WO2024051019A1 - Preparation method for quantum dot sensitized composite photo-anode, and quantum dot sensitized composite photo-anode and use therof - Google Patents

Preparation method for quantum dot sensitized composite photo-anode, and quantum dot sensitized composite photo-anode and use therof Download PDF

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WO2024051019A1
WO2024051019A1 PCT/CN2022/138215 CN2022138215W WO2024051019A1 WO 2024051019 A1 WO2024051019 A1 WO 2024051019A1 CN 2022138215 W CN2022138215 W CN 2022138215W WO 2024051019 A1 WO2024051019 A1 WO 2024051019A1
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quantum dot
photoanode
mos
tio
glass substrate
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PCT/CN2022/138215
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French (fr)
Chinese (zh)
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马明
崔传艺
李蒋
汪毅
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
    • 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
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present application relates to the field of photoelectrocatalytic preparation technology, and in particular to a preparation method of a quantum dot-sensitized composite photoanode, a quantum dot-sensitized composite photoanode and its application.
  • the present application relates to the field of photoelectrocatalytic preparation technology, and in particular to a preparation method of a quantum dot-sensitized composite photoanode, a quantum dot-sensitized composite photoanode and its application.
  • Photoelectrochemical (PEC) cell technology is a hydrogen production system with great development potential that is favored in the world today. It provides a solution to the energy and environmental crisis and achieves my country's strategic goals of "carbon peaking" and “carbon neutrality”. An ideal solution that is efficient, clean and pollution-free.
  • photoelectrocatalyst types and battery design strategies have emerged in endlessly.
  • the current photoelectrocatalytic solar energy conversion efficiency is still low, which greatly limits the industrial application of this technology. Therefore, how to use various ingenious means and strategies to improve the catalytic activity of photoelectrocatalysts has become the primary problem that researchers who are deeply involved in this field need to overcome.
  • TiO 2 can still be used in many photoelectrocatalytic applications due to its excellent resistance to photocorrosion and acid-alkali corrosion, extremely low cost, attractive long-term stable activity, and environmental friendliness. stand out from the material.
  • its excessively wide bandgap about 3.0 eV ⁇ 3.2 eV
  • poor light absorption ability extremely fast surface charge recombination rate and scarce surface active sites also greatly limit its photoelectrocatalytic performance.
  • TiO2 as a photoelectrocatalytic material.
  • quantum dot materials often require only a small amount of load to greatly improve the catalytic performance of the photoanode, providing an attractive shortcut for the industrialization of photoelectrocatalytic hydrogen production.
  • the use of quantum dots to modify and sensitize the surface of TiO 2 materials is a star strategy with outstanding advantages for constructing new photoanode.
  • One of the purposes of this application is to provide a method for preparing a quantum dot-sensitized composite photoanode, which includes the following steps:
  • MoS 2 QDs is dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and is calcined at high temperature under the protection of an inert atmosphere to obtain a MoS 2 /TiO 2 quantum dot-sensitized composite photoanode.
  • the steps of preparing a rutile phase TiO 2 nanorod array photoanode specifically include the following steps:
  • the reacted FTO glass substrate is rinsed and dried with deionized water, then calcined at 400 to 600°C for 2 to 3 hours, and then cooled to room temperature to obtain the rutile phase TiO 2 nanorod array photoanode.
  • the thickness of the FTO glass substrate is 2.0 ⁇ 2.2 mm
  • the light transmittance is more than 80%
  • the sheet resistance is 6 ⁇ 7 ⁇
  • the FTO film thickness is 300 ⁇ 350 nm.
  • a step of pre-processing the FTO glass substrate before using the FTO glass substrate, a step of pre-processing the FTO glass substrate is also included.
  • the pre-processing includes:
  • the cut FTO glass substrate is sequentially immersed in a mixed solution of absolute ethanol, acetone, deionized water, concentrated sulfuric acid and hydrogen peroxide and sonicated for 10 to 20 seconds. min, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide is 7:3;
  • the ultrasonic-treated FTO glass substrate is soaked in deionized water and left to stand for 5 to 15 minutes. min, used to remove the solvent residues in the above ultrasonic cleaning process;
  • the density of the concentrated hydrochloric acid at 20°C is 1.18 g/mL, and the HCl content is 36 ⁇ 38%.
  • MoS 2 QDs are dropped on the surface of the rutile phase TiO 2 nanorod array photoanode and calcined at high temperature under the protection of an inert atmosphere to obtain a MoS 2 /TiO 2 quantum dot-sensitized composite photoanode.
  • the steps specifically include the following steps:
  • the MoS2 QDs solution is dropped on the surface of the rutile phase TiO2 nanorod array photoanode, and then evaporated to dryness at 40-80°C, and then heated to 280°C-320°C with Ar as an inert protective gas.
  • the quantum dot-sensitized composite photoanode of MoS 2 /TiO 2 is obtained by calcining at high temperature for 0.5-1 h at °C.
  • the MoS 2 QDs are synthesized by a hydrothermal method.
  • the step of synthesizing MoS 2 QDs by hydrothermal method specifically includes the following steps:
  • the second purpose of this application is to provide a quantum dot-sensitized composite photoanode, which is prepared by the preparation method of the quantum dot-sensitized composite photoanode.
  • the third purpose of this application is to provide an application of quantum dot-sensitized composite photoanode in photoelectrocatalysis.
  • MoS 2 QDs are dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and the MoS 2 /TiO 2 is calcined at high temperature under the protection of an inert atmosphere.
  • MoS 2 QDs achieves the photosensitization effect by transferring photogenerated electrons to the TiO 2 nanorod array, thereby enhancing the overall light absorption of the composite photoanode, thereby activating the original photoanode under visible light.
  • the oxygen evolution ability of semiconductors promotes the charge separation process and increases the photoresponse current. It has the advantages of easy operation, clean and efficient, and can be produced on a large scale.
  • the quantum dot material can greatly improve the catalytic performance of the photoanode with only a small amount of load, and can be used in the field of photoelectrocatalysis, especially for the realization of the industrialization of photoelectrocatalytic hydrogen production. A shortcut.
  • Figure 1 is a flow chart of the preparation method of the quantum dot-sensitized composite photoanode provided in this application.
  • Figure 2 is a flow chart of steps for preparing a rutile phase TiO2 nanorod array photoanode provided by this application.
  • FIG. 3 is a flow chart of steps for preprocessing the FTO glass substrate provided by this application.
  • Figure 4 is a flow chart of the steps provided by this application for the synthesis of MoS2 QDs through the hydrothermal method.
  • Figure 5 is an SEM image of the TiO 2 photoanode prepared in Example 1 of the present application.
  • Figure 6 is an XRD pattern of the TiO 2 photoanode prepared in Example 1 of the present application.
  • Figure 7 is a TEM image of MoS 2 QDs prepared in Example 2 of the present application.
  • Figure 8 is an XPS pattern of MoS 2 QDs prepared in Example 2 of the present application.
  • Figure 9 is an XRD pattern of the MoS 2 /TiO 2 photoanode prepared in Example 3 of the present application.
  • Figure 10 is a photoresponse current JV diagram of the MoS 2 /TiO 2 photoanode prepared in Example 3 of the present application.
  • first and second are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as “first” and “second” may explicitly or implicitly include one or more of these features.
  • plurality means two or more than two, unless otherwise explicitly and specifically limited.
  • Figure 1 is a method for preparing a quantum dot-sensitized composite photoanode according to an embodiment of the present application, including the following steps S110 to S120. The specific implementation of each step is described in detail below.
  • Step S110 Prepare a rutile phase TiO2 nanorod array photoanode.
  • Figure 2 is a flow chart of steps for preparing a rutile phase TiO2 nanorod array photoanode according to an embodiment of the present application, including the following steps S111 to step S113. The implementation of each step is described in detail below.
  • Step S111 Place the conductive surface of the FTO glass substrate downward into a reaction kettle lined with polytetrafluoroethylene.
  • the thickness of the FTO glass substrate is 2.0 ⁇ 2.2 mm
  • the light transmittance is more than 80%
  • the sheet resistance is 6 ⁇ 7 ⁇
  • the FTO film thickness is 300 ⁇ 350 nm.
  • the thickness and impedance of the FTO film are inversely proportional. The thicker the thickness, the lower the impedance and the better the conductivity.
  • Step S112 Stir deionized water, concentrated hydrochloric acid and tetrabutyl titanate solution evenly, then add them to the reaction kettle, and mix at 150 to 200 °C hydrothermal reaction 15 ⁇ 20 h and then cooled to room temperature to obtain the reacted FTO glass substrate.
  • the density of the concentrated hydrochloric acid at 20°C is 1.18 g/mL, and the HCl content is 36 ⁇ 38%.
  • the optimal temperature for the hydrothermal reaction is 150°C.
  • the prepared rutile phase TiO 2 nanorod array photoanode is relatively uniform and has relatively good performance.
  • Step S113 Rinse and dry the reacted FTO glass substrate with deionized water, then calcine at 400 ⁇ 600°C for 2 ⁇ 3 h, and then cool to room temperature to obtain the rutile phase TiO2 nanorod array photoanode. .
