复合材料器件的水，进行了太阳能水蒸气产生实验。在不同的光功率密度(CoptP0)下，测量了水蒸汽产生速率(m)，计算了能量转化效率(η)。表5和表6是Au/D-NPT和纯水对照组(不使用Au/D-NPT)在不同的光功率密度(CoptP0)下的水蒸汽产生速率(m)和能量转化效率(η)。表7和表8是Al/D-NPT和和纯水对照组(不使用Al/D-NPT)在不同的光功率密度(CoptP0)下的水蒸汽产生速率(m)和能量转化效率(η)。
表5
Figure PCTCN2016105410-appb-000005
表6
Figure PCTCN2016105410-appb-000006
表7
Figure PCTCN2016105410-appb-000007
表8
Figure PCTCN2016105410-appb-000008
如表5所示，对于Au/D-NPT，当CoptP0＝4kW·m-2和6kW·m-2时，太阳能转换为水蒸气的能量转换效率(η)超过90％。如表7所示，当CoptP0＝6kW·m-2时，能量转换效率(η)超过90％。
对比表5和表6，可以发现使用本发明复合材料器件后，水蒸汽产生速率(m)和能量转化效率(η)都有显著提高。图13为使用Au/D-NPT和不使用Au/D-NPT(仅盛水)时，水蒸气产生量随时间变化曲线，其中Copt＝1即CoptP0＝1kW·m-2，Copt＝4即CoptP0＝4kW·m-2。如图13所示，在CoptP0＝1KWm-2和4kWm-2时，使用复合材料器件Au/D-NPT后，水蒸气产生速率是不使用Au/D-NPT时纯水蒸发速率的2.1和3.6倍。以上有益效果主要归功于本发明复合材料器件具有较宽的吸收光谱和较高的光吸收率，进一步可以归功于本发明复合材料器件的金属颗粒的形貌特性，进一步可以归功于本发明复合材料器件的孔的形貌特征。
对于实施例5的Al/D-NPT，在光功率密度CoptP0＝6kW·m-2时，测量了杜瓦瓶中 的水温(T1)以及复合材料器件Al/D-NPT的孔内温度(T2)随光照时间的变化。结果如下表9所示。说明本发明复合材料器件在光功率密度为6kW·m-2时，仅需50分钟即可将温度(T2)升高至超过100℃。这说明本发明复合材料器件能迅速升温，并产生高温的水蒸气。
表9
时间(分钟) 0 5 10 15 20 30 40 50 60
T1(℃) 22.2 68.0 80.3 84.8 88.7 94.9 97.8 100.9 103.1
T2(℃) 22.2 25.7 27 28.4 30.1 33.8 38.1 42.7 47.4
对于实施例5的Al/D-NPT，测试了其在不同光功率密度下的循环性能。具体步骤如下：按照光照功率为1-2-3-4-6-1kW·m-2的顺序对Al/D-NPT进行光照循环试验，每个光功率下循环4次。一个循环是指，将Al/D-NPT光照1小时，然后停止光照闲置20分钟。每个循环的平均水蒸气产生速率(m)如表10所示。
表10
Figure PCTCN2016105410-appb-000009
进一步，在光功率密度分别为2kW·m-2和4kW·m-2的条件下，测量了本发明复合材料器件Al/D-NPT的循环稳定性，循环周数为25周。一个循环是指，将Al/D-NPT光照1小时，然后停止光照闲置20分钟。在2kW·m-2和4kW·m-2的光功率密度下，每个循环的水蒸气产生速率(m)分别如表11和表12所示。
表11
Figure PCTCN2016105410-appb-000010
表12
Figure PCTCN2016105410-appb-000011
如表10、表11和表12所示，本发明复合材料器件具有优异的循环稳定性和热稳定性，在不同光照功率下具有较为平稳的输出。循环25周后，水蒸气产生速率m(kg/m2/h)基本保持稳定，没有衰减。
对本发明复合材料器件Al/D-NPT进行了海水淡化实验。具体步骤包括：用NaCl配制了4种不同浓度的NaCl水溶液，编号为1至4，在CoptP0＝1.75-1.91kW·m-2的光 照密度下，使用本发明复合材料器件(Al/D-NPT)将上述NaCl水溶液蒸发，并将水蒸气冷凝后搜集，得到的淡化水。淡化实验前后，NaCl水溶液的NaCl浓度(C1mg/L)和淡化水中的NaCl浓度(C2mg/L)如下表13所示。
表13
编号 1/Baltic sea 2/Global 3/Red Sea 4/Dead Sea
C1(mg/L) 8000 35000 40000 93600
C2(mg/L 0.86 0.27 0.42 0.25
取中国渤海海水，经本发明复合材料器件(Al/D-NPT)蒸发后，考察了淡化前后水中Na+、Mg2+、Ca2+、K+和B3+几种离子淡化前后的浓度变化，结果如下表14所示：
表14
编号 Na+ Mg2+ Ca2+ K+ B3+
淡化前(mg/L) 8089 1314 410 530 4.18
淡化后(mg/L) 0.34 0.0105 0.23 0.11 0.0105
如表13和表14所示，本发明复合材料器件能够利用光能淡化海水，有效降低海水中Na+、Mg2+、Ca2+、K+和B3+一种或多种离子的含量。
