CN106391055A - ZnO/CdS/CuS nanometer array composite material preparation method - Google Patents
ZnO/CdS/CuS nanometer array composite material preparation method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 26
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002073 nanorod Substances 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003980 solgel method Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 13
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002120 nanofilm Substances 0.000 claims description 5
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002052 molecular layer Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- 230000001699 photocatalysis Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种ZnO/CdS/CuS纳米阵列复合材料的制备方法。首先通过溶胶凝胶法制备ZnO种子层溶液；采用浸渍‑提拉法在ITO玻璃基底上涂覆ZnO种子层，经过热处理后，将长有ZnO种子层的导电玻璃放置在ZnO生长溶液中热水浴处理，得到ZnO纳米棒；将已经生长ZnO纳米阵列的试样放入硫代乙酰胺溶液中，经过水浴后制得ZnO/ZnS纳米阵列；采用离子交换法将CdS、CuS纳米粒子沉积到ZnO纳米层上，得到ZnO/CdS/CuS纳米阵列复合材料。
The invention discloses a preparation method of a ZnO/CdS/CuS nano array composite material. First, the ZnO seed layer solution was prepared by the sol-gel method; the ZnO seed layer was coated on the ITO glass substrate by the dip-pulling method, and after heat treatment, the conductive glass with the ZnO seed layer was placed in the hot water of the ZnO growth solution bath treatment to obtain ZnO nanorods; put the sample that has grown ZnO nanoarrays into a thioacetamide solution, and make a ZnO/ZnS nanoarray after passing through a water bath; deposit CdS and CuS nanoparticles on the ZnO On the nanometer layer, a ZnO/CdS/CuS nanoarray composite material is obtained.
Description
技术领域technical field
本发明属于材料制备技术领域，具体为一种用于光电催化的ZnO/CdS/CuS纳米阵列复合材料的制备方法。The invention belongs to the technical field of material preparation, in particular to a method for preparing a ZnO/CdS/CuS nanometer array composite material used for photoelectric catalysis.
背景技术Background technique
目前，环境污染和能源危机正严重的影响着人类的生产生活，而解决环境污染和能源危机的关键之举是绿色新能源材料的突破。太阳能以其绿色环保、取之不尽用之不竭等特点成为人类解决能源问题，实现可持续发展的良好途径。但太阳能的利用虽可观，其材料问题却是瓶颈。如何研究、开发并高效利用太阳能便成为国内外的研究热点，无疑氢能是解决这一顾虑的绝佳途径。氢能作为绿色高效的二次能源，储量丰富，而且来源为清洁的水，燃烧后无污染，它是利用太阳能的最佳载体。At present, environmental pollution and energy crisis are seriously affecting human production and life, and the key to solving environmental pollution and energy crisis is the breakthrough of green new energy materials. Solar energy has become a good way for human beings to solve energy problems and achieve sustainable development because of its environmental protection, inexhaustibility and other characteristics. However, although the utilization of solar energy is considerable, its material problem is a bottleneck. How to research, develop and efficiently utilize solar energy has become a research hotspot at home and abroad, and hydrogen energy is undoubtedly an excellent way to solve this concern. As a green and efficient secondary energy source, hydrogen energy has abundant reserves, and the source is clean water, which is pollution-free after combustion. It is the best carrier for utilizing solar energy.
所有开发利用太阳能转换为氢能的途径中，利用半导体光催化剂产氢，可以直接将太阳能转换为以氢气为载体的化学能，因此太阳能光解水制氢过程是目前较为理想且较有前途的氢能开发手段之一。光催化分解水制氢主要分为两大类，即光电化学制氢以及光催化制氢。光催化剂的选取对于光解水过程起着举重若轻地作用，其合适的能带结构和光生电子与空穴的有效分离对于促进光解水制氢来说至关重要。因此，寻找合适的方法促进光生电子与空穴的分离、增加光生载流子的利用率，并且开发新型光催化材料就成为提高太阳光能分解水产氢效率的关键之处。目前对于宽禁带的光催化剂，一种有效的拓宽其可见光响应范围的手段是引入过渡金属离子从而形成新的电子供体或者受体。Among all the ways to develop and utilize solar energy into hydrogen energy, the use of semiconductor photocatalysts to produce hydrogen can directly convert solar energy into chemical energy with hydrogen as the carrier. Therefore, the process of solar photolysis of water to produce hydrogen is currently ideal and promising. One of the means of hydrogen energy development. Photocatalytic water splitting for hydrogen production is mainly divided into two categories, namely photoelectrochemical hydrogen production and photocatalytic hydrogen production. The selection of photocatalyst plays an important role in the process of photo-splitting water, and its suitable energy band structure and effective separation of photogenerated electrons and holes are crucial to promote the photo-splitting of water to produce hydrogen. Therefore, finding a suitable method to promote the separation of photogenerated electrons and holes, increasing the utilization rate of photogenerated carriers, and developing new photocatalytic materials are the key points to improve the efficiency of hydrogen production from water splitting by solar energy. At present, for wide-bandgap photocatalysts, an effective means to broaden their visible light response range is to introduce transition metal ions to form new electron donors or acceptors.
