CN105568314A - A preparation method of CuWO4/WO3 heterostructure nanosheet array film - Google Patents
A preparation method of CuWO4/WO3 heterostructure nanosheet array film Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000012546 transfer Methods 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 4
- 238000003491 array Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract 2
- 239000010409 thin film Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910017610 Cu(NO3) Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
本发明公开了一种CuWO4/WO3异质结构纳米片阵列薄膜的制备方法，具体步骤为：仲钨酸铵水合物的水和乙醇溶液中加入浓盐酸和双氧水，搅拌混合均匀后制得WO3前驱物溶液；水热反应制备WO3纳米片阵列；WO3纳米片阵列在二价铜盐的乙醇溶液中浸泡，再退火得到CuWO4/WO3异质结构纳米片阵列薄膜。本发明得到的产品中WO3纳米片垂直于FTO生长，CuWO4纳米颗粒紧紧结合在WO3纳米片表面，CuWO4的导带位置与WO3相比更负，当光照射到薄膜电极上，利于光生电荷的分离，作为光电化学分解水的光阳极，可以提高分解水的效率。The invention discloses a method for preparing a CuWO 4 /WO 3 heterostructure nanosheet array film. The specific steps are: adding concentrated hydrochloric acid and hydrogen peroxide to the water and ethanol solution of ammonium paratungstate hydrate, stirring and mixing uniformly to prepare the WO 3 precursor solution; hydrothermal reaction to prepare WO 3 nanosheet arrays; WO 3 nanosheet arrays were immersed in ethanol solution of divalent copper salt, and then annealed to obtain CuWO 4 /WO 3 heterostructure nanosheet array films. In the product obtained by the present invention, WO 3 nanosheets grow vertically to FTO, and CuWO 4 nanoparticles are tightly combined on the surface of WO 3 nanosheets, and the conduction band position of CuWO 4 is more negative than that of WO 3. When light is irradiated on the thin film electrode , is conducive to the separation of photogenerated charges, and as a photoanode for photoelectrochemical water splitting, it can improve the efficiency of water splitting.
Description
技术领域 technical field
本发明属于无机纳米光电材料的合成技术领域，具体涉及一种CuWO4/WO3异质结构纳米片阵列薄膜的制备方法。 The invention belongs to the technical field of synthesis of inorganic nano-optical materials, and in particular relates to a method for preparing a CuWO 4 /WO 3 heterostructure nanosheet array film.
背景技术 Background technique
随着世界人口的增多和人们对物质的要求越来越高，人类对能源的依赖程度和需求量迅速增加，导致了地球上化石燃料储存量的剧烈下降，并产生了严重的环境问题。寻找一种新的清洁能源是各国政府和科学家们所追求和关注的目标。在这些新兴能源中，太阳能作为取之不尽的无污染能源备受关注。 With the increase of the world's population and people's higher and higher requirements for materials, the dependence and demand of human beings on energy have increased rapidly, resulting in a sharp decline in the storage of fossil fuels on the earth and serious environmental problems. Finding a new clean energy source is the goal that governments and scientists are pursuing and paying attention to. Among these emerging energy sources, solar energy has attracted much attention as an inexhaustible pollution-free energy source.
1972年日本学者Fujishima和Honda采用单晶n-TiO2进行太阳能光催化分解水制氢的成功，揭开了半导体光催化研究的序幕，也使人们认识到太阳能转化为电能和化学能的应用前景。光电化学分解水制氢技术，基于太阳能和水两种可再生物质，没有副产物，不会污染环境，同时光电化学分解水技术兼顾小规模应用与大规模开发，是太阳能制氢最具吸引力的途径之一。 In 1972, Japanese scholars Fujishima and Honda successfully used single crystal n- TiO2 to split water into hydrogen by solar photocatalysis, which opened the prelude to the research of semiconductor photocatalysis and also made people realize the application prospect of converting solar energy into electrical energy and chemical energy. . Photoelectrochemical water splitting technology for hydrogen production is based on two renewable substances, solar energy and water. It has no by-products and will not pollute the environment. At the same time, photoelectrochemical water splitting technology takes into account both small-scale applications and large-scale development, and is the most attractive for solar hydrogen production. one of the ways.
