CN106622293B - A kind of H-TiO2/CdS/Cu2-xThe preparation method of S nanobelt - Google Patents
A kind of H-TiO2/CdS/Cu2-xThe preparation method of S nanobelt Download PDFInfo
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- 239000002127 nanobelt Substances 0.000 title claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 59
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002114 nanocomposite Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- -1 hydrogen Chemical class 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 239000003426 co-catalyst Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B01J27/04—Sulfides
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract
Description
技术领域technical field
本发明涉及一种半导体复合材料的制备方法。The invention relates to a preparation method of a semiconductor composite material.
背景技术Background technique
随着社会的不断发展，在史前形成，孕育数百年的化石燃料，如煤炭、天然气和石油等这些在人类生活中起着重要作用的不可再生能源，正在不断的减少，甚至濒临枯竭。同时这些化石燃料在燃烧使用的过程中，会释放很多氮氧化物、硫氧化物和碳氧化物等空气污染物，使全球气候发生变化，严重影响着人类的健康问题。因此，寻找可再生、清洁的能源，成了当今世界迫在眉睫的任务和使命。通过光催化水分解产生大量的氢，在这个催化过程中，只涉及到质子、能量和水之间的转化，并没有产生任何的副产物和污染物。因此，光催化过程对于能量和环境方面做出了极大的贡献。而制备催化剂，有效的吸收太阳光，促进水分解成为了具有挑战的任务。太阳能光谱包括仅占全谱6.8％的紫外光谱(小于400nm)、38.9％的可见光光谱(400-700nm)、还有54.3％的红外光谱(760-3000nm)。从波谱的分布可以看出，发展可见光下有活性、价廉、有效稳定的催化剂是一项非常有意义的工作。但是，目前多种半导体相结合的复合材料，不能充分的利用太阳能光谱，大多数催化剂依靠贵金属等作为助催化剂，从而使制备成本较高。而如果在光催化领域设计并合成一种能够吸收全波谱的催化剂，对于光催化领域而言，又将会是一个新的突破。With the continuous development of society, fossil fuels formed in prehistoric times and bred for hundreds of years, such as coal, natural gas and oil, which play an important role in human life, are constantly decreasing and are even on the verge of exhaustion. At the same time, during the combustion and use of these fossil fuels, a lot of air pollutants such as nitrogen oxides, sulfur oxides, and carbon oxides will be released, which will change the global climate and seriously affect human health. Therefore, finding renewable and clean energy has become an urgent task and mission in today's world. A large amount of hydrogen is produced by photocatalytic water splitting. In this catalytic process, only the conversion between protons, energy and water is involved, and no by-products and pollutants are produced. Therefore, the photocatalytic process makes a great contribution in terms of energy and environment. However, preparing catalysts to effectively absorb sunlight and promote water splitting has become a challenging task. The solar spectrum includes the ultraviolet spectrum (less than 400nm), 38.9% of the visible light spectrum (400-700nm), and 54.3% of the infrared spectrum (760-3000nm) accounting for only 6.8% of the full spectrum. It can be seen from the distribution of the spectrum that it is a very meaningful work to develop active, inexpensive, effective and stable catalysts under visible light. However, the current composite materials combining multiple semiconductors cannot make full use of the solar spectrum, and most catalysts rely on noble metals as co-catalysts, resulting in high preparation costs. And if a catalyst capable of absorbing the full spectrum is designed and synthesized in the field of photocatalysis, it will be a new breakthrough in the field of photocatalysis.
发明内容Contents of the invention
本发明是要解决现有的催化剂对太阳能转化率较低、成本较高的技术问题，而提供一种H-TiO2/CdS/Cu2-xS纳米带的制备方法。The invention aims to solve the technical problems of low conversion rate of solar energy and high cost of existing catalysts, and provides a preparation method of H-TiO 2 /CdS/Cu 2-x S nanobelts.
本发明的H-TiO2/CdS/Cu2-xS纳米带的制备方法，按以下步骤进行：The preparation method of the H-TiO 2 /CdS/Cu 2-x S nanobelt of the present invention is carried out according to the following steps:
