WO2024045408A1 - Titanium homologous semiconductor heterojunction photoanode and preparation method therefor - Google Patents

Titanium homologous semiconductor heterojunction photoanode and preparation method therefor Download PDF

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WO2024045408A1
WO2024045408A1 PCT/CN2022/137815 CN2022137815W WO2024045408A1 WO 2024045408 A1 WO2024045408 A1 WO 2024045408A1 CN 2022137815 W CN2022137815 W CN 2022137815W WO 2024045408 A1 WO2024045408 A1 WO 2024045408A1
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titanium dioxide
titanium
homologous
nanorod array
semiconductor heterojunction
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PCT/CN2022/137815
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French (fr)
Chinese (zh)
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汪毅
马明
李蒋
崔传艺
宁德
李伟民
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深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/256—Coating containing TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention belongs to the technical field of solar cells, and in particular relates to a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof.
  • FTO glass has high physical and chemical stability, good electrical conductivity and a variety of excellent electrochemical properties.
  • the nanorod array structure has a high specific surface area, which can provide more active sites in electrolyzed water, thereby achieving a more efficient catalytic conversion process.
  • the prepared titanium dioxide material itself still has certain deficiencies in catalytic efficiency and surface reactivity, the charge transfer transfer ability of the prepared photoanode is not strong enough. Therefore, appropriate surface modification is needed to generate more activity on the surface. The sites simultaneously improve its surface charge transport and transfer, thereby improving the efficiency of titanium dioxide catalytic total water splitting.
  • the present invention provides a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof to solve the problem of low water decomposition capability of the existing titanium dioxide photoanode.
  • the present invention first provides a titanium homologous semiconductor heterojunction photoanode.
  • the titanium homologous semiconductor heterojunction photoanode includes a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate.
  • the titanium dioxide nanorod array is decorated with titanium dioxide nanosheets of a non-metal doped phase, and the titanium dioxide nanorod array and the titanium dioxide nanosheets of the non-metal doped phase form a titanium homologous heterojunction.
  • the titanium dioxide nanosheets of the non-metal doped phase are nitrogen-doped titanium dioxide nanosheets.
  • the present invention also provides a method for preparing the titanium homologous semiconductor heterojunction photoanode as described above.
  • the preparation method includes the following steps:
  • step S2 Perform high-temperature annealing treatment on the titanium dioxide nanorod array obtained in step S1;
  • step S4 Use the titanium dioxide nanosheet suspension of the non-metal doped phase to perform surface modification on the titanium dioxide nanorod array obtained in step S2, so that the titanium dioxide nanorod array forms a titanium homologous heterojunction to obtain a titanium dioxide-based nanoheterojunction. ;
  • growing the titanium dioxide nanorod array on the conductive substrate in step S1 includes: placing the conductive substrate in a mixed solution of titanium (IV) isopropoxide and dilute hydrochloric acid after ultrasonic treatment, and treating the isotropic substance containing the conductive substrate at high temperature.
  • the volume ratio of the titanium isopropoxide (IV) to the dilute hydrochloric acid is 1:50 ⁇ 80.
  • the mass fraction of dilute hydrochloric acid is 18% ⁇ 19%.
  • the temperature for high-temperature treatment of the mixed solution of titanium(IV) isopropoxide and dilute hydrochloric acid containing the conductive substrate is 230°C to 300°C, and the treatment time is 2 hours. ⁇ 4h.
  • the temperature at which the titanium dioxide nanorod array is subjected to high-temperature annealing in step S2 is 300°C to 500°C, and the treatment time is 1 hour. ⁇ 3h.
  • the preparation of the titanium dioxide nanosheet suspension of the non-metal doped phase in step S3 includes: calcining cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder at high temperature in an ammonia atmosphere to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4 -x N x powder, put the Cs 0.68 Ti 1.83 O 4 - x N 0.68 Ti 1.83 O 4-x N x is dispersed in the tetrabutylammonium hydroxide solution and shaken well to obtain a nitrogen-doped titanium dioxide nanosheet (N-TiO 2 ) suspension.
  • Cs 0.68 Ti 1.83 O 4 cesium titanate
  • the high-temperature annealing treatment of the titanium dioxide-based nanoheterojunction in step S5 includes: high-temperature annealing of the titanium dioxide-based nanoheterojunction under an argon atmosphere, wherein the treatment temperature is 300°C to 500°C. The time is 1h ⁇ 3h.
  • the invention provides a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof.
  • a titanium dioxide nanorod array is grown on a conductive substrate, and then the titanium dioxide nanorod array is subjected to high-temperature annealing treatment. Titanium dioxide nanorods with a non-metal doping phase are used.
  • the titanium dioxide nanosheet suspension of the non-metal doped phase is prepared from the wafer, and the titanium dioxide nanosheet suspension of the non-metal doped phase is used to modify the titanium dioxide nanorod array after high-temperature annealing treatment, so that the titanium dioxide nanorod array forms a titanium homologous semiconductor heterogeneous
  • the modified titanium dioxide nanorod array is finally subjected to high-temperature annealing treatment to obtain a titanium homologous semiconductor heterojunction photoanode.
  • the preparation method provided by the invention increases the reactive sites on the surface of titanium dioxide by constructing a titanium homologous heterojunction. It also enhances the charge transfer efficiency, thereby improving its surface catalytic activity, achieving efficient total water splitting, and solving the problem of low water splitting ability of titanium dioxide photoanode.
  • Figure 1 is an X-ray diffraction (XRD) pattern of the titanium dioxide nanorod array in Example 1 of the present invention
  • FIG. 2 is a scanning electron microscope (SEM) image of the titanium dioxide nanorod array in Example 1 of the present invention
  • Figure 3 is a scanning transmission electron microscope (TEM) image of the titanium dioxide nanorod array in Example 1 of the present invention.
  • Figure 4 is a scanning electron microscope (SEM) image of the surface-modified titanium dioxide rod nanorod array structure in Example 1 of the present invention
  • Figure 5 is a scanning electron microscope (SEM) image of the surface-modified titanium oxide rod nanorod array structure in Example 2 of the present invention.
  • Figure 6 is a scanning transmission electron microscope (TEM) image of the surface-modified titanium dioxide rod nanorod array structure in Example 2 of the present invention.
  • FIG. 7 is a photoelectrocatalytic performance (LSV) diagram of N- TiO2- modified titanium dioxide nanorod arrays with different loading amounts provided by embodiments of the present invention.
  • the titanium homologous semiconductor heterojunction photoanode includes a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate.
  • the titanium dioxide nanorod array is The titanium dioxide nanosheets are modified with a non-metal doped phase, and the titanium dioxide nanorod array and the titanium dioxide nanosheets of the non-metal doped phase form a titanium homologous semiconductor heterojunction.
  • the titanium dioxide nanosheets of the non-metal doped phase are nitrogen-doped titanium dioxide nanosheets.
  • the titanium homologous heterojunction can increase the reactive sites on the titanium dioxide surface and enhance the charge transfer efficiency, thereby improving the catalytic activity of the titanium dioxide surface.
  • This embodiment also provides a method for preparing the above-mentioned titanium homologous semiconductor heterojunction photoanode.
  • the preparation method includes the following steps:
  • step S2 Perform high-temperature annealing treatment on the titanium dioxide nanorod array obtained in step S1;
  • step S4 Use the titanium dioxide nanosheet suspension of the non-metal doped phase to perform surface modification on the titanium dioxide nanorod array obtained in step S2, so that the titanium dioxide nanorod array forms a titanium homologous heterojunction to obtain a titanium dioxide-based nanoheterojunction. ;
  • the preparation method of the titanium homologous semiconductor heterojunction photoanode provided in the above embodiment is to modify the titanium dioxide nanorod array with a suspension of titanium dioxide nanosheets of a non-metal doped phase to construct a titanium homologous heterojunction and increase the surface reactivity of the titanium dioxide. sites and enhance the charge transfer efficiency, thereby improving its surface catalytic activity, achieving efficient total water splitting, and solving the problem of low water splitting ability of titanium dioxide photoanode.
  • growing the titanium dioxide nanorod array on the conductive substrate in step S1 includes: placing the conductive substrate in a mixed solution of ultrasonic-treated titanium (IV) isopropoxide and dilute hydrochloric acid, and the high-temperature treatment contains conductive A mixed solution of titanium (IV) isopropoxide and dilute hydrochloric acid is used to grow titanium dioxide nanorod arrays on conductive substrates.
  • the volume ratio of the titanium isopropoxide (IV) to the dilute hydrochloric acid is 1:50 ⁇ 80.
  • the mass fraction of dilute hydrochloric acid is 18% ⁇ 19%.
  • the temperature of the mixed solution of titanium (IV) isopropoxide (IV) and dilute hydrochloric acid containing the conductive substrate is treated at a temperature of 230°C to 300°C, and the treatment time is 2 hours. ⁇ 4h.
  • titanium (IV) isopropoxide and dilute hydrochloric acid are mixed and stirred according to the volume ratio for 10 minutes. ⁇ 30 min, followed by ultrasonic treatment for 5 min ⁇ 10min, after ultrasonic treatment, transfer the resulting mixed solution to the reactor liner, then place the conductive substrate in the reactor liner, and finally treat it at high temperature and cool it to room temperature.
