CN103611577B - A visible light catalyst for efficiently degrading organic dye wastewater and its preparation method - Google Patents
A visible light catalyst for efficiently degrading organic dye wastewater and its preparation method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
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- 229920001661 Chitosan Polymers 0.000 claims abstract description 105
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 93
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims abstract description 91
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 68
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 68
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
一种高效降解有机染料废水的可见光催化剂及其制备方法，属于环境和能源技术领域。本发明将铁酸锌和壳聚糖混合，戊二醛交联，得交联壳聚糖/铁酸锌复合物，低温水热条件下，在交联壳聚糖/铁酸锌复合物表面生长氧化亚铜，得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。本发明制备的新型三元复合可见光催化剂能够发挥壳聚糖、铁酸锌和氧化亚铜的多重协同功能性，有效降低电子和空穴的复合几率，降低复合催化剂的表观带隙能，拓宽光谱范围，大大提高可见光的利用率，增强废水的处理效果；性质稳定、无残留，有磁性、易于回收再利用；废水处理工艺简单、可以大大降低成本，是一种绿色、高效的新材料和新方法。
A visible light catalyst for efficiently degrading organic dye wastewater and a preparation method thereof belong to the technical field of environment and energy. In the present invention, zinc ferrite and chitosan are mixed, and glutaraldehyde is cross-linked to obtain a cross-linked chitosan/zinc ferrite complex, which is formed on the surface of the cross-linked chitosan/zinc ferrite complex under low-temperature hydrothermal conditions. Cuprous oxide is grown to obtain a three-component visible light catalyst of cuprous oxide/cross-linked chitosan/zinc ferrite. The novel ternary composite visible light catalyst prepared by the invention can exert the multiple synergistic functions of chitosan, zinc ferrite and cuprous oxide, effectively reduce the recombination probability of electrons and holes, reduce the apparent band gap energy of the composite catalyst, and broaden the The spectral range greatly improves the utilization rate of visible light and enhances the treatment effect of wastewater; it has stable properties, no residue, is magnetic, and is easy to recycle and reuse; the wastewater treatment process is simple and can greatly reduce costs. It is a green and efficient new material and new method.
Description
技术领域 technical field
一种高效降解有机染料废水的可见光催化剂及其制备方法，本发明属于环境和能源技术领域，具体涉及氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的制备及用于处理有机染料废水。 A visible light catalyst for efficiently degrading organic dye wastewater and a preparation method thereof, the invention belongs to the technical field of environment and energy, and specifically relates to the preparation of a three-way composite visible light catalyst of cuprous oxide/cross-linked chitosan/zinc ferrite and its use in treatment organic dye wastewater.
背景技术 Background technique
随着现代工业的迅速发展，工业废水的排放量越来越大。在各类工业废水中，染料废水由于其色度深、COD高、以及含有大量致畸、致癌的偶氮化合物，严重危害生态环境，对人们的生活和健康带来了威胁，是一类难以处理的废水，亟需有新的绿色、高效处理技术。 With the rapid development of modern industry, the discharge of industrial wastewater is increasing. Among all kinds of industrial wastewater, dye wastewater is a kind of difficult-to-use wastewater due to its deep color, high COD, and a large amount of teratogenic and carcinogenic azo compounds, which seriously endanger the ecological environment and pose a threat to people's life and health. The treated wastewater urgently needs new green and efficient treatment technologies.