一、将纳米二氧化钛分散于NaOH溶液中，待超声均匀后，转移至聚四氟乙烯反应釜中，在160～180℃保持48～60h；冷却到室温后，得到Na2Ti3O7粉末；将Na2Ti3O7粉末用去离子水洗涤干净，再加入到HCl溶液中搅拌24h～48h，用去离子水清洗干净后，将得到的H2Ti3O7白色粉末与H2SO4溶液一起放入聚四氟乙烯反应釜中，在80～100℃保持 12～24h；最后，将获得的产物用去离子水和无水乙醇清洗干燥后，放在马弗炉中在 400～600℃煅烧2～6h，得到具有粗糙表面的TiO2纳米带；1. Disperse nano-titanium dioxide in NaOH solution, transfer it to a polytetrafluoroethylene reactor after ultrasonication, and keep it at 160-180°C for 48-60 hours; after cooling to room temperature, Na 2 Ti 3 O 7 powder is obtained; Wash the Na 2 Ti 3 O 7 powder with deionized water, then add it to the HCl solution and stir for 24h to 48h. After washing with deionized water, mix the obtained white powder of H 2 Ti 3 O 7 with H 2 SO 4 Put the solution together into a polytetrafluoroethylene reaction kettle and keep it at 80-100°C for 12-24 hours; finally, after cleaning and drying the obtained product with deionized water and absolute ethanol, put it in a muffle furnace at 400-600 Calcined at ℃ for 2-6 hours to obtain TiO 2 nanoribbons with rough surface;
二、将步骤一得到的粗糙表面的TiO2纳米带在氮气与氢气的混合气体的气氛中，升温至400～600℃并保温4～6h，得到H-TiO2纳米带； 2. Heat up the rough surfaced TiO2nanobelt obtained in step 1 to 400-600°C in an atmosphere of a mixed gas of nitrogen and hydrogen and keep it warm for 4-6h to obtain H - TiO2nanobelt;
三、将步骤二得到的H-TiO2纳米带放入Cd(NO3)2溶液中搅拌30～60min后，离心洗涤，然后再将H-TiO2纳米带放入Na2S溶液中搅拌30～60min，离心洗涤；如此反复用 Cd(NO3)2、Na2S溶液处理多次后，用去离子水和乙醇洗涤干燥后，得到H-TiO2/CdS纳米复合材料；3. Put the H-TiO 2 nanobelts obtained in step 2 into the Cd(NO 3 ) 2 solution and stir for 30-60 minutes, centrifuge and wash, and then put the H-TiO 2 nanobelts into the Na 2 S solution and stir for 30 minutes. ~60min, centrifugal washing; after repeated treatment with Cd(NO 3 ) 2 , Na 2 S solution several times, washing and drying with deionized water and ethanol, H-TiO 2 /CdS nanocomposite material was obtained;
四、将步骤三得到的H-TiO2/CdS纳米复合材料超声分散在甲苯溶液中，然后将[MeCN]4CuPF6的甲醇溶液滴入H-TiO2/CdS纳米复合材料的甲苯溶液中，搅拌15～30min，用甲醇洗涤干燥后，得到H-TiO2/CdS/Cu2-xS纳米带。4. Ultrasonic disperse the H-TiO 2 /CdS nanocomposite obtained in step 3 in a toluene solution, and then drop the methanol solution of [MeCN] 4 CuPF 6 into the toluene solution of the H-TiO 2 /CdS nanocomposite, After stirring for 15-30 min, washing and drying with methanol, H-TiO 2 /CdS/Cu 2-x S nanobelts are obtained.
本发明以酸腐蚀和还原气氛处理的H-TiO2纳米带作为主体材料，硝酸镉作为镉源，硫化钠作为硫源，用化学浴沉积的方法在H-TiO2纳米带上修饰CdS纳米粒子，得到 H-TiO2/CdS纳米复合材料，再利用离子交换的方法，用Cu+部分置换Cd2+，就可以得到催化性能优异的三元异质结构催化剂。In the present invention, the H- TiO2 nanobelt treated with acid corrosion and reducing atmosphere is used as the main material, cadmium nitrate is used as the cadmium source, and sodium sulfide is used as the sulfur source, and the CdS nanoparticle is modified on the H- TiO2 nanobelt by chemical bath deposition. , to obtain H-TiO 2 /CdS nanocomposite material, and then use ion exchange method to partially replace Cd 2+ with Cu + , and then a ternary heterostructure catalyst with excellent catalytic performance can be obtained.
本发明得到的H-TiO2/CdS/Cu2-xS纳米带，对太阳能光谱有很好的光响应，对紫外、可见和近红外区域的光都有很好的吸收。并且三种半导体之间交错的能带更好的促进了电子和空穴的分离，使之作为光催化产氢的催化剂时，在没有贵金属等助催化剂存在的条件下，产氢速率可以达到261.54μmol·g-1·h-1。并且这种三元异质结构的催化剂具有很好的重复利用性，在重复五次实验后，产氢速率依然可以达到210.63μmol·g-1·h-1。The H-TiO 2 /CdS/Cu 2-x S nanobelt obtained by the invention has good photoresponse to solar spectrum and good absorption of light in ultraviolet, visible and near-infrared regions. And the staggered energy bands between the three semiconductors better promote the separation of electrons and holes, so that when it is used as a catalyst for photocatalytic hydrogen production, the hydrogen production rate can reach 261.54 in the absence of co-catalysts such as noble metals. μmol·g -1 ·h -1 . And this ternary heterostructure catalyst has good reusability. After repeating the experiment five times, the hydrogen production rate can still reach 210.63μmol·g -1 ·h -1 .
本材料在没有贵金属材料作为助催化剂的条件下，充分利用了太阳光，增加了太阳能的转化利用率，促进了光生电子和空穴的分离，降低了反应成本，为制备具有高效率的催化剂提供了新思路。Under the condition that there is no noble metal material as a cocatalyst, this material makes full use of sunlight, increases the conversion utilization rate of solar energy, promotes the separation of photogenerated electrons and holes, reduces the reaction cost, and provides a good source for the preparation of high-efficiency catalysts. new ideas.