  • the calcination temperature is 500°C and the heating rate is 5°C/min.
  • the prepared rutile phase TiO 2 nanorod array photoanode has better crystalline form and crystallinity, and better performance.
  • the FTO glass substrate Before using the FTO glass substrate, it also includes a flow chart of steps for preprocessing the FTO glass substrate.
  • the preprocessing includes the following steps S210 to S240. Each step is described in detail below. Method to realize.
  • Step S210 Cut the FTO glass substrate into a size of 1 ⁇ 2 cm2.
  • Step S220 Immerse the trimmed FTO glass substrate in a mixed solution of absolute ethanol, acetone, deionized water, concentrated sulfuric acid and hydrogen peroxide, and perform ultrasonic treatment for 10 to 20 seconds. min, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide is 7:3.
  • Step S230 Soak the ultrasonic-treated FTO glass substrate in deionized water and let it stand for 5 to 15 minutes. min, used to remove the solvent residues in the above ultrasonic cleaning process.
  • Step S240 Finally, the FTO glass substrate after standing is immersed in absolute ethanol for 10 to 20 minutes and then dried.
  • the present invention can remove contaminants attached to the surface of the FTO glass substrate by pretreating the FTO glass substrate, ensure that the surface of the substrate is smooth and clean, and improve the hydrophilicity of the conductive side of the substrate, thereby facilitating the formation of TiO 2 nanopillars on the substrate. Uniform growth on the surface of the sheet.
  • a one-step hydrothermal method was used to grow a rutile phase TiO 2 nanorod array photoanode on the surface of an FTO glass substrate.
  • the resulting product is highly pure, uniform, and regular, has a lighter color after calcination, and has good electrical conductivity.
  • Step S120 Drop MoS 2 QDs (molybdenum disulfide quantum dots) on the surface of the rutile phase TiO 2 nanorod array photoanode, and calcine it at high temperature under the protection of an inert atmosphere to obtain a quantum dot sensitized composite of MoS 2 /TiO 2 Photoanode.
  • MoS 2 QDs mobdenum disulfide quantum dots
  • the MoS 2 QDs solution was dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and then evaporated to dryness at 60°C, and then at 280°C using Ar as an inert protective gas.
  • the quantum dot-sensitized composite photoanode of MoS 2 /TiO 2 was obtained by high-temperature calcination at -320°C for 0.5-1 h.
  • the dropping amount of the above-mentioned MoS 2 QDs is 200 ⁇ L, and the above-mentioned calcination temperature is 300°C.
  • the quantum dot-sensitized composite photoanode of MoS2/TiO2 has the best photoelectric activity.
  • the MoS 2 QDs are synthesized by a hydrothermal method.
  • the steps for synthesizing MoS 2 QDs by hydrothermal method specifically include the following steps S310 to step S330. The implementation of each step is described in detail below.
  • Step S310 Mix and stir (NH 4 ) 2 MoS 4 , deionized water and N 2 H 4 ⁇ 4H 2 O to obtain a mixed solution;
  • Step S320 Place the mixed solution in a polytetrafluoroethylene-lined stainless steel reactor, seal and heat at 150-200°C for 18-24 hours, then cool to room temperature, and centrifuge for 15-30 minutes to precipitate. Removal of larger sized particles;
  • Step S330 Take the supernatant containing MoS 2 QDs from the above mixed solution and filter it to remove large-sized particles to obtain a MoS 2 QDs solution.
  • MoS 2 QDs are dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and then calcined at high temperature under the protection of an inert atmosphere to obtain MoS 2 / Quantum dot-sensitized composite photoanode of TiO 2.
  • MoS 2 QDs achieves the photosensitization effect by transferring photogenerated electrons to the TiO 2 nanorod array, thereby enhancing the overall light absorption of the composite photoanode, thereby reducing the visible light It activates the oxygen evolution ability of the original semiconductor, promotes the charge separation process, increases the photoresponse current, and has the advantages of easy operation, clean efficiency, and large-scale production.
  • the quantum dot-sensitized composite photoanode constructed by a simple dropping method in the above embodiments of the present application shows excellent PEC activity in water decomposition due to the excellent quantum dot sensitization effect.
  • the photocurrent generated by the optimized MoS 2 /TiO 2 photoanode is about 2.8 times that of pure TiO 2 , achieving the effect of 1+1>2 for a single component.
  • the product quality is stable, which is conducive to the realization of large-volume, industrialized production and provides a good foundation for device construction. Strategies open up new possibilities.
  • step (3) Place the pretreated FTO glass substrate in step (1) with the conductive side down into a high-temperature reaction kettle lined with polytetrafluoroethylene, add the mixture obtained in step (2) into the lining, and oven The hydrothermal reaction was carried out at 150 °C for 20 h and then cooled to room temperature.
  • step (3) Take out the sample after the reaction in step (3) from the lining, clean it with deionized water and dry it, then place it in a muffle furnace and calcine it at 500°C for 2 hours. After cooling to room temperature, the rutile phase TiO is obtained. 2 nanorod array photoanode.
  • the top view of the microstructure of the TiO 2 photoanode measured by SEM (top), a TiO 2 array composed of uniform, square nanorods with a diameter of about 200 ⁇ 400 nm can be observed.
  • Microstructural cross-section of the TiO2 photoanode measured by SEM (bottom), it can be observed that the nanorods are about 3 ⁇ m high.
  • the crystal structure of the TiO2 photoanode was determined through the XRD diffraction pattern.
  • the peaks at 36.1°, 41.2°, 54.3°, 62.7°, 69.0° and 69.7° in the spectrum correspond to the rutile phases of (101), (111), (211), (002), (301) and (112) respectively.
  • Seven asterisks ( ⁇ ) mark peaks 26.4°, 33.7°, 37.8°, 51.5°, 61.6°, 65.6° and 78.7° which can be classified as FTO glass substrates.
  • MoS 2 QDs have an elliptical flake morphology with a long semi-axis of about 4.5 nm and a short semi-axis of about 3.1 nm.
  • the internal lattice constant is 0.205 nm, corresponding to the (006) molybdenite-2H phase. Planes. From this, it is basically certain that the material exists in the form of quantum dots in the solution, is uniformly dispersed, and has a clear crystal form.
  • the fine XPS spectrum of S 2p shows that 163.44 eV and 164.55 eV can be assigned to 2p 3/2 and 2p 1/2 of S in MoS 2 QDs, proving that MoS 2 exists in the main form in the material; 163.52 eV
  • the S 2p doublet state around 164.68 eV (2p 3/2 ) and 164.68 eV (2p 1/2 ) can be attributed to disulfide S22 ⁇ or polysulfide Sx 2 ⁇ ; 168.02 eV (2p 3/2 ) and 169.17 eV( 2p 1/2 ) belong to SO bonds respectively, which once again confirms that the surface of MoS 2 QDs material has a thin oxide layer; in summary, it can be seen that MoS 2 QDs is mainly composed of elliptical molybdenum disulfide nanosheet particles with slightly oxidized surface. At the same time, there is very little molybdenum polysulfide present.
  • the MoS 2 QDs solution provided in this application is dropped on the surface of the dry rutile phase TiO 2 nanorod array photoanode, placed on the hot stage to evaporate to dryness at 60°C, and then placed in a tube furnace with Ar as an inert protective gas.
  • High-efficiency quantum dot-sensitized composite photoanode was obtained by high-temperature calcination at 280°C-320°C for 0.5-1 h.
  • the crystal structure of the quantum dot-sensitized composite photoanode was determined through the XRD diffraction pattern. Due to the low concentration of the solution, the loading amount of MoS 2 QDs is also low, which is lower than the lowest detection limit of the XRD test. Therefore, the XRD characteristic peaks of the MoS 2 /TiO 2 material composite photoanode are different from those of the rutile phase TiO prepared in Example 1. The XRD characteristic peaks of the 2 nanorod array photoanode overlap. At the same time, it also shows that a smaller loading of quantum dots can greatly improve the photoelectrocatalytic activity of the photoanode, with low cost and great industrialization potential.
  • LSV linear scan voltammetry
  • the highest photocurrent of the MoS 2 /TiO 2 photoanode is about 1.45 mA/cm 2 (1.23 vs. RHE) at 1.23 V, which is 2.8 times that of the pure TiO 2 photoanode , showing excellent PEC performance, confirming the effective role of the MoS 2 QDs sensitization method in improving the solar light conversion process.

Abstract

Provided in the present application are a quantum dot sensitized composite photo-anode and a preparation method therefor. The preparation method comprises: dripping MoS2 QDs on the surface of a rutile phase TiO2 nanorod array photo-anode, and calcining same at a high temperature under the protection of an inert atmosphere to obtain an MoS2/TiO2 quantum dot sensitized composite photo-anode. In the present application, MoS2 QDs transfer photo-induced electrons into a TiO2 nanorod array to achieve a photosensitization effect thereon, thereby improving the whole light absorption of the composite photo-anode, such that the oxygen evolution capacity of an original semiconductor is activated under visible light, the charge separation process is promoted, the photoresponse current is improved, and the advantages of easiness in terms of operation, cleanness, high efficiency, being suitable for large-scale production, etc., are achieved. In addition, further provided in the present application is the use of the quantum dot sensitized composite photo-anode in photoelectrocatalysis.