  • Titanium dioxide nanorods can be grown on the conductive substrate. array.
  • the temperature for high-temperature annealing of the titanium dioxide nanorod array in step S2 is 300°C to 500°C, and the treatment time is 1 hour. ⁇ 3h.
  • the titanium dioxide nanorod array on the conductive substrate After preparing the titanium dioxide nanorod array on the conductive substrate, it was washed several times with deionized water and dried at 60 Drying is carried out at °C, followed by high temperature annealing.
  • the titanium dioxide nanorod array can be placed in a muffle furnace, raised from room temperature to the temperature of high-temperature annealing treatment in an air atmosphere, reaches the time of high-temperature annealing treatment, and then naturally cooled to room temperature, to Complete annealing.
  • the preparation of the titanium dioxide nanosheet suspension of the non-metal doped phase in step S3 includes: calcining cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder at high temperature in an ammonia atmosphere to obtain nitrogen Doped Cs 0.68 Ti 1.83 O 4 -x N x powder, place the Cs 0.68 Ti 1.83 O 4 - x N , disperse H 0.68 Ti 1.83 O 4-x N x in the tetrabutylammonium hydroxide solution and shake it well to obtain a nitrogen-doped titanium dioxide nanosheet (N-TiO 2 ) suspension.
  • Cs 0.68 Ti 1.83 O 4 cesium titanate
  • the white cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder is calcined at a temperature of 750°C ⁇ 800°C for 2 h ⁇ 3h to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x powder, ion exchange nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x powder with H + in 1mol/L HCl solution for 3 days to obtain H 0.68 Ti 1.83 O 4-x N state); prepare a tetrabutylammonium hydroxide (TABOH) solution with a concentration of 0.2mol/L, and disperse H 0.68 Ti 1.83 O 4-x N x in the prepared tetrabutylammonium hydroxide (TABOH) solution at room temperature. Shake for 8 days, shake well to obtain a uniformly dispersed suspension of nitrogen-doped titanium dioxide nanosheets (Ti 0.91 O 2-x N x , abbreviated as N-T
  • the titanium dioxide nanorod array can be surface treated at different doses by changing the loading amount of the N- TiO2 nanosheet suspension, and after natural drying, a surface-modified titanium dioxide nanorod array can be obtained.
  • the modified titanium dioxide nanorod array Formation of titanium homogeneous heterojunction.
  • the loading amount of the N-TiO 2 nanosheet suspension is preferably 100 ⁇ L ⁇ 400 ⁇ L.
  • the concentration of the N-TiO 2 nanosheet suspension is preferably 1 mg/mL ⁇ 10 mg/mL.
  • the loading capacity of the N-TiO 2 nanosheet suspension is 200 ⁇ L, and the concentration of the N-TiO 2 nanosheet suspension is 1.5 mg/mL. Performance of titanium homologous semiconductor heterojunction photoanode prepared optimal.
  • the high-temperature annealing treatment of the titanium dioxide-based nanoheterojunction in step S5 includes: high-temperature annealing of the titanium dioxide-based nanoheterojunction under an argon atmosphere, wherein the processing temperature is 300°C to 500°C. °C, the processing time is 1h ⁇ 3h.
  • the modified titanium dioxide nanorod array is placed in a tube furnace, heated from room temperature to the annealing temperature at 2.3°C/min in an argon atmosphere, and then cooled naturally after 1h to 3h of annealing. to room temperature, the final titanium homologous semiconductor heterojunction photoanode can be obtained.
  • step S1 the conductive substrate is pretreated FTO glass, wherein the method for pretreating FTO glass is:
  • the FTO glass is immersed in a mixed solution of acetone and absolute ethanol for ultrasonic cleaning, and the cleaned FTO glass is immersed in a mixed solution of hydrogen peroxide and sulfuric acid; secondly, the FTO glass is cleaned with absolute ethanol; finally, Dry the FTO glass under nitrogen atmosphere.
  • the volume ratio of acetone and absolute ethanol is 1:1, and the ultrasonic cleaning time is more than 30 minutes.
  • the volume ratio of hydrogen peroxide and sulfuric acid in the mixed solution of hydrogen peroxide and sulfuric acid is 3:1.
  • the mixed solution of hydrogen peroxide and sulfuric acid for FTO glass is used to enhance the hydrophilicity of FTO glass.
  • This embodiment provides a method for preparing a titanium homologous semiconductor heterojunction photoanode, which includes the following steps:
  • FTO glass as the substrate, with a size of 4cm ⁇ 2cm. Then the substrate is pretreated, specifically by placing the FTO glass in a mixed solution of acetone and absolute ethanol.
  • the volume ratio of the mixed solution of acetone and absolute ethanol is 1:1, and ultrasonic cleaning for 30 minutes to remove impurities on the surface of the substrate; then Immerse the FTO glass in a mixed solution of hydrogen peroxide and sulfuric acid.
  • the volume ratio of the mixed solution of hydrogen peroxide and sulfuric acid is 3:1, and soak for 10 minutes to further remove impurities and enhance its hydrophilicity; then use anhydrous Clean with ethanol; finally use nitrogen to dry the FTO glass.
  • Titanium dioxide nanorod arrays were prepared using hydrothermal synthesis. Use a hydrothermal explosion-proof reactor with a volume of 50 mL as the reaction vessel, and use a pipette in the glove box to extract 0.4 mL of titanium(IV) isopropoxide (Ti(OCH(CH 3 ) 2 ) 4 ) and 30 mL of dilute hydrochloric acid solution ( The mass fraction is 18 ⁇ 19%); add titanium isopropoxide (IV) to the dilute hydrochloric acid solution, stir for 10 minutes and then ultrasonic for 5 minutes to make it become a transparent solution, and then transfer the solution to the 50 mL reactor liner.
  • the pretreated FTO glass with the conductive surface tilted downward in the reactor liner keep it at 230°C for 2 hours, cool to room temperature, and prepare a titanium dioxide nanorod array on the FTO glass; clean it with deionized water several times, and placed in a drying box for drying at 60°C.
  • the titanium dioxide nanorod array was subjected to high-temperature annealing treatment in an air atmosphere to obtain a titanium dioxide nanorod array with a stable structure.
  • Figure 1 is the X-ray diffraction (XRD) pattern of the titanium dioxide nanorod array in Example 1 of the present invention. According to the diffraction angle corresponding to the peak of the pattern, it can be determined that Titanium dioxide nanorod array.
  • XRD X-ray diffraction
  • FIG. 1 is a scanning electron microscope (SEM) image of the titanium dioxide nanorod array in Example 1 of the present invention. From Figure 2, it can be seen that a uniform nanorod array structure can be seen.
  • Figure 3 is a scanning transmission electron microscope (TEM) image of the titanium dioxide nanorod array in Example 1 of the present invention. From Figure 3, the shape and smooth side walls of the nanorods can be seen.
  • Nitrogen-doped titanium dioxide nanosheets (N-TiO 2 ) suspension was prepared using powder calcination and ion exchange methods.
  • White cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder was heated in an ammonia atmosphere at 750°C using the powder calcination method. After medium calcination for 2 hours, nitrogen-doped Cs 0.68 Ti 1.83 O 4 - x N x powder was obtained.
  • the obtained Cs 0.68 Ti 1.83 O 4-x N obtain H 0.68 Ti 1.83 O 4-x N x (protonated state), and use the configured TABOH solution with a concentration of 0.2 mol/L to disperse the obtained H 0.68 Ti 1.83 O 4-x N x in it, at room temperature Shake for 8 days and shake evenly to obtain a uniformly dispersed suspension of nitrogen-doped titanium dioxide nanosheets (Ti 0.91 O 2-x N x , referred to as N-TiO 2 ).
  • the titanium dioxide nanorod array was surface treated using a N- TiO2 nanosheet suspension with a loading volume of 100 ⁇ L, and then dried naturally at room temperature. After annealing, a surface-modified titanium dioxide heterojunction photoanode sample 1 was obtained. Among them, the obtained surface-modified titanium dioxide heterojunction photoanode sample 1 was scanned by an electron microscope, as shown in Figure 4.
  • Figure 4 is a scanning electron microscope (SEM) of the surface-modified titanium dioxide rod nanorod array structure in Example 1 of the present invention. picture.
  • This embodiment provides a method for preparing a titanium homologous semiconductor heterojunction photoanode, which includes the following steps:
  • the titanium dioxide nanorod array was surface treated using a N- TiO2 nanosheet suspension with a loading capacity of 200 ⁇ L, and then dried naturally at room temperature. After annealing, a surface-modified titanium dioxide heterojunction photoanode sample 2 was obtained. The remaining steps are the same as in Example 1. Among them, the obtained surface-modified titanium dioxide heterojunction photoanode sample 2 was scanned by an electron microscope, as shown in Figure 5.
  • Figure 5 is a scanning electron microscope (SEM) of the surface-modified titanium oxide rod nanorod array structure in Example 2 of the present invention.
  • Figure 6 is a scanning transmission electron microscope (TEM) image of the surface-modified titanium dioxide rod nanorod array structure in Example 2 of the present invention.