附图说明Description of drawings
图1是试验1中制备的未经H2SO4处理的光滑TiO2纳米带的扫描电子显微镜(SEM)图；Figure 1 is a scanning electron microscope (SEM) image of the smooth TiO2 nanoribbons prepared in Experiment 1 without H2SO4 treatment;
图2是试验1中未经H2SO4处理的光滑TiO2纳米带的低倍率扫描电子显微镜(SEM)图；Figure 2 is a low-magnification scanning electron microscope (SEM) image of smooth TiO2 nanoribbons without H2SO4 treatment in Experiment 1;
图3是试验1中制备的粗糙H-TiO2纳米带的扫描电子显微镜(SEM)图；Fig. 3 is the scanning electron microscope (SEM) figure of rough H- TiO nanoribbon prepared in test 1;
图4是试验1制备的粗糙H-TiO2纳米带的透射电子显微镜(TEM)图；Fig. 4 is the rough H- TiO that test 1 prepares The transmission electron microscope (TEM) picture of nanobelt;
图5是试验1制备的H-TiO2/CdS纳米复合材料的透射电子显微镜(TEM)图；Fig. 5 is the transmission electron microscope (TEM) picture of the H-TiO 2 /CdS nanocomposite material prepared in test 1;
图6是试验1制备的H-TiO2/CdS纳米复合材料的粒径分析图；Figure 6 is a particle size analysis diagram of the H-TiO 2 /CdS nanocomposite prepared in Test 1;
图7是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的透射电子显微镜(TEM)图；Figure 7 is a transmission electron microscope (TEM) image of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Experiment 1;
图8是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的高倍透射电子显微镜(HRTEM)图；Fig. 8 is the high magnification transmission electron microscope (HRTEM) picture of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Experiment 1;
图9是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的高角环形暗场像-扫描透射电子像的元素分布图；Figure 9 is a high-angle annular dark field image-scanning transmission electron image element distribution diagram of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Experiment 1;
图10是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的X射线光电子能谱图；Figure 10 is the X-ray photoelectron energy spectrum diagram of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Experiment 1;
图11是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的XRD谱图；Figure 11 is the XRD spectrum of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Test 1;
图12是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的UV-Vis-NIR谱图；Figure 12 is the UV-Vis-NIR spectrum of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Experiment 1;
图13是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的产氢速率对比图谱；Fig. 13 is a comparison diagram of the hydrogen production rate of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Experiment 1;
图14是试验1制备的H-TiO2/CdS/Cu2-xS纳米带的循环使用后产氢速率图谱。Fig. 14 is the hydrogen production rate spectrum of the H-TiO 2 /CdS/Cu 2-x S nanobelt prepared in Experiment 1 after recycling.
具体实施方式Detailed ways
具体实施方式一：本实施方式的H-TiO2/CdS/Cu2-xS纳米带的制备方法，按以下步骤进行：Specific implementation mode 1: The preparation method of the H-TiO 2 /CdS/Cu 2-x S nanobelt of this implementation mode is carried out according to the following steps:
一、将纳米二氧化钛分散于NaOH溶液中，待超声均匀后，转移至聚四氟乙烯反应釜中，在160～180℃保持48～60h；冷却到室温后，得到Na2Ti3O7粉末；将Na2Ti3O7粉末用去离子水洗涤干净，再加入到HCl溶液中搅拌24h～48h，用去离子水清洗干净后，将得到的H2Ti3O7白色粉末与H2SO4溶液一起放入聚四氟乙烯反应釜中，在80～100℃保持 12～24h；最后，将获得的产物用去离子水和无水乙醇清洗干燥后，放在马弗炉中在 400～600℃煅烧2～6h，得到具有粗糙表面的TiO2纳米带；1. Disperse nano-titanium dioxide in NaOH solution, transfer it to a polytetrafluoroethylene reactor after ultrasonication, and keep it at 160-180°C for 48-60 hours; after cooling to room temperature, Na 2 Ti 3 O 7 powder is obtained; Wash the Na 2 Ti 3 O 7 powder with deionized water, then add it to the HCl solution and stir for 24h to 48h. After washing with deionized water, mix the obtained white powder of H 2 Ti 3 O 7 with H 2 SO 4 Put the solution together into a polytetrafluoroethylene reaction kettle and keep it at 80-100°C for 12-24 hours; finally, after cleaning and drying the obtained product with deionized water and absolute ethanol, put it in a muffle furnace at 400-600 Calcined at ℃ for 2-6 hours to obtain TiO 2 nanoribbons with rough surface;
二、将步骤一得到的粗糙表面的TiO2纳米带在氮气与氢气的混合气体的气氛中，升温至400～600℃并保温4～6h，得到H-TiO2纳米带； 2. Heat up the rough surfaced TiO2nanobelt obtained in step 1 to 400-600°C in an atmosphere of a mixed gas of nitrogen and hydrogen and keep it warm for 4-6h to obtain H - TiO2nanobelt;
三、将步骤二得到的H-TiO2纳米带放入Cd(NO3)2溶液中搅拌30～60min后，离心洗涤，然后再将H-TiO2纳米带放入Na2S溶液中搅拌30～60min，离心洗涤；如此反复用 Cd(NO3)2、Na2S溶液处理多次后，用去离子水和乙醇洗涤干燥后，得到H-TiO2/CdS纳米复合材料；3. Put the H-TiO 2 nanobelts obtained in step 2 into the Cd(NO 3 ) 2 solution and stir for 30-60 minutes, centrifuge and wash, and then put the H-TiO 2 nanobelts into the Na 2 S solution and stir for 30 minutes. ~60min, centrifugal washing; after repeated treatment with Cd(NO 3 ) 2 , Na 2 S solution several times, washing and drying with deionized water and ethanol, H-TiO 2 /CdS nanocomposite material was obtained;
四、将步骤三得到的H-TiO2/CdS纳米复合材料超声分散在甲苯溶液中，然后将[MeCN]4CuPF6的甲醇溶液滴入H-TiO2/CdS纳米复合材料的甲苯溶液中，搅拌15～30min，用甲醇洗涤干燥后，得到H-TiO2/CdS/Cu2-xS纳米带。4. Ultrasonic disperse the H-TiO 2 /CdS nanocomposite obtained in step 3 in a toluene solution, and then drop the methanol solution of [MeCN] 4 CuPF 6 into the toluene solution of the H-TiO 2 /CdS nanocomposite, After stirring for 15-30 min, washing and drying with methanol, H-TiO 2 /CdS/Cu 2-x S nanobelts are obtained.