Description

一种量子点敏化复合光阳极的制备方法、量子点敏化复合光阳极及应用A preparation method of quantum dot-sensitized composite photoanode, quantum dot-sensitized composite photoanode and application 技术领域Technical field
本申请涉及光电催化制备技术领域，特别涉及一种量子点敏化复合光阳极的制备方法、量子点敏化复合光阳极及应用。本申请涉及光电催化制备技术领域，特别涉及一种量子点敏化复合光阳极的制备方法、量子点敏化复合光阳极及应用。The present application relates to the field of photoelectrocatalytic preparation technology, and in particular to a preparation method of a quantum dot-sensitized composite photoanode, a quantum dot-sensitized composite photoanode and its application. The present application relates to the field of photoelectrocatalytic preparation technology, and in particular to a preparation method of a quantum dot-sensitized composite photoanode, a quantum dot-sensitized composite photoanode and its application.
背景技术Background technique
光电化学（PEC）电池技术是当今世界备受青睐的一种极具发展潜力的制氢***，为解决能源和环境危机，实现我国“碳达峰”、“碳中和”的战略目标提供了一种高效、清洁、无污染的理想方案。经过全世界科研工作者半个世纪的不懈努力，光电催化剂种类和电池设计策略层出不穷，然而，目前光电催化太阳能转化效率仍然较低，这极大地限制了该技术的工业化应用。因此，如何利用各种巧妙的手段和策略来提高光电催化剂的催化活性便成为了深耕于该领域的科研工作者们亟需攻克的首要难题。Photoelectrochemical (PEC) cell technology is a hydrogen production system with great development potential that is favored in the world today. It provides a solution to the energy and environmental crisis and achieves my country's strategic goals of "carbon peaking" and "carbon neutrality". An ideal solution that is efficient, clean and pollution-free. After half a century of unremitting efforts by scientific researchers around the world, photoelectrocatalyst types and battery design strategies have emerged in endlessly. However, the current photoelectrocatalytic solar energy conversion efficiency is still low, which greatly limits the industrial application of this technology. Therefore, how to use various ingenious means and strategies to improve the catalytic activity of photoelectrocatalysts has become the primary problem that researchers who are deeply involved in this field need to overcome.
BiVO 4、WO 3、ZnO以及新型的g-C 3N 4、MOFs等光阳极材料已经被来自世界各地的科学家们所广泛报道。相比于上述材料，TiO 2以其极优的抗光腐蚀和酸碱腐蚀的能力、极低廉的成本、极诱人的长效稳定活性和环境友好性等固有优势，仍然能够在众多光电催化材料中脱颖而出。然而，其过宽的禁带宽度（约为3.0 eV~3.2 eV）、较差的光吸收能力、极快的表面电荷复合速率和稀少的表面活性位点也极大地限制了其光电催化性能，严重阻碍了TiO 2作为光电催化材料的发展。 BiVO 4 , WO 3 , ZnO, new gC 3 N 4 , MOFs and other photoanode materials have been widely reported by scientists from all over the world. Compared with the above materials, TiO 2 can still be used in many photoelectrocatalytic applications due to its excellent resistance to photocorrosion and acid-alkali corrosion, extremely low cost, attractive long-term stable activity, and environmental friendliness. stand out from the material. However, its excessively wide bandgap (about 3.0 eV~3.2 eV), poor light absorption ability, extremely fast surface charge recombination rate and scarce surface active sites also greatly limit its photoelectrocatalytic performance. Seriously hinders the development of TiO2 as a photoelectrocatalytic material.
通过带隙工程（如杂质掺杂）、缺陷控制、表面等离子体共振(SPR)效应以及量子点和有机染料的表面敏化，可以增加可见光吸收和最大限度地分离载流子，并达到极大促进原始半导体光电催化性能的效果。与此同时，由于其独特的形貌和结构以及特殊的化学特性，二维二硫化物（MoS 2、WS 2和MoSe 2等）在催化领域同样引起了极大关注。同时，量子点因其极小的尺寸、极大的表面积、以及神奇的量子效应等等独特的优势，在催化性能上往往极大地优于其对应的大尺度材料。因此，量子点材料往往只需少量的负载，即可极大地提升光阳极的催化性能，为光电催化制氢的工业化的实现提供了一条诱人的捷径。综上所述，利用量子点对TiO 2材料表面进行修饰和敏化，是一种具有突出优势的构建新型光阳极的明星策略。 Through band gap engineering (such as impurity doping), defect control, surface plasmon resonance (SPR) effects, and surface sensitization of quantum dots and organic dyes, visible light absorption and maximum carrier separation can be increased to the maximum The effect of promoting the photoelectrocatalytic performance of pristine semiconductors. At the same time, due to their unique morphology and structure as well as special chemical properties, two-dimensional disulfides (MoS 2 , WS 2 , MoSe 2 , etc.) have also attracted great attention in the field of catalysis. At the same time, due to their unique advantages such as extremely small size, large surface area, and magical quantum effects, quantum dots are often greatly superior to their corresponding large-scale materials in catalytic performance. Therefore, quantum dot materials often require only a small amount of load to greatly improve the catalytic performance of the photoanode, providing an attractive shortcut for the industrialization of photoelectrocatalytic hydrogen production. In summary, the use of quantum dots to modify and sensitize the surface of TiO 2 materials is a star strategy with outstanding advantages for constructing new photoanode.
技术问题technical problem
鉴于此，有必要针对现有技术中存在的缺陷提供一种制备效果优良、工艺简单、且具有工业前景的量子点敏化复合光阳极及其制备方法。In view of this, it is necessary to provide a quantum dot-sensitized composite photoanode and a preparation method thereof that have excellent preparation effects, simple processes, and industrial prospects to address the shortcomings in the existing technology.
技术解决方案Technical solutions
为解决上述问题，本申请采用下述技术方案：In order to solve the above problems, this application adopts the following technical solutions:
本申请目的之一，提供了一种量子点敏化复合光阳极的制备方法，包括下述步骤：One of the purposes of this application is to provide a method for preparing a quantum dot-sensitized composite photoanode, which includes the following steps:
制备金红石相TiO 2纳米棒阵列光阳极； Preparation of rutile phase TiO 2 nanorod array photoanode;
将MoS 2 QDs滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，并于惰性氛围保护下高温煅烧得到MoS 2/TiO 2的量子点敏化复合光阳极。 MoS 2 QDs is dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and is calcined at high temperature under the protection of an inert atmosphere to obtain a MoS 2 /TiO 2 quantum dot-sensitized composite photoanode.
在其中一些实施例中，在制备金红石相TiO 2纳米棒阵列光阳极的步骤中，具体包括下述步骤： In some of the embodiments, the steps of preparing a rutile phase TiO 2 nanorod array photoanode specifically include the following steps:
将FTO玻璃基片的导电面朝下置入反应釜中，所述反应釜以聚四氟乙烯为内衬；Place the conductive surface of the FTO glass substrate face down into a reactor lined with polytetrafluoroethylene;
将去离子水、浓盐酸及钛酸四丁酯溶液搅拌均匀后加入所述反应釜中，并在150~200 ℃水热反应15~20 h后冷却至室温得到反应后的FTO玻璃基片；Stir deionized water, concentrated hydrochloric acid and tetrabutyl titanate solution evenly and then add them to the reaction kettle, and stir at 150~200 ℃ hydrothermal reaction 15~20 After h, cool to room temperature to obtain the reacted FTO glass substrate;
将所述反应后的FTO玻璃基片用去离子水冲洗晾干后于400~600℃下煅烧2~3 h，再冷却至室温，得到所述金红石相TiO 2纳米棒阵列光阳极。 The reacted FTO glass substrate is rinsed and dried with deionized water, then calcined at 400 to 600°C for 2 to 3 hours, and then cooled to room temperature to obtain the rutile phase TiO 2 nanorod array photoanode.
在其中一些实施例中，所述FTO玻璃基片的厚度为2.0~2.2 mm，透光率为80%以上，方阻6~7 Ω，FTO膜层厚度为300~350 nm。In some embodiments, the thickness of the FTO glass substrate is 2.0~2.2 mm, the light transmittance is more than 80%, the sheet resistance is 6~7 Ω, and the FTO film thickness is 300~350 nm.