  • This embodiment provides a method for preparing a titanium homologous semiconductor heterojunction photoanode, which includes the following steps:
  • the titanium dioxide nanorod array was surface treated using a N- TiO2 nanosheet suspension with a loading volume of 400 ⁇ L, and then dried naturally at room temperature. After annealing, a surface-modified titanium dioxide heterojunction photoanode sample 3 was obtained. The remaining steps are the same as in Example 1.
  • Sample 1 Sample 2 and sample 3 prepared in Example 1, Example 2 and Example 3 were subjected to cyclic voltammetry scanning, and then their photoelectrocatalytic performance was tested.
  • the sample was tested by cyclic voltammetry to eliminate the contingency of the experiment and make the water electrolysis performance of the sample tend to be stable.
  • the cyclic voltammetry test voltage range is -0.2 V to 1.5 V (vs RHE), scan speed 50 m V/s, gap voltage 0.001 V, cycle 20 times.
  • the FTO in the sample was cut into 2cm ⁇ 1cm size, and an electrochemical workstation was used to test the photoelectrochemical performance of the sample using a three-electrode system to conduct photoelectrocatalytic water splitting.
  • the electrolyte for the electrochemical test was 0.05M Na 2 SO4 solution.
  • Figure 7 is a photoelectrocatalytic performance (LSV) diagram of N- TiO2- modified titanium dioxide nanorod arrays with different loading amounts provided by embodiments of the present invention. It can be seen from Figure 7 that 200 ⁇ L N-TiO is loaded The sample corresponding to 2 has the best photoelectrocatalytic performance.
  • LSV photoelectrocatalytic performance
  • the embodiments of the present invention provide a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof.
  • a titanium dioxide nanorod array is grown on a conductive substrate, and then the titanium dioxide nanorod array is subjected to high-temperature annealing treatment.
  • the titanium dioxide nanosheets of the metal doped phase are used to prepare the titanium dioxide nanosheet suspension of the non-metal doped phase.
  • the titanium dioxide nanosheet suspension of the non-metal doped phase is used to modify the titanium dioxide nanorod array after high temperature annealing to make the titanium dioxide nanorods.
  • the array forms a titanium homologous heterojunction
  • the modified titanium dioxide nanorod array is subjected to high-temperature annealing to obtain a titanium homologous semiconductor heterojunction photoanode.
  • the preparation method provided by the embodiment of the present invention by constructing a titanium homologous heterojunction The junction increases the reactive active sites on the titanium dioxide surface and enhances the charge transfer efficiency, thereby improving its surface catalytic activity, achieving efficient total water splitting, and solving the problem of low water decomposition ability of the titanium dioxide photoanode.

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Abstract

Disclosed in the present invention are a titanium homologous semiconductor heterojunction photoanode and a preparation method therefor. The titanium homologous semiconductor heterojunction photoanode comprises a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate, the titanium dioxide nanorod array being modified with titanium dioxide nanosheets of a non-metal doped phase to form a titanium homologous heterojunction. The preparation method comprises: growing a titanium dioxide nanorod array on the conductive substrate; performing high-temperature annealing treatment on the titanium dioxide nanorod array; performing surface modification on the obtained titanium dioxide nanorod array by using a titanium dioxide nanosheet suspension of a non-metal doped phase, such that the titanium dioxide nanorod array forms a titanium homologous heterojunction, and a nano heterojunction based on titanium dioxide is obtained; and annealing the nano heterojunction based on titanium dioxide at a high temperature to obtain a titanium homologous semiconductor heterojunction photoanode. By constructing a heterojunction, the preparation method provided by the present invention solves the problem of low water decomposition capability of a titanium dioxide photoanode.

Description

一种钛同源半导体异质结光阳极及其制备方法A titanium homologous semiconductor heterojunction photoanode and its preparation method 技术领域Technical field
本发明属于太阳能电池技术领域，尤其涉及一种钛同源半导体异质结光阳极及其制备方法。The invention belongs to the technical field of solar cells, and in particular relates to a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof.
背景技术Background technique
氢能作为解决化石燃料带来的环境和污染问题最有前景的清洁能源受到了广泛关注，而在各种制氢方法中，光电化学水分解被认为是一种优良的制氢技术。光电分解水制氢在不同的催化剂的作用下性能会有所不同，所以要得到高纯度高效率的氢能源就需要高效的光电催化剂材料。其中二氧化钛由于成本低、无毒、化学稳定性和光学稳定性良好，是一种具有前景的光电催化剂。但其较宽的禁带宽度、较差的捕光能力和较慢的表面水氧化动力学使其难以到达理论的性能峰值，前已有多种策略来改善二氧化钛的光电催化性能，如元素掺杂、晶面修饰、异质结构建等。Hydrogen energy has received widespread attention as the most promising clean energy source to solve the environmental and pollution problems caused by fossil fuels. Among various hydrogen production methods, photoelectrochemical water splitting is considered an excellent hydrogen production technology. The performance of photoelectric water splitting to produce hydrogen will be different under the action of different catalysts. Therefore, to obtain high-purity and high-efficiency hydrogen energy, efficient photoelectrocatalyst materials are needed. Among them, titanium dioxide is a promising photoelectrocatalyst due to its low cost, non-toxicity, good chemical stability and optical stability. However, its wide bandgap, poor light-harvesting ability and slow surface water oxidation kinetics make it difficult to reach the theoretical performance peak. There have been many strategies to improve the photoelectrocatalytic performance of titanium dioxide, such as element doping. Hybrid, crystal face modification, heterostructure construction, etc.
FTO玻璃具有高的物理与化学稳定性、良好的导电性以及多种优良的电化学性能。而纳米棒阵列结构具有高比表面积，可以在电解水中提供更多的活性位点，从而实现更加高效的催化转化过程。但由于所制备的二氧化钛材料本身在催化效率及表面反应活性上仍存在一定的不足，制备形成的光阳极电荷传输转移能力不够强，因此需要进行适当的表面改性使其表面产生更多的活性位点同时提高其表面电荷传输转移，进而提高二氧化钛催化全分解水效率。FTO glass has high physical and chemical stability, good electrical conductivity and a variety of excellent electrochemical properties. The nanorod array structure has a high specific surface area, which can provide more active sites in electrolyzed water, thereby achieving a more efficient catalytic conversion process. However, since the prepared titanium dioxide material itself still has certain deficiencies in catalytic efficiency and surface reactivity, the charge transfer transfer ability of the prepared photoanode is not strong enough. Therefore, appropriate surface modification is needed to generate more activity on the surface. The sites simultaneously improve its surface charge transport and transfer, thereby improving the efficiency of titanium dioxide catalytic total water splitting.
在多种材料表面改性手段中，构建异质结从而改善其电化学性质是十分高效、便捷的处理方法，同样也是提高二氧化钛催化性能的有效策略。Among various material surface modification methods, constructing heterojunctions to improve their electrochemical properties is a very efficient and convenient method. It is also an effective strategy to improve the catalytic performance of titanium dioxide.
技术问题technical problem
鉴于现有技术存在的不足，本发明提供了一种钛同源半导体异质结光阳极及其制备方法，以解决现有的二氧化钛光阳极水分解能力低的问题。In view of the shortcomings of the existing technology, the present invention provides a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof to solve the problem of low water decomposition capability of the existing titanium dioxide photoanode.
技术解决方案Technical solutions
为了解决以上问题，本发明首先提供了一种钛同源半导体异质结光阳极，所述钛同源半导体异质结光阳极包括导电基底以及生长在导电基底上的二氧化钛纳米棒阵列，所述二氧化钛纳米棒阵列上修饰有非金属掺杂相的二氧化钛纳米片，所述二氧化钛纳米棒阵列与所述非金属掺杂相的二氧化钛纳米片形成钛同源异质结。In order to solve the above problems, the present invention first provides a titanium homologous semiconductor heterojunction photoanode. The titanium homologous semiconductor heterojunction photoanode includes a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate. The titanium dioxide nanorod array is decorated with titanium dioxide nanosheets of a non-metal doped phase, and the titanium dioxide nanorod array and the titanium dioxide nanosheets of the non-metal doped phase form a titanium homologous heterojunction.
优选地，所述非金属掺杂相的二氧化钛纳米片为氮掺杂二氧化钛纳米片。Preferably, the titanium dioxide nanosheets of the non-metal doped phase are nitrogen-doped titanium dioxide nanosheets.
本发明还提供了一种如上述所述的钛同源半导体异质结光阳极的制备方法，所述制备方法包括以下步骤：The present invention also provides a method for preparing the titanium homologous semiconductor heterojunction photoanode as described above. The preparation method includes the following steps:
S1、在导电基底上生长二氧化钛纳米棒阵列；S1. Growth of titanium dioxide nanorod arrays on conductive substrates;
S2、将步骤S1中得到的二氧化钛纳米棒阵列进行高温退火处理；S2. Perform high-temperature annealing treatment on the titanium dioxide nanorod array obtained in step S1;
S3、使用非金属掺杂相的二氧化钛纳米片制备非金属掺杂相的二氧化钛纳米片悬浊液；S3. Use titanium dioxide nanosheets of non-metal doped phase to prepare titanium dioxide nanosheet suspension of non-metal doped phase;
S4、使用非金属掺杂相的二氧化钛纳米片悬浊液对步骤S2中得到的二氧化钛纳米棒阵列进行表面修饰，使二氧化钛纳米棒阵列形成钛同源异质结，得到基于二氧化钛的纳米异质结；S4. Use the titanium dioxide nanosheet suspension of the non-metal doped phase to perform surface modification on the titanium dioxide nanorod array obtained in step S2, so that the titanium dioxide nanorod array forms a titanium homologous heterojunction to obtain a titanium dioxide-based nanoheterojunction. ;
S5、将基于二氧化钛的纳米异质结进行高温退火处理，获得钛同源半导体异质结光阳极。S5. Perform high-temperature annealing treatment on the titanium dioxide-based nanoheterojunction to obtain a titanium homologous semiconductor heterojunction photoanode.
