WO2023169017A1 - 一种氧化锌纳米棒阵列光阳极及其制备方法 - Google Patents

一种氧化锌纳米棒阵列光阳极及其制备方法 Download PDF

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WO2023169017A1
WO2023169017A1 PCT/CN2022/136986 CN2022136986W WO2023169017A1 WO 2023169017 A1 WO2023169017 A1 WO 2023169017A1 CN 2022136986 W CN2022136986 W CN 2022136986W WO 2023169017 A1 WO2023169017 A1 WO 2023169017A1
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zinc oxide
oxide nanorod
nanorod array
photoanode
conductive substrate
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马明
汪毅
李蒋
崔传艺
宁德
李伟民
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Shenzhen Institute of Advanced Technology of CAS
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • 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
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    • 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
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    • C25B1/04—Hydrogen or oxygen by electrolysis of water
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    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/087—Photocatalytic compound
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/216—ZnO
    • 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
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating

Definitions

  • the invention belongs to the technical field of photoelectrochemical water splitting, and in particular relates to a zinc oxide nanorod array photoanode and a preparation method thereof.
  • Oxygen evolution reaction (OER) catalysts such as metal oxyhydroxides (FeOOH, NiOOH, etc.) and hybrid metal oxides (FeNiOx), are currently widely used in PEC systems to promote the space between the photoanode and the electrolyte. hole transport, thereby improving water oxidation.
  • OER Oxygen evolution reaction
  • the introduction of the cocatalyst layer not only requires complex procedures, but also brings additional interfacial energy barriers between the photoanode and the cocatalyst.
  • the existing solution is to use defect engineering, that is, to generate oxygen vacancies on the oxide type photoanode through various surface modification methods, which can adjust the PEC performance and improve water oxidation.
  • Zinc oxide has a highly ordered crystal structure and a surface chemical state that is easy to modify.
  • the surface reactivity of zinc oxide is insufficient in the existing process of preparing zinc oxide photoanode materials, and zinc oxide itself has low catalytic efficiency. Therefore, it is necessary to carry out appropriate surface modification of zinc oxide to generate more active sites on the surface of zinc oxide, improve charge transport and transfer on the surface of zinc oxide, and thereby improve the efficiency of catalytic total water splitting.
  • the present invention provides a zinc oxide nanorod array photoanode and a preparation method thereof to solve the problem of insufficient surface reactivity and low catalytic efficiency of existing zinc oxide as a photoanode material. question.
  • the present invention provides a zinc oxide nanorod array photoanode, which includes a conductive substrate and a zinc oxide nanorod array grown on the conductive substrate.
  • the surface of the zinc oxide nanorod array has oxygen-rich vacancies.
  • Zinc oxide nanorods have a wire diameter of 50 nm ⁇ 500 nm, height 1 ⁇ m ⁇ 3 ⁇ m.
  • the present invention also provides a method for preparing the zinc oxide nanorod array photoanode as described above.
  • the preparation method includes the following steps:
  • step S20 Under an inert gas atmosphere, soak the zinc oxide nanorod array in step S10 in an electron solution to obtain a zinc oxide nanorod array photoanode with oxygen-rich vacancies.
  • the electron solution is prepared by dissolving Li metal in anhydrous ethylenediamine solvent to obtain the electron solution.
  • the concentration of Li metal in the anhydrous ethylenediamine solvent is: 0.1 M ⁇ 0.5M.
  • the soaking time in step S20 is 10s ⁇ 100s.
  • the growth method of the zinc oxide nanorod array in step S10 includes the following steps:
  • step S102 Place the ZnO seed crystal in step S101 into a mixed solution of Zn(NO 3 ) 2 and hexamethylenetetramine, heat and cool to obtain a zinc oxide nanorod array precursor;
  • step S103 Heat-treat the zinc oxide nanorod array precursor in step S102 to obtain a zinc oxide nanorod array.
  • the heat treatment temperature in step S101 and step S103 is 350°C ⁇ 450°C, and the heat treatment time is 1 h ⁇ 3 h.
  • the heating temperature in step S102 is 90°C to 100°C, and the heating time is 3h to 10h.
  • the substance concentration ratio of Zn(NO 3 ) 2 and hexamethylenetetramine is 1:1.
  • the conductive substrate is FTO glass.
  • the embodiments of the present invention provide a zinc oxide nanorod array photoanode and a preparation method thereof. Under an inert gas atmosphere, the zinc oxide surface is modified, and the zinc oxide nanorod array is immersed in an electron solution to obtain oxygen-rich vacancies. Zinc oxide nanorod array photoanode, the surface of the zinc oxide nanorod array rich in oxygen vacancies has more active sites, which can improve the charge transfer and transfer on the zinc oxide surface, thereby improving the catalytic total water splitting efficiency.