具体实施方式二：本实施方式与具体实施方式一不同的是步骤一中NaOH溶液的浓度为5～10mol/L；其它与具体实施方式一相同。Embodiment 2: This embodiment differs from Embodiment 1 in that the concentration of the NaOH solution in step 1 is 5-10 mol/L; other aspects are the same as Embodiment 1.
具体实施方式三：本实施方式与具体实施方式一或二不同的是步骤一中HCl溶液的浓度为0.1～0.5mol/L；其它与具体实施方式一或二相同。Embodiment 3: This embodiment differs from Embodiment 1 or Embodiment 2 in that the concentration of the HCl solution in Step 1 is 0.1-0.5 mol/L; other aspects are the same as Embodiment 1 or Embodiment 2.
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是步骤一中的H2SO4溶液的浓度为0.02～0.05mol/L；其它与具体实施方式一至三之一相同。Embodiment 4: This embodiment differs from Embodiments 1 to 3 in that the concentration of the H 2 SO 4 solution in step 1 is 0.02-0.05 mol/L; other aspects are the same as Embodiments 1 to 3.
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是步骤二中所述的氮气与氢气的混合气体中H2占混合气体体积的5％～10％；其它与具体实施方式一至四之一相同。Embodiment 5: The difference between this embodiment and one of Embodiments 1 to 4 is that in the mixed gas of nitrogen and hydrogen described in step 2, H 2 accounts for 5% to 10% of the volume of the mixed gas; other and specific embodiments One to four are the same.
具体实施方式六：本实施方式与具体实施方式一至五之一不同的是步骤二中所述的升温速率为2～5℃/min；其它与具体实施方式一至五之一相同。Embodiment 6: The difference between this embodiment and one of Embodiments 1 to 5 is that the heating rate in step 2 is 2-5° C./min; the others are the same as Embodiments 1 to 5.
具体实施方式七：本实施方式与具体实施方式一至六之一不同的是步骤三中 Cd(NO3)2溶液的浓度为0.05～0.1mol/L；其它与具体实施方式一至六之一相同。Embodiment 7: This embodiment differs from Embodiments 1 to 6 in that the concentration of the Cd(NO 3 ) 2 solution in Step 3 is 0.05-0.1 mol/L; other aspects are the same as Embodiments 1 to 6.
具体实施方式八：本实施方式与具体实施方式一至七之一不同的是步骤三中Na2S溶液溶液的浓度为0.05～0.1mol/L；其它与具体实施方式一至七之一相同。Embodiment 8: This embodiment differs from Embodiments 1 to 7 in that the concentration of the Na 2 S solution in Step 3 is 0.05-0.1 mol/L; other aspects are the same as Embodiments 1 to 7.
具体实施方式九：本实施方式与具体实施方式一至八之一不同的是步骤三中反复用 Cd(NO3)2、Na2S溶液处理的次数为4～5次；其它与具体实施方式一至八之一相同。Embodiment 9: The difference between this embodiment and one of Embodiments 1 to 8 is that the number of times of repeated treatment with Cd(NO 3 ) 2 and Na 2 S solution in step 3 is 4 to 5 times; other embodiments are the same as Embodiments 1 to 8. One in eight is the same.
具体实施方式十：本实施方式与具体实施方式一至九之一不同的是步骤四中[MeCN]4CuPF6甲醇溶液的浓度为2.5～10mg/mL；其它与具体实施方式一至九之一相同。Embodiment 10: This embodiment differs from Embodiment 1 to Embodiment 9 in that the concentration of [MeCN] 4 CuPF 6 methanol solution in Step 4 is 2.5-10 mg/mL; other aspects are the same as Embodiment 1 to Embodiment 9.
用以下试验验证本发明的有益效果：Verify beneficial effect of the present invention with following test:
试验1：本试验的H-TiO2/CdS/Cu2-xS纳米带的制备方法，按以下步骤进行：Test 1: The preparation method of the H-TiO 2 /CdS/Cu 2-x S nanoribbon in this test is carried out according to the following steps:
一、将0.5g纳米二氧化钛P25分散于20mL浓度为5mol/L的NaOH溶液中，待超声分散均匀后，转移至聚四氟乙烯反应釜中，在180℃保持48h；冷却到室温后，将得到的Na2Ti3O7粉末用去离子水洗涤干净，再在浓度为0.5mol/L的HCl溶液中搅拌24h，用去离子水清洗干净后，将得到的H2Ti3O7白色粉末与20mL浓度为0.05mol/L的H2SO4溶液一起放入聚四氟乙烯反应釜中，在100℃保持12h；最后，将获得的产物用去离子水和无水乙醇清洗干燥后，放在马弗炉中在500℃煅烧2h，得到具有粗糙表面的TiO2纳米带；1. Disperse 0.5g of nano-titanium dioxide P25 in 20mL of NaOH solution with a concentration of 5mol/L. After the ultrasonic dispersion is uniform, transfer it to a polytetrafluoroethylene reactor and keep it at 180°C for 48h; after cooling to room temperature, you will get The Na 2 Ti 3 O 7 powder was washed with deionized water, then stirred in the HCl solution with a concentration of 0.5mol/L for 24 hours, and after being cleaned with deionized water, the obtained white powder of H 2 Ti 3 O 7 was mixed with 20 mL of H 2 SO 4 solution with a concentration of 0.05 mol/L was put into a polytetrafluoroethylene reactor and kept at 100°C for 12 hours; finally, the obtained product was washed and dried with deionized water and absolute ethanol, and placed in Calcined at 500°C for 2h in a muffle furnace to obtain TiO nanobelts with rough surfaces;