ZnO作为一种新型的重要的II-VI族直接宽禁带半导体材料，具有优异的光学和电学特性。ZnO的能带隙和激子束缚能较大，在室温下ZnO禁带宽度为3.37eV，它的激子束缚能高达60meV。ZnO本身没有任何杂质的情况下具有N型半导体的特征。在太阳能光解水产氢半导体材料研究领域，ZnO纳米材料被认为是继TiO2后最理想的半导体材料，理由如下：首先，ZnO属于宽禁带半导体材料(Eg：3.37eV)；其次，电子在ZnO中具有更大的迁移率，能够减少光生电子-空穴复合的几率；此外，ZnO的成本低廉。除此之外，一维ZnO纳米材料(纳米线、纳米棒、纳米管等)以其粒径均匀、长径比大等优点作为当今的研究热点。As a new type of important II-VI direct wide bandgap semiconductor material, ZnO has excellent optical and electrical properties. ZnO has a large energy band gap and exciton binding energy. At room temperature, the ZnO band gap is 3.37eV, and its exciton binding energy is as high as 60meV. ZnO itself has the characteristics of an N-type semiconductor without any impurities. In the research field of semiconductor materials for solar photolysis of water to produce hydrogen, ZnO nanomaterials are considered to be the most ideal semiconductor materials after TiO 2 for the following reasons: first, ZnO is a wide bandgap semiconductor material (Eg: 3.37eV); second, electrons in ZnO has greater mobility, which can reduce the probability of photogenerated electron-hole recombination; in addition, ZnO is low in cost. In addition, one-dimensional ZnO nanomaterials (nanowires, nanorods, nanotubes, etc.) are currently a research hotspot due to their uniform particle size and large aspect ratio.
由于ZnO其较宽的禁带宽度，只能对紫外光响应而不能被可见光激发，所以需要通过无机窄带隙半导体敏化宽带隙半导体材料。而CdS、CuS等硫族半导体作为窄禁带光催化剂能够大幅度增加光阳极对可见光区域的光响应。因此，我们提出一种全新的方案，将CdS、CuS与ZnO纳米阵列复合形成ZnO/CdS/CuS纳米阵列复合材料，旨在改善其光电催化性能。Due to its wide forbidden band width, ZnO can only respond to ultraviolet light but cannot be excited by visible light, so it is necessary to sensitize wide-bandgap semiconductor materials through inorganic narrow-bandgap semiconductors. However, chalcogenide semiconductors such as CdS and CuS as narrow-bandgap photocatalysts can greatly increase the photoresponse of the photoanode to the visible light region. Therefore, we propose a new scheme to combine CdS, CuS and ZnO nanoarrays to form ZnO/CdS/CuS nanoarray composites, aiming at improving their photocatalytic performance.
发明内容Contents of the invention
本发明的目的在于提出一种ZnO/CdS/CuS纳米阵列复合材料的制备方法，能够改善ZnO的光电催化性能。The purpose of the present invention is to propose a preparation method of ZnO/CdS/CuS nano-array composite material, which can improve the photoelectric catalytic performance of ZnO.