  • Figure 1 is a schematic diagram of the preparation method of the zinc oxide nanorod array photoanode provided by the implementation of the present invention
  • Figure 2 is an X-ray diffraction (XRD) pattern of the zinc oxide nanorod array structure in Example 1;
  • Figure 3 is a scanning electron microscope (SEM) image of the oxygen-rich vacancy zinc oxide nanorod array structure in Example 1;
  • Figure 4 is a high-resolution scanning transmission electron microscope (HR-TEM) image of the oxygen-rich vacancy zinc oxide nanorod array structure in Example 1;
  • FIG. 5 is a PEC test (LSV) diagram of the zinc oxide nanorod array in Embodiment 1;
  • Figure 6 is a PEC test (LSV) diagram of the zinc oxide nanorod array of Implementation 2;
  • Figure 7 is a PEC test (LSV) chart of the zinc oxide nanorod array of Embodiment 3.
  • Embodiments of the present invention provide a zinc oxide nanorod array photoanode, which includes a conductive substrate and a zinc oxide nanorod array grown on the conductive substrate.
  • the surface of the zinc oxide nanorod array has oxygen-rich vacancies, and the oxygen-rich vacancies are Zinc oxide nanorods have a wire diameter of 50 nm ⁇ 500 nm, height 1 ⁇ m ⁇ 3 ⁇ m.
  • Embodiments of the present invention also provide a method for preparing a zinc oxide nanorod array photoanode as described above.
  • Figure 1 is a schematic diagram of a method for preparing a zinc oxide nanorod array photoanode provided by the implementation of the present invention. As shown in Figure 1, The preparation method includes the following steps:
  • step S20 Under an inert gas atmosphere, soak the zinc oxide nanorod array in step S10 in an electron solution to obtain a zinc oxide nanorod array photoanode with oxygen-rich vacancies.
  • the zinc oxide nanorod array is soaked in an electron solution, and while ensuring that the structure of the nanorod array is not affected, oxygen species are introduced on the surface of the zinc oxide nanorod array to affect the zinc oxide nanorods.
  • the array is surface-modified to generate atomic defects on its surface, and finally a surface-modified zinc oxide nanorod array photoanode with oxygen-rich vacancies is obtained.
  • the zinc oxide surface is modified under an inert gas atmosphere, and the zinc oxide nanorod array is immersed in an electron solution to obtain zinc oxide with oxygen-rich vacancies.
  • Nanorod array photoanode the surface of the zinc oxide nanorod array rich in oxygen vacancies has more active sites, which can improve the charge transfer and transfer on the zinc oxide surface, thereby improving the catalytic total water splitting efficiency.
  • the electron solution is prepared by dissolving a metal in an anhydrous ethylenediamine solvent to obtain the electron solution.
  • the metal is lithium (Li) metal.
  • the concentration of Li metal in the anhydrous ethylenediamine solvent is: 0.1 M ⁇ 0.5M.
  • the soaking time in step S20 is 10s ⁇ 100s.
  • the growth method of the zinc oxide nanorod array in step S10 includes the following steps:
  • a zinc acetate ((CH 3 COO) 2 Zn) solution is spin-coated onto a conductive substrate and thermally annealed to obtain ZnO seed crystals, where the conductive substrate is a pretreated conductive substrate.
  • This implementation also provides a pretreatment method for conductive substrates, specifically as follows:
  • step S102 Place the ZnO seed crystal in step S101 into a mixed solution of Zn(NO 3 ) 2 and hexamethylenetetramine, heat and cool to obtain a zinc oxide nanorod array precursor.
  • the ZnO seed crystal is placed in the reactor liner containing a mixed solution of Zn(NO 3 ) 2 and hexamethylenetetramine. Finally, the reactor liner is placed in an oven, and the oven temperature is raised from room temperature. Heating to the heating temperature and cooling to room temperature, a zinc oxide nanorod array precursor was obtained.
  • step S103 Heat-treat the zinc oxide nanorod array precursor in step S102 to obtain a zinc oxide nanorod array.
  • the zinc oxide nanorod array precursor was washed multiple times with deionized water and dried at 60°C.
  • the dried zinc oxide nanorod array precursor was placed in a muffle furnace at 5
  • the zinc oxide nanorod array precursor is heat treated at a heating rate of °C/min from room temperature to the heat treatment temperature, and finally cooled to room temperature to obtain a zinc oxide nanorod array on the conductive substrate.