在其中一些实施例中，在使用所述FTO玻璃基片前，还包括对所述FTO玻璃基片进行预处理的步骤，所述预处理包括：In some of the embodiments, before using the FTO glass substrate, a step of pre-processing the FTO glass substrate is also included. The pre-processing includes:
将所述FTO玻璃基片剪裁为1×2 cm 2大小； Cut the FTO glass substrate into a size of 1×2 cm2;
将剪裁后的所述FTO玻璃基片依次浸入无水乙醇、丙酮、去离子水、浓硫酸和过氧化氢的混合溶液中超声处理10~20 min，其中，所述浓硫酸和过氧化氢的体积比7:3；The cut FTO glass substrate is sequentially immersed in a mixed solution of absolute ethanol, acetone, deionized water, concentrated sulfuric acid and hydrogen peroxide and sonicated for 10 to 20 seconds. min, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide is 7:3;
再将超声处理后的所述FTO玻璃基片浸泡在去离子水中静置5~15 min，用以除去上述超声清洗过程中的各溶剂残留；Then, the ultrasonic-treated FTO glass substrate is soaked in deionized water and left to stand for 5 to 15 minutes. min, used to remove the solvent residues in the above ultrasonic cleaning process;
最后将静置后的所述FTO玻璃基片浸于无水乙醇10~20 min后干燥处理。Finally, the FTO glass substrate after standing was immersed in absolute ethanol for 10 to 20 minutes and then dried.
在其中一些实施例中，所述浓盐酸在20℃的密度为1.18 g/mL，HCl含量36~38%。In some embodiments, the density of the concentrated hydrochloric acid at 20°C is 1.18 g/mL, and the HCl content is 36~38%.
在其中一些实施例中，在将MoS 2 QDs滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，并于惰性氛围保护下高温煅烧得到MoS 2/TiO 2的量子点敏化复合光阳极的步骤中，具体包括下述步骤： In some embodiments, MoS 2 QDs are dropped on the surface of the rutile phase TiO 2 nanorod array photoanode and calcined at high temperature under the protection of an inert atmosphere to obtain a MoS 2 /TiO 2 quantum dot-sensitized composite photoanode. The steps specifically include the following steps:
将所述的MoS2 QDs溶液滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，再置于40-80℃ 蒸干，之后再以Ar为惰性保护气的条件下，在280℃-320℃下高温煅烧0.5-1 h得到MoS 2/TiO 2的量子点敏化复合光阳极。 The MoS2 QDs solution is dropped on the surface of the rutile phase TiO2 nanorod array photoanode, and then evaporated to dryness at 40-80°C, and then heated to 280°C-320°C with Ar as an inert protective gas. The quantum dot-sensitized composite photoanode of MoS 2 /TiO 2 is obtained by calcining at high temperature for 0.5-1 h at ℃.
在其中一些实施例中，所述MoS 2 QDs通过水热法合成。 In some of these embodiments, the MoS 2 QDs are synthesized by a hydrothermal method.
在其中一些实施例中，在所述MoS 2 QDs通过水热法合成的步骤中，具体包括下述步骤： In some embodiments, the step of synthesizing MoS 2 QDs by hydrothermal method specifically includes the following steps:
将(NH 4) 2MoS 4、去离子水及N 2H 4·4H 2O混合搅拌后得到混合溶液； (NH 4 ) 2 MoS 4 , deionized water and N 2 H 4 ·4H 2 O are mixed and stirred to obtain a mixed solution;
将所述混合溶液置于以聚四氟乙烯为内衬的不锈钢反应釜中，密封并在150-200℃下加热18-24 h后冷却至室温，再离心15-30 min 以沉淀除去更大尺寸的粒子；Place the mixed solution in a stainless steel reactor lined with polytetrafluoroethylene, seal and heat at 150-200°C for 18-24 hours, then cool to room temperature, and then centrifuge for 15-30 minutes to precipitate and remove larger particles. size particles;
在上述混合溶液中取含有MoS 2 QDs的上清液并经过滤后以除去大尺寸颗粒，得到MoS 2 QDs溶液。 Take the supernatant containing MoS 2 QDs from the above mixed solution and filter it to remove large-sized particles to obtain a MoS 2 QDs solution.
本申请目的之二，提供了一种量子点敏化复合光阳极，由所述的量子点敏化复合光阳极的制备方法制备得到。The second purpose of this application is to provide a quantum dot-sensitized composite photoanode, which is prepared by the preparation method of the quantum dot-sensitized composite photoanode.
本申请目的之三，提供了一种量子点敏化复合光阳极在光电催化中的应用。The third purpose of this application is to provide an application of quantum dot-sensitized composite photoanode in photoelectrocatalysis.
有益效果beneficial effects
本申请采用上述技术方案，其有益效果如下：This application adopts the above technical solution, and its beneficial effects are as follows:
本申请提供的量子点敏化复合光阳极及制备方法，将MoS 2 QDs滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，并于惰性氛围保护下高温煅烧得到MoS 2/TiO 2的量子点敏化复合光阳极，本申请将MoS 2 QDs通过将光生电子转移到TiO 2纳米棒阵列中达到对其光敏化的效果，增强了复合光阳极整体的光吸收，从而在可见光下激活原始半导体的析氧能力，促进了电荷分离过程，提高了光响应电流，具有易于操作、清洁高效、可规模化生产等优点。 In the quantum dot-sensitized composite photoanode and preparation method provided by this application, MoS 2 QDs are dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and the MoS 2 /TiO 2 is calcined at high temperature under the protection of an inert atmosphere. Quantum dot-sensitized composite photoanode. In this application, MoS 2 QDs achieves the photosensitization effect by transferring photogenerated electrons to the TiO 2 nanorod array, thereby enhancing the overall light absorption of the composite photoanode, thereby activating the original photoanode under visible light. The oxygen evolution ability of semiconductors promotes the charge separation process and increases the photoresponse current. It has the advantages of easy operation, clean and efficient, and can be produced on a large scale.
本申请提供的量子点敏化复合光阳极，量子点材料只需少量的负载，即可极大地提升光阳极的催化性能，可用于光电催化领域，特别为光电催化制氢的工业化的实现提供了一条捷径。In the quantum dot-sensitized composite photoanode provided by this application, the quantum dot material can greatly improve the catalytic performance of the photoanode with only a small amount of load, and can be used in the field of photoelectrocatalysis, especially for the realization of the industrialization of photoelectrocatalytic hydrogen production. A shortcut.
附图说明Description of the drawings
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to explain the technical solutions of the embodiments of the present application more clearly, the drawings needed to be used in the description of the embodiments of the present application or the prior art will be briefly introduced below. Obviously, the drawings described below are only the drawings of the present application. For some embodiments, for those of ordinary skill in the art, other drawings can be obtained based on these drawings without exerting creative efforts.
图1为本本申请提供的量子点敏化复合光阳极的制备方法的步骤流程图。Figure 1 is a flow chart of the preparation method of the quantum dot-sensitized composite photoanode provided in this application.
图2为本申请提供的制备金红石相TiO2纳米棒阵列光阳极的步骤流程图。Figure 2 is a flow chart of steps for preparing a rutile phase TiO2 nanorod array photoanode provided by this application.
图3为本申请提供的对所述FTO玻璃基片进行预处理的步骤流程图。Figure 3 is a flow chart of steps for preprocessing the FTO glass substrate provided by this application.
图4为本申请提供的在所述MoS2 QDs通过水热法合成的步骤流程图。Figure 4 is a flow chart of the steps provided by this application for the synthesis of MoS2 QDs through the hydrothermal method.
图5为本申请实施例1制备得到TiO 2光阳极的SEM图。 Figure 5 is an SEM image of the TiO 2 photoanode prepared in Example 1 of the present application.
图6为本申请实施例1制备得到TiO 2光阳极的XRD图。 Figure 6 is an XRD pattern of the TiO 2 photoanode prepared in Example 1 of the present application.
图7为本申请实施例2制备得到MoS 2 QDs的TEM图。 Figure 7 is a TEM image of MoS 2 QDs prepared in Example 2 of the present application.
图8为本申请实施例2制备得到MoS 2 QDs的XPS图。 Figure 8 is an XPS pattern of MoS 2 QDs prepared in Example 2 of the present application.
图9为本申请实施例3制备得到MoS 2/TiO 2光阳极的XRD图。 Figure 9 is an XRD pattern of the MoS 2 /TiO 2 photoanode prepared in Example 3 of the present application.
图10为本申请实施例3制备得到MoS 2/TiO 2光阳极的光响应电流J-V图。 Figure 10 is a photoresponse current JV diagram of the MoS 2 /TiO 2 photoanode prepared in Example 3 of the present application.
本发明的实施方式Embodiments of the invention
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。The embodiments of the present application are described in detail below. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements with the same or similar functions. The embodiments described below with reference to the drawings are exemplary and are intended to explain the present application, but should not be construed as limiting the present application.
在本申请的描述中，需要理解的是，术语“上”、“下”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本申请的限制。In the description of this application, it should be understood that the orientation or positional relationship indicated by the terms "upper", "lower", "level", "inner", "outer", etc. is based on the orientation or positional relationship shown in the drawings. , is only for the convenience of describing the present application and simplifying the description, but does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation of the present application.
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In addition, the terms “first” and “second” are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Therefore, features defined as "first" and "second" may explicitly or implicitly include one or more of these features. In the description of this application, "plurality" means two or more than two, unless otherwise explicitly and specifically limited.
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。In order to make the purpose, technical solutions and advantages of the present application more clear, the present application will be further described in detail below with reference to the drawings and embodiments.
请参阅图1，为本申请一实施例提供的一种量子点敏化复合光阳极的制备方法，包括下述步骤S110至S120，以下详细说明各个步骤的具体实现方式。Please refer to Figure 1 , which is a method for preparing a quantum dot-sensitized composite photoanode according to an embodiment of the present application, including the following steps S110 to S120. The specific implementation of each step is described in detail below.