ZnO/CdS/CuS纳米阵列复合材料的制备方法，其特征在于，首先通过溶胶凝胶法制备ZnO种子层溶液；采用浸渍-提拉法在ITO玻璃基底上涂覆ZnO种子层，经过热处理后，将长有ZnO种子层的导电玻璃放置在ZnO生长溶液中热水浴处理，得到ZnO纳米棒；将已经生长ZnO纳米阵列的试样放入硫代乙酰胺溶液中，经过水浴后制得ZnO/ZnS纳米阵列；采用离子交换法将CdS、CuS纳米粒子沉积到ZnO纳米层上，得到ZnO/CdS/CuS纳米阵列复合材料。The preparation method of ZnO/CdS/CuS nano-array composite material is characterized in that, firstly, a ZnO seed layer solution is prepared by a sol-gel method; a ZnO seed layer is coated on an ITO glass substrate by a dipping-pulling method, and after heat treatment, Place the conductive glass with the ZnO seed layer in a ZnO growth solution in a hot water bath to obtain ZnO nanorods; put the sample that has grown ZnO nanoarrays into a thioacetamide solution, and make ZnO/ ZnS nano-array: CdS and CuS nanoparticles are deposited on the ZnO nano-layer by ion exchange method to obtain ZnO/CdS/CuS nano-array composite material.
本发明进一步给出在上述方法基础上的具体工艺参数：The present invention further provides concrete process parameters on the basis of the above-mentioned method:
1、ZnO种子层配制的工艺参数：将醋酸锌(Zn(CH3COO)2·2H2O)和乙二醇甲醚(CH3OCH2CH2OH)混合并逐滴加入少量单乙醇胺(H2NCH2CH2OH)，配制0.2～0.5mol/L ZnO种子层溶胶。1. Process parameters for ZnO seed layer preparation: mix zinc acetate (Zn(CH 3 COO) 2 2H 2 O) and ethylene glycol methyl ether (CH 3 OCH 2 CH 2 OH) and add a small amount of monoethanolamine ( H 2 NCH 2 CH 2 OH), and prepare 0.2-0.5 mol/L ZnO seed layer sol.
2、制备ZnO镀膜的工艺参数：采用浸渍-提拉法在ITO导电玻璃上完成ZnO镀膜，在80℃下烘干后，重复上述步骤对ITO导电玻璃进行第二次拉膜，两次拉膜结束后将ITO导电玻璃放置烘箱中干燥1～4h。2. Process parameters for preparing ZnO coating: use the dipping-pulling method to complete the ZnO coating on the ITO conductive glass, after drying at 80°C, repeat the above steps to pull the ITO conductive glass for the second time, and pull the film twice After finishing, place the ITO conductive glass in an oven to dry for 1-4 hours.
3、制备ZnO纳米棒的工艺参数：将样品进行退火处理后放入0.02～0.05mol/L硝酸锌和六次甲基四胺的混合生长溶液中，90℃下热水浴反应5～12h，60℃条件下干燥，得到ZnO纳米棒。3. Process parameters for preparing ZnO nanorods: After the sample is annealed, it is placed in a mixed growth solution of 0.02-0.05mol/L zinc nitrate and hexamethylenetetramine, and reacted in a hot water bath at 90°C for 5-12 hours. Dry at 60°C to obtain ZnO nanorods.
4、制备ZnO/ZnS纳米阵列的工艺参数：配制0.3～0.6mol/L硫代乙酰胺溶液(TAA)，将ZnO纳米棒试样放入TAA溶液中，烧杯密封后放入90℃的水浴锅中5～12h，得到在ZnO纳米阵列上生长ZnS纳米薄膜的ZnO/ZnS纳米阵列。4. Process parameters for preparing ZnO/ZnS nanoarrays: prepare 0.3-0.6mol/L thioacetamide solution (TAA), put the ZnO nanorod sample into the TAA solution, seal the beaker and put it into a 90°C water bath 5-12h, and obtain the ZnO/ZnS nano-array in which the ZnS nano-film is grown on the ZnO nano-array.
5、制备ZnO/CdS纳米阵列复合材料的工艺参数：采用离子交换法将CdS纳米粒子沉积到ZnO纳米层上。配制0.005～0.01mol/L的硝酸镉(Cd(NO3)2)水溶液并转移至水热釜中，然后将处理后的导电玻璃置于水热釜中，在140℃条件下置于烘箱中加热2h，取出后用去离子水洗净烘干得到ZnO/CdS纳米阵列复合材料。5. Process parameters for preparing ZnO/CdS nano-array composite material: CdS nanoparticles were deposited on the ZnO nano-layer by ion exchange method. Prepare a 0.005-0.01mol/L cadmium nitrate (Cd(NO 3 ) 2 ) aqueous solution and transfer it to a hydrothermal kettle, then place the treated conductive glass in the hydrothermal kettle, and place it in an oven at 140°C Heating for 2 hours, taking it out, washing and drying with deionized water to obtain a ZnO/CdS nanoarray composite material.