  • the heat treatment temperature in step S101 and step S103 is 350°C to 450°C, and the heat treatment time is 1 h to 3 h.
  • the heating temperature in step S102 is 90°C ⁇ 100°C, and the heating time is 3 h ⁇ 10h.
  • the substance concentration ratio of Zn(NO 3 ) 2 and hexamethylenetetramine is 1:1.
  • the conductive substrate is FTO glass.
  • This embodiment provides a zinc oxide nanorod array photoanode and a preparation method thereof.
  • the preparation method includes the following steps:
  • FTO glass as the substrate, with a size of 2 cm * 4 cm. Then pretreat the substrate, specifically: immerse the FTO glass in a mixed solution of acetone and absolute ethanol with a volume ratio of 1:1, and clean it ultrasonically for 20 minutes; then immerse the FTO glass in a solution with a volume ratio of 3:1. The glass was immersed in a mixed solution of hydrogen oxide and sulfuric acid for 10 minutes to enhance hydrophilicity; then the FTO glass was rinsed with absolute ethanol; and finally dried with nitrogen to obtain the pretreated FTO glass.
  • a 0.2 M zinc acetate ((CH 3 COO) 2 Zn) solution was spin-coated onto the pretreated FTO substrate and followed by thermal annealing at 400°C for 1 hour to prepare ZnO seeds.
  • the resulting ZnO seeds were transferred to a solution containing 40 mL of 0.02 M Zn(NO 3 ) 2 and 0.02 M hexamethylenetetramine (HMT) mixed solution were placed in the inner tank of the reactor (capacity: 50 mL), placed in an oven, and raised from room temperature to 95°C for 6 hours, cooled to room temperature to obtain the zinc oxide nanorod precursor, and then placed the obtained zinc oxide nanorod precursor in a muffle furnace, raised it from room temperature to 400°C at a heating rate of 5°C/min and kept it warm for 1 hours, and then naturally cooled to room temperature to obtain a zinc oxide nanorod array.
  • HMT hexamethylenetetramine
  • a solution prepared by dissolving 0.02g Li metal in 15ml anhydrous ethylenediamine solvent was used as an electron solution.
  • the zinc oxide nanorod array was post-processed using the electron solution.
  • the processing times were 10s, 20s, At 40s and 100s, surface oxygen species are introduced for surface modification to generate atomic defects on the surface, and finally a zinc oxide nanorod array with oxygen-rich vacancies on the surface is obtained.
  • Figure 2 is an X-ray diffraction (XRD) pattern of the zinc oxide nanorod array with oxygen-rich vacancies on the surface prepared in this embodiment. According to the diffraction angle corresponding to the peak in the XRD pattern, it can be determined that the zinc oxide nanorods have been prepared. array. Figure 2 also shows the spectrum of the zinc oxide nanorod array without surface modification (i.e., 0.02M-ZnO-0s).
  • Figure 3 is a scanning electron microscope (SEM) image of the zinc oxide nanorod array with oxygen-rich vacancies on the surface prepared in this embodiment, wherein (a1 ⁇ a3) in Figure 3 are zinc oxide nanorods with a surface modification treatment time of 10 seconds.
  • Figure 4 is a high-resolution scanning transmission electron microscope (HR-TEM) image of the zinc oxide nanorod array with oxygen-rich vacancies on the surface prepared in this example, where (a) in Figure 4 is the surface modification treatment time of 10 seconds HR-TEM image of the zinc oxide nanorod array; (b) in Figure 4 is the HR-TEM image of the zinc oxide nanorod array with a surface modification treatment time of 20 s; (c) in Figure 4 is a surface modification treatment time of 40 s HR-TEM image of the zinc oxide nanorod array; (d) in Figure 4 is the HR-TEM image of the zinc oxide nanorod array with a surface modification treatment time of 100 s. It can be seen from the HR-TEM image in Figure 4 that the modified zinc oxide nanorod array structure has a 0.26 direction pointing to the (002) plane. nm clear lattice fringes.
  • HR-TEM high-resolution scanning transmission electron microscope
  • This embodiment provides a zinc oxide nanorod array photoanode and a preparation method thereof.
  • the preparation method includes the following steps:
  • a 0.2 M zinc acetate ((CH 3 COO) 2 Zn) solution was spin-coated onto the treated FTO substrate and accompanied by thermal annealing at 400°C for 1 hour to prepare ZnO seeds.
  • the resulting ZnO seeds were transferred to a solution containing 40 mL of 0.01 M Zn. (NO 3 ) 2 and 0.01M hexamethylenetetramine (HMT) mixed solution in the inner tank of the reactor (capacity is 50 mL), place it in an oven, and raise it from room temperature to 95°C for 6 hours.