优选地，所述步骤S1中在导电基底上生长二氧化钛纳米棒阵列包括：将导电基底置于超声处理后的异丙氧钛(IV)和稀盐酸的混合溶液中，高温处理含有导电基底的异丙氧钛(IV)和稀盐酸的混合溶液，以在导电基底上生长二氧化钛纳米棒阵列。Preferably, growing the titanium dioxide nanorod array on the conductive substrate in step S1 includes: placing the conductive substrate in a mixed solution of titanium (IV) isopropoxide and dilute hydrochloric acid after ultrasonic treatment, and treating the isotropic substance containing the conductive substrate at high temperature. A mixed solution of titanium(IV) propoxide and dilute hydrochloric acid to grow titanium dioxide nanorod arrays on conductive substrates.
优选地，所述异丙氧钛(IV)与所述稀盐酸的体积比为1:50~80。Preferably, the volume ratio of the titanium isopropoxide (IV) to the dilute hydrochloric acid is 1:50~80.
优选地，所述稀盐酸的质量分数为18% ~19%。Preferably, the mass fraction of dilute hydrochloric acid is 18% ~ 19%.
优选地，高温处理含有导电基底的异丙氧钛(IV)和稀盐酸的混合溶液的温度为230℃~300℃，处理时间为2h ~ 4h。Preferably, the temperature for high-temperature treatment of the mixed solution of titanium(IV) isopropoxide and dilute hydrochloric acid containing the conductive substrate is 230°C to 300°C, and the treatment time is 2 hours. ~4h.
优选地，所述步骤S2中对二氧化钛纳米棒阵列进行高温退火处理的温度为300℃~500℃，处理时间为1h ~3h。Preferably, the temperature at which the titanium dioxide nanorod array is subjected to high-temperature annealing in step S2 is 300°C to 500°C, and the treatment time is 1 hour. ~3h.
优选地，所述步骤S3中非金属掺杂相的二氧化钛纳米片悬浊液的制备包括：在氨气氛围中，高温煅烧钛酸铯（Cs 0.68Ti 1.83O 4）粉末，得到氮掺杂的Cs 0.68Ti 1.83O 4-xN x粉末，将Cs 0.68Ti 1.83O 4-xN x粉末置于HCl溶液中与H +发生离子交换，得到H 0.68Ti 1.83O 4-xN x，将H 0.68Ti 1.83O 4-xN x分散在四丁基氢氧化铵溶液中并摇匀处理，得到氮掺杂二氧化钛纳米片（N-TiO 2）悬浊液。 Preferably, the preparation of the titanium dioxide nanosheet suspension of the non-metal doped phase in step S3 includes: calcining cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder at high temperature in an ammonia atmosphere to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4 -x N x powder, put the Cs 0.68 Ti 1.83 O 4 - x N 0.68 Ti 1.83 O 4-x N x is dispersed in the tetrabutylammonium hydroxide solution and shaken well to obtain a nitrogen-doped titanium dioxide nanosheet (N-TiO 2 ) suspension.
优选地，所述步骤S5中对基于二氧化钛的纳米异质结进行高温退火处理包括：氩气氛围下，高温退火处理基于二氧化钛的纳米异质结，其中，处理温度为300℃~500℃，处理时间为1h~3h。Preferably, the high-temperature annealing treatment of the titanium dioxide-based nanoheterojunction in step S5 includes: high-temperature annealing of the titanium dioxide-based nanoheterojunction under an argon atmosphere, wherein the treatment temperature is 300°C to 500°C. The time is 1h~3h.
有益效果beneficial effects
本发明提供的一种钛同源半导体异质结光阳极及其制备方法，在导电基底上生长二氧化钛纳米棒阵列，接着对二氧化钛纳米棒阵列进行高温退火处理，使用非金属掺杂相的二氧化钛纳米片制备非金属掺杂相的二氧化钛纳米片悬浊液，利用非金属掺杂相的二氧化钛纳米片悬浊液修饰高温退火处理后的二氧化钛纳米棒阵列，使得二氧化钛纳米棒阵列形成钛同源半导体异质结，最后对修饰后的二氧化钛纳米棒阵列进行高温退火处理，获得钛同源半导体异质结光阳极，本发明提供的制备方法，通过构建钛同源异质结，增加二氧化钛表面反应活性位点并增强电荷传输效率，从而提高其表面催化活性，实现高效全水分解，解决了二氧化钛光阳极水分解能力低的问题。The invention provides a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof. A titanium dioxide nanorod array is grown on a conductive substrate, and then the titanium dioxide nanorod array is subjected to high-temperature annealing treatment. Titanium dioxide nanorods with a non-metal doping phase are used. The titanium dioxide nanosheet suspension of the non-metal doped phase is prepared from the wafer, and the titanium dioxide nanosheet suspension of the non-metal doped phase is used to modify the titanium dioxide nanorod array after high-temperature annealing treatment, so that the titanium dioxide nanorod array forms a titanium homologous semiconductor heterogeneous The modified titanium dioxide nanorod array is finally subjected to high-temperature annealing treatment to obtain a titanium homologous semiconductor heterojunction photoanode. The preparation method provided by the invention increases the reactive sites on the surface of titanium dioxide by constructing a titanium homologous heterojunction. It also enhances the charge transfer efficiency, thereby improving its surface catalytic activity, achieving efficient total water splitting, and solving the problem of low water splitting ability of titanium dioxide photoanode.
附图说明Description of drawings
图1是本发明实施例1中二氧化钛纳米棒阵列的X射线衍射（XRD）图，；Figure 1 is an X-ray diffraction (XRD) pattern of the titanium dioxide nanorod array in Example 1 of the present invention;
图2是本发明实施例1中二氧化钛纳米棒阵列的扫描电镜（SEM）图；Figure 2 is a scanning electron microscope (SEM) image of the titanium dioxide nanorod array in Example 1 of the present invention;
图3是本发明实施例1中二氧化钛纳米棒阵列的扫描透射电镜（TEM）图；Figure 3 is a scanning transmission electron microscope (TEM) image of the titanium dioxide nanorod array in Example 1 of the present invention;
图4是本发明实施例1中表面修饰的二氧化钛棒纳米棒阵列结构的扫描电镜（SEM）图；Figure 4 is a scanning electron microscope (SEM) image of the surface-modified titanium dioxide rod nanorod array structure in Example 1 of the present invention;
图5是本发明实施例2中表面修饰的氧化钛棒纳米棒阵列结构的扫描电镜（SEM）图；Figure 5 is a scanning electron microscope (SEM) image of the surface-modified titanium oxide rod nanorod array structure in Example 2 of the present invention;
图6是本发明实施例2中表面修饰的二氧化钛棒纳米棒阵列结构的扫描透射电镜（TEM）图；Figure 6 is a scanning transmission electron microscope (TEM) image of the surface-modified titanium dioxide rod nanorod array structure in Example 2 of the present invention;
图7是本发明实施例提供的不同负载量的N-TiO 2修饰的二氧化钛纳米棒阵列的光电催化性能（LSV）图。 Figure 7 is a photoelectrocatalytic performance (LSV) diagram of N- TiO2- modified titanium dioxide nanorod arrays with different loading amounts provided by embodiments of the present invention.
本发明的实施方式Embodiments of the invention
为使本发明的目的、技术方案和优点更加清楚，下面结合附图对本发明的具体实施方式进行详细说明。这些优选实施方式的示例在附图中进行了例示。附图中所示和根据附图描述的本发明的实施方式仅仅是示例性的，并且本发明并不限于这些实施方式。In order to make the purpose, technical solutions and advantages of the present invention clearer, specific implementation modes of the present invention will be described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in and described with reference to the drawings are merely exemplary and the invention is not limited to these embodiments.
在此，还需要说明的是，为了避免因不必要的细节而模糊了本发明，在附图中仅仅示出了与根据本发明的方案密切相关的结构和/或处理步骤，而省略了与本发明关系不大的其他细节。Here, it should also be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the solution according to the present invention are shown in the drawings, and the details related to them are omitted. Other details are less relevant to the invention.
本实施例首先提供一种钛同源半导体异质结光阳极，所述钛同源半导体异质结光阳极包括导电基底以及生长在导电基底上的二氧化钛纳米棒阵列，所述二氧化钛纳米棒阵列上修饰有非金属掺杂相的二氧化钛纳米片，所述二氧化钛纳米棒阵列与所述非金属掺杂相的二氧化钛纳米片形成钛同源半导体异质结。This embodiment first provides a titanium homologous semiconductor heterojunction photoanode. The titanium homologous semiconductor heterojunction photoanode includes a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate. The titanium dioxide nanorod array is The titanium dioxide nanosheets are modified with a non-metal doped phase, and the titanium dioxide nanorod array and the titanium dioxide nanosheets of the non-metal doped phase form a titanium homologous semiconductor heterojunction.
