CN103433060B - Core-shell type TiO2/ZnIn2S4 composite photocatalyst and its preparation method and application - Google Patents
Core-shell type TiO2/ZnIn2S4 composite photocatalyst and its preparation method and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000011258 core-shell material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 8
- 239000011592 zinc chloride Substances 0.000 claims abstract description 8
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 52
- 239000000725 suspension Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 10
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
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Abstract
Description
技术领域 technical field
本发明涉及一种光催化剂，特别是涉及一种核‐壳型TiO2/ZnIn2S4复合光催化剂及其制备方法与应用；属于新型结构光催化材料技术领域，用于降解有机染料废水。 The invention relates to a photocatalyst, in particular to a core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst and its preparation method and application; it belongs to the technical field of new structured photocatalytic materials and is used for degrading organic dye wastewater.
背景技术 Background technique
随着全球能源紧缺和环境污染等问题的出现，新型能源的开发和利用成为当今时代倍受关注的主题。太阳能由于其取之不尽、洁净无污染、可再生等优点，所以利用半导体光催化剂将光能转化为电能和化学能已成为广大学者研究的热点。 With the emergence of problems such as global energy shortage and environmental pollution, the development and utilization of new energy sources has become a topic of great concern in today's era. Due to its inexhaustible, clean, non-polluting, and renewable advantages, solar energy has become a hot topic for scholars to use semiconductor photocatalysts to convert light energy into electrical energy and chemical energy. the
ZnIn2S4是一种十分重要的具有可见光响应性能的半导体材料，其禁带宽度只有约2.3eV，这也使得它能够高效的吸收利用太阳能。在过去的十几年中，ZnIn2S4己被广泛用于可见光下光催化分解水制氢以及光催化降解水或空气中有机、无机污染物的研究中。然而，作为一种光催化剂ZnIn2S4在应用中也存在光催化量子效率较低的问题。为了提高ZnIn2S4的光催化量子效率，科研作者做出了许多探索，如通过控制形貌来达到改变ZnIn2S4纳米颗粒的表面结构；将ZnIn2S4颗粒负载于石墨烯或多层碳纳米管上达到均匀分散的ZnIn2S4颗粒；掺杂过渡金属离子以及将两种半导体复合以期达到光生电荷的有效分离，从而提高ZnIn2S4的量子效率。 ZnIn 2 S 4 is a very important semiconductor material with visible light response performance, and its forbidden band width is only about 2.3eV, which also enables it to absorb and utilize solar energy efficiently. In the past ten years, ZnIn 2 S 4 has been widely used in the research of photocatalytic water splitting to produce hydrogen and photocatalytic degradation of organic and inorganic pollutants in water or air under visible light. However, as a photocatalyst, ZnIn 2 S 4 also has the problem of low photocatalytic quantum efficiency in its application. In order to improve the photocatalytic quantum efficiency of ZnIn 2 S 4 , researchers have made many explorations, such as changing the surface structure of ZnIn 2 S 4 nanoparticles by controlling the morphology; loading ZnIn 2 S 4 particles on graphene or poly The uniform dispersion of ZnIn 2 S 4 particles on the layer of carbon nanotubes; the doping of transition metal ions and the compounding of the two semiconductors in order to achieve the effective separation of photogenerated charges, thereby improving the quantum efficiency of ZnIn 2 S 4 .
发明内容 Contents of the invention
本发明的目的在于提供一种宽可见光响应范围、高光催化活性的核‐壳型TiO2/ZnIn2S4复合光催化剂。 The purpose of the present invention is to provide a core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst with wide visible light response range and high photocatalytic activity.
本发明另一目的在于提供上述可见光响应的核‐壳型TiO2/ZnIn2S4复合光催化剂的制备方法。 Another object of the present invention is to provide a method for preparing the above-mentioned visible light responsive core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst.
本发明还有一目的在于提供核‐壳型TiO2/ZnIn2S4复合光催化剂在降解有机染料废水中的应用。 Another object of the present invention is to provide the application of core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst in degrading organic dye wastewater.