步骤S110：制备金红石相TiO 2纳米棒阵列光阳极。 Step S110: Prepare a rutile phase TiO2 nanorod array photoanode.
请参阅图2，为本申请实施例提供的制备金红石相TiO 2纳米棒阵列光阳极的步骤流程图，包括下述步骤S111至步骤S113，以下详细说明各个步骤的实现方式。 Please refer to Figure 2, which is a flow chart of steps for preparing a rutile phase TiO2 nanorod array photoanode according to an embodiment of the present application, including the following steps S111 to step S113. The implementation of each step is described in detail below.
步骤S111：将FTO玻璃基片的导电面朝下置入反应釜中，所述反应釜以聚四氟乙烯为内衬。Step S111: Place the conductive surface of the FTO glass substrate downward into a reaction kettle lined with polytetrafluoroethylene.
可以理解，采用聚四氟乙烯内衬，可以更好提高耐高温性能。It can be understood that using polytetrafluoroethylene lining can better improve high temperature resistance.
在其中一些实施例中，所述FTO玻璃基片的厚度为2.0~2.2 mm，透光率为80%以上，方阻6~7 Ω，FTO膜层厚度为300~350 nm。In some embodiments, the thickness of the FTO glass substrate is 2.0~2.2 mm, the light transmittance is more than 80%, the sheet resistance is 6~7 Ω, and the FTO film thickness is 300~350 nm.
可以理解， FTO膜的厚度和阻抗是成反比的，厚度越厚，阻抗越低，导电性越好。It can be understood that the thickness and impedance of the FTO film are inversely proportional. The thicker the thickness, the lower the impedance and the better the conductivity.
步骤S112：将去离子水、浓盐酸及钛酸四丁酯溶液搅拌均匀后加入所述反应釜中，并在150~200 ℃水热反应15~20 h后冷却至室温得到反应后的FTO玻璃基片。Step S112: Stir deionized water, concentrated hydrochloric acid and tetrabutyl titanate solution evenly, then add them to the reaction kettle, and mix at 150 to 200 ℃ hydrothermal reaction 15~20 h and then cooled to room temperature to obtain the reacted FTO glass substrate.
在其中一些实施例中，所述浓盐酸在20℃的密度为1.18 g/mL，HCl含量36~38%。In some embodiments, the density of the concentrated hydrochloric acid at 20°C is 1.18 g/mL, and the HCl content is 36~38%.
优选地，水热反应的最佳温度为150 ℃。Preferably, the optimal temperature for the hydrothermal reaction is 150°C.
需要说明的是，当水热温度控制在150 ℃，制备得到的金红石相TiO 2纳米棒阵列光阳极比较均匀，性能相对较好。 It should be noted that when the hydrothermal temperature is controlled at 150°C, the prepared rutile phase TiO 2 nanorod array photoanode is relatively uniform and has relatively good performance.
步骤S113：将所述反应后的FTO玻璃基片用去离子水冲洗晾干后于400~600℃下煅烧2~3 h，再冷却至室温，得到所述金红石相TiO 2纳米棒阵列光阳极。 Step S113: Rinse and dry the reacted FTO glass substrate with deionized water, then calcine at 400~600°C for 2~3 h, and then cool to room temperature to obtain the rutile phase TiO2 nanorod array photoanode. .
优选地，煅烧温度为500 ℃，升温速率为5 ℃/min。Preferably, the calcination temperature is 500°C and the heating rate is 5°C/min.
需要说明的是，当煅烧温度为500 ℃，制备的金红石相TiO 2纳米棒阵列光阳极晶型和结晶度较好，性能较好。 It should be noted that when the calcination temperature is 500°C, the prepared rutile phase TiO 2 nanorod array photoanode has better crystalline form and crystallinity, and better performance.
请参阅图3，在使用所述FTO玻璃基片前，还包括对所述FTO玻璃基片进行预处理的步骤流程图，所述预处理包括下述步骤S210至S240，以下详细说明各个步骤的实现方式。Please refer to Figure 3. Before using the FTO glass substrate, it also includes a flow chart of steps for preprocessing the FTO glass substrate. The preprocessing includes the following steps S210 to S240. Each step is described in detail below. Method to realize.
步骤S210：将所述FTO玻璃基片剪裁为1×2 cm 2大小。 Step S210: Cut the FTO glass substrate into a size of 1×2 cm2.
步骤S220：将剪裁后的所述FTO玻璃基片依次浸入无水乙醇、丙酮、去离子水、浓硫酸和过氧化氢的混合溶液中超声处理10~20 min，其中，所述浓硫酸和过氧化氢的体积比7:3。Step S220: Immerse the trimmed FTO glass substrate in a mixed solution of absolute ethanol, acetone, deionized water, concentrated sulfuric acid and hydrogen peroxide, and perform ultrasonic treatment for 10 to 20 seconds. min, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide is 7:3.
步骤S230：再将超声处理后的所述FTO玻璃基片浸泡在去离子水中静置5~15 min，用以除去上述超声清洗过程中的各溶剂残留。Step S230: Soak the ultrasonic-treated FTO glass substrate in deionized water and let it stand for 5 to 15 minutes. min, used to remove the solvent residues in the above ultrasonic cleaning process.
步骤S240：最后将静置后的所述FTO玻璃基片浸于无水乙醇10~20 min后干燥处理。Step S240: Finally, the FTO glass substrate after standing is immersed in absolute ethanol for 10 to 20 minutes and then dried.
可以理解，本发明通过对FTO玻璃基片进行预处理可以去除基片表面附着的污染物，保证基片表面平整干净，改善基片导电侧的亲水性，从而有利于TiO 2纳米柱在基片表面的均匀生长。 It can be understood that the present invention can remove contaminants attached to the surface of the FTO glass substrate by pretreating the FTO glass substrate, ensure that the surface of the substrate is smooth and clean, and improve the hydrophilicity of the conductive side of the substrate, thereby facilitating the formation of TiO 2 nanopillars on the substrate. Uniform growth on the surface of the sheet.
本申请上述实施例，利用一步水热法在FTO玻璃基片表面生长出以金红石相TiO 2纳米棒阵列光阳极，所得产品高纯、均匀、规整，煅烧后颜色较浅，导电性能良好。 In the above-mentioned embodiment of the present application, a one-step hydrothermal method was used to grow a rutile phase TiO 2 nanorod array photoanode on the surface of an FTO glass substrate. The resulting product is highly pure, uniform, and regular, has a lighter color after calcination, and has good electrical conductivity.
步骤S120：将MoS 2 QDs（二硫化钼量子点）滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，并于惰性氛围保护下高温煅烧得到MoS 2/TiO 2的量子点敏化复合光阳极。 Step S120: Drop MoS 2 QDs (molybdenum disulfide quantum dots) on the surface of the rutile phase TiO 2 nanorod array photoanode, and calcine it at high temperature under the protection of an inert atmosphere to obtain a quantum dot sensitized composite of MoS 2 /TiO 2 Photoanode.
具体地，将所述的MoS 2 QDs溶液滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，再置于60℃蒸干，之后再以Ar为惰性保护气的条件下，在280℃-320℃下高温煅烧0.5-1 h得到MoS 2/TiO 2的量子点敏化复合光阳极。 Specifically, the MoS 2 QDs solution was dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and then evaporated to dryness at 60°C, and then at 280°C using Ar as an inert protective gas. The quantum dot-sensitized composite photoanode of MoS 2 /TiO 2 was obtained by high-temperature calcination at -320°C for 0.5-1 h.
优选地，上述MoS 2 QDs滴加量为200 μL，上述煅烧温度为300 ℃。 Preferably, the dropping amount of the above-mentioned MoS 2 QDs is 200 μL, and the above-mentioned calcination temperature is 300°C.
需要说明的是，当MoS 2 QDs滴加量为200 μL，煅烧温度为300 ℃，得到MoS2/TiO2的量子点敏化复合光阳极的光电活性最好。 It should be noted that when the dropping amount of MoS 2 QDs is 200 μL and the calcination temperature is 300 °C, the quantum dot-sensitized composite photoanode of MoS2/TiO2 has the best photoelectric activity.
在其中一些实施例中，所述MoS 2 QDs通过水热法合成。 In some of these embodiments, the MoS 2 QDs are synthesized by a hydrothermal method.
请参阅图4，本申请提供的在所述MoS 2 QDs通过水热法合成的步骤中，具体包括下述步骤S310至步骤S330，以下详细说明各个步骤的实现方式。 Please refer to Figure 4. The steps for synthesizing MoS 2 QDs by hydrothermal method provided in this application specifically include the following steps S310 to step S330. The implementation of each step is described in detail below.