二、将步骤一得到的粗糙表面的TiO2纳米带在H2的质量百分数为5％的N2与H2的混合气体的气氛中，以2℃/min的升温速率升温至600℃并保温4h，得到黑色的H-TiO2纳米带；2. Raise the rough surface TiO2 nanobelt obtained in step 1 to 600°C at a rate of 2°C/min in an atmosphere of a mixed gas of N2 and H2 with a mass percent of H2 of 5% and keep it warm 4h, obtain black H-TiO 2 nanobelts;
三、将步骤二得到的200mg H-TiO2纳米带放入50mL浓度为0.1mol/L的Cd(NO3)2溶液中，搅拌30min后，离心洗涤，然后再将H-TiO2纳米带放入50mL浓度为0.1mol/L 的Na2S溶液中，搅拌30min，离心洗涤；如此反复用Cd(NO3)2、Na2S溶液处理4次后，用去离子水和乙醇洗涤干燥后，得到淡黄色的H-TiO2/CdS纳米复合材料；3. Put 200mg of H-TiO 2 nanobelts obtained in step 2 into 50mL of Cd(NO 3 ) 2 solution with a concentration of 0.1mol/L, stir for 30min, centrifuge and wash, and then put the H-TiO 2 nanobelts in into 50 mL of Na 2 S solution with a concentration of 0.1 mol/L, stirred for 30 min, and washed by centrifugation; after repeated treatment with Cd(NO 3 ) 2 and Na 2 S solution for 4 times, washed with deionized water and ethanol and dried, Obtain light yellow H-TiO 2 /CdS nanocomposite material;
四、将步骤三得到的100mg H-TiO2/CdS纳米复合材料超声分散在20mL甲苯溶液中待用，然后将50mg的[MeCN]4CuPF6溶于10mL甲醇中得到[MeCN]4CuPF6甲醇溶液，将[MeCN]4CuPF6甲醇溶液逐滴滴入到H-TiO2/CdS纳米复合材料甲苯溶液中，搅拌15 min，用甲醇洗涤3次，干燥后，得到H-TiO2/CdS/Cu2-xS纳米带催化剂。4. Ultrasonic disperse the 100mg H-TiO 2 /CdS nanocomposite material obtained in step 3 in 20mL toluene solution for use, then dissolve 50mg of [MeCN] 4 CuPF 6 in 10mL methanol to obtain [MeCN] 4 CuPF 6 methanol solution, drop [MeCN] 4 CuPF 6 methanol solution into the H-TiO 2 /CdS nanocomposite toluene solution drop by drop, stir for 15 min, wash with methanol three times, and dry to obtain H-TiO 2 /CdS/ Cu 2-x S nanobelt catalysts.
本试验经步骤一制备的TiO2纳米带的扫描电子显微镜(SEM)图如图1和图2所示，从图1和图2可以看出，TiO2纳米带的宽度为100-200nm左右，长度超出50μm。The scan electron microscope (SEM) figure of the TiO2nanobelt prepared by step 1 in this test is as shown in Figure 1 and Figure 2, as can be seen from Figure 1 and Figure 2 , the width of TiO2nanobelt is about 100-200nm, The length exceeds 50 μm.
本试验经步骤二得到的黑色的H-TiO2纳米带的SEM图如图3所示，透射电子显微镜(TEM)图如图4所示，从图3和图4可以看出，经过酸处理和还原气氛处理后，TiO2纳米带的表面变得很粗糙，这样就为下一步CdS纳米粒子的附着提供了很好的基底同时可以增加材料的氧空穴密度，从而增加在可见光区的响应。The SEM figure of the black H- TiO nanoribbon that this test obtains through step 2 is as shown in Figure 3, and the transmission electron microscope (TEM) figure is as shown in Figure 4, as can be seen from Figure 3 and Figure 4, after acid treatment After treatment with reducing atmosphere, the surface of TiO 2 nanoribbons becomes very rough, which provides a good substrate for the next step of CdS nanoparticle attachment and can increase the oxygen hole density of the material, thereby increasing the response in the visible light region .
本试验步骤三得到的H-TiO2/CdS纳米复合材料的TEM照片如图5所示，H-TiO2/CdS纳米复合材料的粒径分析图如图6所示，从图5和图6可知，经过化学浴沉积的方法，制备的CdS纳米颗粒尺寸为3-5nm，并且均匀的分布在H-TiO2纳米带上。The TEM photo of the H-TiO 2 /CdS nanocomposite material obtained in the third step of this test is shown in Figure 5, and the particle size analysis diagram of the H-TiO 2 /CdS nanocomposite material is shown in Figure 6. From Figure 5 and Figure 6 It can be seen that the size of the prepared CdS nanoparticles is 3-5nm through the method of chemical bath deposition, and they are uniformly distributed on the H-TiO 2 nanobelts.
本试验经步骤四得到的H-TiO2/CdS/Cu2-xS纳米带的TEM图如图7所示，从图7中可以看出，Cu+部分取代Cd2+，同样的均匀分布在H-TiO2纳米带上。H-TiO2/CdS/Cu2-xS 纳米带的HRTEM照片如图8所示，从图8可以看出，TiO2的晶面间距为0.352nm，对应着其(101)晶面；CdS的晶面间距为0.336nm，对应其(111)晶面。图中黑色线圈出来的部分为CdS纳米颗粒，白色线圈出来的部分为环绕在CdS纳米颗粒周围的无定形的 Cu2-xS纳米粒子。The TEM image of the H-TiO 2 /CdS/Cu 2-x S nanobelt obtained through step 4 of this experiment is shown in Figure 7. It can be seen from Figure 7 that Cu + partially replaces Cd 2+ , and the same uniform distribution on H- TiO2 nanobelts. The HRTEM photo of H-TiO 2 /CdS/Cu 2-x S nanoribbons is shown in Figure 8. It can be seen from Figure 8 that the interplanar spacing of TiO 2 is 0.352nm, corresponding to its (101) crystal plane; The interplanar spacing of 0.336nm corresponds to its (111) crystal plane. The part of the black circle in the figure is the CdS nanoparticle, and the part of the white circle is the amorphous Cu 2-x S nanoparticle surrounding the CdS nanoparticle.