  • NO 3 0.01 M Zn.
  • HMT hexamethylenetetramine
  • This embodiment provides a zinc oxide nanorod array photoanode and a preparation method thereof.
  • the preparation method includes the following steps:
  • a 0.2 M zinc acetate ((CH 3 COO) 2 Zn) solution was spin-coated onto the treated FTO substrate and accompanied by thermal annealing at 400°C for 1 hour to prepare ZnO seeds.
  • the resulting ZnO seeds were transferred to a solution containing 40 mL of 0.03M Zn(NO 3 ) 2 and 0.03M hexamethylenetetramine (HMT) mixed solution are placed in the inner tank of the reactor (capacity is 50 mL), placed in an oven, and raised from room temperature to 95°C for 6 hours, cooled to room temperature to obtain the zinc oxide nanorod precursor, and then placed the obtained zinc oxide nanorod precursor in a muffle furnace, raised it from room temperature to 400°C at a heating rate of 5°C/min and kept it warm for 1 hours, and then naturally cooled to room temperature to obtain a zinc oxide nanorod array.
  • HMT hexamethylenetetramine
  • Electrochemical tests were performed on the zinc oxide nanorod arrays with oxygen-rich vacancies obtained in Example 1, Example 2 and Example 3 respectively, and the obtained surface-modified zinc oxide nanorod arrays were tested using an electrochemical workstation and a three-electrode system. Electrochemical PEC test, the specific test methods are as follows:
  • silver paste was used to enhance the conductivity between the fixture and the FTO glass.
  • the working area of the working electrode was controlled by an aperture of 1cm ⁇ 1cm.
  • a silicon reference cell was used to calibrate the solar simulator to stabilize the test conditions and reduce external interference. factors interfere.
  • Figure 5 is a PEC test (LSV) chart of the zinc oxide nanorod array of Example 1;
  • Figure 6 is a PEC test (LSV) chart of the zinc oxide nanorod array of Example 2;
  • Figure 7 is a zinc oxide nanorod array of Example 3 PEC test (LSV) plot of rod array.
  • LSV PEC test