具体地，所述非金属掺杂相的二氧化钛纳米片为氮掺杂二氧化钛纳米片。Specifically, the titanium dioxide nanosheets of the non-metal doped phase are nitrogen-doped titanium dioxide nanosheets.
钛同源异质结，可增加二氧化钛表面反应活性位点并增强电荷传输效率，从而提高二氧化钛表面催化活性。The titanium homologous heterojunction can increase the reactive sites on the titanium dioxide surface and enhance the charge transfer efficiency, thereby improving the catalytic activity of the titanium dioxide surface.
本实施例还提供了一种上述所述的钛同源半导体异质结光阳极的制备方法，所述制备方法包括以下步骤：This embodiment also provides a method for preparing the above-mentioned titanium homologous semiconductor heterojunction photoanode. The preparation method includes the following steps:
S1、在导电基底上生长二氧化钛纳米棒阵列；S1. Growth of titanium dioxide nanorod arrays on conductive substrates;
S2、将步骤S1中得到的二氧化钛纳米棒阵列进行高温退火处理；S2. Perform high-temperature annealing treatment on the titanium dioxide nanorod array obtained in step S1;
S3、使用非金属掺杂相的二氧化钛纳米片制备非金属掺杂相的二氧化钛纳米片悬浊液；S3. Use titanium dioxide nanosheets of non-metal doped phase to prepare titanium dioxide nanosheet suspension of non-metal doped phase;
S4、使用非金属掺杂相的二氧化钛纳米片悬浊液对步骤S2中得到的二氧化钛纳米棒阵列进行表面修饰，使二氧化钛纳米棒阵列形成钛同源异质结，得到基于二氧化钛的纳米异质结；S4. Use the titanium dioxide nanosheet suspension of the non-metal doped phase to perform surface modification on the titanium dioxide nanorod array obtained in step S2, so that the titanium dioxide nanorod array forms a titanium homologous heterojunction to obtain a titanium dioxide-based nanoheterojunction. ;
S5、将基于二氧化钛的纳米异质结进行高温退火处理，获得钛同源半导体异质结光阳极。S5. Perform high-temperature annealing treatment on the titanium dioxide-based nanoheterojunction to obtain a titanium homologous semiconductor heterojunction photoanode.
以上实施例提供的钛同源半导体异质结光阳极的制备方法，通过非金属掺杂相的二氧化钛纳米片悬浊液修饰二氧化钛纳米棒阵列，构建钛同源异质结，增加二氧化钛表面反应活性位点并增强电荷传输效率，从而提高其表面催化活性，实现高效全水分解，解决了二氧化钛光阳极水分解能力低的问题。The preparation method of the titanium homologous semiconductor heterojunction photoanode provided in the above embodiment is to modify the titanium dioxide nanorod array with a suspension of titanium dioxide nanosheets of a non-metal doped phase to construct a titanium homologous heterojunction and increase the surface reactivity of the titanium dioxide. sites and enhance the charge transfer efficiency, thereby improving its surface catalytic activity, achieving efficient total water splitting, and solving the problem of low water splitting ability of titanium dioxide photoanode.
在优选的方案中，所述步骤S1中在导电基底上生长二氧化钛纳米棒阵列包括：将导电基底置于超声处理后的异丙氧钛(IV)和稀盐酸的混合溶液中，高温处理含有导电基底的异丙氧钛(IV)和稀盐酸的混合溶液，以在导电基底上生长二氧化钛纳米棒阵列。In a preferred solution, growing the titanium dioxide nanorod array on the conductive substrate in step S1 includes: placing the conductive substrate in a mixed solution of ultrasonic-treated titanium (IV) isopropoxide and dilute hydrochloric acid, and the high-temperature treatment contains conductive A mixed solution of titanium (IV) isopropoxide and dilute hydrochloric acid is used to grow titanium dioxide nanorod arrays on conductive substrates.
在优选的方案中，所述异丙氧钛(IV)与所述稀盐酸的体积比为1:50~80。In a preferred solution, the volume ratio of the titanium isopropoxide (IV) to the dilute hydrochloric acid is 1:50~80.
在优选的方案中，所述稀盐酸的质量分数为18% ~19%。In a preferred solution, the mass fraction of dilute hydrochloric acid is 18% ~ 19%.
在优选的方案中，高温处理含有导电基底的异丙氧钛(IV)和稀盐酸的混合溶液的温度为230℃~300℃，处理时间为2h ~ 4h。In a preferred solution, the temperature of the mixed solution of titanium (IV) isopropoxide (IV) and dilute hydrochloric acid containing the conductive substrate is treated at a temperature of 230°C to 300°C, and the treatment time is 2 hours. ~4h.
具体地，本实例中，在手套箱内，将异丙氧钛(IV)和稀盐酸按照体积比混合搅拌10min ~ 30 min，接着超声处理5min ~10min，超声处理后将所得混合溶液转移至反应釜内胆中，然后把导电基底置于反应釜内胆中，最后将其高温处理，冷却至室温，可在导电基底上生长出二氧化钛纳米棒阵列。Specifically, in this example, in a glove box, titanium (IV) isopropoxide and dilute hydrochloric acid are mixed and stirred according to the volume ratio for 10 minutes. ~30 min, followed by ultrasonic treatment for 5 min ~10min, after ultrasonic treatment, transfer the resulting mixed solution to the reactor liner, then place the conductive substrate in the reactor liner, and finally treat it at high temperature and cool it to room temperature. Titanium dioxide nanorods can be grown on the conductive substrate. array.
在优选的方案中，所述步骤S2中对二氧化钛纳米棒阵列进行高温退火处理的温度为300℃~500℃，处理时间为1h ~3h。In a preferred solution, the temperature for high-temperature annealing of the titanium dioxide nanorod array in step S2 is 300°C to 500°C, and the treatment time is 1 hour. ~3h.
具体地，在导电基底上制备得到的二氧化钛纳米棒阵列后，用去离子水进行清洗数次，并在60 ℃下进行干燥处理，随后再进行高温退火处理。Specifically, after preparing the titanium dioxide nanorod array on the conductive substrate, it was washed several times with deionized water and dried at 60 Drying is carried out at ℃, followed by high temperature annealing.
具体地，本实例中，可将二氧化钛纳米棒阵列置于马弗炉中，在空气氛围下，从室温升到高温退火处理的温度，达到高温退火处理的时间，后自然冷却至室温，以完成退火处理。Specifically, in this example, the titanium dioxide nanorod array can be placed in a muffle furnace, raised from room temperature to the temperature of high-temperature annealing treatment in an air atmosphere, reaches the time of high-temperature annealing treatment, and then naturally cooled to room temperature, to Complete annealing.
在优选的方案中，所述步骤S3中非金属掺杂相的二氧化钛纳米片悬浊液的制备包括：在氨气氛围中，高温煅烧钛酸铯（Cs 0.68Ti 1.83O 4）粉末，得到氮掺杂的Cs 0.68Ti 1.83O 4-xN x粉末，将Cs 0.68Ti 1.83O 4-xN x粉末置于HCl溶液中与H +发生离子交换，得到H 0.68Ti 1.83O 4-xN x，将H 0.68Ti 1.83O 4-xN x分散在四丁基氢氧化铵溶液中并摇匀处理，得到氮掺杂二氧化钛纳米片（N-TiO 2）悬浊液。 In a preferred solution, the preparation of the titanium dioxide nanosheet suspension of the non-metal doped phase in step S3 includes: calcining cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder at high temperature in an ammonia atmosphere to obtain nitrogen Doped Cs 0.68 Ti 1.83 O 4 -x N x powder, place the Cs 0.68 Ti 1.83 O 4 - x N , disperse H 0.68 Ti 1.83 O 4-x N x in the tetrabutylammonium hydroxide solution and shake it well to obtain a nitrogen-doped titanium dioxide nanosheet (N-TiO 2 ) suspension.
具体地，在氨气氛围中，保持温度750℃~ 800℃煅烧白色的钛酸铯（Cs 0.68Ti 1.83O 4）粉末2 h~3h，可得到氮掺杂的Cs 0.68Ti 1.83O 4-xN x粉末，将氮掺杂的Cs 0.68Ti 1.83O 4-xN x粉末与H +在1mol/L HCl溶液中进行3天离子交换，得到H 0.68Ti 1.83O 4-xN x (质子化状态)；将配置浓度为 0.2mol/L的四丁基氢氧化铵（TABOH）溶液，并将H 0.68Ti 1.83O 4-xN x分散于配置好的四丁基氢氧化铵（TABOH）溶液中，在室温下振荡8天，摇匀处理得到分散均匀的氮掺杂二氧化钛纳米片（Ti 0.91O 2-xN x，缩写为N-TiO 2）悬浊液。 Specifically, in an ammonia atmosphere, the white cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder is calcined at a temperature of 750°C ~ 800°C for 2 h ~ 3h to obtain nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x powder, ion exchange nitrogen-doped Cs 0.68 Ti 1.83 O 4-x N x powder with H + in 1mol/L HCl solution for 3 days to obtain H 0.68 Ti 1.83 O 4-x N state); prepare a tetrabutylammonium hydroxide (TABOH) solution with a concentration of 0.2mol/L, and disperse H 0.68 Ti 1.83 O 4-x N x in the prepared tetrabutylammonium hydroxide (TABOH) solution at room temperature. Shake for 8 days, shake well to obtain a uniformly dispersed suspension of nitrogen-doped titanium dioxide nanosheets (Ti 0.91 O 2-x N x , abbreviated as N-TiO 2 ).