本试验经步骤四得到的H-TiO2/CdS/Cu2-xS纳米带的高角环形暗场像-扫描透射电子像中扫描透射显微镜照片如图9所示，从图9可以看出，Ti、O、Cd、Cu和S五种元素均匀分布在H-TiO2纳米带上，同时这也说明了本试验已经成功制备出H-TiO2/CdS/Cu2-xS纳米带。The H-TiO 2 /CdS/Cu 2-x S nanoribbon high-angle annular dark field image-scanning transmission electron image of the H-TiO 2 /CdS/Cu 2-x S nanoribbon obtained through step 4 of this experiment is shown in Figure 9, as can be seen from Figure 9 Ti, O, Cd, Cu and S are evenly distributed on the H-TiO 2 nanobelts, which also shows that the experiment has successfully prepared H-TiO 2 /CdS/Cu 2-x S nanobelts.
为了更进一步的分析样品的存在形式，分析本试验经步骤四得到的H-TiO2/CdS/Cu2-xS 纳米带的XPS图谱如图10所示，从图10全谱(a)中可以看出，该物质内包含Ti、O、Cd、Cu和S五种元素。从(b)中可以看出，Cd元素的3d轨道中405.8eV和412.5eV的能级分别对应Cd的3d5/2和3d3/2；从(c)可以看出Cu元素的2p轨道中932.5eV和952.1eV 的能级分别对应Cu的2p3/2和2p1/2；从(d)位于162.1eV处的峰归属于S元素的2p轨道，而位于169.2eV处的峰则是由于S2-的部分氧化所引起的。In order to further analyze the existing form of the sample, the XPS spectrum of the H-TiO 2 /CdS/Cu 2-x S nanobelt obtained through step 4 of this test is shown in Figure 10, from the full spectrum (a) of Figure 10 It can be seen that the substance contains five elements: Ti, O, Cd, Cu and S. It can be seen from (b) that the energy levels of 405.8eV and 412.5eV in the 3d orbital of Cd element correspond to 3d 5/2 and 3d 3/2 of Cd respectively; from (c) it can be seen that in the 2p orbital of Cu element The energy levels of 932.5eV and 952.1eV correspond to 2p 3/2 and 2p 1/2 of Cu, respectively; from (d) the peak at 162.1eV is attributed to the 2p orbital of S element, while the peak at 169.2eV is due to caused by partial oxidation of S 2- .
图11为本试验所制备的H-TiO2、H-TiO2/CdS和H-TiO2/CdS/Cu2-xS纳米带的XRD 图谱，从图11中可以看出，H-TiO2纳米带的主要晶型是锐钛矿，对应PDF卡片21-1272，还有少量的单斜晶型的二氧化钛存在，对应PDF卡片46-1238；从H-TiO2/CdS纳米复合材料的XRD图可以看出，CdS纳米粒子的晶型为立方晶系，对应PDF卡片10-0454，其中位于2θ为26.5°、43.9°和52.1°处的峰分别对应着CdS纳米粒子的(111)、(220) 和(311)晶面。并且在XRD图中，没有发现归属于Cu2-xS纳米粒子的特征峰，这也进一步证实了我们通过离子交换方法制备的Cu2-xS纳米粒子是以无定形的方式存在的。Figure 11 shows the XRD patterns of H-TiO 2 , H-TiO 2 /CdS and H-TiO 2 /CdS/Cu 2-x S nanoribbons prepared in this experiment. It can be seen from Figure 11 that H-TiO 2 The main crystal form of the nanobelt is anatase, corresponding to PDF card 21-1272, and a small amount of monoclinic titanium dioxide exists, corresponding to PDF card 46-1238; from the XRD pattern of H-TiO 2 /CdS nanocomposite It can be seen that the crystal form of CdS nanoparticles is a cubic system, corresponding to PDF card 10-0454, where the peaks at 2θ of 26.5°, 43.9° and 52.1° correspond to (111), (220 ) and (311) planes. And in the XRD pattern, no characteristic peaks attributed to Cu 2-x S nanoparticles were found, which further confirmed that the Cu 2-x S nanoparticles prepared by the ion exchange method existed in an amorphous form.