光催化作为一种绿色能源技术，因处理能力强、反应条件温和、无二次污染而引起了国内外学者的广泛关注。光催化剂本质上是一种半导体材料，当吸收能量大于或等于其带隙能的光线时，价带上的电子会激发跃迁至导带，从而形成空穴电子对。这些空穴和电子，是具有很强氧化、还原能力的载流子，可以将吸附在半导体表面及周围的化学物质分解，甚至矿化为H2O和CO2等无机小分子。目前，光催化领域中研究较为深入的是纳米二氧化钛基光催化剂，它们具有化学性质稳定、抗磨损、耐光腐蚀、成本低和无毒等特点，除被用于降解有机物和杀菌外，在光解水和太阳能电池的制备等方面也有广泛的应用。然而，二氧化钛的带隙能(3.2eV)过宽，其激发波长为387.5nm，属于紫外光区。而对于太阳光谱，主要能量集中于460nm～600nm波长范围，紫外光所占比例不足4%，因此二氧化钛对太阳光的利用效率极低；二氧化钛的光生载流子(电子和空穴)的复合几率高，导致量子效率降低，影响光催化效率；此外，处理废水时，悬浮于体系中的二氧化钛纳米颗粒容易发生团聚、失活，反应结束后回收较为困难，难以循环使用。因此，从充分利用太阳光的角度出发，制备一种易于回收循环利用、高光电转化效率的可见光催化剂在能源和环境领域均具有重要的意义。 As a green energy technology, photocatalysis has attracted widespread attention from scholars at home and abroad due to its strong processing capacity, mild reaction conditions, and no secondary pollution. A photocatalyst is essentially a semiconductor material. When light with an energy greater than or equal to its band gap energy is absorbed, electrons in the valence band will be excited to jump to the conduction band, thereby forming hole-electron pairs. These holes and electrons are carriers with strong oxidation and reduction capabilities, which can decompose the chemical substances adsorbed on and around the semiconductor surface, and even mineralize them into small inorganic molecules such as H 2 O and CO 2 . At present, nano-titanium dioxide-based photocatalysts are more in-depth research in the field of photocatalysis. They have the characteristics of stable chemical properties, wear resistance, light corrosion resistance, low cost and non-toxicity. There are also a wide range of applications in the preparation of water and solar cells. However, the bandgap energy (3.2eV) of titanium dioxide is too wide, and its excitation wavelength is 387.5nm, which belongs to the ultraviolet region. For the solar spectrum, the main energy is concentrated in the wavelength range of 460nm to 600nm, and the proportion of ultraviolet light is less than 4%, so the utilization efficiency of titanium dioxide to sunlight is extremely low; the recombination probability of photogenerated carriers (electrons and holes) in titanium dioxide High, resulting in a decrease in quantum efficiency and affecting photocatalytic efficiency; in addition, when treating wastewater, titanium dioxide nanoparticles suspended in the system are prone to agglomeration and deactivation, and it is difficult to recover after the reaction and recycle. Therefore, from the perspective of fully utilizing sunlight, it is of great significance to prepare a visible light catalyst that is easy to recycle and reuse and has high photoelectric conversion efficiency in the fields of energy and environment.
铁酸锌（ZnFe2O4）是一种半导体（带隙能为1.9eV），有转化可见光的潜力，对可见光敏感。然而，其价带电势较低、光电转化效率低，使其不适合直接用于光催化降解有机染料，但铁酸锌有磁性，可通过外加磁场低成本回收循环利用，且具有对可见光敏感的优势。氧化亚铜，一种p-型半导体，带隙能为2.17eV，成本低廉，是一种很有前景的新型可见光催化材料，近期开始引起关注。但氧化亚铜有易团聚、从而大大降低催化比表面积，影响光催化效率；难以回收、易残留；电子和空穴对的复合几率高等问题。因此有必要对光催化剂进行复合改性，以期得到稳定、易于回收循环利用的高性能可见光催化剂。 Zinc ferrite (ZnFe 2 O 4 ) is a semiconductor (with a band gap of 1.9eV), which has the potential to convert visible light and is sensitive to visible light. However, its low valence band potential and low photoelectric conversion efficiency make it unsuitable for direct photocatalytic degradation of organic dyes. However, zinc ferrite is magnetic and can be recycled at low cost by applying an external magnetic field, and it is sensitive to visible light. Advantage. Cuprous oxide, a p-type semiconductor with a bandgap energy of 2.17eV and low cost, is a promising new visible light photocatalytic material and has recently attracted attention. However, cuprous oxide is easy to agglomerate, which greatly reduces the catalytic specific surface area and affects the photocatalytic efficiency; it is difficult to recycle and easy to remain; the recombination probability of electron and hole pairs is high. Therefore, it is necessary to compound and modify photocatalysts in order to obtain high-performance visible light catalysts that are stable and easy to recycle.
发明内容 Contents of the invention
本发明的目的是为解决现有技术存在的缺陷，提供一种高效降解有机染料废水的可见光催化剂及其制备方法，以期得到稳定、易于回收循环利用的高性能可见光催化剂，实现绿色、高效、低成本地处理有机染料废水。 The purpose of the present invention is to solve the defects in the prior art, to provide a visible light catalyst for efficiently degrading organic dye wastewater and its preparation method, in order to obtain a high-performance visible light catalyst that is stable, easy to recycle, and realize green, high efficiency, low Inexpensive treatment of organic dye wastewater.