WO3是一种间接带隙跃迁的半导体材料，具有良好的化学稳定性，是少数自身具有抗光腐蚀能力的n-型半导体材料之一。WO3的带隙宽度为~2.65eV，吸收光的波长可延伸至可见光区域（~470nm），是一种理想的光电化学分解水的光阳极材料。WO3纳米颗粒薄膜由于存在大量晶界，不利于光生电荷的传输；WO3纳米片阵列由于具有准直的电子传输通道，利用光生电荷的传输。为了提高WO3光阳极光生电荷的分离效率，与其他能带匹配的半导体（如CuWO4）形成异质结是一种有效的方法。 WO 3 is a semiconductor material with an indirect bandgap transition, which has good chemical stability and is one of the few n-type semiconductor materials that have the ability to resist photocorrosion. The bandgap width of WO 3 is ~2.65eV, and the wavelength of light absorption can extend to the visible region (~470nm), making it an ideal photoanode material for photoelectrochemical water splitting. The WO 3 nanoparticle film is not conducive to the transport of photogenerated charges due to the existence of a large number of grain boundaries; the WO 3 nanosheet array utilizes the transport of photogenerated charges due to its collimated electron transport channels. To improve the separation efficiency of the photogenerated charges at the WO photoanode, forming heterojunctions with other band-matched semiconductors (such as CuWO 4 ) is an effective approach.
发明内容 Contents of the invention
本发明解决的技术问题是提供了一种操作简单、成本低廉且环境友好的CuWO4/WO3异质结构纳米片阵列薄膜的制备方法。 The technical problem solved by the invention is to provide a method for preparing CuWO 4 /WO 3 heterostructure nanosheet array film with simple operation, low cost and environmental friendliness.
本发明为解决上述技术问题采用如下技术方案，一种CuWO4/WO3异质结构纳米片阵列薄膜的制备方法，其特征在于具体步骤为： In order to solve the above technical problems, the present invention adopts the following technical scheme, a method for preparing a CuWO 4 /WO 3 heterostructure nanosheet array film, which is characterized in that the specific steps are:
（1）将0.2-0.4g仲钨酸铵水合物分散到水和乙醇的混合溶剂中，再加入1-2mL质量浓度为37%的浓盐酸和1-2mL质量浓度为35%的双氧水，搅拌混合均匀后制得WO3前驱物溶液； (1) Disperse 0.2-0.4g of ammonium paratungstate hydrate into a mixed solvent of water and ethanol, then add 1-2mL of concentrated hydrochloric acid with a mass concentration of 37% and 1-2mL of hydrogen peroxide with a mass concentration of 35%, and stir and mix evenly Prepare WO 3 precursor solution;
（2）将步骤（1）所得的WO3前驱物溶液转移至水热反应釜中，并将FTO导电面朝下放入水热反应釜中，将FTO导电面朝下于140-180℃水热反应2-6h，反应结束后随炉冷却至室温，取出FTO冲洗后室温干燥，然后置于马弗炉中于500℃退火2h制得WO3纳米片阵列； (2) Transfer the WO 3 precursor solution obtained in step (1) to a hydrothermal reaction kettle, put the FTO conductive side down into the hydrothermal reaction kettle, put the FTO conductive side down in 140-180℃ water Thermal reaction for 2-6 hours, after the reaction is completed, cool down to room temperature with the furnace, take out the FTO, wash it, dry it at room temperature, and then place it in a muffle furnace for annealing at 500°C for 2 hours to prepare a WO 3 nanosheet array;
（3）将步骤（2）所得的WO3纳米片阵列垂直浸入二价铜盐的乙醇溶液中反应0.5-2h后取出，其中二价铜盐的乙醇溶液中Cu2+的摩尔浓度为30-70mmol/L，室温干燥后置于马弗炉中于500℃退火2h制得CuWO4/WO3异质结构纳米片阵列薄膜。 (3) Vertically immerse the WO 3 nanosheet array obtained in step (2) in the ethanol solution of divalent copper salt and take it out after reacting for 0.5-2h, wherein the molar concentration of Cu 2+ in the ethanol solution of divalent copper salt is 30- 70mmol/L, dried at room temperature, placed in a muffle furnace and annealed at 500°C for 2h to prepare a CuWO 4 /WO 3 heterostructure nanosheet array film.
进一步优选，步骤（1）所述的水和乙醇的混合溶剂中水与乙醇的体积比为1:4~4:1。 Further preferably, the volume ratio of water and ethanol in the mixed solvent of water and ethanol in step (1) is 1:4-4:1.