本发明通过溶剂热法将ZnIn2S4生长在TiO2表面上，形成特殊的核‐壳结构复合光催化剂，两者界面之间的异质结有利于光生电子对的传递，降低其光生电子与空穴的复合率，从而提高催化剂的光催化效率。 In the present invention, ZnIn 2 S 4 is grown on the surface of TiO 2 by solvothermal method to form a special core-shell structure composite photocatalyst. The recombination rate with holes, thereby improving the photocatalytic efficiency of the catalyst.
本发明的目的通过如下技术方案实现： The purpose of the present invention is achieved through the following technical solutions:
一种核‐壳型TiO2/ZnIn2S4复合光催化剂的制备方法，包括以下步骤： A preparation method of core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst, comprising the following steps:
(1)将TiO2在乙醇溶剂中超声分散，制得悬浮液；每3mL乙醇溶剂加入1mg～4mg的TiO2； (1) ultrasonically disperse TiO 2 in ethanol solvent to obtain a suspension; add 1 mg to 4 mg of TiO 2 for every 3 mL of ethanol solvent;
(2)将氯化锌和硝酸铟在乙醇溶剂中搅拌溶解； (2) zinc chloride and indium nitrate are stirred and dissolved in ethanol solvent;
(3)将步骤(1)制得的悬浮液与步骤(2)制得的溶液混合，加入硫代乙酰胺并搅拌均匀；控制氯化锌、氯化铟与硫代乙酰胺的摩尔比为1：2：6； (3) the suspension that step (1) is made is mixed with the solution that step (2) makes, add thioacetamide and stir evenly; Control the mol ratio of zinc chloride, indium chloride and thioacetamide to be 1:2:6;
(4)将步骤(3)的反应体系转移至高压釜中进行溶剂热反应；控制反应温度为160‐200℃，反应时间为6‐12小时； (4) Transfer the reaction system of step (3) to an autoclave for solvothermal reaction; control the reaction temperature to be 160-200°C, and the reaction time to be 6-12 hours;
(5)将步骤(4)产物倒入真空抽滤装置中抽滤，用去离子水洗涤，干燥，研磨后获得核‐壳型TiO2/ZnIn2S4复合光催化剂。 (5) Pour the product of step (4) into a vacuum filtration device for suction filtration, wash with deionized water, dry, and grind to obtain a core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst.
优选地，步骤(1)中超声处理的频率为40‐45KHz，功率为50‐75W，时间为10‐15分钟。步骤(3)中，搅拌的时间为20‐40分钟。所述干燥温度为60‐80℃，干燥时间为4‐6小时。 Preferably, the frequency of the ultrasonic treatment in step (1) is 40-45KHz, the power is 50-75W, and the time is 10-15 minutes. In step (3), the time of stirring is 20-40 minutes. The drying temperature is 60-80°C, and the drying time is 4-6 hours. the
一种核‐壳型TiO2/ZnIn2S4复合光催化剂，由上述制备方法制得。 A core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst is prepared by the above preparation method.
所述的核‐壳型TiO2/ZnIn2S4复合光催化剂在有机染料废水降解中的应用。 Application of the core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst in the degradation of organic dye wastewater.
相对于现有技术，本发明具有如下优点和有益效果： Compared with prior art, the present invention has following advantage and beneficial effect:
(1)本发明通过溶剂热法将ZnIn2S4生长在TiO2表面上，形成特殊的核‐壳结构复合光催化剂，两者界面之间的异质结有利于光生电子对的传递，降低其光生电子与空穴的复合率，从而提高催化剂的光催化效率。 (1) The present invention grows ZnIn 2 S 4 on the surface of TiO 2 by solvothermal method to form a special core-shell structure composite photocatalyst, and the heterojunction between the two interfaces is conducive to the transfer of photogenerated electron pairs, reducing The recombination rate of photogenerated electrons and holes can improve the photocatalytic efficiency of the catalyst.