6、制备ZnO/CdS/CuS纳米阵列复合材料的工艺参数：选用三乙二醇作为溶剂，配制0.005～0.01mol/L的硝酸铜(Cu(NO3)2)溶液，加热搅拌直至全溶并冷却至室温，将已经制备好的ZnO/CdS加入上述溶液，室温下反应1～4h后，洗净烘干得到ZnO/CdS/CuS纳米阵列复合材料。6. Process parameters for the preparation of ZnO/CdS/CuS nano-array composite materials: use triethylene glycol as a solvent, prepare a 0.005-0.01mol/L copper nitrate (Cu(NO 3 ) 2 ) solution, heat and stir until completely dissolved and Cool to room temperature, add the prepared ZnO/CdS to the above solution, react at room temperature for 1-4 hours, wash and dry to obtain ZnO/CdS/CuS nano-array composite material.
本发明的作用机理是：半导体光催化剂受光照射时，吸收等于或者大于其禁带宽度的光子使得电子受激发，从价带跃迁至导带产生光生电子，并在价带相应位置上产生光生空穴，形成光生电子空穴对。光生电子及光生空穴均具有很强的氧化能力和还原能力。在光电同时作用下，H2O被空穴氧化生成O2，而水中的H+被还原生成H2。The action mechanism of the present invention is: when the semiconductor photocatalyst is irradiated by light, it absorbs photons equal to or greater than its forbidden band width, so that electrons are excited, jump from the valence band to the conduction band to generate photo-generated electrons, and generate photo-generated holes in the corresponding positions of the valence band. holes to form photogenerated electron-hole pairs. Both photogenerated electrons and photogenerated holes have strong oxidizing and reducing abilities. Under the simultaneous action of photoelectricity, H 2 O is oxidized by holes to generate O 2 , while H + in water is reduced to generate H 2 .
本发明所获得的ZnO/CdS/CuS纳米阵列复合材料，生长比较密集，而且分布均匀，扫描电镜观察测试结果如图1所示。本发明所获得的ZnO/CdS/CuS纳米阵列复合材料紫外可见光分光光度计和电化学工作站测试后，吸光达到395nm，光电流达到1.71mA·cm2(1.2Vvs Ag/AgCl)，测试结果分别如图2、图3所示。The ZnO/CdS/CuS nano-array composite material obtained in the present invention has relatively dense growth and uniform distribution, and the scanning electron microscope observation test results are shown in FIG. 1 . After the ZnO/CdS/CuS nano-array composite material obtained by the present invention is tested by an ultraviolet-visible light spectrophotometer and an electrochemical workstation, the light absorption reaches 395nm, and the photocurrent reaches 1.71mA cm 2 (1.2Vvs Ag/AgCl), and the test results are as follows: Shown in Figure 2 and Figure 3.
有益效果Beneficial effect
1、一种ZnO/CdS/CuS纳米阵列复合材料，能够有效改善光生电子空穴易复合的缺点，增强对可见光的吸收。1. A ZnO/CdS/CuS nano-array composite material, which can effectively improve the shortcoming of easy recombination of photogenerated electrons and holes, and enhance the absorption of visible light.
2、一种ZnO/CdS/CuS纳米阵列复合材料的制备方法，制备工艺简单，生产成本低廉，有利于太阳能的推广利用。2. A method for preparing a ZnO/CdS/CuS nano-array composite material, the preparation process is simple, the production cost is low, and it is beneficial to the popularization and utilization of solar energy.
附图说明Description of drawings
图1为实施例中所得的ZnO/CdS/CuS纳米阵列复合材料的扫描电镜图像。Fig. 1 is a scanning electron microscope image of the ZnO/CdS/CuS nano-array composite material obtained in the embodiment.