具体地，可通过改变N-TiO 2纳米片悬浊液的负载量对二氧化钛纳米棒阵列进行不同剂量的表面处理，自然干燥后得到表面修饰后的二氧化钛纳米棒阵列，修饰后的二氧化钛纳米棒阵列形成钛同源异质结。 Specifically, the titanium dioxide nanorod array can be surface treated at different doses by changing the loading amount of the N- TiO2 nanosheet suspension, and after natural drying, a surface-modified titanium dioxide nanorod array can be obtained. The modified titanium dioxide nanorod array Formation of titanium homogeneous heterojunction.
其中，N-TiO 2纳米片悬浊液的负载量优选为100μL ~ 400μL。 Among them, the loading amount of the N-TiO 2 nanosheet suspension is preferably 100 μL ~ 400 μL.
其中，N-TiO 2纳米片悬浊液的浓度优选为1 mg/mL ~10 mg/mL。 Among them, the concentration of the N-TiO 2 nanosheet suspension is preferably 1 mg/mL ~ 10 mg/mL.
更优选的方案中，N-TiO 2纳米片悬浊液的负载量为200μL，N-TiO 2纳米片悬浊液的浓度1 .5mg/mL制备出的钛同源半导体异质结光阳极性能最佳。 In a more preferred solution, the loading capacity of the N-TiO 2 nanosheet suspension is 200 μL, and the concentration of the N-TiO 2 nanosheet suspension is 1.5 mg/mL. Performance of titanium homologous semiconductor heterojunction photoanode prepared optimal.
在优选的方案中，所述步骤S5中对基于二氧化钛的纳米异质结进行高温退火处理包括：氩气氛围下，高温退火处理基于二氧化钛的纳米异质结，其中，处理温度为300℃~500℃，处理时间为1h~3h。In a preferred solution, the high-temperature annealing treatment of the titanium dioxide-based nanoheterojunction in step S5 includes: high-temperature annealing of the titanium dioxide-based nanoheterojunction under an argon atmosphere, wherein the processing temperature is 300°C to 500°C. ℃, the processing time is 1h~3h.
具体地，本实施例中，将修饰后的二氧化钛纳米棒阵列置于管式炉内，在氩气氛围下以2.3℃/min从室温升温到退火处理的温度，退火处理1h~3h后自然冷却至室温，可得到最终的钛同源半导体异质结光阳极。Specifically, in this example, the modified titanium dioxide nanorod array is placed in a tube furnace, heated from room temperature to the annealing temperature at 2.3°C/min in an argon atmosphere, and then cooled naturally after 1h to 3h of annealing. to room temperature, the final titanium homologous semiconductor heterojunction photoanode can be obtained.
在优选的方案中，所述步骤S1中，导电基底为预处理后FTO玻璃，其中，对FTO玻璃进行预处理的方法为：In a preferred solution, in step S1, the conductive substrate is pretreated FTO glass, wherein the method for pretreating FTO glass is:
首先，将FTO玻璃浸于丙酮和无水乙醇的混合溶液中超声清洗，将清洗后的FTO玻璃浸于过氧化氢和硫酸的混合溶液中；其次，将FTO玻璃用无水乙醇清洗；最后在氮气氛围下对FTO玻璃进行干燥处理。First, the FTO glass is immersed in a mixed solution of acetone and absolute ethanol for ultrasonic cleaning, and the cleaned FTO glass is immersed in a mixed solution of hydrogen peroxide and sulfuric acid; secondly, the FTO glass is cleaned with absolute ethanol; finally, Dry the FTO glass under nitrogen atmosphere.
具体地，在丙酮和无水乙醇的混合溶液中丙酮和无水乙醇的体积比为1:1，超声清洗的时间为30min以上。Specifically, in the mixed solution of acetone and absolute ethanol, the volume ratio of acetone and absolute ethanol is 1:1, and the ultrasonic cleaning time is more than 30 minutes.
在过氧化氢和硫酸的混合溶液中过氧化氢和硫酸的体积比为3:1，将FTO玻璃过氧化氢和硫酸的混合溶液是为了增强FTO玻璃的亲水性。The volume ratio of hydrogen peroxide and sulfuric acid in the mixed solution of hydrogen peroxide and sulfuric acid is 3:1. The mixed solution of hydrogen peroxide and sulfuric acid for FTO glass is used to enhance the hydrophilicity of FTO glass.
实施例1Example 1
本实施例提供一种钛同源半导体异质结光阳极的制备方法，包括如下步骤：This embodiment provides a method for preparing a titanium homologous semiconductor heterojunction photoanode, which includes the following steps:
（1）基底的选择及预处理(1) Substrate selection and pretreatment
选择FTO玻璃为基底，大小为4cm×2cm。然后对基底进行预处理，具体为将FTO玻璃放在丙酮和无水乙醇混合溶液中，丙酮和无水乙醇混合溶液的体积比为1:1，超声清洗30分钟，去除基底表面的杂质；再将FTO玻璃浸于过氧化氢和硫酸混合溶液中，过氧化氢和硫酸混合溶液的体积比为3:1，浸泡10分钟，进一步去除杂质并增强其亲水性；接着将FTO玻璃利用无水乙醇清洗；最后利用氮气将FTO玻璃干燥。Choose FTO glass as the substrate, with a size of 4cm×2cm. Then the substrate is pretreated, specifically by placing the FTO glass in a mixed solution of acetone and absolute ethanol. The volume ratio of the mixed solution of acetone and absolute ethanol is 1:1, and ultrasonic cleaning for 30 minutes to remove impurities on the surface of the substrate; then Immerse the FTO glass in a mixed solution of hydrogen peroxide and sulfuric acid. The volume ratio of the mixed solution of hydrogen peroxide and sulfuric acid is 3:1, and soak for 10 minutes to further remove impurities and enhance its hydrophilicity; then use anhydrous Clean with ethanol; finally use nitrogen to dry the FTO glass.
（2）二氧化钛纳米棒阵列的制备(2) Preparation of titanium dioxide nanorod arrays
采用水热合成的方法，制备二氧化钛纳米棒阵列。使用50mL容积的水热防爆反应釜作为反应容器，在手套箱内使用移液枪分别提取0.4mL异丙氧钛(IV)（Ti(OCH(CH 3) 2) 4）与30mL稀盐酸溶液（质量分数为18~19%）；将异丙氧钛(IV)加入稀盐酸溶液中，搅拌10分钟之后超声5分钟，使其成为透明溶液，然后将溶液转移至50 mL的反应釜内胆中，最后把预处理后的FTO玻璃导电面朝下倾斜放置在反应釜内胆中，230℃下保温2小时，冷却至室温，在FTO玻璃上制备得到二氧化钛纳米棒阵列；用去离子水进行清洗数次，并置于干燥箱中60℃下进行干燥，最后在空气氛围下，对二氧化钛纳米棒阵列进行高温退火处理，得到结构稳定的二氧化钛纳米棒阵列。 Titanium dioxide nanorod arrays were prepared using hydrothermal synthesis. Use a hydrothermal explosion-proof reactor with a volume of 50 mL as the reaction vessel, and use a pipette in the glove box to extract 0.4 mL of titanium(IV) isopropoxide (Ti(OCH(CH 3 ) 2 ) 4 ) and 30 mL of dilute hydrochloric acid solution ( The mass fraction is 18~19%); add titanium isopropoxide (IV) to the dilute hydrochloric acid solution, stir for 10 minutes and then ultrasonic for 5 minutes to make it become a transparent solution, and then transfer the solution to the 50 mL reactor liner. , finally place the pretreated FTO glass with the conductive surface tilted downward in the reactor liner, keep it at 230°C for 2 hours, cool to room temperature, and prepare a titanium dioxide nanorod array on the FTO glass; clean it with deionized water several times, and placed in a drying box for drying at 60°C. Finally, the titanium dioxide nanorod array was subjected to high-temperature annealing treatment in an air atmosphere to obtain a titanium dioxide nanorod array with a stable structure.
对制备得到的二氧化钛纳米棒阵列进行X射线衍射分析，其中，图1是本发明实施例1中二氧化钛纳米棒阵列的X射线衍射（XRD）图，根据图谱峰对应的衍射角度，可确定获得了二氧化钛纳米棒阵列。The prepared titanium dioxide nanorod array was subjected to X-ray diffraction analysis. Figure 1 is the X-ray diffraction (XRD) pattern of the titanium dioxide nanorod array in Example 1 of the present invention. According to the diffraction angle corresponding to the peak of the pattern, it can be determined that Titanium dioxide nanorod array.