进一步优选，步骤（3）所述的二价铜盐为CuSO4、Cu(NO3)2或Cu(CH3COO)2。 Further preferably, the divalent copper salt in step (3) is CuSO 4 , Cu(NO 3 ) 2 or Cu(CH 3 COO) 2 .
本发明制得的CuWO4/WO3异质结构纳米片阵列薄膜具有较高的比表面积和准直的电子传输通道，利于对入射光的捕获和光电荷的传输；CuWO4/WO3异质结构还利于光生电荷的分离，因此作为光电化学分解水的光阳极将表现出优异的性质。另外，水热法结合溶液浸泡的方法制备CuWO4/WO3操作简单、成本低廉且环境友好，利于推广和应用。 The CuWO 4 /WO 3 heterostructure nanosheet array film prepared by the present invention has a high specific surface area and collimated electron transport channels, which is beneficial to the capture of incident light and the transmission of photocharges; the CuWO 4 /WO 3 heterostructure It is also beneficial to the separation of photogenerated charges, so it will exhibit excellent properties as a photoanode for photoelectrochemical water splitting. In addition, the method of hydrothermal method combined with solution immersion to prepare CuWO 4 /WO 3 has simple operation, low cost and environmental friendliness, which is beneficial to popularization and application.
具体实施方式 detailed description
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。 The above-mentioned contents of the present invention are described in further detail below through the embodiments, but this should not be interpreted as the scope of the above-mentioned themes of the present invention being limited to the following embodiments, and all technologies realized based on the above-mentioned contents of the present invention all belong to the scope of the present invention.
实施例1 Example 1
（1）将0.2g仲钨酸铵水合物H42N10O42W12·xH2O(HMT)分散到水和乙醇的混合溶剂中，其中水和乙醇的体积比为4:1，再加入1mL质量浓度为37%的浓盐酸和1mL质量浓度为35%的双氧水，搅拌混合均匀后制得WO3前驱物溶液； (1) Disperse 0.2g of ammonium paratungstate hydrate H 42 N 10 O 42 W 12 ·xH 2 O (HMT) into a mixed solvent of water and ethanol, where the volume ratio of water and ethanol is 4:1, and then add 1mL of mass Concentrated hydrochloric acid with a concentration of 37% and 1 mL of hydrogen peroxide with a mass concentration of 35% were stirred and mixed uniformly to prepare a WO 3 precursor solution;
（2）将步骤（1）所得的WO3前驱物溶液液转移至水热反应釜中，并将FTO导电面朝下放入该水热反应釜内，将其导电面朝下于140℃反应2小时，反应结束后随炉冷却至室温，取出FTO，冲洗后室温干燥，并在马弗炉中于500℃退火2小时制得WO3纳米片阵列； (2) Transfer the WO 3 precursor solution obtained in step (1) to a hydrothermal reaction kettle, put the FTO conductive side down into the hydrothermal reaction kettle, and react at 140°C with its conductive side down After 2 hours, cool down to room temperature with the furnace after the reaction, take out the FTO, rinse and dry at room temperature, and anneal in a muffle furnace at 500°C for 2 hours to prepare WO 3 nanosheet arrays;
（3）将步骤（2）所得的WO3纳米片阵列垂直浸入摩尔浓度为30mmol/L的CuSO4的乙醇溶液中，反应0.5小时后取出，室温干燥后置于马弗炉中于500℃退火2小时制得CuWO4/WO3异质结纳米片阵列薄膜。 (3) Vertically immerse the WO 3 nanosheet array obtained in step (2) into an ethanol solution of CuSO 4 with a molar concentration of 30 mmol/L, take it out after 0.5 hours of reaction, dry it at room temperature, place it in a muffle furnace and anneal at 500 °C CuWO 4 /WO 3 heterojunction nanosheet array film was prepared in 2 hours.
