CN108067267B - Visible light response cadmium telluride/titanium dioxide Z-type photocatalyst and preparation method and application thereof - Google Patents
Visible light response cadmium telluride/titanium dioxide Z-type photocatalyst and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 132
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 58
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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Abstract
本发明公开了一种可见光响应碲化镉/二氧化钛Z型光催化剂，该催化剂以二氧化钛为载体，在二氧化钛上负载有碲化镉。主要采用水热法制得。本发明的碲化镉/二氧化钛Z型光催化剂中碲化镉和二氧化钛交错的导带/价带分布能够促进光生电子和空穴对的分离；Z型的光生载流子传递路径使电子和空穴具有强氧化还原能力；碲化镉的窄带隙能够增强碲化镉/二氧化钛Z型光催化剂可见光响应能力；从而碲化镉/二氧化钛Z型光催化剂具有优异的可见光光催化降解抗生素活性。本发明的制备工艺简单、条件温和、操作方便、成本低廉，易于实现工艺规模化应用，在污水处理等领域有着广阔的应用前景。
The invention discloses a visible light-responsive cadmium telluride/titanium dioxide Z-type photocatalyst. The catalyst uses titanium dioxide as a carrier and supports cadmium telluride on the titanium dioxide. Mainly obtained by hydrothermal method. The staggered conduction band/valence band distribution of cadmium telluride and titanium dioxide in the cadmium telluride/titanium dioxide Z-type photocatalyst of the invention can promote the separation of photogenerated electron and hole pairs; The hole has strong redox ability; the narrow band gap of cadmium telluride can enhance the visible light response ability of cadmium telluride/titanium dioxide Z-type photocatalyst; thus the cadmium telluride/titanium dioxide Z-type photocatalyst has excellent visible light photocatalytic degradation of antibiotics. The preparation process of the invention is simple, the conditions are mild, the operation is convenient, the cost is low, the large-scale application of the process is easy to be realized, and the invention has broad application prospects in the fields of sewage treatment and the like.
Description
技术领域technical field
本发明属于光催化材料领域，具体涉及一种可见光响应碲化镉/二氧化钛Z型光催化剂及其制备方法和应用。The invention belongs to the field of photocatalytic materials, in particular to a visible light-responsive cadmium telluride/titanium dioxide Z-type photocatalyst and a preparation method and application thereof.
背景技术Background technique
目前全球性的环境污染问题日趋严重，并威胁着人类的生存和发展。纺织印染、石油化工、皮革加工、抗生素在临床医疗、水产养殖和畜牧业的广泛应用造成大量有毒有害的有机物排放到水体环境中，并逐渐累积造成对生态环境和人类健康的危害。半导体光催化技术通过吸收利用太阳光在常温下降解有毒有害有机污染物。由于其具有能耗低、反应条件温和、成本低廉、操作简单、无二次污染的优点，光催化降解污染物是公认的最有前景的绿色环保治理环境污染的技术。At present, the global environmental pollution problem is becoming more and more serious, threatening the survival and development of human beings. The wide application of textile printing and dyeing, petrochemical, leather processing, and antibiotics in clinical medicine, aquaculture and animal husbandry has caused a large number of toxic and harmful organic substances to be discharged into the water environment, and gradually accumulate to cause harm to the ecological environment and human health. Semiconductor photocatalysis technology degrades toxic and harmful organic pollutants at room temperature by absorbing and utilizing sunlight. Due to its advantages of low energy consumption, mild reaction conditions, low cost, simple operation, and no secondary pollution, photocatalytic degradation of pollutants is recognized as the most promising green technology for environmental pollution control.