对制备得到的二氧化钛纳米棒阵列进行电镜扫描，图2是本发明实施例1中二氧化钛纳米棒阵列的扫描电镜（SEM）图，从图2中可以看到可看到均匀的纳米棒阵列结构。图3是本发明实施例1中二氧化钛纳米棒阵列的扫描透射电镜（TEM）图，从图3中可看到纳米棒的形状和光滑的侧壁。The prepared titanium dioxide nanorod array was scanned by an electron microscope. Figure 2 is a scanning electron microscope (SEM) image of the titanium dioxide nanorod array in Example 1 of the present invention. From Figure 2, it can be seen that a uniform nanorod array structure can be seen. Figure 3 is a scanning transmission electron microscope (TEM) image of the titanium dioxide nanorod array in Example 1 of the present invention. From Figure 3, the shape and smooth side walls of the nanorods can be seen.
（3）氮掺杂二氧化钛纳米片（N-TiO 2）悬浊液的制备与处理 (3) Preparation and processing of nitrogen-doped titanium dioxide nanosheets (N-TiO 2 ) suspension
采用粉末煅烧与离子交换法制备氮掺杂二氧化钛纳米片（N-TiO 2）悬浊液，利用粉末煅烧法将白色的钛酸铯（Cs 0.68Ti 1.83O 4）粉末在750℃的氨气氛围中煅烧2个小时，得到氮掺杂的Cs 0.68Ti 1.83O 4-xN x粉末，所得Cs 0.68Ti 1.83O 4-xN x粉末与H+在1 mol/L HCl溶液中进行3天离子交换，得到H 0.68Ti 1.83O 4-xN x(质子化状态)，利用配置好的浓度为0.2 mol/L的TABOH溶液使所得H 0.68Ti 1.83O 4-xN x分散于其中，在室温下振荡8天，摇匀处理得到分散均匀的氮掺杂二氧化钛纳米片（Ti 0.91O 2-xN x，简称N-TiO 2）悬浊液。 Nitrogen-doped titanium dioxide nanosheets (N-TiO 2 ) suspension was prepared using powder calcination and ion exchange methods. White cesium titanate (Cs 0.68 Ti 1.83 O 4 ) powder was heated in an ammonia atmosphere at 750°C using the powder calcination method. After medium calcination for 2 hours, nitrogen-doped Cs 0.68 Ti 1.83 O 4 - x N x powder was obtained. The obtained Cs 0.68 Ti 1.83 O 4-x N , obtain H 0.68 Ti 1.83 O 4-x N x (protonated state), and use the configured TABOH solution with a concentration of 0.2 mol/L to disperse the obtained H 0.68 Ti 1.83 O 4-x N x in it, at room temperature Shake for 8 days and shake evenly to obtain a uniformly dispersed suspension of nitrogen-doped titanium dioxide nanosheets (Ti 0.91 O 2-x N x , referred to as N-TiO 2 ).
（4）表面修饰二氧化钛纳米棒阵列(4) Surface-modified titanium dioxide nanorod array
使用负载量为100μL的N-TiO 2纳米片悬浊液对二氧化钛纳米棒阵列进行表面处理，然后自然室温干燥，退火处理后得到表面修饰的二氧化钛异质结光阳极样品1。其中，对得到的表面修饰的二氧化钛异质结光阳极样品1进行电镜扫描，如图4所示，图4是本发明实施例1中表面修饰的二氧化钛棒纳米棒阵列结构的扫描电镜（SEM）图。 The titanium dioxide nanorod array was surface treated using a N- TiO2 nanosheet suspension with a loading volume of 100 μL, and then dried naturally at room temperature. After annealing, a surface-modified titanium dioxide heterojunction photoanode sample 1 was obtained. Among them, the obtained surface-modified titanium dioxide heterojunction photoanode sample 1 was scanned by an electron microscope, as shown in Figure 4. Figure 4 is a scanning electron microscope (SEM) of the surface-modified titanium dioxide rod nanorod array structure in Example 1 of the present invention. picture.
实施例2Example 2
本实施例提供一种钛同源半导体异质结光阳极的制备方法，包括如下步骤：This embodiment provides a method for preparing a titanium homologous semiconductor heterojunction photoanode, which includes the following steps:
使用负载量为200μL的N-TiO 2纳米片悬浊液对二氧化钛纳米棒阵列进行表面处理，然后自然室温干燥，退火处理后得到表面修饰的二氧化钛异质结光阳极样品2。其余步骤与实施例1相同。其中，对得到的表面修饰的二氧化钛异质结光阳极样品2进行电镜扫描，如图5所示，图5是本发明实施例2中表面修饰氧化钛棒纳米棒阵列结构的扫描电镜（SEM）图。图6是本发明实施例2中表面修饰的二氧化钛棒纳米棒阵列结构的扫描透射电镜（TEM）图。 The titanium dioxide nanorod array was surface treated using a N- TiO2 nanosheet suspension with a loading capacity of 200 μL, and then dried naturally at room temperature. After annealing, a surface-modified titanium dioxide heterojunction photoanode sample 2 was obtained. The remaining steps are the same as in Example 1. Among them, the obtained surface-modified titanium dioxide heterojunction photoanode sample 2 was scanned by an electron microscope, as shown in Figure 5. Figure 5 is a scanning electron microscope (SEM) of the surface-modified titanium oxide rod nanorod array structure in Example 2 of the present invention. picture. Figure 6 is a scanning transmission electron microscope (TEM) image of the surface-modified titanium dioxide rod nanorod array structure in Example 2 of the present invention.
实施例3Example 3
本实施例提供一种钛同源半导体异质结光阳极的制备方法，包括如下步骤：This embodiment provides a method for preparing a titanium homologous semiconductor heterojunction photoanode, which includes the following steps:
使用负载量为400μL的N-TiO 2纳米片悬浊液对二氧化钛纳米棒阵列进行表面处理，然后自然室温干燥，退火处理后得到表面修饰的二氧化钛异质结光阳极样品3。其余步骤与实施例1相同。 The titanium dioxide nanorod array was surface treated using a N- TiO2 nanosheet suspension with a loading volume of 400 μL, and then dried naturally at room temperature. After annealing, a surface-modified titanium dioxide heterojunction photoanode sample 3 was obtained. The remaining steps are the same as in Example 1.
对实施例1、实施例2和实施例3中制备得到的样品1、样品2和样品3进行循环伏安扫描，而后对其进行光电催化性能测试。Sample 1, sample 2 and sample 3 prepared in Example 1, Example 2 and Example 3 were subjected to cyclic voltammetry scanning, and then their photoelectrocatalytic performance was tested.
首先对样品进行循环伏安法测试，排除实验的偶然性，使得样品的电解水性能趋于稳定，循环伏安法测试电压范围为-0.2 V到1.5 V (vs RHE)、扫描速度为50 m V/s、间隔电压为0.001 V，循环20次。First, the sample was tested by cyclic voltammetry to eliminate the contingency of the experiment and make the water electrolysis performance of the sample tend to be stable. The cyclic voltammetry test voltage range is -0.2 V to 1.5 V (vs RHE), scan speed 50 m V/s, gap voltage 0.001 V, cycle 20 times.
其次，对样品分别进行光电化学性能测试，采用电化学工作站的Linear Sweep Voltammetry（LSV）模式对样品进行光电催化水分解反应的测试。Secondly, the photoelectrochemical properties of the samples were tested separately, using the Linear electrochemical workstation. Sweep Voltammetry (LSV) mode is used to test the photoelectrocatalytic water splitting reaction of the sample.
具体地，将样品中的FTO切成2cm × 1cm 大小，利用电化学工作站，采用三电极***对样品进行光电化学性能测试，进行光电催化水分解，其中电化学测试电解液为0.05M的Na 2SO 4溶液。 Specifically, the FTO in the sample was cut into 2cm × 1cm size, and an electrochemical workstation was used to test the photoelectrochemical performance of the sample using a three-electrode system to conduct photoelectrocatalytic water splitting. The electrolyte for the electrochemical test was 0.05M Na 2 SO4 solution.
如图7所示，图7是本发明实施例提供的不同负载量的N-TiO 2修饰的二氧化钛纳米棒阵列的光电催化性能（LSV）图，从图7中可以看出负载200μL N-TiO 2对应的样品具备最好的光电催化性能。 As shown in Figure 7, Figure 7 is a photoelectrocatalytic performance (LSV) diagram of N- TiO2- modified titanium dioxide nanorod arrays with different loading amounts provided by embodiments of the present invention. It can be seen from Figure 7 that 200 μL N-TiO is loaded The sample corresponding to 2 has the best photoelectrocatalytic performance.