(2)通过溶剂热反应，核‐壳型TiO2/ZnIn2S4复合光催化剂的形成一步完成，制备工艺简单、成本低廉，有利于大规模制备。 (2) Through solvothermal reaction, the formation of core-shell TiO 2 /ZnIn 2 S 4 composite photocatalyst is completed in one step. The preparation process is simple and the cost is low, which is conducive to large-scale preparation.
(3)本发明复合光催化剂具有宽可见光响应范围、高光催化活性，适用于太阳能转化利用和环境治理等领域，如含有亚甲基蓝有机染料工业废水的降解。 (3) The composite photocatalyst of the present invention has a wide visible light response range and high photocatalytic activity, and is suitable for the fields of solar energy conversion and utilization and environmental treatment, such as the degradation of industrial wastewater containing methylene blue organic dyes. the
附图说明 Description of drawings
图1是实施例1中TiO2和制备的ZnIn2S4、核‐壳型TiO2/ZnIn2S4复合光催化剂的X射线衍射图； Fig. 1 is the X-ray diffraction figure of TiO 2 and the prepared ZnIn 2 S 4 , core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst in embodiment 1;
图2是实施例1中TiO2和制备的ZnIn2S4、核‐壳型TiO2/ZnIn2S4复合光催化剂的紫外‐可见吸收光谱图； Fig. 2 is the ultraviolet-visible absorption spectrogram of TiO 2 and the prepared ZnIn 2 S 4 , core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst in embodiment 1;
图3是实施例1中制备的核‐壳型TiO2/ZnIn2S4复合光催化剂透射电镜图； Fig. 3 is the transmission electron micrograph of the core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst prepared in embodiment 1;
图4是实施例1中TiO2和制备的ZnIn2S4、核‐壳型TiO2/ZnIn2S4复合光催化剂对亚甲基蓝的降解率随降解时间的变化曲线。 Fig. 4 is the variation curve of the degradation rate of methylene blue with the degradation time of TiO 2 and prepared ZnIn 2 S 4 , core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst in Example 1.
具体实施方式 Detailed ways
为更好地理解本发明，下面结合附图和实施例对本发明作进一步的描述，但是本发明的实施方式不限于此。 In order to better understand the present invention, the present invention will be further described below in conjunction with the accompanying drawings and examples, but the embodiments of the present invention are not limited thereto. the
实施例1 Example 1
一种可见光响应的核‐壳型TiO2/ZnIn2S4复合光催化剂的制备方法，包括以下步骤： A method for preparing a visible light-responsive core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst, comprising the following steps:
(1)将20mg TiO2在30ml乙醇溶剂中超声分散10分钟，超声处理的频率为40KHz，功率为50W； (1) Ultrasonic disperse 20mg TiO2 in 30ml ethanol solvent for 10 minutes, the frequency of ultrasonic treatment is 40KHz, and the power is 50W;
(2)将2mmol氯化锌和4mmol硝酸铟在30ml乙醇溶剂中搅拌溶解； (2) 2mmol zinc chloride and 4mmol indium nitrate are stirred and dissolved in 30ml ethanol solvent;
(3)将步骤(1)制得的悬浮液与步骤(2)制得的溶液混合，加入12mmol硫代乙酰胺并以500r/min的转速搅拌20分钟； (3) The suspension obtained in step (1) was mixed with the solution obtained in step (2), and 12 mmol thioacetamide was added and stirred at a speed of 500 r/min for 20 minutes;
(4)将步骤(3)的反应体系转移至高压釜中，160℃条件进行反应6小时； (4) Transfer the reaction system of step (3) to an autoclave, and react at 160°C for 6 hours;
(5)将步骤(4)产物倒入真空抽滤装置中抽滤，用去离子水洗涤，60℃条件下干燥6小时，研磨后获得核‐壳型TiO2/ZnIn2S4复合光催化剂。 (5) Pour the product of step (4) into a vacuum filtration device for suction filtration, wash with deionized water, dry at 60°C for 6 hours, and obtain a core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst after grinding .