图2为实施例1中所得的ZnO/CdS/CuS纳米阵列复合材料经紫外-可见光分光光度计测试结果。FIG. 2 shows the results of testing the ZnO/CdS/CuS nanoarray composite material obtained in Example 1 by an ultraviolet-visible spectrophotometer.
图3为实施例1中所得的ZnO/CdS/CuS纳米阵列复合材料经电化学工作站测试结果。Fig. 3 is the result of testing the ZnO/CdS/CuS nano-array composite material obtained in Example 1 by an electrochemical workstation.
具体实施方式detailed description
下面的实施例可以使本专业技术人员更全面的理解本发明，但不以任何方式限制本发明。The following examples can enable those skilled in the art to understand the present invention more comprehensively, but do not limit the present invention in any way.
实施例1Example 1
首先，将醋酸锌(Zn(CH3COO)2·2H2O)和乙二醇甲醚(CH3OCH2CH2OH)混合并逐滴加入少量单乙醇胺(H2NCH2CH2OH)，配制0.2mol/L的ZnO种子层溶胶；采用浸渍-提拉法以1mm/s的速度在ITO导电玻璃上完成ZnO镀膜并在溶胶中停留20s，在80℃下烘干后，重复上述步骤对ITO导电玻璃进行第二次拉膜，两次拉膜结束后将ITO导电玻璃放置烘箱中干燥1h；将样品以400℃进行退火处理并保温1h后放入0.04mol/L硝酸锌和六次甲基四胺的混合生长溶液中，90℃下热水浴反应9h，60℃条件下干燥，得到ZnO纳米棒。配制0.5mol/L硫代乙酰胺溶液(TAA)，将ZnO纳米棒试样放入TAA溶液中，烧杯密封后放入90℃的水浴锅中7h，得到在ZnO纳米阵列上生长ZnS纳米薄膜的ZnO/ZnS纳米阵列。采用离子交换法将CdS纳米粒子沉积到ZnO纳米层上。配制0.007mol/L的硝酸镉(Cd(NO3)2)水溶液并转移至水热釜中，然后将处理后的导电玻璃置于水热釜中，在140℃条件下置于烘箱中加热2h，取出后用去离子水洗净烘干得到ZnO/CdS纳米阵列复合材料。配制0.007mol/L的硝酸铜(Cu(NO3)2)溶液，加热搅拌直至全溶并冷却至室温，将已经制备好的ZnO/CdS置于上述溶液，室温下反应2h后，洗净烘干得到ZnO/CdS/CuS纳米阵列复合材料。First, zinc acetate (Zn(CH 3 COO) 2 2H 2 O) and ethylene glycol methyl ether (CH 3 OCH 2 CH 2 OH) were mixed and a small amount of monoethanolamine (H 2 NCH 2 CH 2 OH) was added dropwise , prepare a 0.2mol/L ZnO seed layer sol; use the dipping-pulling method to complete the ZnO coating on the ITO conductive glass at a speed of 1mm/s and stay in the sol for 20s. After drying at 80°C, repeat the above steps The ITO conductive glass is drawn for the second time, and after the two times of drawing, the ITO conductive glass is dried in an oven for 1 hour; the sample is annealed at 400°C and kept for 1 hour, then put in 0.04mol/L zinc nitrate and six times In the mixed growth solution of methyltetramine, react in a hot water bath at 90° C. for 9 h, and dry at 60° C. to obtain ZnO nanorods. Prepare a 0.5mol/L thioacetamide solution (TAA), put the ZnO nanorod sample into the TAA solution, put the beaker into a 90°C water bath for 7h after sealing, and obtain a ZnS nanofilm grown on the ZnO nanoarray. ZnO/ZnS nanoarrays. CdS nanoparticles were deposited onto ZnO nanolayers by ion exchange method. Prepare a 0.007mol/L cadmium nitrate (Cd(NO 3 ) 2 ) aqueous solution and transfer it to a hydrothermal kettle, then place the treated conductive glass in the hydrothermal kettle, and heat it in an oven at 140°C for 2h , take it out, wash and dry it with deionized water to obtain a ZnO/CdS nano-array composite material. Prepare 0.007mol/L copper nitrate (Cu(NO 3 ) 2 ) solution, heat and stir until it is completely dissolved and cool to room temperature, place the prepared ZnO/CdS in the above solution, react at room temperature for 2 hours, wash and dry Dry to get ZnO/CdS/CuS nano-array composite material.