步骤S310：将(NH 4) 2MoS 4、去离子水及N 2H 4·4H 2O混合搅拌后得到混合溶液； Step S310: Mix and stir (NH 4 ) 2 MoS 4 , deionized water and N 2 H 4 ·4H 2 O to obtain a mixed solution;
步骤S320：将所述混合溶液置于以聚四氟乙烯为内衬的不锈钢反应釜中，密封并在150-200℃下加热18-24 h后冷却至室温，再离心15-30 min以沉淀除去更大尺寸的粒子；Step S320: Place the mixed solution in a polytetrafluoroethylene-lined stainless steel reactor, seal and heat at 150-200°C for 18-24 hours, then cool to room temperature, and centrifuge for 15-30 minutes to precipitate. Removal of larger sized particles;
步骤S330：在上述混合溶液中取含有MoS 2 QDs的上清液并经过滤后以除去大尺寸颗粒，得到MoS 2 QDs溶液。 Step S330: Take the supernatant containing MoS 2 QDs from the above mixed solution and filter it to remove large-sized particles to obtain a MoS 2 QDs solution.
本申请上述实施例，采用直接滴加的方法在所述金红石相TiO 2纳米棒阵列光阳极的表面滴加了一定量的MoS 2 QDs溶液，其中，二硫化钼量子点作为光敏剂可将光阳极的吸光范围从紫外光有效拓展至可见光，只需极少量负载即可明显抑制载流子复合，极大提高了TiO 2光阳极的光电催化活性。 In the above embodiments of the present application, a certain amount of MoS 2 QDs solution was dropped on the surface of the rutile phase TiO 2 nanorod array photoanode by direct dropping, wherein the molybdenum disulfide quantum dots serve as photosensitizers to convert light The light absorption range of the anode is effectively extended from ultraviolet light to visible light, and carrier recombination can be significantly suppressed with only a very small amount of load, greatly improving the photoelectrocatalytic activity of the TiO 2 photoanode.
本申请上述实施例提供的量子点敏化复合光阳极及制备方法，将MoS 2 QDs滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，并于惰性氛围保护下高温煅烧得到MoS 2/TiO 2的量子点敏化复合光阳极，本申请将MoS 2 QDs通过将光生电子转移到TiO 2纳米棒阵列中达到对其光敏化的效果，增强了复合光阳极整体的光吸收，从而在可见光下激活原始半导体的析氧能力，促进了电荷分离过程，提高了光响应电流，具有易于操作、清洁高效、可规模化生产等优点。 In the quantum dot sensitized composite photoanode and preparation method provided in the above embodiments of the present application, MoS 2 QDs are dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and then calcined at high temperature under the protection of an inert atmosphere to obtain MoS 2 / Quantum dot-sensitized composite photoanode of TiO 2. In this application, MoS 2 QDs achieves the photosensitization effect by transferring photogenerated electrons to the TiO 2 nanorod array, thereby enhancing the overall light absorption of the composite photoanode, thereby reducing the visible light It activates the oxygen evolution ability of the original semiconductor, promotes the charge separation process, increases the photoresponse current, and has the advantages of easy operation, clean efficiency, and large-scale production.
此外，本申请上述实施例利用简单滴加法构建的量子点敏化复合光阳极，由于优秀的量子点敏化效应，该工艺在水分解方面表现出出色的PEC活性。经过优化的MoS 2/TiO 2光阳极产生的光电流约为纯TiO 2的2.8倍，实现单个元件1+1＞2的效果，产品质量稳定，有利于实现大批量、工业化生产，为器件构建策略开辟新的可能性。 In addition, the quantum dot-sensitized composite photoanode constructed by a simple dropping method in the above embodiments of the present application shows excellent PEC activity in water decomposition due to the excellent quantum dot sensitization effect. The photocurrent generated by the optimized MoS 2 /TiO 2 photoanode is about 2.8 times that of pure TiO 2 , achieving the effect of 1+1>2 for a single component. The product quality is stable, which is conducive to the realization of large-volume, industrialized production and provides a good foundation for device construction. Strategies open up new possibilities.
以下结合具体实施例对本申请上述技术方案进行详细说明。The above technical solution of the present application will be described in detail below with reference to specific embodiments.
实施例1Example 1
金红石相TiO 2纳米棒阵列光阳极的制备 Preparation of rutile phase TiO2 nanorod array photoanode
（1）对FTO玻璃基片进行预处理，具体包括如下步骤：(1) Preprocess the FTO glass substrate, including the following steps:
a、将FTO玻璃基片使用玻璃刀剪裁为1×2 cm 2大小； a. Use a glass knife to cut the FTO glass substrate into a size of 1×2 cm2;
b、将剪裁后的FTO玻璃基片依次浸入无水乙醇、丙酮、去离子水、浓硫酸和过氧化氢的混合溶液中超声处理10~20 min，其中，所述浓硫酸和过氧化氢的体积比7:3；b. Immerse the cut FTO glass substrate in a mixed solution of absolute ethanol, acetone, deionized water, concentrated sulfuric acid and hydrogen peroxide for 10 to 20 minutes, where the concentration of concentrated sulfuric acid and hydrogen peroxide is Volume ratio 7:3;
c、再将超声处理后的FTO玻璃基片浸泡在去离子水中静置5~15 min，用以除去上述超声清洗过程中的各溶剂残留；c. Then soak the ultrasonic-treated FTO glass substrate in deionized water and let it stand for 5 to 15 minutes to remove the solvent residues in the above ultrasonic cleaning process;
d、最后将静置后的FTO玻璃基片浸于无水乙醇10~20 min后干燥处理。d. Finally, immerse the FTO glass substrate in absolute ethanol for 10 to 20 minutes and then dry it.
（2）将15 ml去离子水、15 ml浓盐酸和0.5 ml钛酸四丁酯加入烧杯中，室温下搅拌15 min，得到混合液；(2) Add 15 ml of deionized water, 15 ml of concentrated hydrochloric acid and 0.5 ml of tetrabutyl titanate into the beaker, and stir at room temperature for 15 minutes to obtain a mixed solution;
（3）将步骤（1）预处理后的FTO玻璃基片导电面朝下放入以聚四氟乙烯为内衬的高温反应釜中，将步骤（2）所得混合液加入内衬中，烘箱150 ℃水热反应20 h后冷却至室温。(3) Place the pretreated FTO glass substrate in step (1) with the conductive side down into a high-temperature reaction kettle lined with polytetrafluoroethylene, add the mixture obtained in step (2) into the lining, and oven The hydrothermal reaction was carried out at 150 °C for 20 h and then cooled to room temperature.
（4）将步骤（3）反应后的样品从内衬中取出，使用去离子水清洗并烘干后，置于马弗炉内500 ℃下煅烧2 h，待冷却至室温，得到金红石相TiO 2纳米棒阵列光阳极。 (4) Take out the sample after the reaction in step (3) from the lining, clean it with deionized water and dry it, then place it in a muffle furnace and calcine it at 500°C for 2 hours. After cooling to room temperature, the rutile phase TiO is obtained. 2 nanorod array photoanode.
如图5所示，通过SEM测定TiO 2光阳极的微观结构顶视图（上），可以观察到均匀的、方形的、直径约为200~400 nm的纳米棒组成的TiO 2阵列。通过SEM测定TiO 2光阳极的微观结构截面图（下），可以观察到纳米棒高约3 µm。 As shown in Figure 5, the top view of the microstructure of the TiO 2 photoanode measured by SEM (top), a TiO 2 array composed of uniform, square nanorods with a diameter of about 200~400 nm can be observed. Microstructural cross-section of the TiO2 photoanode measured by SEM (bottom), it can be observed that the nanorods are about 3 µm high.
如图6所示，通过XRD衍射图谱确定了TiO 2光阳极的晶体结构。光谱中36.1°、41.2°、54.3°、62.7°、69.0°和69.7°的峰值分别对应于(101)、(111)、(211)、(002)、(301)和(112)的金红石相晶面(JCPDS No. 21-1276)。七个星号（♦）标记峰26.4°、33.7°、37.8°、51.5°、61.6°、65.6°和78.7°可归类为FTO玻璃基片。 As shown in Figure 6, the crystal structure of the TiO2 photoanode was determined through the XRD diffraction pattern. The peaks at 36.1°, 41.2°, 54.3°, 62.7°, 69.0° and 69.7° in the spectrum correspond to the rutile phases of (101), (111), (211), (002), (301) and (112) respectively. Crystal plane (JCPDS No. 21-1276). Seven asterisks (♦) mark peaks 26.4°, 33.7°, 37.8°, 51.5°, 61.6°, 65.6° and 78.7° which can be classified as FTO glass substrates.
实施例2Example 2
二硫化钼量子点的合成策略Synthesis strategy of molybdenum disulfide quantum dots
（A）将5mg (NH 4) 2MoS 4溶解于20 mL去离子水中得到无色透明溶液，然后向该溶液中滴加500 μL水合肼(N2H 4·4H 2O)。所得溶液体系搅拌5 min后装入以聚四氟乙烯为内衬的不锈钢反应釜中，密封并在200 ℃下加热24 h后冷却至室温，11500r/min离心15 min以沉淀出去更大尺寸的粒子； (A) Dissolve 5 mg (NH 4 ) 2 MoS 4 in 20 mL deionized water to obtain a colorless and transparent solution, and then add 500 μL hydrazine hydrate (N2H 4 ·4H 2 O) dropwise to the solution. The resulting solution system was stirred for 5 minutes and then put into a polytetrafluoroethylene-lined stainless steel reactor, sealed and heated at 200°C for 24 hours, then cooled to room temperature, and centrifuged at 11500r/min for 15 minutes to precipitate larger sized particles. particle;
（B）上述体系取含有二硫化钼量子点的上清液装入10 mL注射器,通过孔径为0.22 μm的过滤头除去大尺寸颗粒，得到MoS 2 QDs溶液。 (B) From the above system, put the supernatant containing molybdenum disulfide quantum dots into a 10 mL syringe, and remove large-sized particles through a filter head with a pore size of 0.22 μm to obtain a MoS 2 QDs solution.