再来制备作为对比的材料TiO2/CdS纳米复合材料和TiO2/CdS/Cu2-xS纳米带，其制备方法如下：将0.5g纳米二氧化钛P25分散于20mL浓度为5mol/L的NaOH溶液中，待超声分散均匀后，转移至聚四氟乙烯反应釜中，在180℃保持48h；冷却到室温后，将得到的Na2Ti3O7粉末用去离子水洗涤干净，再在浓度为0.5mol/L的HCl溶液中搅拌24h，用去离子水清洗干净后，放在马弗炉中在500℃煅烧2h，得到TiO2纳米带；200mg TiO2纳米带放入50mL浓度为0.1mol/L的Cd(NO3)2溶液中，搅拌30min后，离心洗涤，然后再将TiO2纳米带放入50mL浓度为0.1mol/L的Na2S溶液中，搅拌30min，离心洗涤；如此反复用Cd(NO3)2、Na2S溶液处理4次后，用去离子水和乙醇洗涤干燥后，得到 TiO2/CdS纳米复合材料。再将100mg TiO2/CdS纳米复合材料超声分散在20mL甲苯溶液中待用，然后将50mg的[MeCN]4CuPF6溶于10mL甲醇中得到[MeCN]4CuPF6甲醇溶液，将[MeCN]4CuPF6甲醇溶液逐滴滴入到TiO2/CdS纳米复合材料甲苯溶液中，搅拌15min，用甲醇洗涤3次，干燥后得到。Then prepare as contrasting materials TiO 2 /CdS nanocomposite material and TiO 2 /CdS/Cu 2-x S nanobelts, the preparation method is as follows: disperse 0.5g nano titanium dioxide P25 in 20mL NaOH solution whose concentration is 5mol/L , after the ultrasonic dispersion is uniform, transfer it to a polytetrafluoroethylene reactor and keep it at 180°C for 48h; after cooling to room temperature, wash the obtained Na 2 Ti 3 O 7 powder with deionized water, and then prepare it at a concentration of 0.5 mol/L HCl solution for 24 hours, cleaned with deionized water, then placed in a muffle furnace and calcined at 500°C for 2 hours to obtain TiO 2 nanobelts ; Cd(NO 3 ) 2 solution, stirred for 30 minutes, then washed by centrifugation, then put the TiO 2 nanobelts into 50 mL Na 2 S solution with a concentration of 0.1mol/L, stirred for 30 minutes, and washed by centrifugation; (NO 3 ) 2 and Na 2 S solution were treated for 4 times, washed and dried with deionized water and ethanol, and the TiO 2 /CdS nanocomposite material was obtained. Then ultrasonically disperse 100mg of TiO 2 /CdS nanocomposite in 20mL of toluene solution for use, then dissolve 50mg of [MeCN] 4 CuPF 6 in 10mL of methanol to obtain [MeCN] 4 CuPF 6 methanol solution, and [MeCN] 4 The methanol solution of CuPF 6 was added dropwise into the toluene solution of the TiO 2 /CdS nanocomposite material, stirred for 15 min, washed with methanol three times, and dried.
将对比试验制备的TiO2/CdS与TiO2/CdS/Cu2-xS、本试验经步骤三制备的H-TiO2/CdS 和本试验经步骤四制备的H-TiO2/CdS/Cu2-xS四种样品进行吸收光谱测试，得到的吸收光谱图如图12所示。从图12可以看出，TiO2/CdS和H-TiO2/CdS的吸收范围在400-520nm 之间，这表明了CdS纳米粒子的加入，促进了材料在可见光区的响应。因为具有等离激元吸收的Cu2-xS纳米粒子的存在，使得材料对太阳能光谱的吸收达到近红外区域。此外，通过图谱可以看出，以H-TiO2为基底的材料具有更强的吸收能力，这是由于氢化以后的 H-TiO2表面无序和氧空穴存在的原因。The TiO 2 /CdS and TiO 2 /CdS/Cu 2-x S prepared by the comparative test, the H-TiO 2 /CdS prepared by the third step of this test and the H-TiO 2 /CdS/Cu prepared by the fourth step of this test The absorption spectra of the four samples of 2-x S are tested, and the obtained absorption spectra are shown in Figure 12. It can be seen from Figure 12 that the absorption range of TiO 2 /CdS and H-TiO 2 /CdS is between 400-520nm, which indicates that the addition of CdS nanoparticles promotes the response of the material in the visible light region. Because of the existence of Cu 2-x S nanoparticles with plasmonic absorption, the material absorbs the solar spectrum to the near-infrared region. In addition, it can be seen from the spectra that the H- TiO2 -based material has a stronger absorption capacity, which is due to the surface disorder and the presence of oxygen holes on the H- TiO2 surface after hydrogenation.
将将对比试验制备的TiO2/CdS与TiO2/CdS/Cu2-xS、本试验经步骤三制备的 H-TiO2/CdS和本试验经步骤四制备的H-TiO2/CdS/Cu2-xS四种样品应用到光催化分解水制氢的反应中得到的不同材料的产氢速率图如图13所示，从图13可知H-TiO2/CdS/Cu2-xS 纳米带催化剂有很好的催化性能，产氢速率可以达到261.51μmol·g-1·h-1。The TiO 2 /CdS and TiO 2 /CdS/Cu 2-x S prepared in the comparative test, the H-TiO 2 /CdS prepared in the third step of this test and the H-TiO 2 /CdS/ Figure 13 shows the hydrogen production rate graph of different materials obtained by applying four samples of Cu 2 - x S to the reaction of photocatalytic water splitting to produce hydrogen. The nanobelt catalyst has good catalytic performance, and the hydrogen production rate can reach 261.51μmol·g -1 ·h -1 .
图14为将本试验制备的H-TiO2/CdS/Cu2-xS应用到光催化分解水制氢的反应中，重复五次实验得到的数据结果，可以从图中看出，该催化剂具有很好的催化性能和循环稳定性，在重复五次实验后，产氢速率依然很高，可以达到210.63μmol·g-1-h-1。Figure 14 shows the data obtained by repeating the experiment for five times by applying the H-TiO 2 /CdS/Cu 2-x S prepared in this experiment to the reaction of photocatalytic water splitting to produce hydrogen. It can be seen from the figure that the catalyst It has good catalytic performance and cycle stability. After repeating the experiment five times, the hydrogen production rate is still high, reaching 210.63μmol·g -1 -h -1 .