本发明所获得的ZnO/CdS/CuS纳米阵列复合材料，生长比较密集，而且分布均匀，扫描电镜观察测试结果如图1所示。本发明所获得的ZnO/CdS/CuS纳米阵列复合材料紫外可见光分光光度计和电化学工作站测试后，吸光达到395nm，光电流达到1.71mA·cm2(1.2Vvs Ag/AgCl)，测试结果分别如图2、图3所示。The ZnO/CdS/CuS nano-array composite material obtained in the present invention has relatively dense growth and uniform distribution, and the scanning electron microscope observation test results are shown in FIG. 1 . After the ZnO/CdS/CuS nano-array composite material obtained by the present invention is tested by an ultraviolet-visible light spectrophotometer and an electrochemical workstation, the light absorption reaches 395nm, and the photocurrent reaches 1.71mA cm 2 (1.2Vvs Ag/AgCl), and the test results are as follows: Shown in Figure 2 and Figure 3.
实施例2Example 2
首先，将醋酸锌(Zn(CH3COO)2·2H2O)和乙二醇甲醚(CH3OCH2CH2OH)混合并逐滴加入少量单乙醇胺(H2NCH2CH2OH)，配制0.3mol/L的ZnO种子层溶胶；采用浸渍-提拉法以1mm/s的速度在ITO导电玻璃上完成ZnO镀膜并在溶胶中停留20s，在80℃下烘干后，重复上述步骤对ITO导电玻璃进行第二次拉膜，两次拉膜结束后将ITO导电玻璃放置烘箱中干燥2.5h；将样品以400℃进行退火处理并保温1h后放入0.02mol/L硝酸锌和六次甲基四胺的混合生长溶液中，90℃下热水浴反应5h，60℃条件下干燥，得到ZnO纳米棒。配制0.3mol/L硫代乙酰胺溶液(TAA)，将ZnO纳米棒试样放入TAA溶液中，烧杯密封后放入90℃的水浴锅中5h，得到在ZnO纳米阵列上生长ZnS纳米薄膜的ZnO/ZnS纳米阵列。采用离子交换法将CdS纳米粒子沉积到ZnO纳米层上。配制0.005mol/L的硝酸镉(Cd(NO3)2)水溶液并转移至水热釜中，然后将处理后的导电玻璃置于水热釜中，在140℃条件下置于烘箱中加热2h，取出后用去离子水洗净烘干得到ZnO/CdS纳米阵列复合材料。配制0.005mol/L的硝酸铜(Cu(NO3)2)溶液，加热搅拌直至全溶并冷却至室温，将已经制备好的ZnO/CdS置于上述溶液，室温下反应1h后，洗净烘干得到ZnO/CdS/CuS纳米阵列复合材料。First, zinc acetate (Zn(CH 3 COO) 2 2H 2 O) and ethylene glycol methyl ether (CH 3 OCH 2 CH 2 OH) were mixed and a small amount of monoethanolamine (H 2 NCH 2 CH 2 OH) was added dropwise , prepare a 0.3mol/L ZnO seed layer sol; use the dip-pulling method to complete the ZnO coating on the ITO conductive glass at a speed of 1mm/s and stay in the sol for 20s. After drying at 80°C, repeat the above steps The ITO conductive glass was drawn for the second time, and after the two times of drawing, the ITO conductive glass was dried in an oven for 2.5 hours; the sample was annealed at 400°C and kept for 1 hour, and then 0.02mol/L zinc nitrate and six In the mixed growth solution of methylenetetramine, react in a hot water bath at 90° C. for 5 h, and dry at 60° C. to obtain ZnO nanorods. Prepare a 0.3mol/L thioacetamide solution (TAA), put the ZnO nanorod sample into the TAA solution, put the beaker into a 90°C water bath for 5h after sealing, and obtain the ZnS nanofilm growth method on the ZnO nanoarray. ZnO/ZnS nanoarrays. CdS nanoparticles were deposited onto ZnO nanolayers by ion exchange method. Prepare a 0.005mol/L cadmium nitrate (Cd(NO 3 ) 2 ) aqueous solution and transfer it to a hydrothermal kettle, then place the treated conductive glass in the hydrothermal kettle, and heat it in an oven at 140°C for 2h , take it out, wash and dry it with deionized water to obtain a ZnO/CdS nano-array composite material. Prepare 0.005mol/L copper nitrate (Cu(NO 3 ) 2 ) solution, heat and stir until it is completely dissolved and cool to room temperature, place the prepared ZnO/CdS in the above solution, react at room temperature for 1 hour, wash and dry Dry to get ZnO/CdS/CuS nano-array composite material.