本发明的技术方案：一种高效降解有机染料废水的可见光催化剂及其制备方法，可通过以下技术方案实现：将铁酸锌和壳聚糖醋酸溶液混合，加入戊二醛交联，得到交联壳聚糖/铁酸锌复合物；低温水热条件下，在交联壳聚糖/铁酸锌复合物表面生长氧化亚铜，得到表面树枝状的球形氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂，用于有机染料废水的处理。 The technical scheme of the present invention: a visible light catalyst for efficiently degrading organic dye wastewater and its preparation method can be realized by the following technical scheme: mixing zinc ferrite and chitosan acetic acid solution, adding glutaraldehyde for crosslinking, and obtaining crosslinking Chitosan/zinc ferrite complex; under low temperature hydrothermal conditions, grow cuprous oxide on the surface of cross-linked chitosan/zinc ferrite complex to obtain spherical cuprous oxide/cross-linked chitosan/ The zinc ferrite ternary composite visible light catalyst is used for the treatment of organic dye wastewater.
一种高效降解有机染料废水的可见光催化剂及其制备方法，包括如下步骤： A visible light catalyst for efficiently degrading organic dye wastewater and a preparation method thereof, comprising the following steps:
纳米磁性铁酸锌（ZnFe2O4）晶体的制备：根据文献（ShihongXu，JournalofPhysicalChemistryC，2009，113（6），2463-2467），采用水热法制备。为褐色晶体，尖晶石型，XRD(2θ)：29.86o，35.28o，42.61o，56.53o，61.94o，见图3，文献值为：30.00o，35.31o，42.91o，56.53o，62.11o；FT-IR(KBr)：558cm-1(Zn-O)，425cm-1(Fe-O)。 Preparation of nanomagnetic zinc ferrite (ZnFe 2 O 4 ) crystals: According to the literature (ShihongXu, Journal of Physical Chemistry C, 2009, 113 (6), 2463-2467), it was prepared by hydrothermal method. It is brown crystal, spinel type, XRD (2θ): 29.86 o , 35.28 o , 42.61 o , 56.53 o , 61.94 o , see Figure 3, literature values: 30.00 o , 35.31 o , 42.91 o , 56.53 o , 62.11 o ; FT-IR (KBr): 558cm -1 (Zn-O), 425cm -1 (Fe-O).
氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的制备： Preparation of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst:
（1）交联壳聚糖/铁酸锌复合物的制备：将壳聚糖加入到0.50mol/L的醋酸水溶液中，搅拌溶解，壳聚糖与醋酸水溶液的质量比为1：25～50，得壳聚糖醋酸溶液；向壳聚糖醋酸溶液中加入纳米铁酸锌，壳聚糖与铁酸锌的质量比为2～8：1；搅拌分散0.5～2h；向上述溶液中慢慢滴加10wt%稀氨水调节溶液的pH值为7～9，然后滴加25wt%的戊二醛水溶液进行交联反应，戊二醛水溶液与壳聚糖的质量比4～15:1，50～80℃下，反应3～8h，外加磁场分离，得到的球形产物依次用无水乙醇、去离子水充分洗涤，50℃真空干燥，得交联壳聚糖/铁酸锌复合物； (1) Preparation of cross-linked chitosan/zinc ferrite complex: add chitosan to 0.50mol/L acetic acid aqueous solution, stir to dissolve, the mass ratio of chitosan to acetic acid aqueous solution is 1:25～50 , to obtain chitosan acetic acid solution; add nano-zinc ferrite to the chitosan acetic acid solution, the mass ratio of chitosan to zinc ferrite is 2-8:1; stir and disperse for 0.5-2h; slowly add to the above solution Add dropwise 10wt% dilute ammonia water to adjust the pH of the solution to 7-9, then add dropwise 25wt% glutaraldehyde aqueous solution to carry out cross-linking reaction, the mass ratio of glutaraldehyde aqueous solution to chitosan is 4-15:1, 50- At 80°C, react for 3-8 hours, apply a magnetic field to separate, and the obtained spherical product is fully washed with absolute ethanol and deionized water in turn, and vacuum-dried at 50°C to obtain a cross-linked chitosan/zinc ferrite complex;