如图7所示，MoS 2 QDs为长半轴约4.5 nm、短半轴约3.1 nm的椭圆形片状形貌，内部晶格常数为0.205 nm, 对应辉钼矿-2H相的（006）晶面。由此，基本可确定该材料以量子点的形式在溶液中存在，且分散均匀，晶型明确。 As shown in Figure 7, MoS 2 QDs have an elliptical flake morphology with a long semi-axis of about 4.5 nm and a short semi-axis of about 3.1 nm. The internal lattice constant is 0.205 nm, corresponding to the (006) molybdenite-2H phase. Planes. From this, it is basically certain that the material exists in the form of quantum dots in the solution, is uniformly dispersed, and has a clear crystal form.
如图8所示，为了确定MoS 2 QDs材料表面的化学组成，对负载于玻璃表面的MoS 2 QDs进行了XPS测量。Mo 3d的精细XPS谱图（左）表明，MoS 2 QDs材料表面的Mo元素同时以+4（Mo 4+ 3d 5/2~228.8 eV; Mo 4+ 3d 3/2~232.0 eV）、+5（Mo 5+ 3d 5/2~231.9 eV; Mo 5+ 3d 3/2~235.1 eV）、+6（Mo 6+ 3d 5/2~233.1 eV; Mo 6+ 3d 3/2~236.3 eV）三种状态存在，证明暴露在空气中的MoS2 QDs材料表面被逐步轻微地氧化。S 2p的精细XPS谱图（右）表明，163.44 eV和164.55 eV可被分配到MoS 2 QDs中S的2p 3/2和2p 1/2，证明了材料中MoS 2以主要形式存在；163.52 eV (2p 3/2)和164.68 eV (2p 1/2)左右的S 2p双态可归因于二硫化物S22−或多硫化物Sx 2−；168.02 eV(2p 3/2)和169.17 eV(2p 1/2)分别归属于S-O键，再次证实了MoS 2 QDs材料表面具有薄薄的氧化层；综上可知，MoS 2 QDs主要由表面轻微氧化的椭圆形二硫化钼纳米片颗粒所构成，同时具有极少的多硫化钼存在。 As shown in Figure 8, in order to determine the chemical composition of the MoS 2 QDs material surface, XPS measurements were performed on MoS 2 QDs loaded on the glass surface. The fine XPS spectrum of Mo 3d (left) shows that the Mo element on the surface of MoS 2 QDs material simultaneously changes with +4 (Mo 4+ 3d 5/2 ~228.8 eV; Mo 4+ 3d 3/2 ~232.0 eV), +5 (Mo 5+ 3d 5/2 ~231.9 eV; Mo 5+ 3d 3/2 ~235.1 eV), +6 (Mo 6+ 3d 5/2 ~233.1 eV; Mo 6+ 3d 3/2 ~236.3 eV) three The existence of this state proves that the surface of the MoS2 QDs material exposed to the air is gradually and slightly oxidized. The fine XPS spectrum of S 2p (right) shows that 163.44 eV and 164.55 eV can be assigned to 2p 3/2 and 2p 1/2 of S in MoS 2 QDs, proving that MoS 2 exists in the main form in the material; 163.52 eV The S 2p doublet state around 164.68 eV (2p 3/2 ) and 164.68 eV (2p 1/2 ) can be attributed to disulfide S22− or polysulfide Sx 2− ; 168.02 eV (2p 3/2 ) and 169.17 eV( 2p 1/2 ) belong to SO bonds respectively, which once again confirms that the surface of MoS 2 QDs material has a thin oxide layer; in summary, it can be seen that MoS 2 QDs is mainly composed of elliptical molybdenum disulfide nanosheet particles with slightly oxidized surface. At the same time, there is very little molybdenum polysulfide present.
实施例3Example 3
一种量子点敏化复合光阳极的构筑策略A construction strategy for quantum dot-sensitized composite photoanode
将本申请提供的MoS 2 QDs溶液滴于干燥金红石相TiO 2纳米棒阵列光阳极的表面，置于热台上60 ℃蒸干，之后以Ar为惰性保护气的条件下，在管式炉中280 ℃-320 ℃下高温煅烧0.5-1 h得到量子点敏化的高效复合光阳极。 The MoS 2 QDs solution provided in this application is dropped on the surface of the dry rutile phase TiO 2 nanorod array photoanode, placed on the hot stage to evaporate to dryness at 60°C, and then placed in a tube furnace with Ar as an inert protective gas. High-efficiency quantum dot-sensitized composite photoanode was obtained by high-temperature calcination at 280°C-320°C for 0.5-1 h.
如图9所示，通过XRD衍射图谱确定了量子点敏化复合光阳极（MoS 2/TiO 2光阳极）的晶体结构。由于溶液浓度较低，致使MoS 2 QDs负载量也较低，低于XRD测试的最低检出限，因此，MoS 2/TiO 2材料复合光阳极的XRD特征峰与实施例1制备的金红石相TiO 2纳米棒阵列光阳极的XRD特征峰相重合。同时也说明，较少的量子点负载量即可大幅度提升光阳极的光电催化活性，成本低廉，极具工业化潜力。 As shown in Figure 9, the crystal structure of the quantum dot-sensitized composite photoanode (MoS 2 /TiO 2 photoanode) was determined through the XRD diffraction pattern. Due to the low concentration of the solution, the loading amount of MoS 2 QDs is also low, which is lower than the lowest detection limit of the XRD test. Therefore, the XRD characteristic peaks of the MoS 2 /TiO 2 material composite photoanode are different from those of the rutile phase TiO prepared in Example 1. The XRD characteristic peaks of the 2 nanorod array photoanode overlap. At the same time, it also shows that a smaller loading of quantum dots can greatly improve the photoelectrocatalytic activity of the photoanode, with low cost and great industrialization potential.
实施例4Example 4
一种量子点敏化的高效复合光阳极光电化学测试A quantum dot-sensitized high-efficiency composite photoanode for photoelectrochemical testing
1、所有光电化学测量均使用CHI660e恒电位仪在室温下的典型三电极电池中进行，其中光阳极（上述所制备样品）为工作电极，Pt箔为对电极，Ag/AgCl为参比电极。1. All photoelectrochemical measurements were performed in a typical three-electrode cell at room temperature using a CHI660e potentiostat, in which the photoanode (sample prepared above) was the working electrode, Pt foil was the counter electrode, and Ag/AgCl was the reference electrode.
2、电解液为0.05 M Na 2SO 4溶液，PH= 5.6。 2. The electrolyte is 0.05 M Na 2 SO 4 solution, PH= 5.6.
3、将制备好的MoS 2/TiO 2复合光阳极，***电解液中，测试面积为1×1 cm 2。 3. Insert the prepared MoS 2 /TiO 2 composite photoanode into the electrolyte, with a test area of 1×1 cm 2 .
4、使用集成了100 W氙弧灯和AM 1.5滤光片的peccell PEC-L01太阳模拟器在1个模拟太阳光光照下进行光电化学测量。4. Use the peccell PEC-L01 solar simulator integrated with a 100 W xenon arc lamp and AM 1.5 filter to perform photoelectrochemical measurements under 1 simulated sunlight illumination.
5、对于光电流测量，使用线性扫描伏安法(LSV)，扫描速率保持在0.05 V/s。5. For photocurrent measurements, linear scan voltammetry (LSV) was used with the scan rate maintained at 0.05 V/s.
6、根据Nernst方程(ERHE = EAg/AgCl + 0.0591pH + EɵAg/Cl)，将测得的Ag/AgCl电极(饱和KCl溶液)电势转换为可逆氢电极(VRHE)电势。6. According to the Nernst equation (ERHE = EAg/AgCl + 0.0591pH + EɵAg/Cl), convert the measured Ag/AgCl electrode (saturated KCl solution) potential into the reversible hydrogen electrode (VRHE) potential.
如图10所示，从J-V曲线可以看出，MoS 2/TiO 2光阳极在1.23 V下光电流最高约为1.45 mA/cm 2(1.23 vs. RHE)，是纯TiO 2光阳极的2.8倍，表现出优异的PEC性能，证实了MoS 2 QDs敏化方法在改善太阳光转换过程中的有效作用。 As shown in Figure 10, it can be seen from the JV curve that the highest photocurrent of the MoS 2 /TiO 2 photoanode is about 1.45 mA/cm 2 (1.23 vs. RHE) at 1.23 V, which is 2.8 times that of the pure TiO 2 photoanode , showing excellent PEC performance, confirming the effective role of the MoS 2 QDs sensitization method in improving the solar light conversion process.