实施例2 Example 2
（1）将0.3g仲钨酸铵水合物H42N10O42W12·xH2O(HMT)分散到水和乙醇的混合溶剂中，其中水和乙醇的体积比为1:1，再加入1mL质量浓度为37%的浓盐酸和1mL质量浓度为35%的双氧水，搅拌混合均匀后制得WO3前驱物溶液； (1) Disperse 0.3g of ammonium paratungstate hydrate H 42 N 10 O 42 W 12 xH 2 O (HMT) into a mixed solvent of water and ethanol, where the volume ratio of water and ethanol is 1:1, and then add 1mL of mass Concentrated hydrochloric acid with a concentration of 37% and 1 mL of hydrogen peroxide with a mass concentration of 35% were stirred and mixed uniformly to prepare a WO 3 precursor solution;
（2）将步骤（1）所得的WO3前驱物溶液转移至水热反应釜中，并将FTO导电面朝下放入该水热反应釜内，将其导电面朝下于160℃反应4小时，反应结束后随炉冷却至室温，取出FTO，冲洗后室温干燥，并在马弗炉中于500℃退火2小时制得WO3纳米片阵列； (2) Transfer the WO 3 precursor solution obtained in step (1) to a hydrothermal reactor, put the FTO conductive side down into the hydrothermal reactor, and put its conductive side down at 160°C for 4 Hours, after the reaction was completed, the furnace was cooled to room temperature, the FTO was taken out, rinsed and dried at room temperature, and annealed in a muffle furnace at 500°C for 2 hours to obtain a WO 3 nanosheet array;
（3）将步骤（2）得到的WO3纳米片阵列垂直浸入摩尔浓度为50mmol/L的Cu(CH3COO)2的乙醇溶液中，反应1小时后取出，室温干燥后置于马弗炉中于500℃退火2小时制得CuWO4/WO3异质结纳米片阵列薄膜。 (3) Vertically immerse the WO 3 nanosheet array obtained in step (2) into a Cu(CH 3 COO) 2 ethanol solution with a molar concentration of 50 mmol/L, take it out after 1 hour of reaction, dry it at room temperature and place it in a muffle furnace CuWO 4 /WO 3 heterojunction nanosheet array films were prepared by annealing at 500°C for 2 hours.
实施例3 Example 3
（1）将0.4g仲钨酸铵水合物H42N10O42W12·xH2O(HMT)分散到水和乙醇的混合溶剂中，其中水和乙醇的体积比为4:1，再加入2mL质量浓度为37%的浓盐酸和2mL质量浓度为35%的双氧水，搅拌混合均匀后制得WO3前驱物溶液； (1) Disperse 0.4g of ammonium paratungstate hydrate H 42 N 10 O 42 W 12 ·xH 2 O (HMT) into a mixed solvent of water and ethanol, where the volume ratio of water and ethanol is 4:1, and then add 2mL of mass Concentrated hydrochloric acid with a concentration of 37% and 2 mL of hydrogen peroxide with a mass concentration of 35% were stirred and mixed uniformly to prepare a WO3 precursor solution;
（2）将步骤（1）所得的WO3前驱物溶液转移至水热反应釜中，并将FTO导电面朝下放入该水热反应釜内，将其导电面朝下于180℃反应6小时，反应结束后随炉冷却至室温，取出FTO，冲洗后室温干燥，并在马弗炉中500℃退火2小时制得WO3纳米片阵列； (2) Transfer the WO 3 precursor solution obtained in step (1) to a hydrothermal reactor, put the FTO conductive side down into the hydrothermal reactor, and put its conductive side down at 180°C for 6 Hours, after the reaction was completed, the furnace was cooled to room temperature, the FTO was taken out, rinsed and dried at room temperature, and annealed in a muffle furnace at 500°C for 2 hours to obtain a WO 3 nanosheet array;
（3）将步骤（2）所得的WO3纳米片阵列垂直浸入摩尔浓度为70mmol/L的Cu(NO3)2的乙醇溶液中，反应2小时后取出，室温干燥后置于马弗炉中于500℃退火2小时制得CuWO4/WO3异质结纳米片阵列薄膜。 (3) Vertically immerse the WO 3 nanosheet array obtained in step (2) into an ethanol solution of Cu(NO3) 2 with a molar concentration of 70mmol/L, take it out after 2 hours of reaction, dry it at room temperature, and place it in a muffle furnace at The CuWO 4 /WO 3 heterojunction nanosheet array film was prepared by annealing at 500°C for 2 hours.
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。 The above embodiments have described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. What are described in the above embodiments and description are only to illustrate the principles of the present invention. Without departing from the scope of the principle of the present invention, there will be various changes and improvements in the present invention, and these changes and improvements all fall within the protection scope of the present invention.
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| CN106252101A (en) * | 2016-09-27 | 2016-12-21 | 西北工业大学 | The preparation method of ultracapacitor nanometer Cupric wolframate. polyhedron electrode material |
| CN106252101B (en) * | 2016-09-27 | 2018-06-08 | 西北工业大学 | The preparation method of ultracapacitor nanometer copper tungstate polyhedron electrode material |
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