图1是实施例1中TiO2和制备的ZnIn2S4、核‐壳型TiO2/ZnIn2S4复合光催化剂的X射线衍射图。由图1可知，TiO2/ZnIn2S4样品的衍射特征峰中可以观察到TiO2和ZnIn2S4两种物质的特征峰，说明成功制备了TiO2/ZnIn2S4复合光催化剂；由图2可知，TiO2/ZnIn2S4在可见光范围内有强烈的吸光度，说明TiO2/ZnIn2S4具有可见光催化活性；从图3透射电镜照片中可以观察到明显的核‐壳结构，证实了成功制得核‐壳型TiO2/ZnIn2S4复合光催化剂。 Fig. 1 is the X-ray diffraction pattern of TiO 2 and the prepared ZnIn 2 S 4 , core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst in Example 1. It can be seen from Figure 1 that the characteristic peaks of TiO 2 and ZnIn 2 S 4 can be observed in the diffraction characteristic peaks of the TiO 2 /ZnIn 2 S 4 sample, indicating that the TiO 2 /ZnIn 2 S 4 composite photocatalyst was successfully prepared; It can be seen from Figure 2 that TiO 2 /ZnIn 2 S 4 has a strong absorbance in the visible light range, indicating that TiO 2 /ZnIn 2 S 4 has visible light catalytic activity; from the transmission electron microscope photos in Figure 3, an obvious core-shell structure can be observed , confirmed the successful preparation of core-shell TiO 2 /ZnIn 2 S 4 composite photocatalysts.
实施例2 Example 2
一种可见光响应的核‐壳型TiO2/ZnIn2S4复合光催化剂的制备方法，包括以下步骤： A method for preparing a visible light-responsive core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst, comprising the following steps:
(1)将40mg TiO2在30ml乙醇溶剂中超声分散12分钟；超声处理的频率为40KHz，功率为50W； (1) Ultrasonic dispersion of 40mg TiO2 in 30ml ethanol solvent for 12 minutes; the frequency of ultrasonic treatment is 40KHz, and the power is 50W;
(2)将2mmol氯化锌和4mmol硝酸铟在30ml乙醇溶剂中搅拌溶解； (2) 2mmol zinc chloride and 4mmol indium nitrate are stirred and dissolved in 30ml ethanol solvent;
(3)将步骤(1)制得的悬浮液与步骤(2)制得的溶液混合，加入12mmol硫代乙酰胺并以500r/min的转速搅拌30分钟； (3) The suspension prepared in step (1) was mixed with the solution prepared in step (2), and 12 mmol thioacetamide was added and stirred at a speed of 500 r/min for 30 minutes;
(4)将步骤(3)的反应体系转移至高压釜中，180℃条件进行反应8小时； (4) Transfer the reaction system of step (3) to an autoclave, and react at 180°C for 8 hours;
(5)将步骤(4)产物倒入真空抽滤装置中抽滤，用去离子水洗涤，70℃条件下干燥5小时，研磨后获得核‐壳型TiO2/ZnIn2S4复合光催化剂。 (5) Pour the product of step (4) into a vacuum filtration device for suction filtration, wash with deionized water, dry at 70°C for 5 hours, and obtain a core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst after grinding .
本实施例中TiO2/ZnIn2S4复合光催化剂的X射线衍射图、可见光催化活性和核‐壳结构与图1‐3相似。 The X-ray diffraction pattern, visible light catalytic activity and core-shell structure of the TiO 2 /ZnIn 2 S 4 composite photocatalyst in this example are similar to those in Figure 1-3.