可以理解，以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。It can be understood that the technical features of the above-described embodiments can be combined in any way. To simplify the description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as the combination of these technical features does not If there is any contradiction, it should be considered to be within the scope of this manual.
以上仅为本申请的较佳实施例而已，仅具体描述了本申请的技术原理，这些描述只是为了解释本申请的原理，不能以任何方式解释为对本申请保护范围的限制。基于此处解释，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进，及本领域的技术人员不需要付出创造性的劳动即可联想到本申请的其他具体实施方式，均应包含在本申请的保护范围之内。The above are only preferred embodiments of the present application and only specifically describe the technical principles of the present application. These descriptions are only for explaining the principles of the present application and cannot be construed as limiting the protection scope of the present application in any way. Based on the explanation here, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application, and those skilled in the art can think of other specific implementations of the present application without having to exert creative efforts. should be included in the protection scope of this application.

Claims (10)

  1. 一种量子点敏化复合光阳极的制备方法，其特征在于，包括下述步骤：A method for preparing a quantum dot-sensitized composite photoanode, which is characterized by including the following steps:
    制备金红石相TiO 2纳米棒阵列光阳极； Preparation of rutile phase TiO 2 nanorod array photoanode;
    将MoS 2 QDs滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，并于惰性氛围保护下高温煅烧得到MoS 2/TiO 2的量子点敏化复合光阳极。 MoS 2 QDs is dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and is calcined at high temperature under the protection of an inert atmosphere to obtain a MoS 2 /TiO 2 quantum dot-sensitized composite photoanode.
  2. 如权利要求1所述的量子点敏化复合光阳极的制备方法，其特征在于，在制备金红石相TiO 2纳米棒阵列光阳极的步骤中，具体包括下述步骤： The method for preparing a quantum dot-sensitized composite photoanode as claimed in claim 1, wherein the step of preparing a rutile phase TiO2 nanorod array photoanode specifically includes the following steps:
    将FTO玻璃基片的导电面朝下置入反应釜中，所述反应釜以聚四氟乙烯为内衬；Place the conductive surface of the FTO glass substrate face down into a reactor lined with polytetrafluoroethylene;
    将去离子水、浓盐酸及钛酸四丁酯溶液搅拌均匀后加入所述反应釜中，并在150~200 ℃水热反应15~20 h后冷却至室温得到反应后的FTO玻璃基片；Stir deionized water, concentrated hydrochloric acid and tetrabutyl titanate solution evenly and then add them to the reaction kettle, and stir at 150~200 ℃ hydrothermal reaction 15~20 After h, cool to room temperature to obtain the reacted FTO glass substrate;
    将所述反应后的FTO玻璃基片用去离子水冲洗晾干后于400~600℃下煅烧2~3 h，再冷却至室温，得到所述金红石相TiO 2纳米棒阵列光阳极。 The reacted FTO glass substrate is rinsed and dried with deionized water, then calcined at 400 to 600°C for 2 to 3 hours, and then cooled to room temperature to obtain the rutile phase TiO 2 nanorod array photoanode.
  3. 如权利要求2所述的量子点敏化复合光阳极的制备方法，其特征在于，所述FTO玻璃基片的厚度为2.0~2.2 mm，透光率为80%以上，方阻6~7 Ω，FTO膜层厚度为300~350 nm。The preparation method of quantum dot-sensitized composite photoanode according to claim 2, characterized in that the thickness of the FTO glass substrate is 2.0~2.2 mm, the light transmittance is more than 80%, and the square resistance is 6~7 Ω. , FTO film thickness is 300~350 nm.
  4. 如权利要求3所述的量子点敏化复合光阳极的制备方法，其特征在于，在使用所述FTO玻璃基片前，还包括对所述FTO玻璃基片进行预处理的步骤，所述预处理包括：The method for preparing a quantum dot-sensitized composite photoanode according to claim 3, characterized in that, before using the FTO glass substrate, it further includes the step of pre-processing the FTO glass substrate, and the pre-processing step is Processing includes:
    将所述FTO玻璃基片剪裁为1×2 cm 2大小； Cut the FTO glass substrate into a size of 1×2 cm2;
    将剪裁后的所述FTO玻璃基片依次浸入无水乙醇、丙酮、去离子水、浓硫酸和过氧化氢的混合溶液中超声处理10~20 min，其中，所述浓硫酸和过氧化氢的体积比7:3；The cut FTO glass substrate is sequentially immersed in a mixed solution of absolute ethanol, acetone, deionized water, concentrated sulfuric acid and hydrogen peroxide and sonicated for 10 to 20 seconds. min, wherein the volume ratio of concentrated sulfuric acid and hydrogen peroxide is 7:3;
    再将超声处理后的所述FTO玻璃基片浸泡在去离子水中静置5~15 min，用以除去上述超声清洗过程中的各溶剂残留；Then, the ultrasonic-treated FTO glass substrate is soaked in deionized water and left to stand for 5 to 15 minutes. min, used to remove the solvent residues in the above ultrasonic cleaning process;
    最后将静置后的所述FTO玻璃基片浸于无水乙醇10~20 min后干燥处理。Finally, the FTO glass substrate after standing was immersed in absolute ethanol for 10 to 20 minutes and then dried.
  5. 如权利要求4所述的量子点敏化复合光阳极的制备方法，其特征在于，所述浓盐酸在20℃的密度为1.18 g/mL，HCl含量36~38%。The method for preparing a quantum dot-sensitized composite photoanode according to claim 4, wherein the density of the concentrated hydrochloric acid at 20°C is 1.18 g/mL, and the HCl content is 36 to 38%.
  6. 如权利要求1所述的量子点敏化复合光阳极的制备方法，其特征在于，在将MoS 2 QDs滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，并于惰性氛围保护下高温煅烧得到MoS 2/TiO 2的量子点敏化复合光阳极的步骤中，具体包括下述步骤： The preparation method of quantum dot-sensitized composite photoanode according to claim 1, characterized in that, after MoS 2 QDs is dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and the temperature is maintained at high temperature under the protection of an inert atmosphere The steps of calcining to obtain a quantum dot-sensitized composite photoanode of MoS 2 /TiO 2 specifically include the following steps:
    将所述的MoS 2 QDs溶液滴于所述金红石相TiO 2纳米棒阵列光阳极的表面，再置于40-80℃蒸干，之后再以Ar为惰性保护气的条件下，在280℃-320℃下高温煅烧0.5-1 h得到MoS 2/TiO 2的量子点敏化复合光阳极。 The MoS 2 QDs solution was dropped on the surface of the rutile phase TiO 2 nanorod array photoanode, and then evaporated to dryness at 40-80°C, and then used Ar as an inert protective gas at 280°C- The quantum dot-sensitized composite photoanode of MoS 2 /TiO 2 was obtained by high-temperature calcination at 320°C for 0.5-1 h.
  7. 如权利要求6所述的量子点敏化复合光阳极的制备方法，其特征在于，所述MoS 2 QDs通过水热法合成。 The method for preparing a quantum dot-sensitized composite photoanode according to claim 6, wherein the MoS 2 QDs are synthesized by a hydrothermal method.
  8. 如权利要求7所述的量子点敏化复合光阳极的制备方法，其特征在于，在所述MoS 2 QDs通过水热法合成的步骤中，具体包括下述步骤： The method for preparing a quantum dot-sensitized composite photoanode according to claim 7, wherein the step of synthesizing MoS 2 QDs by a hydrothermal method specifically includes the following steps:
    将(NH 4) 2MoS 4、去离子水及N 2H 4·4H 2O混合搅拌后得到混合溶液； (NH 4 ) 2 MoS 4 , deionized water and N 2 H 4 ·4H 2 O are mixed and stirred to obtain a mixed solution;
    将所述混合溶液置于以聚四氟乙烯为内衬的不锈钢反应釜中，密封并在150-200℃下加热18-24 h后冷却至室温，再离心15-30 min以沉淀除去更大尺寸的粒子；Place the mixed solution into a stainless steel reactor lined with polytetrafluoroethylene, seal and heat at 150-200°C for 18-24 hours, then cool to room temperature, and then centrifuge for 15-30 minutes to precipitate and remove larger particles. size particles;
    在上述混合溶液中取含有MoS 2 QDs的上清液并经过滤后以除去大尺寸颗粒，得到MoS 2 QDs溶液。 Take the supernatant containing MoS 2 QDs from the above mixed solution and filter it to remove large-sized particles to obtain a MoS 2 QDs solution.
  9. 一种量子点敏化复合光阳极，其特征在于，由权利要求1至8任一项所述的量子点敏化复合光阳极的制备方法制备得到。A quantum dot-sensitized composite photoanode is characterized in that it is prepared by the preparation method of a quantum dot-sensitized composite photoanode according to any one of claims 1 to 8.
  10. 一种如权利要求9所述的量子点敏化复合光阳极在光电催化中的应用。An application of the quantum dot-sensitized composite photoanode as claimed in claim 9 in photoelectrocatalysis.
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