最后应当说明的是：以上实施例仅用以说明本发明的技术方案而非对其限制；尽管参照较佳实施例对本发明进行了详细的说明，所属领域的普通技术人员应当理解：依然可以对本发明的具体实施方式进行修改或者对部分技术特征进行等同替换；而不脱离本发明技术方案的精神，其均应涵盖在本发明请求保护的技术方案范围当中。

Claims (82)

  1. 一种复合材料器件，所述器件包括基体，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒，所述金属颗粒的粒径为1～200纳米，所述多个金属颗粒具有至少x种不同的颗粒粒径d，x大于或等于2。
  2. 权利要求1的复合材料器件，所述金属颗粒的粒径为1～150纳米。
  3. 权利要求1的复合材料器件，所述金属颗粒的粒径为1～100纳米。
  4. 权利要求1的复合材料器件，x等于2、3、4、5、6、7、8、9或10。
  5. 权利要求4的复合材料器件，x种不同的颗粒粒径d选自以下d1至d10中的任意x种：1纳米≤d1＜10纳米、10纳米≤d2＜20纳米、20纳米≤d3＜30纳米、30纳米≤d4＜40纳米、40纳米≤d5＜50纳米、50纳米≤d6＜60纳米、60纳米≤d7＜70纳米、70纳米≤d8≤80纳米、80纳米≤d9≤90纳米、90纳米≤d10≤100纳米。
  6. 权利要求4的复合材料器件，x种不同的颗粒粒径d选自以下d11至d15中的任意x种：1纳米≤d11＜20纳米、20纳米≤d12＜40纳米、40纳米≤d13＜60纳米、60纳米≤d14≤80纳米；80纳米≤d15≤100纳米；x等于2、3或4或5。
  7. 权利要求1的复合材料器件，所述金属颗粒的长宽比为1～10(例如1～8，再例如1～6)。
  8. 权利要求1的复合材料器件，所述多个金属颗粒的具有至少y种长宽比e，y大于或等于2。
  9. 权利要求8的复合材料器件，y等于2、3、4、5、6、7或8。
  10. 权利要求9的复合材料器件，y种长宽比e选自以下e1至e8中任意y种：1≤e1＜1.2、1.2≤e2＜1.5、1.5≤e3＜2、2≤e4＜3、3≤e5＜4、4≤e6＜6、6≤e7≤8、8≤e8≤10。
  11. 权利要求8的复合材料器件，y种长宽比e选自以下e9至e12中任意y种：1≤e9＜2、2≤e10＜3、3≤e11＜4、4≤e12≤6；y等于2、3或4。
  12. 权利要求1的复合材料器件，所述金属纳米颗粒的形状选自以下的1种、2种或3种：棒状、椭球状、球状。
  13. 权利要求1的复合材料器件，相邻金属纳米颗粒之间的间距为1～50纳米，例如1～30纳米，例如1～15纳米。
  14. 权利要求1的复合材料器件，金属颗粒在孔内壁的分布密度为约102～104个/微米2，例如为约103～104个/微米2，例如为约2×103～5×103个/微米2。
  15. 权利要求1的权利要求1的复合材料器件，金颗粒分布在从基体的一侧表面自表向里深度为g～h微米的范围，g＜h；
    g≥0，优选为0～5，优选为约0、1、2、3、4或5；
    h≥0，优选为0～10，优选为约1、2、3、4、5、6、7、8、9或10。
  16. 权利要求1的复合材料器件，从所述基体的一侧到另一侧，金属颗粒的粒径存在梯度。
  17. 权利要求1的复合材料器件，从所述基体的一侧到另一侧，金属颗粒的长宽比存在梯度。
  18. 权利要求1的复合材料器件，从所述基体一侧到另一侧，金属颗粒的形状发生变化。
  19. 权利要求1的复合材料器件，所述金属颗粒的形状由棒状变化为椭圆状，再变化为类球状。
  20. 权利要求1的复合材料器件，所述多个金属颗粒在所述孔的内壁上无序分布。
  21. 权利要求1的复合材料器件，所述金属颗粒的材质选自以下的一种或多种：贵金属(例如金、银或铂)、过渡金属(例如铜)和轻金属(例如铝)。
  22. 权利要求1的复合材料器件，所述金属颗粒的材质为金或铝。
  23. 权利要求1～22任一项的复合材料器件，所述多个孔至少包括z种孔径f，z大于或等于2。
  24. 一种复合材料器件，所述器件包括基体，所述基体上有多个孔，所述孔的内壁附着有多个金属颗粒，所述多个孔至少包括z种孔径f，z大于或等于2。
  25. 权利要求23或24的复合材料器件，z等于3、4、5、6、7或8。
  26. 权利要求25的复合材料器件，所述z种不同的孔径f选自以下f1至f8中的任意z种：100≤f1＜150、150≤f2＜200、200≤f3＜250、250≤f4＜300、300≤f5＜350、350≤f6＜400，400≤f7＜450，450≤f8≤500，z等于2、3、4、5、6、7或8。
  27. 权利要求23或24的复合材料器件，所述z种不同的孔径f选自以下f9至f13中的任意z种：160≤f9＜200、200≤f10＜250、250≤f11＜300、300≤f12＜350、350≤f13≤380；z等于2、3、4或5。
  28. 权利要求1～24任一项的复合材料器件，所述孔的平均孔径为200～1000纳米。