二氧化钛是一种成本低廉、稳定性高、环境友好的半导体光催化剂，在光催化净化环境领域有良好的应用前景。但是二氧化钛大规模广泛应用的“瓶颈”是其宽带隙(仅能吸收占太阳能谱中5％的紫外光)和高电子-空穴复合率。因此，拓展二氧化钛光吸收范围为可见光响应(占太阳光总能量的43％)，同时抑制光生电子-空穴复合是本领域亟待解决的关键技术问题。为了克服上述问题，可以将其他窄带隙半导体材料与二氧化钛复合制备异质结复合光催化剂，通过构筑这样的异质结复合光催化剂可以拓展光吸收范围并一直光生电子、空穴的复合。专利申请(CN101722013A；CN102658180A；CN103736512A；CN104475129A；CN104475129A；CN105013469A；CN106040276A；)中公开了不同半导体材料复合TiO2而成的异质结光催化剂，如PbS/TiO2、CdS/TiO2、BiOCl/TiO2、g-C3N4/TiO2、CuS/TiO2、Na0.9Mg0.45Ti3.55O8/TiO2、mpg-C3N4/BiVO4/TiO2。这些复合异质结光催化剂都要优于TiO2。Titanium dioxide is a semiconductor photocatalyst with low cost, high stability and environmental friendliness, and has good application prospects in the field of photocatalytic purification of the environment. But the "bottleneck" of TiO2 is its wide bandgap (absorbing only 5% of the ultraviolet light in the solar spectrum) and high electron-hole recombination rate. Therefore, expanding the light absorption range of titanium dioxide to respond to visible light (accounting for 43% of the total sunlight energy) and simultaneously suppressing photogenerated electron-hole recombination are key technical problems to be solved urgently in this field. In order to overcome the above problems, other narrow-bandgap semiconductor materials can be combined with titanium dioxide to prepare a heterojunction composite photocatalyst. By constructing such a heterojunction composite photocatalyst, the light absorption range can be expanded and the photogenerated electrons and holes can be combined. The patent application (CN101722013A; CN102658180A; CN103736512A; CN104475129A; CN104475129A; CN105013469A; CN106040276A;) discloses heterojunction photocatalysts formed by compounding TiO2 with different semiconductor materials, such as PbS/ TiO2 , CdS/ TiOBiOClTiO2 , 2. gC3N4 / TiO2 , CuS / TiO2 , Na0.9Mg0.45Ti3.55O8 / TiO2, mpg - C3N4/ BiVO4 / TiO2 . These composite heterojunction photocatalysts are superior to TiO 2 .
但是异质结光催化剂仍然存在一个不利于实现高效光催化降解有机污染物的问题，即光生电子的还原能力和空穴的氧化能力变弱，这是由于在异质结光催化剂中光生电子和空穴分别向导带更低和价带更高的半导体材料中转移。近年来提出的Z型光催化剂的设计为解决这一关键技术问题提出了新的思路。除了具有异质结光催化剂提高可见光吸收和促进光生载流子分离的优点以外，Z型机制还可以保留两种半导体材料中电势更负的导带电子(还原能力更强)和电势更正的价带空穴(氧化能力更强)。However, heterojunction photocatalysts still have a problem that is not conducive to the realization of high-efficiency photocatalytic degradation of organic pollutants, that is, the reduction ability of photogenerated electrons and the oxidative ability of holes are weakened. Holes are transferred into semiconductor materials with lower and higher valence bands, respectively. The design of Z-type photocatalysts proposed in recent years provides new ideas for solving this key technical problem. In addition to the advantages of heterojunction photocatalysts that enhance visible light absorption and facilitate separation of photogenerated charge carriers, the Z-type mechanism can also preserve the more negatively-potential conduction band electrons (more reducing power) and more-potentially-positive valences in the two semiconductor materials. With holes (more oxidizing ability).
碲化镉(CdTe)是一种禁带宽度为1.4eV的窄带隙半导体，具有优异的可见光吸收能力。并且CdTe的导带比TiO2的导带电位更负，而CdTe的价带TiO2的价带电位更正。因此CdTe是一种理想的与TiO2构筑复合光催化剂的窄带半导体材料。开发碲化镉/二氧化钛Z型半导体光催化剂可以提高光催化剂的可见光吸收能力，促进光生电子和空穴的分离并同时保留电子和空穴的强氧化还原能力，对于高效降解废水中的污染物在(如抗生素)具有重要意义。Cadmium telluride (CdTe) is a narrow-bandgap semiconductor with a forbidden band width of 1.4 eV, which exhibits excellent visible light absorption. And the conduction band of CdTe is more negative than the conduction band potential of TiO2 , while the valence band potential of CdTe is more positive than that of TiO2 . Therefore, CdTe is an ideal narrow-band semiconductor material for building composite photocatalysts with TiO2 . The development of cadmium telluride/titanium dioxide Z-type semiconductor photocatalysts can improve the visible light absorption capacity of photocatalysts, promote the separation of photogenerated electrons and holes, and at the same time retain the strong redox ability of electrons and holes. (such as antibiotics) are of great significance.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是克服现有技术不足，提供一种可见光响应、光生电子-空穴对分离效率高、氧化还原能力强、光催化效率高的碲化镉/二氧化钛Z型光催化剂及其制备方法和应用。本发明具有成本低廉、制备条件温和、操作简单等优点，适用于工业化生产。The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art, and to provide a cadmium telluride/titanium dioxide Z-type photocatalyst with visible light response, high photo-generated electron-hole pair separation efficiency, strong redox ability and high photocatalytic efficiency, and Its preparation method and application. The invention has the advantages of low cost, mild preparation conditions, simple operation and the like, and is suitable for industrial production.