  • the embodiments of the present invention provide a zinc oxide nanorod array photoanode and a preparation method thereof. Under an inert gas atmosphere, the zinc oxide surface is modified, and the zinc oxide nanorod array is immersed in an electron solution to obtain a zinc oxide nanorod array with rich electronic properties.
  • the zinc oxide nanorod array photoanode with oxygen vacancies and the zinc oxide nanorod array with rich oxygen vacancies have more active sites on the surface, which can improve the charge transfer and transfer on the zinc oxide surface, thereby improving the catalytic total water splitting efficiency.

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Abstract

一种氧化锌纳米棒阵列光阳极，包括导电基底和生长在导电基底上的氧化锌纳米棒阵列，所述氧化锌纳米棒阵列表面具有富氧空位，所述氧化锌纳米棒线径为50nm～500nm，高度为1μm～3μm。所述氧化锌纳米棒阵列光阳极的制备方法包括如下步骤：在导电基底上生长氧化锌纳米棒阵列；在惰性气体氛围下，将氧化锌纳米棒阵列浸泡在电子溶液中，获得具有富氧空位的氧化锌纳米棒阵列光阳极。具有富氧空位的氧化锌纳米棒阵列的表面具有更多的活性位点，可以提高氧化锌表面电荷传输转移，进而提高催化全分解水效率。

Description

一种氧化锌纳米棒阵列光阳极及其制备方法 技术领域
本发明属于光电化学水分解技术领域，尤其涉及一种氧化锌纳米棒阵列光阳极及其制备方法。
 背景技术
由于全球能源需求的爆炸式增长和环境污染，以可再生能源生产的氢已成为最重要的替代燃料之一。在各种技术中，光电化学（PEC）水分解在制氢方面引起了全世界的广泛关注。然而，光阳极缓慢的表面水氧化反应动力学伴随着电荷的复合，在很大程度上限制了整体水分解的效率。因此，半导体-电解质界面高效的电荷迁移至关重要。
析氧反应 (OER) 催化剂，例如金属羟基氧化物（FeOOH、NiOOH等）和杂化金属氧化物（FeNiOx），目前在PEC系统中得到了广泛的应用，可以促进光阳极和电解质之间的空穴传输，从而改善水氧化。然而，助催化剂层的引入不仅需要复杂的程序，而且还会在光阳极和助催化剂间带来额外的界面能垒。为此，现有的解决方式是采用缺陷工程，即通过各种表面改性的方式在氧化物类型的光阳极上产生氧空位，可以调节PEC性能，提升水氧化。
氧化锌具有高度有序的晶体结构，又具有易于修饰的表面化学状态。在使用氧化锌作为光阳极材料时，现有的制备氧化锌光阳极材料过程中氧化锌的表面反应活性存在不足，且氧化锌本身在催化效率方面较低。因此，需要对氧化锌进行适当的表面改性使氧化锌表面产生更多的活性位点，提高氧化锌表面电荷传输转移，进而提高催化全分解水效率。
 技术问题
鉴于现有技术存在的不足，本发明提供了一种氧化锌纳米棒阵列光阳极及其制备方法，以解决现有的氧化锌作为光阳极材料时表面反应活性存在不足，催化效率方面较低的问题。
 技术解决方案
为了解决以上问题，本发明提供了一种氧化锌纳米棒阵列光阳极，包括导电基底和生长在导电基底上的氧化锌纳米棒阵列，所述氧化锌纳米棒阵列表面具有富氧空位，所述氧化锌纳米棒线径为50 nm ~500 nm，高度为1μm ~3μm。
本发明还提供了一种如上述所述的氧化锌纳米棒阵列光阳极的制备方法，所述制备方法包括如下步骤：
S10、在导电基底上生长氧化锌纳米棒阵列；
S20、在惰性气体氛围下，将所述步骤S10中的氧化锌纳米棒阵列浸泡在电子溶液中，获得具有富氧空位的氧化锌纳米棒阵列光阳极。
优选地，所述电子溶液的制备方法为：将Li金属溶解在无水乙二胺溶剂中获得所述电子溶液。
优选地，所述Li金属在所述无水乙二胺溶剂中的浓度为：0.1 M ~0.5 M。
优选地，所述步骤S20中浸泡时间为10s ~100s。
优选地，所述步骤S10中氧化锌纳米棒阵列的生长方法包括如下步骤：
S101、在导电基底上旋涂醋酸锌并热处理获得ZnO晶种；
S102、将所述步骤S101中的ZnO晶种置于Zn(NO 3) 2和六亚甲基四胺的混合溶液中加热并冷却获得氧化锌纳米棒阵列前驱体；