实施例3 Example 3
一种可见光响应的核‐壳型TiO2/ZnIn2S4复合光催化剂的制备方法，包括以下步骤： A method for preparing a visible light-responsive core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst, comprising the following steps:
(1)将80mg TiO2在30ml乙醇溶剂中超声分散15分钟；超声处理的频率为45KHz，功率为75W； (1) Ultrasonic disperse 80mg TiO2 in 30ml ethanol solvent for 15 minutes; the frequency of ultrasonic treatment is 45KHz, and the power is 75W;
(2)将2mmol氯化锌和4mmol硝酸铟在30ml乙醇溶剂中搅拌溶解； (2) 2mmol zinc chloride and 4mmol indium nitrate are stirred and dissolved in 30ml ethanol solvent;
(3)将步骤(1)制得的悬浮液与步骤(2)制得的溶液混合，加入12mmol硫代乙酰胺并以500r/min的转速搅拌40分钟； (3) The suspension obtained in step (1) was mixed with the solution obtained in step (2), and 12 mmol thioacetamide was added and stirred at a speed of 500 r/min for 40 minutes;
(4)将步骤(3)的反应体系转移至高压釜中，200℃条件进行反应12小时； (4) Transfer the reaction system of step (3) to an autoclave, and react at 200°C for 12 hours;
(5)将步骤(4)产物倒入真空抽滤装置中抽滤，用去离子水洗涤，80℃条件下干燥4小时，研磨后获得核‐壳型TiO2/ZnIn2S4复合光催化剂。 (5) Pour the product of step (4) into a vacuum filtration device for suction filtration, wash with deionized water, dry at 80°C for 4 hours, and obtain a core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst after grinding .
本实施例中TiO2/ZnIn2S4复合光催化剂的X射线衍射图、可见光催化活性和核‐壳结构与图1‐3相似。 The X-ray diffraction pattern, visible light catalytic activity and core-shell structure of the TiO 2 /ZnIn 2 S 4 composite photocatalyst in this example are similar to those in Figure 1-3.
应用实施例 Application example
使用制备的核‐壳型TiO2/ZnIn2S4复合光催化剂光降解有机染料：以亚甲基蓝水溶液为模拟污水来评价该催化剂的光催化活性。实验条件设置为：(1)将实施例1中制备的20mg核‐壳型TiO2/ZnIn2S4复合光催化剂分散到120mL浓度为20mg·L‐1的亚甲基蓝水溶液中，光照反应前，先将悬浮液置于黑暗环境中磁力搅拌1h，以使体系达到吸附/解吸平衡；(2)打开模拟太阳光源，每次光照30分钟后取样，离心，检测溶液中亚甲基蓝溶液的紫外‐可见吸光度值的变化。 Photodegradation of organic dyes using the prepared core‐shell TiO 2 /ZnIn 2 S 4 composite photocatalyst: The photocatalytic activity of the catalyst was evaluated by using methylene blue aqueous solution as simulated sewage. The experimental conditions were set as follows: (1) Disperse 20 mg of the core-shell TiO 2 /ZnIn 2 S 4 composite photocatalyst prepared in Example 1 into 120 mL of methylene blue aqueous solution with a concentration of 20 mg·L -1 . Place the suspension in a dark environment and stir magnetically for 1 hour to make the system reach adsorption/desorption equilibrium; (2) Turn on the simulated sunlight light source, take samples after 30 minutes of each illumination, centrifuge, and detect the UV-visible absorbance value of the methylene blue solution in the solution The change.
图4是实施例1中TiO2和制备的ZnIn2S4、核‐壳型TiO2/ZnIn2S4复合光催化剂对亚甲基蓝的降解率随光照时间的变化曲线。结合图4可知，在可见光照射下，TiO2对亚甲基蓝降解没有催化活性；光照4小时后，ZnIn2S4可降解71％的亚甲基蓝，而核‐壳型TiO2/ZnIn2S4复合光催化剂对亚甲基蓝的降解率可达92％，极大地提高了TiO2和ZnIn2S4的可见光催化活性。 Fig. 4 is the variation curve of the degradation rate of methylene blue by TiO 2 and prepared ZnIn 2 S 4 , core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst in Example 1 as a function of light time. Combined with Figure 4, it can be seen that under visible light irradiation, TiO 2 has no catalytic activity for the degradation of methylene blue; after 4 hours of light, ZnIn 2 S 4 can degrade 71% of methylene blue, and the core-shell type TiO 2 /ZnIn 2 S 4 composite photocatalyst The degradation rate of methylene blue can reach 92%, which greatly improves the visible light catalytic activity of TiO 2 and ZnIn 2 S 4 .
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