为解决上述技术问题，本发明提供的技术方案是：一种可见光响应Z型光催化剂，所述的光催化剂是碲化镉/二氧化钛复合物，所述的的复合物以TiO2为载体，所述的CdTe负载在二氧化钛粉末上。In order to solve the above technical problems, the technical solution provided by the present invention is: a visible light responsive Z-type photocatalyst, the photocatalyst is a cadmium telluride/titanium dioxide composite, and the composite uses TiO2 as a carrier, so The described CdTe is supported on titanium dioxide powder.
优选的，所述碲化镉/氧化钛Z型光催化剂中，所述碲化镉的质量含量为11％,所述二氧化钛的质量含量为88％。Preferably, in the cadmium telluride/titanium oxide Z-type photocatalyst, the mass content of the cadmium telluride is 11%, and the mass content of the titanium dioxide is 88%.
上述碲化镉/二氧化钛Z型光催化剂的制备方法,包括以下步骤：The preparation method of the above cadmium telluride/titanium dioxide Z-type photocatalyst comprises the following steps:
1)在无氧条件下，向反应容器中加入硼氢化钠、碲粉与去离子水；直到碲粉完全溶解、溶液由浑浊变澄清，制得NaHTe前驱体溶液；1) Under anaerobic conditions, add sodium borohydride, tellurium powder and deionized water to the reaction vessel; until the tellurium powder is completely dissolved and the solution becomes clear from turbidity, the NaHTe precursor solution is obtained;
2)在无氧条件下，向反应容器中加入二氧化钛粉末和去离子水，磁力搅拌至二氧化钛粉末均匀分散在去离子水；加入镉源搅拌至完全溶解，然后加入稳定剂巯基丙酸；2) Under oxygen-free conditions, add titanium dioxide powder and deionized water to the reaction vessel, stir magnetically until the titanium dioxide powder is uniformly dispersed in the deionized water; add a cadmium source and stir until it is completely dissolved, and then add a stabilizer mercaptopropionic acid;
3)将步骤1)制备的NaHTe前驱体溶液注入步骤2)配置的混合液中,继续在无氧条件下搅拌10分钟；3) inject the NaHTe precursor solution prepared in step 1) into the mixed solution prepared in step 2), and continue to stir for 10 minutes under anaerobic conditions;
4)将步骤3)中得到的混合物溶液转移到高压水热反应釜中，120-160℃加热；冷却至室温，离心，清洗，干燥，得到碲化镉/二氧化钛Z型光催化剂。4) Transfer the mixture solution obtained in step 3) into a high-pressure hydrothermal reactor, heat at 120-160° C.; cool to room temperature, centrifuge, wash, and dry to obtain a cadmium telluride/titanium dioxide Z-type photocatalyst.
上述方法中，优选的，步骤4)中水热反应温度为120℃，加热时间为6h。In the above method, preferably, the hydrothermal reaction temperature in step 4) is 120° C., and the heating time is 6h.