S103、对所述步骤S102中的所述氧化锌纳米棒阵列前驱体进行热处理获得氧化锌纳米棒阵列。
优选地，所述步骤S101和所述步骤S103中热处理温度为350℃~450℃，热处理时间为1 h ~3 h。
优选地，所述步骤S102中加热温度为90℃~100℃，加热时间为3h ~10h。
优选地，所述Zn(NO 3) 2和所述六亚甲基四胺的物质的量浓度比为1:1。
优选地，所述导电基底为FTO玻璃。
 有益效果
本发明实施例提供的一种氧化锌纳米棒阵列光阳极及其制备方法，在惰性气体氛围下，对氧化锌表面进行改性，将氧化锌纳米棒阵列浸泡在电子溶液中获得具有富氧空位的氧化锌纳米棒阵列光阳极，富氧空位的氧化锌纳米棒阵列表面具有更多的活性位点，可以提高氧化锌表面电荷传输转移，进而提高催化全分解水效率。
 附图说明
图1是本发明实施提供的氧化锌纳米棒阵列光阳极的制备方法示意图；
图2为实施例1中氧化锌纳米棒阵列结构的X射线衍射（XRD）图；
图3是实施例1中富氧空位氧化锌纳米棒阵列结构的电镜扫描（SEM）图；
图4是实施例1中富氧空位氧化锌纳米棒阵列结构的高分辨率扫描透射电镜（HR-TEM）图；
图5是实施1的氧化锌纳米棒阵列的PEC测试（LSV）图；
图6是实施2的氧化锌纳米棒阵列的PEC测试（LSV）图；
图7是实施3的氧化锌纳米棒阵列的PEC测试（LSV）图。
 本发明的实施方式
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。
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。
本发明实施例提供一种氧化锌纳米棒阵列光阳极，包括导电基底和生长在导电基底上的氧化锌纳米棒阵列，所述氧化锌纳米棒阵列表面具有富氧空位，所述富氧空位的氧化锌纳米棒线径为50 nm ~500 nm，高度为1μm ~3μm。
本发明实施例还提供一种如上述所述氧化锌纳米棒阵列光阳极的制备方法，图1是本发明实施提供的氧化锌纳米棒阵列光阳极的制备方法示意图，如图1所示，所述制备方法包括如下步骤：
S10、在导电基底上生长氧化锌纳米棒阵列。
S20、在惰性气体氛围下，将所述步骤S10中的氧化锌纳米棒阵列浸泡在电子溶液中，获得具有富氧空位的氧化锌纳米棒阵列光阳极。
具体地，在惰性气体的氛围下，利用电子溶液对氧化锌纳米棒阵列进行浸泡，在保证纳米棒阵列结构不受影响的情况下，在氧化锌纳米棒阵列表面引入氧物种对氧化锌纳米棒阵列进行表面修饰，使其表面产生原子缺陷，最后得到表面修饰的具有富氧空位的氧化锌纳米棒阵列光阳极。
以上实施例提供的氧化锌纳米棒阵列光阳极及其制备方法，在惰性气体氛围下，对氧化锌表面进行改性，将氧化锌纳米棒阵列浸泡在电子溶液中获得具有富氧空位的氧化锌纳米棒阵列光阳极，富氧空位的氧化锌纳米棒阵列表面具有更多的活性位点，可以提高氧化锌表面电荷传输转移，进而提高催化全分解水效率。
在优选的方案中，所述电子溶液的制备方法为：将金属溶解在无水乙二胺溶剂中获得所述电子溶液，具体地，所述金属采用锂（Li）金属。
在优选的方案中，所述Li金属在所述无水乙二胺溶剂中的浓度为：0.1 M ~0.5 M。
在优选的方案中，所述步骤S20中浸泡时间为10s ~100s。
在优选的方案中，所述步骤S10中氧化锌纳米棒阵列的生长方法包括如下步骤：
S101、在导电基底上旋涂醋酸锌并热处理获得ZnO晶种。
具体地，将醋酸锌（(CH 3COO) 2Zn）溶液旋涂到导电基底上并热退火处理获得ZnO晶种，其中导电基底为预处理后的导电基底。
本实施还提供一种导电基底的预处理方法，具体如下：
将导电基底浸于丙酮和无水乙醇混合溶液中，超声清洗20min~60min，其中丙酮和无水乙醇的体积比为1:1；再将导电基底浸于过氧化氢和硫酸混合溶液中10min~30min，增强亲水性，其中过氧化氢和硫酸混合溶液的体积比为3:1；接着将导电基底用无水乙醇冲洗，最后利用氮气进行干燥处理获得预处理后的导电基底。
S102、将所述步骤S101中的ZnO晶种置于Zn(NO 3) 2和六亚甲基四胺的混合溶液中加热并冷却获得氧化锌纳米棒阵列前驱体。
具体地，将ZnO晶种置于含有Zn(NO 3) 2和六亚甲基四胺混合溶液的反应釜内胆中，最后将反应釜内胆置于烘箱中，将烤箱温度从室温升至加热温度加热，冷却至室温后获得得到氧化锌纳米棒阵列前驱体。
S103、对所述步骤S102中的所述氧化锌纳米棒阵列前驱体进行热处理获得氧化锌纳米棒阵列。
具体地，用去离子水对氧化锌纳米棒阵列前驱体进行多次清洗，并在60℃下进行干燥处理，将干燥处理后的氧化锌纳米棒阵列前驱体置于马弗炉中，以5℃/min的升温速率从室温升至热处理的温度对氧化锌纳米棒阵列前驱体进行热处理，最后冷却至室温，可在导电基底上得到氧化锌纳米棒阵列。
在优选的方案中，所述步骤S101和所述步骤S103中热处理温度为350℃~450℃，热处理时间为1 h ~3 h。