实施例3Example 3
首先，将醋酸锌(Zn(CH3COO)2·2H2O)和乙二醇甲醚(CH3OCH2CH2OH)混合并逐滴加入少量单乙醇胺(H2NCH2CH2OH)，配制0.5mol/L的ZnO种子层溶胶；采用浸渍-提拉法以1mm/s的速度在ITO导电玻璃上完成ZnO镀膜并在溶胶中停留20s，在80℃下烘干后，重复上述步骤对ITO导电玻璃进行第二次拉膜，两次拉膜结束后将ITO导电玻璃放置烘箱中干燥4h；将样品以400℃进行退火处理并保温1h后放入0.05mol/L硝酸锌和六次甲基四胺的混合生长溶液中，90℃下热水浴反应12h，60℃条件下干燥，得到ZnO纳米棒。配制0.6mol/L硫代乙酰胺溶液(TAA)，将ZnO纳米棒试样放入TAA溶液中，烧杯密封后放入90℃的水浴锅中12h，得到在ZnO纳米阵列上生长ZnS纳米薄膜的ZnO/ZnS纳米阵列。采用离子交换法将CdS纳米粒子沉积到ZnO纳米层上。配制0.01mol/L的硝酸镉(Cd(NO3)2)水溶液并转移至水热釜中，然后将处理后的导电玻璃置于水热釜中，在140℃条件下置于烘箱中加热2h，取出后用去离子水洗净烘干得到ZnO/CdS纳米阵列复合材料。配制0.01mol/L的硝酸铜(Cu(NO3)2)溶液，加热搅拌直至全溶并冷却至室温，将已经制备好的ZnO/CdS置于上述溶液，室温下反应4h后，洗净烘干得到ZnO/CdS/CuS纳米阵列复合材料。First, zinc acetate (Zn(CH 3 COO) 2 2H 2 O) and ethylene glycol methyl ether (CH 3 OCH 2 CH 2 OH) were mixed and a small amount of monoethanolamine (H 2 NCH 2 CH 2 OH) was added dropwise , prepare a 0.5mol/L ZnO seed layer sol; use the dip-pulling method to complete the ZnO coating on the ITO conductive glass at a speed of 1mm/s and stay in the sol for 20s. After drying at 80°C, repeat the above steps The ITO conductive glass is drawn for the second time. After the two times of drawing, the ITO conductive glass is placed in an oven to dry for 4 hours; the sample is annealed at 400°C and kept for 1 hour, then put in 0.05mol/L zinc nitrate and six times In the mixed growth solution of methyltetramine, react in a hot water bath at 90° C. for 12 hours, and dry at 60° C. to obtain ZnO nanorods. Prepare 0.6mol/L thioacetamide solution (TAA), put the ZnO nanorod sample into the TAA solution, put the beaker into a 90°C water bath for 12h after sealing, and obtain the ZnS nanofilm growth method on the ZnO nanoarray. ZnO/ZnS nanoarrays. CdS nanoparticles were deposited onto ZnO nanolayers by ion exchange method. Prepare a 0.01mol/L cadmium nitrate (Cd(NO 3 ) 2 ) aqueous solution and transfer it to a hydrothermal kettle, then place the treated conductive glass in the hydrothermal kettle, and heat it in an oven at 140°C for 2h , take it out, wash and dry it with deionized water to obtain a ZnO/CdS nano-array composite material. Prepare a 0.01mol/L copper nitrate (Cu(NO 3 ) 2 ) solution, heat and stir until it is completely dissolved and cool to room temperature, place the prepared ZnO/CdS in the above solution, react at room temperature for 4 hours, wash and dry Dry to get ZnO/CdS/CuS nano-array composite material.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求的保护范围为准。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed in the present invention can easily think of changes or Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.
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