上述方法中，碲粉、硼氢化钠、去离子水的用量比优选为0.1mmol:1mmol:2ml；镉源可为乙酸镉和氯化镉中的一种；二氧化钛通常采用德固赛P25；二氧化钛、镉源、去离子水、巯基丙酸的用量比优选为250mg:0.4mmol:68mL:53μL；步骤3)中NaHTe前驱体溶液与步骤2)的混合液体积比优选为2mL:68mL。In the above method, the consumption ratio of tellurium powder, sodium borohydride and deionized water is preferably 0.1mmol:1mmol:2ml; the cadmium source can be one of cadmium acetate and cadmium chloride; titanium dioxide usually adopts Degussa P25; titanium dioxide The dosage ratio of cadmium source, deionized water and mercaptopropionic acid is preferably 250mg:0.4mmol:68mL:53μL; the volume ratio of the mixed solution of NaHTe precursor solution in step 3) and step 2) is preferably 2mL:68mL.
上述方法制备的碲化镉/二氧化钛Z型光催化剂，应用于可见光下降解抗生素废水中四环素，展现出优异的光催化性能。本发明以目前已经实现规模化生产的德固赛P25为载体，具有成本低廉、易获得、产量大的优点。同时，本发明制备方法简单，条件温和，易于实现工业规模化应用。The cadmium telluride/titanium dioxide Z-type photocatalyst prepared by the above method is applied to degrade tetracycline in antibiotic wastewater under visible light, and exhibits excellent photocatalytic performance. The present invention uses Degussa P25, which has achieved large-scale production at present, as a carrier, and has the advantages of low cost, easy acquisition and large output. Meanwhile, the preparation method of the invention is simple, the conditions are mild, and the industrial-scale application is easy to be realized.
附图说明Description of drawings
图1为本发明实施例1中合成的CdTe/TiO2的透射电镜(TEM)图，其中(a)和(b)为低倍TEM图，(c)为高分辨TEM图，(d-g)为Cd、Te、Ti、O的能谱图。Figure 1 is a transmission electron microscope (TEM) image of CdTe/TiO 2 synthesized in Example 1 of the present invention, wherein (a) and (b) are low-magnification TEM images, (c) is a high-resolution TEM image, and (dg) is Energy spectra of Cd, Te, Ti, O.
图2为本发明实施例1、2、5中合成的CdTe/TiO2的拉曼光谱图，作为对比的TiO2的拉曼光谱图，从图中可以观察到属于TiO2的拉曼振动，以及负载CdTe纳米晶体相关的拉曼振动。Fig. 2 is the Raman spectrogram of CdTe/TiO2 synthesized in Examples 1, 2 , and 5 of the present invention. As the Raman spectrogram of TiO2 for comparison, the Raman vibration belonging to TiO2 can be observed from the figure, and the Raman vibrations associated with loaded CdTe nanocrystals.
图3为本发明实施例1中合成的CdTe/TiO2的吸收光谱图，作为对比的TiO2的吸收光谱图。FIG. 3 is an absorption spectrum diagram of CdTe/TiO 2 synthesized in Example 1 of the present invention, and an absorption spectrum diagram of TiO 2 as a comparison.
图4为本发明实施例1中合成的CdTe/TiO2的电化学阻抗谱的Nyquist图，作为对比的TiO2的电化学阻抗谱的Nyquist图。4 is a Nyquist diagram of the electrochemical impedance spectrum of CdTe/TiO 2 synthesized in Example 1 of the present invention, and a Nyquist diagram of the electrochemical impedance spectrum of TiO 2 as a comparison.
图5为本发明实施例1中合成的CdTe/TiO2的可见光下光催化降解四环素效率图，作为对比的TiO2的电化学阻抗谱的的可见光下光催化降解四环素效率图。5 is the photocatalytic degradation efficiency of tetracycline under visible light of CdTe/TiO 2 synthesized in Example 1 of the present invention, and the photocatalytic degradation efficiency of tetracycline under visible light of the electrochemical impedance spectrum of TiO 2 as a comparison.
图6为本发明实施例1中合成的Z型CdTe/TiO2光催化剂降解四环素机制图。FIG. 6 is a schematic diagram of the degradation mechanism of tetracycline by the Z-type CdTe/TiO 2 photocatalyst synthesized in Example 1 of the present invention.