  29. 权利要求1～24任一项的复合材料器件，所述孔的平均孔径为300～600纳米。
  30. 权利要求1～24任一项的复合材料器件，所述孔的平均孔径为300～500纳米。
  31. 权利要求1～24任一项的复合材料器件，所述孔的平均孔径为350～500纳米。
  32. 权利要求1～24任一项的复合材料器件，所述孔的平均孔径为350～400纳米。
  33. 权利要求1～24任一项的复合材料器件，所述孔的长宽比在1～3范围内分布，例如在1～2范围内分布，再例如在1～1.5范围内分布。
  34. 权利要求1～24任一项的复合材料器件，所述孔包括长宽比为约1、1.1、1.2、1.3、1.4和1.5的孔。
  35. 权利要求1～24任一项的复合材料器件，所述孔包括长宽比为约1、1.2、1.4、1.5、1.8和2的孔。
  36. 权利要求1～24任一项的复合材料器件，所述孔的平均孔间距为300～600纳米，优选为400～500纳米。
  37. 权利要求1～24任一项的复合材料器件，所述孔的形状选自以下的2种、3种、4种、5种或6种：三角形、四边形、五边形、六边形、圆形、椭圆形。
  38. 权利要求1～24任一项的复合材料器件，在所述基体的至少一个表面上，所述孔的孔隙率为20～80％，优选为40～70％，再优选为50～60％。
  39. 权利要求1～24任一项的复合材料器件，所述孔在所述基体的表面的分布是无序的。
  40. 权利要求1～24任一项的复合材料器件，对基体靠近金属颗粒的一侧表面的扫描电子显微镜照片的进行傅里叶变换，获得的傅里叶变换图中的圆环的外径和内径之比为2以上，优选为2.5以上，再优选为2.5～5，再优选为2.5～3.5，再优选为2.8～3.2。
  41. 权利要求1～24任一项的复合材料器件，所述孔的路径为直线或者曲线。
  42. 权利要求1～24任一项的复合材料器件，所述孔的路径可以与基体表面呈90度或其它角度。
  43. 权利要求1～24任一项的复合材料器件，所述孔为通孔或非通孔。
  44. 权利要求1～24任一项的复合材料器件，所述复合材料器件的形状为平面板状或曲面板状。
  45. 权利要求1～24任一项的复合材料器件，所述复合材料器件的总厚度为20～200微米，优选为50～100微米。
  46. 权利要求1～24任一项的复合材料器件，所述基体靠近金属颗粒的的一侧的表面覆盖有金属层。
  47. 权利要求46的复合材料器件，所述金属层仅覆盖所述表面的没有孔的区域。
  48. 权利要求46的复合材料器件，所述金属层的厚度为50～100nm，优选为60～90纳米。
  49. 权利要求46的复合材料器件，所述孔为非通孔，所述金属层覆盖在没有孔的的一侧的表面。
  50. 权利要求46的复合材料器件，所述孔为通孔，靠近金颗粒一侧的表面沉积有金属层。
  51. 权利要求1～24任一项的复合材料器件，所述金属层的材质选自以下的一种或多种：贵金属(例如金、银或铂)、过渡金属(例如铜)或轻金属(例如铝)。
  52. 权利要求1～24任一项的复合材料器件，所述基体的材质是电介质。
  53. 权利要求1～24任一项的复合材料器件，所述基体的材质是金属氧化物。
  54. 权利要求1～24任一项的复合材料器件，所述基体的材质是氧化铝或二氧化钛。
  55. 权利要求1～24任一项的复合材料器件，采用阳极氧化法制备得到所述基体。
  56. 权利要求1～24任一项的复合材料器件，采用物理气相沉积的方法获得所述金属颗粒。
  57. 权利要求56的的复合材料器件，所述物理气相沉积的参数包括：真空度：4×10-4～6×10-4Pa。
  58. 权利要求56的复合材料器件，所述物理气相沉积的方法选自溅射、蒸镀的一种或多种。
  59. 权利要求56的复合材料器件，所述物理气相沉积的方法为离子束溅射。
  60. 权利要求59的的复合材料器件，所述离子束溅射的参数选自以下(i)～(iv)的一项或多项：
    i)真空度：4×10-4～6×10-4Pa，例如约5×10-4Pa；
    ii)离子枪电压：6～8keV，例如约7keV；
    iii)离子电流：200～400μA，例如约300μA；
    iv)溅射时间：5～20分钟，例如8～16min。
  61. 权利要求56的复合材料器件，所述物理气相沉积的方法为电子束蒸发。
  62. 权利要求61的的复合材料器件，所述电子束蒸发的条件的参数选自以下(i)～(ii)的一项或多项：
    (i)真空度：4×10-4～6×10-4Pa，例如6×10-4Pa；
    (ii)镀膜速度：
    Figure PCTCN2016105410-appb-100001
  63. 权利要求1～24任一项的复合材料器件，所述复合材料器件的对光的平均吸收效率高于85％，优选高于90％，再优选高于95％，再优选高于99％。
  64. 权利要求1～24任一项的复合材料器件，所述光的波长范围为1纳米～50微米，例如200纳米～25微米，例如从200纳米～20微米，再例如从200纳米～10微米，再例如从400纳米～20微米，再例如从400纳米～10微米，再例如从400纳米～5微米，再例如400纳米～2.5微米。