在优选的方案中，所述步骤S102中加热温度为90℃~100℃，加热时间为3 h ~10h。
在优选的方案中，所述Zn(NO 3) 2和所述六亚甲基四胺的物质的量浓度比为1:1。
在优选的方案中，所述导电基底为FTO玻璃。
实施例1
本实施例提供一种所述氧化锌纳米棒阵列光阳极及其制备方法，所述制备方法包括如下步骤：
（1）基底的选择及预处理。
选择FTO玻璃为基底，大小为2 cm * 4 cm。然后对基底进行预处理，具体为：将FTO玻璃浸于体积比为1:1的丙酮和无水乙醇混合溶液中，超声清洗20分钟；再将FTO玻璃浸于体积比为3:1的过氧化氢和硫酸混合溶液中10分钟，增强亲水性；接着将FTO玻璃用无水乙醇冲洗；最后利用氮气进行干燥处理，得到预处理后的FTO玻璃。
（2）氧化锌纳米棒阵列的制备。
首先，将0.2 M醋酸锌（(CH 3COO) 2Zn）溶液旋涂到预处理后的FTO 基底上并伴随400℃热退火1小时制备ZnO晶种，所得ZnO晶种转移至含有40mL 0.02 M Zn(NO 3­) 2和0.02 M六亚甲基四胺（HMT）混合溶液的反应釜内胆（容量为50 mL）中，将其置于烘箱中，从室温升至95℃保持6个小时，冷却至室温，得到氧化锌纳米棒的前驱体，而后将得到的氧化锌纳米棒前驱体置于马弗炉中，以5℃/min的升温速率从室温升至400℃并保温1小时，自然冷却至室温得到氧化锌纳米棒阵列。
（3）氧化锌纳米棒阵列的表面修饰。
通过将0.02g Li金属溶解在15ml无水乙二胺溶剂中制备的溶液作为电子溶液，在惰性气体的氛围下，利用电子溶液对氧化锌纳米棒阵列进行后处理，处理时间为10s、20s、40s和100s，引入表面氧物种进行表面修饰，使其表面产生原子缺陷，最后得到表面具有富氧空位的氧化锌纳米棒阵列。
图2为本实施例制备得到的表面具有富氧空位的氧化锌纳米棒阵列的X射线衍射（XRD）图，根据XRD图中的图谱峰对应的衍射角度，可确定制备获得了氧化锌纳米棒阵列。图2中还示出了没有进行表面修饰的氧化锌纳米棒阵列的图谱（即0.02M-ZnO-0s）。
图3是本实施例制备得到的表面具有富氧空位的氧化锌纳米棒阵列的电镜扫描（SEM）图，其中，图3中的（a1~ a3）是表面修饰处理时间10s的氧化锌纳米棒阵列的SEM图；图3中的（b1~ b3）是表面修饰处理时间20s的氧化锌纳米棒阵列的SEM图；图3中的（c1~ c3）是表面修饰处理时间40s的氧化锌纳米棒阵列的SEM图；图3中的（d1~ d3）是表面修饰处理时间100s的氧化锌纳米棒阵列的SEM图。从图3的SEM图中可以看出，本实施例制备得到了均匀的氧化锌纳米棒阵列结构。
图4是本实施例制备得到的表面具有富氧空位的氧化锌纳米棒阵列的高分辨率扫描透射电镜（HR-TEM）图，其中，图4中的（a）是表面修饰处理时间10s的氧化锌纳米棒阵列的HR-TEM图；图4中的（b）是表面修饰处理时间20s的氧化锌纳米棒阵列的HR-TEM图；图4中的（c）是表面修饰处理时间40s的氧化锌纳米棒阵列的HR-TEM图；图4中的（d）是表面修饰处理时间100s的氧化锌纳米棒阵列的HR-TEM图。从图4的HR-TEM图可以看到，修饰后的氧化锌纳米棒阵列结构中具有指向（002）平面的 0.26 nm 清晰晶格条纹。
实施例2
本实施例提供一种所述氧化锌纳米棒阵列光阳极及其制备方法，所述制备方法包括如下步骤：
（1）基底的选择及预处理。选择FTO玻璃为基底，其预处理方法与实施例1相同。
（2）氧化锌纳米棒阵列的制备。
首先，将0.2 M醋酸锌（(CH 3COO) 2Zn）溶液旋涂到处理后的FTO 基底上并伴随400℃热退火1小时制备ZnO晶种，所得ZnO晶种转移至含有40mL 0.01M Zn(NO 3) 2和0.01M六亚甲基四胺（HMT）混合溶液的反应釜内胆（容量为50 mL）中，将其置于烘箱中，从室温升至95℃保持6个小时，冷却至室温，得到氧化锌纳米棒的前驱体，而后将得到的氧化锌纳米棒前驱体置于马弗炉中，以5℃/min的升温速率从室温升至400℃并保温1小时，自然冷却至室温得到氧化锌纳米棒阵列。
（3）氧化锌纳米片棒阵列的表面修饰。采用与实施例1相同的表面修饰方法获得具有富氧空位的氧化锌纳米棒阵列。
实施例3
本实施例提供一种所述氧化锌纳米棒阵列光阳极及其制备方法，所述制备方法包括如下步骤：
（1）基底的选择及预处理。选择FTO玻璃为基底，其预处理方法与实施例1相同。
（2）氧化锌纳米棒阵列的制备。
首先，将0.2 M醋酸锌（(CH 3COO) 2Zn）溶液旋涂到处理后的FTO基底上并伴随400℃热退火1小时制备ZnO晶种，所得ZnO晶种转移至含有40 mL 0.03M Zn(NO 3) 2和0.03M六亚甲基四胺（HMT）混合溶液的反应釜内胆（容量为50 mL）中，将其置于烘箱中，从室温升至95℃保持6个小时，冷却至室温，得到氧化锌纳米棒的前驱体，而后将得到的氧化锌纳米棒前驱体置于马弗炉中，以5℃/min的升温速率从室温升至400℃并保温1小时，自然冷却至室温得到氧化锌纳米棒阵列。