具体实施方式Detailed ways
下面结合具体实施方式，进一步阐明本发明。应理解，这些实施例仅用于说明本发明而不是用于限制本发明的范围。此外，在阅读了本发明的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附后权利要求书限定的范围。The present invention will be further illustrated below in conjunction with specific embodiments. It should be understood that these examples are only intended to illustrate the present invention and not to limit the scope of the present invention. In addition, after reading the content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
实施例1:Embodiment 1:
(1)光催化剂的制备(1) Preparation of photocatalyst
(a)NaHTe前驱体溶液的制备：(a) Preparation of NaHTe precursor solution:
在25mL三颈圆底烧瓶中加入12.8mg碲粉、37.8mg硼氢化钠、2mL去离子水，密封，磁力搅拌，通氮气保护除氧气，直至碲粉完全溶解，制得澄清的NaHTe前驱体溶液备用。Add 12.8mg tellurium powder, 37.8mg sodium borohydride, 2mL deionized water to a 25mL three-neck round-bottomed flask, seal it, stir magnetically, and pass nitrogen protection to remove oxygen until the tellurium powder is completely dissolved to obtain a clear NaHTe precursor solution spare.
(b)CdTe/TiO2光催化剂制备：(b) Preparation of CdTe/ TiO photocatalyst:
在150mL三颈圆底烧瓶中加入250mg二氧化钛、68mL去离子水，磁力搅拌至二氧化钛粉末均匀分散在水中；然后加入107mg乙酸镉，搅拌至溶解；然后加入53μL巯基丙酸，搅拌，密封，通氮气除氧气；迅速注入2mL步骤1)中准备的NaHTe前驱体溶液，搅拌10分钟；将上述混合液转移到高压水热反应釜中，置于烘箱120℃反应6小时；冷却到室温后，离心、用去离子水和异丙醇洗涤、干燥，得到CdTe/TiO2光催化剂。Add 250mg titanium dioxide and 68mL deionized water to a 150mL three-neck round bottom flask, stir magnetically until the titanium dioxide powder is evenly dispersed in the water; then add 107mg cadmium acetate, stir until dissolved; then add 53μL mercaptopropionic acid, stir, seal, and pass nitrogen Remove oxygen; quickly inject 2 mL of the NaHTe precursor solution prepared in step 1), and stir for 10 minutes; transfer the above mixed solution to a high-pressure hydrothermal reactor, place it in an oven at 120 ° C for 6 hours; after cooling to room temperature, centrifuge, Wash with deionized water and isopropanol, and dry to obtain CdTe/ TiO2 photocatalyst.
图1为合成的CdTe/TiO2透射电镜图和能谱图，从图中可以看出，成功制备出CdTe纳米晶粒，CdTe纳米晶粒均匀负载在TiO2粉末上。Figure 1 shows the TEM image and energy spectrum of the synthesized CdTe/ TiO2 . It can be seen from the figure that the CdTe nanocrystals were successfully prepared, and the CdTe nanocrystals were uniformly loaded on the TiO2 powder.
图2为合成的CdTe/TiO2的拉曼光谱图，通过与TiO2的拉曼谱对比可以发现在复合样品CdTe-TiO2中仍然可以观察到属于TiO2晶体的拉曼振动模，表明CdTe复合并没有改变TiO2的晶体结构；实施例1中CdTe的拉曼振动并不明显，实施例2(反应温度升高到140℃)和实施例5(反应温度升高到140℃)中还可以观察到属于CdTe的拉曼峰，表明成功制备出CdTe/TiO2。Figure 2 shows the Raman spectrum of the synthesized CdTe/TiO 2. By comparing with the Raman spectrum of TiO 2 , it can be found that the Raman vibration mode belonging to the TiO 2 crystal can still be observed in the composite sample CdTe-TiO 2 , indicating that CdTe The recombination did not change the crystal structure of TiO2 ; the Raman vibration of CdTe was not obvious in Example 1, and also in Example 2 (the reaction temperature was raised to 140°C) and Example 5 (the reaction temperature was raised to 140°C). Raman peaks belonging to CdTe can be observed, indicating successful preparation of CdTe/TiO 2 .
图3为合成的CdTe/TiO2的吸收光谱图，从图中可以看出，CdTe复合明显可以TiO2拓展光响应范围，CdTe/TiO2在紫外和可见光区都具有优异的光吸收，可以作为一种可见光响应光催化剂。Figure 3 shows the absorption spectrum of the synthesized CdTe/TiO 2. It can be seen from the figure that the CdTe composite can obviously expand the photoresponse range of TiO 2. CdTe/TiO 2 has excellent light absorption in both the ultraviolet and visible regions, and can be used as a A visible-light-responsive photocatalyst.