  65. 权利要求1～24任一项的复合材料器件，其受光照时，将吸收的光用于将液态水转化为水蒸气，该转化的能量转化效率高于80％，优选高于90％，再优选高于95％。
  66. 权利要求1～24任一项的复合材料器件，所述光照的光功率密度为1kWm-2以上，优选为2～6kWm-2，再优选为3～4kWm-2。
  67. 权利要求1～24任一项所述的复合材料器件，所述金属颗粒上有能够改善所述金属颗粒的性能的材料。
  68. 权利要求1～24任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料能够改善所述金属颗粒的抗氧化性能和/或耐腐蚀性能。
  69. 权利要求1～24任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料为抗氧化材料和/或耐腐蚀材料。
  70. 权利要求1～24任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料包括金属材料、无机非金属材料和/或有机物。
  71. 权利要求1～24任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料包括氧化物，例如金属氧化物，再例如氧化铝。
  72. 权利要求1～24任一项所述的复合材料器件，所述能够改善所述金属颗粒的性能的材料与所述金属颗粒的材质不同。
  73. 制备权利要求1～72任一项的复合材料器件的方法，其包括采用物理气相沉积的方法在所述基体的表面及孔内壁沉积金属颗粒。
  74. 权利要求73的制备方法，所述物理气相沉积是离子束溅射。
  75. 权利要求74的制备方法，所述离子束溅射的参数选自以下(i)～(iv)的一项或多项：
    (i)真空度：4×10-4～6×10-4Pa，例如约5×10-4Pa；
    (ii)离子枪电压：6～8keV，例如约7keV；
    (iii)离子电流：200～400μA，例如约300μA；
    (iv)溅射时间：5～20分钟，例如8～16min。
  76. 权利要求73的制备方法，所述物理气相沉积是电子束蒸发。
  77. 权利要求76的制备方法，所述电子束蒸发的条件的参数选自以下(i)～(ii)的一项或多项：
    (i)真空度：4×10-4～6×10-4Pa，例如6×10-4Pa；
    (ii)镀膜速度
    Figure PCTCN2016105410-appb-100002
  78. 权利要求73的制备方法，还包括在所述金属颗粒上施加能够改善所述金属颗粒的性能的材料。
  79. 权利要求78的制备方法，采用氧化、生长、沉积、溅射和/或镀覆的手段在所述金属颗粒上施加能够改善所述金属颗粒的性能的材料
  80. 权利要求1～72任一项的复合材料器件用于吸收光的用途。
  81. 权利要求1～72任一项的复合材料器件用于光热转换的用途。
  82. 权利要求1～72任一项的复合材料器件用于淡化海水的用途。
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CN105442014B (zh) * 2015-11-12 2019-05-03 南京大学 一种复合材料器件
US11187655B2 (en) * 2018-05-16 2021-11-30 Sensera, Inc. Compact gas sensors
CN109487315B (zh) * 2018-09-21 2021-08-10 上海大学 结合碳黑薄膜的多孔材料、其应用及其制备方法
CN109795979B (zh) * 2018-12-28 2021-11-09 南京大学 具有内嵌金属环的纳米孔阵列结构的制备方法
CN109879344B (zh) * 2019-03-06 2020-06-19 华北电力大学 一种光热蒸发表面及其制备和应用
RU2724308C1 (ru) * 2019-03-20 2020-06-22 Сергей Евгеньевич Кушнир Оптический фильтр с многослойной структурой из анодного оксида алюминия и способ его формирования с помощью анодирования
CN111074324A (zh) * 2019-12-11 2020-04-28 上海航天设备制造总厂有限公司 一种空间环境用基材表面抗菌结构及其制备方法
CN116106997A (zh) * 2022-12-31 2023-05-12 南京大学 一种等离激元吸收器件及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020109134A1 (en) * 1999-04-27 2002-08-15 Tatsuya Iwasaki Nano-structures, process for preparing nano-structures and devices