（3）氧化锌纳米片棒阵列的表面修饰。采用与实施例1相同的表面修饰方法获得具有富氧空位的氧化锌纳米棒阵列。
分别对实施例1、实施例2和实施例3得到的具有富氧空位的氧化锌纳米棒阵列进行电化学测试，利用电化学工作站，采用三电极系统对所得表面修饰的氧化锌纳米棒阵列进行电化学PEC测试，具体测试方法如下：
（1）使用无水乙醇和去离子水多次清洗待测的氧化锌纳米棒阵列，将清洗后的氧化锌纳米棒阵列在60℃下进行干燥。
（2）利用电化学工作站中的LSV模式，采用三电极系统对清洗后的氧化锌纳米棒阵列进行光电化学测试，其中，使用0.5 M Na 2SO 4溶液（pH缓冲至7）作为电解液，选用Pt箔作为电极，选用Ag/AgCl（3 M NaCl）作为参比电极。
在进行测试之前，使用银膏来增强夹具和 FTO 玻璃之间的导电性，工作电极的工作面积由1cm×1cm大小的孔径控制，使用硅参考电池校准太阳能模拟器，使测试条件稳定，减少外因素干扰。
图5是实施例1的氧化锌纳米棒阵列的PEC测试（LSV）图；图6是实施例2的氧化锌纳米棒阵列的PEC测试（LSV）图；图7是实施例3的氧化锌纳米棒阵列的PEC测试（LSV）图。根据图5、图6和图7可看出，使用电子溶液浸泡氧化锌纳米棒阵列可使得氧化锌纳米棒阵列产生更高的光电流，电子溶液对氧化锌纳米棒阵列进行浸泡处理的优选时间为10s ~100s。
综上所述，本发明实施例提供氧化锌纳米棒阵列光阳极及其制备方法，在惰性气体氛围下，对氧化锌表面进行改性，将氧化锌纳米棒阵列浸泡在电子溶液中获得具有富氧空位的氧化锌纳米棒阵列光阳极，富氧空位的氧化锌纳米棒阵列表面具有更多的活性位点，可以提高氧化锌表面电荷传输转移，进而提高催化全分解水效率。
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。

Claims (10)

  1. 一种氧化锌纳米棒阵列光阳极，包括导电基底和生长在导电基底上的氧化锌纳米棒阵列，其特征在于，所述氧化锌纳米棒阵列表面具有富氧空位，所述氧化锌纳米棒线径为50 nm ~500 nm，高度为1μm~3μm。
  2. 一种如权利要求1所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述制备方法包括如下步骤：
    S10、在导电基底上生长氧化锌纳米棒阵列；
    S20、在惰性气体氛围下，将所述步骤S10中的氧化锌纳米棒阵列浸泡在电子溶液中，获得具有富氧空位的氧化锌纳米棒阵列光阳极。
  3. 根据权利要求2所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述电子溶液的制备方法为：将Li金属溶解在无水乙二胺溶剂中获得所述电子溶液。
  4. 根据权利要求3所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述Li金属在无水乙二胺中的浓度为：0.1 M~0.5 M。
  5. 根据权利要求2所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述步骤S20中浸泡时间为10s ~100s。
  6. 根据权利要求2所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述步骤S10中氧化锌纳米棒阵列的生长方法包括如下步骤：
    S101、在导电基底上旋涂醋酸锌并热处理获得ZnO晶种；
    S102、将所述步骤S101中的ZnO晶种置于Zn(NO 3) 2和六亚甲基四胺的混合溶液中加热并冷却获得氧化锌纳米棒阵列前驱体；
    S103、对所述步骤S102中的所述氧化锌纳米棒阵列前驱体进行热处理获得氧化锌纳米棒阵列。
  7. 根据权利要求6所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述步骤S101和所述步骤S103中热处理温度为350℃~450℃，热处理时间为1h~3h。
  8. 根据权利要求6所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述步骤S102中加热温度为90℃~100℃，加热时间为3h ~10h。
  9. 根据权利要求6所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述Zn(NO 3) 2和所述六亚甲基四胺的物质的量浓度比为1:1。
  10. 根据权利要求2所述的氧化锌纳米棒阵列光阳极的制备方法，其特征在于，所述导电基底为FTO玻璃。
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