图4为合成的CdTe/TiO2的电化学阻抗谱的Nyquist图，从图中可以看出，CdTe/TiO2光催化剂阻抗圆弧半径小于TiO2，表明CdTe复合TiO2可以抑制光生电子、空穴分离，催进光催化效率。Figure 4 is the Nyquist diagram of the electrochemical impedance spectrum of the synthesized CdTe/TiO 2 . It can be seen from the figure that the impedance arc radius of the CdTe/TiO 2 photocatalyst is smaller than that of the TiO 2 , indicating that the CdTe composite TiO 2 can inhibit the photogenerated electrons, empty space Hole separation, boosting photocatalytic efficiency.
(2)光催化实验(2) Photocatalysis experiment
将上述光催化剂(0.6g/L)分散在浓度为0.02g/L四环素溶液(50mL)中，磁力搅拌条件下，暗反应30分钟后；打开氙灯光源，放置截止波长为400nm(作为可见光源)的滤光片，分别进行光催化反应。每隔10分钟取一定量的四环素溶液，用紫外-可见分光光度计测试溶液的吸收光谱，通过吸收峰强度的变化可以计算出四环素的降解率。The above-mentioned photocatalyst (0.6g/L) was dispersed in a tetracycline solution (50mL) with a concentration of 0.02g/L, under the condition of magnetic stirring, after dark reaction for 30 minutes; turned on the xenon lamp light source, and placed the cut-off wavelength at 400nm (as a visible light source) The filters were used for photocatalytic reactions. A certain amount of tetracycline solution was taken every 10 minutes, and the absorption spectrum of the solution was tested with an ultraviolet-visible spectrophotometer, and the degradation rate of tetracycline could be calculated through the change of absorption peak intensity.
图5为合成的CdTe/TiO2的光催化效率图。其中横坐标为光照时间，纵坐标为光照下溶液中四环素浓度与未光照时四环素浓度的比值。从图中可以看出，随着时间增加，四环素降解率增加，30分钟后四环素降解率为78％，高于TiO2的降解效率62％。Figure 5 is a graph of the photocatalytic efficiency of the synthesized CdTe/ TiO2 . The abscissa is the illumination time, and the ordinate is the ratio of the concentration of tetracycline in the solution under illumination to the concentration of tetracycline in the absence of illumination. It can be seen from the figure that the degradation rate of tetracycline increases with the increase of time, and the degradation rate of tetracycline is 78% after 30 minutes, which is higher than the degradation efficiency of TiO2 , which is 62%.
图6为本发明实施例1中合成的Z型CdTe/TiO2光催化剂降解四环素机制图。在Z型机制中，保留了氧化还原能力更强的CdTe导带中的电子和TiO2价带中的空穴，参与光催化反应；而氧化还原能力较弱的TiO2导带中的电子和CdTe价带中的空穴通过界面转移、复合；因而Z型光催化剂更有利于提高光催化活性。FIG. 6 is a schematic diagram of the degradation mechanism of tetracycline by the Z-type CdTe/TiO 2 photocatalyst synthesized in Example 1 of the present invention. In the Z-type mechanism, the electrons in the conduction band of CdTe with stronger redox ability and the holes in the valence band of TiO2 are retained to participate in the photocatalytic reaction; while the electrons in the conduction band of TiO2 with weaker redox ability and The holes in the CdTe valence band are transferred and recombined through the interface; therefore, the Z-type photocatalyst is more conducive to improving the photocatalytic activity.
实施例2:Embodiment 2:
(1)光催化剂的制备(1) Preparation of photocatalyst
(a)NaHTe前驱体溶液的制备：与实施例1相同(a) Preparation of NaHTe precursor solution: same as Example 1
(b)CdTe/TiO2光催化剂制备:(b) Preparation of CdTe/ TiO photocatalyst:
与实施例1不同在于:烘箱加热温度为140℃。The difference from Example 1 is that the oven heating temperature is 140°C.
采用实施例1所述方法测试本例制得的光催化剂在可见光照射下对四环素的降解活性。其30分钟后光催化性降解效率为72％。The method described in Example 1 was used to test the degradation activity of the photocatalyst prepared in this example on tetracycline under visible light irradiation. Its photocatalytic degradation efficiency was 72% after 30 minutes.