CN1715458A (zh) * 2004-06-30 2006-01-04 中南大学 铝基吸波材料及制备方法
CN102621126A (zh) * 2012-03-28 2012-08-01 上海大学 金纳米点阵表面增强拉曼活性基底及其制备方法
CN104195518A (zh) * 2014-08-28 2014-12-10 华南师范大学 一种黑色吸光薄膜及其制备方法
CN105442014A (zh) * 2015-11-12 2016-03-30 南京大学 一种复合材料器件

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7079250B2 (en) 2002-01-08 2006-07-18 Fuji Photo Film Co., Ltd. Structure, structure manufacturing method and sensor using the same
JP2006083451A (ja) 2004-09-17 2006-03-30 Fuji Photo Film Co Ltd 微細構造体およびその製造方法
WO2007008151A1 (en) * 2005-07-08 2007-01-18 Portendo Ab Sensor structures, methods of manufacturing them and detectors including sensor structures
US7453565B2 (en) * 2006-06-13 2008-11-18 Academia Sinica Substrate for surface-enhanced raman spectroscopy, sers sensors, and method for preparing same
AU2009221652A1 (en) * 2008-03-07 2009-09-11 The Curators Of The University Of Missouri Sensor electrode and method for the electrochemical detection of nucleotides
CN101635316A (zh) * 2008-07-24 2010-01-27 财团法人工业技术研究院 具有等离体子结构的叠层薄膜光伏元件及其用途
CN101950785B (zh) * 2010-07-28 2013-01-23 山东大学 一种GaN基LED管芯P型GaN层的结构
US9493876B2 (en) * 2012-09-14 2016-11-15 Apple Inc. Changing colors of materials
CN103862031B (zh) * 2014-02-20 2017-01-18 天津大学 与有序多孔载体或粗糙表面结合制备的复合纳米金属材料及方法
US10596125B2 (en) * 2014-12-15 2020-03-24 The Regents Of The University Of California Nanowire-coated microdevice and method of making and using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020109134A1 (en) * 1999-04-27 2002-08-15 Tatsuya Iwasaki Nano-structures, process for preparing nano-structures and devices
CN1715458A (zh) * 2004-06-30 2006-01-04 中南大学 铝基吸波材料及制备方法
CN102621126A (zh) * 2012-03-28 2012-08-01 上海大学 金纳米点阵表面增强拉曼活性基底及其制备方法
CN104195518A (zh) * 2014-08-28 2014-12-10 华南师范大学 一种黑色吸光薄膜及其制备方法
CN105442014A (zh) * 2015-11-12 2016-03-30 南京大学 一种复合材料器件

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP3375912A4 *
WANG, YINHAI ET AL.: "Nano-Cu/A1203 Assemblies Template Synthesis and Optical Absorption", ACTA PHYSICA SINICA, vol. 50, no. 09, 12 September 2001 (2001-09-12), XP009510519 *

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