综上所述，本发明实施例提供的一种钛同源半导体异质结光阳极及其制备方法，在导电基底上生长二氧化钛纳米棒阵列，接着对二氧化钛纳米棒阵列进行高温退火处理，使用非金属掺杂相的二氧化钛纳米片制备非金属掺杂相的二氧化钛纳米片悬浊液，利用非金属掺杂相的二氧化钛纳米片悬浊液修饰高温退火处理后的二氧化钛纳米棒阵列，使得二氧化钛纳米棒阵列形成钛同源异质结，最后对修饰后的二氧化钛纳米棒阵列进行高温退火处理，获得钛同源半导体异质结光阳极，本发明实施例提供的制备方法，通过构建钛同源异质结，增加二氧化钛表面反应活性位点并增强电荷传输效率，从而提高其表面催化活性，实现高效全水分解，解决了二氧化钛光阳极水分解能力低的问题。In summary, the embodiments of the present invention provide a titanium homologous semiconductor heterojunction photoanode and a preparation method thereof. A titanium dioxide nanorod array is grown on a conductive substrate, and then the titanium dioxide nanorod array is subjected to high-temperature annealing treatment. The titanium dioxide nanosheets of the metal doped phase are used to prepare the titanium dioxide nanosheet suspension of the non-metal doped phase. The titanium dioxide nanosheet suspension of the non-metal doped phase is used to modify the titanium dioxide nanorod array after high temperature annealing to make the titanium dioxide nanorods. The array forms a titanium homologous heterojunction, and finally the modified titanium dioxide nanorod array is subjected to high-temperature annealing to obtain a titanium homologous semiconductor heterojunction photoanode. The preparation method provided by the embodiment of the present invention, by constructing a titanium homologous heterojunction The junction increases the reactive active sites on the titanium dioxide surface and enhances the charge transfer efficiency, thereby improving its surface catalytic activity, achieving efficient total water splitting, and solving the problem of low water decomposition ability of the titanium dioxide photoanode.
以上所述仅是本申请的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。The above are only specific embodiments of the present application. It should be noted that those of ordinary skill in the technical field can also make several improvements and modifications without departing from the principles of the present application. These improvements and modifications can also be made. should be regarded as the scope of protection of this application.

Claims (10)

  1. 一种钛同源半导体异质结光阳极，其特征在于，所述钛同源半导体异质结光阳极包括导电基底以及生长在导电基底上的二氧化钛纳米棒阵列，所述二氧化钛纳米棒阵列上修饰有非金属掺杂相的二氧化钛纳米片，所述二氧化钛纳米棒阵列与所述非金属掺杂相的二氧化钛纳米片形成钛同源异质结。A titanium homologous semiconductor heterojunction photoanode, characterized in that the titanium homologous semiconductor heterojunction photoanode includes a conductive substrate and a titanium dioxide nanorod array grown on the conductive substrate, and the titanium dioxide nanorod array is modified There are titanium dioxide nanosheets with a non-metal doping phase, and the titanium dioxide nanorod array and the titanium dioxide nanosheets with a non-metal doping phase form a titanium homologous heterojunction.
  2. 根据权利要求1所述的钛同源半导体异质结光阳极，其特征在于，所述非金属掺杂相的二氧化钛纳米片为氮掺杂二氧化钛纳米片。The titanium homologous semiconductor heterojunction photoanode according to claim 1, wherein the titanium dioxide nanosheets of the non-metal doped phase are nitrogen-doped titanium dioxide nanosheets.
  3. 一种如权利要求1所述的钛同源半导体异质结光阳极的制备方法，其特征在于，所述制备方法包括以下步骤：A method for preparing a titanium homologous semiconductor heterojunction photoanode as claimed in claim 1, characterized in that the preparation method includes the following steps:
    S1、在导电基底上生长二氧化钛纳米棒阵列；S1. Growth of titanium dioxide nanorod arrays on conductive substrates;
    S2、将步骤S1中得到的二氧化钛纳米棒阵列进行高温退火处理；S2. Perform high-temperature annealing treatment on the titanium dioxide nanorod array obtained in step S1;
    S3、使用非金属掺杂相的二氧化钛纳米片制备非金属掺杂相的二氧化钛纳米片悬浊液；S3. Use titanium dioxide nanosheets of non-metal doped phase to prepare titanium dioxide nanosheet suspension of non-metal doped phase;
    S4、使用非金属掺杂相的二氧化钛纳米片悬浊液对步骤S2中得到的二氧化钛纳米棒阵列进行表面修饰，使二氧化钛纳米棒阵列形成钛同源异质结，得到基于二氧化钛的纳米异质结；S4. Use the titanium dioxide nanosheet suspension of the non-metal doped phase to perform surface modification on the titanium dioxide nanorod array obtained in step S2, so that the titanium dioxide nanorod array forms a titanium homologous heterojunction to obtain a titanium dioxide-based nanoheterojunction. ;
    S5、将基于二氧化钛的纳米异质结进行高温退火处理，获得钛同源半导体异质结光阳极。S5. Perform high-temperature annealing treatment on the titanium dioxide-based nanoheterojunction to obtain a titanium homologous semiconductor heterojunction photoanode.
  4. 根据权利要求3所述的钛同源半导体异质结光阳极的制备方法，其特征在于，所述步骤S1中在导电基底上生长二氧化钛纳米棒阵列包括：将导电基底置于超声处理后的异丙氧钛(IV)和稀盐酸的混合溶液中，高温处理含有导电基底的异丙氧钛(IV)和稀盐酸的混合溶液，以在导电基底上生长二氧化钛纳米棒阵列。The method for preparing a titanium homologous semiconductor heterojunction photoanode according to claim 3, wherein growing the titanium dioxide nanorod array on the conductive substrate in step S1 includes: placing the conductive substrate on a different surface after ultrasonic treatment. A mixed solution of titanium (IV) isopropoxide and dilute hydrochloric acid containing a conductive substrate is treated at high temperature to grow a titanium dioxide nanorod array on the conductive substrate.
  5. 根据权利要求4所述的钛同源半导体异质结光阳极的制备方法，其特征在于，所述异丙氧钛(IV)与所述稀盐酸的体积比为1:50~80。The method for preparing a titanium homologous semiconductor heterojunction photoanode according to claim 4, wherein the volume ratio of the titanium isopropoxide (IV) to the dilute hydrochloric acid is 1:50~80.
  6. 根据权利要求4所述的钛同源半导体异质结光阳极的制备方法，其特征在于，所述稀盐酸的质量分数为18% ~19%。The method for preparing a titanium homologous semiconductor heterojunction photoanode according to claim 4, wherein the mass fraction of the dilute hydrochloric acid is 18% to 19%.
  7. 根据权利要求4所述的钛同源半导体异质结光阳极的制备方法，其特征在于，高温处理含有导电基底的异丙氧钛(IV)和稀盐酸的混合溶液的温度为230℃~300℃，处理时间为2h ~ 4h。The method for preparing a titanium homologous semiconductor heterojunction photoanode according to claim 4, characterized in that the temperature of the mixed solution of high-temperature treatment of titanium isopropoxide (IV) containing the conductive substrate and dilute hydrochloric acid is 230° C. to 300° C. ℃, treatment time is 2h ~4h.
  8. 根据权利要求3所述的钛同源半导体异质结光阳极的制备方法，其特征在于，所述步骤S2中对二氧化钛纳米棒阵列进行高温退火处理的温度为300℃~500℃，处理时间为1h ~3h。The method for preparing a titanium homologous semiconductor heterojunction photoanode according to claim 3, characterized in that in step S2, the temperature at which the titanium dioxide nanorod array is subjected to high-temperature annealing treatment is 300°C to 500°C, and the treatment time is 1h ~3h.
  9. 根据权利要求3所述的钛同源半导体异质结光阳极的制备方法，其特征在于，所述步骤S3中非金属掺杂相的二氧化钛纳米片悬浊液的制备包括：在氨气氛围中，高温煅烧钛酸铯（Cs 0.68Ti 1.83O 4）粉末，得到氮掺杂的Cs 0.68Ti 1.83O 4-xN x粉末，将Cs 0.68Ti 1.83O 4-xN x粉末置于HCl溶液中与H +发生离子交换，得到H 0.68Ti 1.83O 4-xN x，将H 0.68Ti 1.83O 4-xN x分散在四丁基氢氧化铵溶液中并摇匀处理，得到氮掺杂二氧化钛纳米片（N-TiO 2）悬浊液。 The method for preparing a titanium homologous semiconductor heterojunction photoanode according to claim 3, wherein the preparation of the titanium dioxide nanosheet suspension of the non-metal doped phase in step S3 includes: in an ammonia atmosphere , calcining cesium titanate ( Cs 0.68 Ti 1.83 O 4 ) powder at high temperature to obtain nitrogen - doped Cs 0.68 Ti 1.83 O 4 -x N Ion exchange occurs with H + to obtain H 0.68 Ti 1.83 O 4-x N x . Disperse H 0.68 Ti 1.83 O 4-x N (N-TiO 2 ) suspension.
  10. 根据权利要求3所述的钛同源半导体异质结光阳极的制备方法，其特征在于，所述步骤S5中对基于二氧化钛的纳米异质结进行高温退火处理包括：氩气氛围下，高温退火处理基于二氧化钛的纳米异质结，其中，处理温度为300℃~500℃，处理时间为1h~3h。The preparation method of titanium homologous semiconductor heterojunction photoanode according to claim 3, characterized in that, in step S5, performing high-temperature annealing treatment on the titanium dioxide-based nano-heterojunction includes: high-temperature annealing in an argon atmosphere The nanoheterojunction based on titanium dioxide is processed, wherein the processing temperature is 300°C~500°C and the processing time is 1h~3h.
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