实施例3:Embodiment 3:
(1)光催化剂的制备(1) Preparation of photocatalyst
(a)NaHTe前驱体溶液的制备：与实施例1相同(a) Preparation of NaHTe precursor solution: same as Example 1
(b)CdTe/TiO2光催化剂制备:(b) Preparation of CdTe/ TiO photocatalyst:
与实施例1不同在于:在注入NaHTe前驱体溶液前，将本发明步骤2)制得的混合液(含TiO2)pH值调节为4；烘箱中加热温度为140℃。The difference from Example 1 is: before injecting the NaHTe precursor solution, the pH value of the mixed solution (containing TiO 2 ) prepared in step 2) of the present invention is adjusted to 4; the heating temperature in the oven is 140° C.
采用实施例1所述方法测试本例制得的光催化剂在可见光照射下对四环素的降解活性。其30分钟后光催化性降解效率为76％。The method described in Example 1 was used to test the degradation activity of the photocatalyst prepared in this example on tetracycline under visible light irradiation. Its photocatalytic degradation efficiency was 76% after 30 minutes.
实施例4:Embodiment 4:
(1)光催化剂的制备(1) Preparation of photocatalyst
(a)NaHTe前驱体溶液的制备：与实施例1相同(a) Preparation of NaHTe precursor solution: same as Example 1
(b)CdTe/TiO2光催化剂制备:(b) Preparation of CdTe/ TiO photocatalyst:
与实施例1不同在于:在注入NaHTe前驱体溶液前，将本发明步骤2)制得的混合液(含TiO2)pH值调节为12；烘箱中加热温度为140℃。The difference from Example 1 is that: before injecting the NaHTe precursor solution, the pH value of the mixed solution (containing TiO 2 ) prepared in step 2) of the present invention is adjusted to 12; the heating temperature in the oven is 140° C.
采用实施例1所述方法测试本例制得的光催化剂在可见光照射下对四环素的降解活性。其30分钟后光催化性降解效率为66％。The method described in Example 1 was used to test the degradation activity of the photocatalyst prepared in this example on tetracycline under visible light irradiation. Its photocatalytic degradation efficiency was 66% after 30 minutes.
实施例5:Embodiment 5:
(1)光催化剂的制备(1) Preparation of photocatalyst
(a)NaHTe前驱体溶液的制备：与实施例1相同(a) Preparation of NaHTe precursor solution: same as Example 1
(b)CdTe/TiO2光催化剂制备:(b) Preparation of CdTe/ TiO photocatalyst:
与实施例1不同在于：烘箱加热温度为160℃。The difference from Example 1 is that the oven heating temperature is 160°C.
采用实施例1所述方法测试本例制得的光催化剂在可见光照射下对四环素的降解活性。其30分钟后光催化性降解效率为43％。The method described in Example 1 was used to test the degradation activity of the photocatalyst prepared in this example on tetracycline under visible light irradiation. Its photocatalytic degradation efficiency was 43% after 30 minutes.
可见，本发明的碲化镉/二氧化钛Z型光催化剂具有优异的可见光催化活性，无污染，成本低等一系列优点，是一种高效可见光响应的Z型光催化剂。本发明的制备工艺简单，温度较低，条件温和，操作方便，成本低廉，适合于工业化生产。It can be seen that the cadmium telluride/titanium dioxide Z-type photocatalyst of the present invention has a series of advantages such as excellent visible light catalytic activity, no pollution, low cost, etc., and is an efficient visible light-responsive Z-type photocatalyst. The preparation process of the invention is simple, the temperature is low, the conditions are mild, the operation is convenient, the cost is low, and is suitable for industrial production.
以上为对本发明实施案例的描述，通过对所公开的实施案例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施案例的多种修改对本领域的救民于水火技术人员来说将是显面易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施案例中实现。因此本发明不会被限制于本文所示的这些实施案例中同，而是要符合与本文所公开的原理和新颖等特点想一致的最宽范围。The above is a description of the implementation cases of the present invention. The above description of the disclosed implementation cases enables those skilled in the art to realize or use the present invention. Various modifications to these implementations will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other implementations without departing from the spirit or scope of the present invention. realized in the case. Accordingly, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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