根据上述试验1制备的产品的表征结果可以得出，采用本试验成功地制备了具有高太阳能转化效率，并且低成本的H-TiO2/CdS/Cu2-xS纳米带。该催化剂在光催化水分解的实验应用中，具有优异的催化性能。According to the characterization results of the products prepared in the above experiment 1, it can be concluded that the H-TiO 2 /CdS/Cu 2-x S nanoribbons with high solar energy conversion efficiency and low cost were successfully prepared by this experiment. The catalyst has excellent catalytic performance in the experimental application of photocatalytic water splitting.
试验2：本试验的H-TiO2/CdS/Cu2-xS纳米带的制备方法，按以下步骤进行：Test 2: The preparation method of the H-TiO 2 /CdS/Cu 2-x S nanoribbon in this test is carried out according to the following steps:
一、将0.3g纳米二氧化钛P25分散于20mL浓度为8mol/L的NaOH溶液中，待超声分散均匀后，转移至聚四氟乙烯反应釜中，在170℃保持48h；冷却到室温后，将得到的Na2Ti3O7粉末用去离子水洗涤干净，再在浓度为0.4mol/L的HCl溶液中搅拌24h，用去离子水清洗干净后，将得到的H2Ti3O7白色粉末与20mL浓度为0.04mol/L的H2SO4溶液一起放入聚四氟乙烯反应釜中，在90℃保持12h；最后，将获得的产物用去离子水和无水乙醇清洗干燥后，放在马弗炉中在600℃煅烧2h，得到具有粗糙表面的TiO2纳米带；1. Disperse 0.3g of nano-titanium dioxide P25 in 20mL of NaOH solution with a concentration of 8mol/L. After the ultrasonic dispersion is uniform, transfer it to a polytetrafluoroethylene reactor and keep it at 170°C for 48h; after cooling to room temperature, you will get The Na 2 Ti 3 O 7 powder was washed with deionized water, then stirred in the HCl solution with a concentration of 0.4mol/L for 24 hours, and after being cleaned with deionized water, the obtained white powder of H 2 Ti 3 O 7 was mixed with 20 mL of H 2 SO 4 solution with a concentration of 0.04 mol/L was put into a polytetrafluoroethylene reactor and kept at 90°C for 12 hours; finally, the obtained product was washed and dried with deionized water and absolute ethanol, and placed in Calcined at 600°C for 2h in a muffle furnace to obtain TiO nanobelts with rough surfaces;
二、将步骤一得到的粗糙表面的TiO2纳米带在H2的质量百分数为5％的N2与H2的混合气体的气氛中，以2℃/min的升温速率升温至600℃并保温4h，得到黑色的H-TiO2纳米带；2. Raise the rough surface TiO2 nanobelt obtained in step 1 to 600°C at a rate of 2°C/min in an atmosphere of a mixed gas of N2 and H2 with a mass percent of H2 of 5% and keep it warm 4h, obtain black H-TiO 2 nanobelts;
三、将步骤二得到的150mg H-TiO2纳米带放入50mL浓度为0.05mol/L的Cd(NO3)2溶液中，搅拌30min后，离心洗涤，然后再将H-TiO2纳米带放入50mL浓度为0.05mol/L 的Na2S溶液中，搅拌30min，离心洗涤；如此反复用Cd(NO3)2、Na2S溶液处理4次后，用去离子水和乙醇洗涤干燥后，得到淡黄色的H-TiO2/CdS纳米复合材料；3. Put the 150 mg H-TiO 2 nanobelts obtained in step 2 into 50 mL of Cd(NO 3 ) 2 solution with a concentration of 0.05 mol/L, stir for 30 minutes, then centrifuge and wash, and then put the H-TiO 2 nanobelts in into 50 mL of Na 2 S solution with a concentration of 0.05 mol/L, stirred for 30 min, and washed by centrifugation; after repeated treatment with Cd(NO 3 ) 2 and Na 2 S solution for 4 times, washed with deionized water and ethanol and dried, Obtain light yellow H-TiO 2 /CdS nanocomposite material;
四、将步骤三得到的50mg H-TiO2/CdS纳米复合材料超声分散在20mL甲苯溶液中待用，然后将20mg的[MeCN]4CuPF6溶于10mL甲醇中得到[MeCN]4CuPF6甲醇溶液，将 [MeCN]4CuPF6甲醇溶液逐滴滴入到H-TiO2/CdS纳米复合材料甲苯溶液中，搅拌15min，用甲醇洗涤3次，干燥后，得到H-TiO2/CdS/Cu2-xS纳米带催化剂。4. Ultrasonic disperse 50mg of the H-TiO 2 /CdS nanocomposite material obtained in step 3 in 20mL of toluene solution for use, then dissolve 20mg of [MeCN] 4 CuPF 6 in 10mL of methanol to obtain [MeCN] 4 CuPF 6 methanol solution, drop [MeCN] 4 CuPF 6 methanol solution into the H-TiO 2 /CdS nanocomposite toluene solution, stir for 15 min, wash with methanol 3 times, and dry to obtain H-TiO 2 /CdS/Cu 2-x S nanoribbon catalysts.
本试验得到的H-TiO2/CdS/Cu2-xS纳米带催化剂应用到光催化分解水制氢的反应中，其产氢速率为240.18μmol·g-1·h-1。The H-TiO 2 /CdS/Cu 2-x S nanobelt catalyst obtained in this experiment was applied to the reaction of photocatalytic water splitting to produce hydrogen, and the hydrogen production rate was 240.18 μmol·g -1 ·h -1 .
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