（2）氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的制备：将水合硫酸铜（CuSO4·5H2O）加入到去离子水中，搅拌至完全溶解，得浓度为0.05～0.5mol/L的硫酸铜水溶液，加入一定量的聚乙二醇PEG-8000、交联壳聚糖/铁酸锌复合物，搅拌10～20min，分散均匀后，加入1～5mol/L的氢氧化钠水溶液，搅拌30～60min，使Cu(OH)2沉淀完全；然后，边搅拌边滴加浓度为0.1～0.5mol/L的抗坏血酸水溶液，其中氢氧化钠：水合硫酸铜：抗坏血酸的摩尔比为:6～4：2：1；水合硫酸铜：PEG-8000的摩尔比为：400～600：1；交联壳聚糖/铁酸锌复合物：水合硫酸铜的质量比为5～10：1，室温、100rpm下，反应2～4h，外加磁场分离，分别用无水乙醇、去离子水各洗涤3次，50℃真空干燥，得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。 (2) Preparation of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst: add hydrated copper sulfate (CuSO 4 5H 2 O) into deionized water, stir until completely dissolved, and obtain a concentration of 0.05-0.5mol/L copper sulfate aqueous solution, add a certain amount of polyethylene glycol PEG-8000, cross-linked chitosan/zinc ferrite complex, stir for 10-20min, after dispersing evenly, add 1-5mol/L Aqueous sodium hydroxide solution, stirred for 30-60min to make Cu(OH) 2 precipitate completely; then, while stirring, add dropwise an aqueous solution of ascorbic acid with a concentration of 0.1-0.5mol/L, wherein sodium hydroxide: hydrated copper sulfate: ascorbic acid The molar ratio is 6～4:2:1; the molar ratio of copper sulfate hydrate: PEG-8000 is 400～600:1; the mass ratio of cross-linked chitosan/zinc ferrite complex: copper sulfate hydrate is 5 ～10:1, at room temperature, 100rpm, react for 2～4h, apply magnetic field to separate, wash 3 times with absolute ethanol and deionized water respectively, and vacuum dry at 50℃ to obtain cuprous oxide/cross-linked chitosan/iron Zinc acid ternary composite visible light catalyst.
制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的应用，用于处理有机染料废水，包括如下步骤：将有机染料废水样，用氢氧化钠或盐酸调节pH值为7～9，常温下加入制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂，用量为：0.5～1.5g/L，以300W的氙灯为光源，用滤光片滤去紫外光部分。用紫外可见分光光度法测量染料废水的吸光度随光照时间的变化，计算有机染料的去除率。 The application of the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is used to treat organic dye wastewater, comprising the following steps: adjusting the pH value of the organic dye wastewater sample with sodium hydroxide or hydrochloric acid 7-9, add the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst at room temperature, the dosage is: 0.5-1.5g/L, use a 300W xenon lamp as the light source, and use a filter to filter Go to the UV section. The change of absorbance of dye wastewater with light time was measured by UV-Vis spectrophotometry, and the removal rate of organic dyes was calculated.
本发明的有益效果是：与现有技术相比，本发明以交联壳聚糖三维网络固定铁酸锌复合物为核，表面定向生长的树枝状氧化亚铜为壳，制备了一种新型氧化亚铜/交联壳聚糖/铁酸锌三元复合核壳型可见光催化剂。本发明所制备的三元复合可见光催化剂，其树枝状的外壳有利于可见光的介入，有利于氧化亚铜和铁酸锌的有效、均匀接触，以强化协同作用，从而提高对可见光的敏感度和降低电子和空穴的复合几率；有效降低复合催化剂的表观带隙能，拓宽光谱范围，提高可见光的利用效率；其树枝状的外壳可有效避免团聚、增大与染料的接触面积，提高催化效率；交联壳聚糖优异的吸附能力，可有效吸附废水中的染料到催化剂表面上，从而提高染料的光催化降解效率；交联壳聚糖对铁酸锌的三维网络固定和对壳层树枝状氧化亚铜生长的导向和固定作用，使本发明所得三元复合可见光催化剂非常稳定、废水中无残留；催化剂中磁性铁酸锌使得该催化剂可通过外加磁场方便、低成本地回收再利用；废水处理工艺简单、可以大大降低成本，是一种有工业应用前景的绿色、高效的新材料和新方法。这种氧化亚铜/交联壳聚糖/铁酸锌三元复合核壳型可见光催化剂的制备方法及其产品和应用都属于首创性的工作。 The beneficial effects of the present invention are: compared with the prior art, the present invention uses the cross-linked chitosan three-dimensional network immobilized zinc ferrite complex as the core, and the dendritic cuprous oxide grown oriented on the surface as the shell to prepare a new Cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite core-shell type visible light catalyst. The dendritic shell of the ternary composite visible light catalyst prepared by the present invention is conducive to the intervention of visible light, and is conducive to the effective and uniform contact between cuprous oxide and zinc ferrite, so as to strengthen the synergistic effect, thereby improving the sensitivity and sensitivity to visible light. Reduce the recombination probability of electrons and holes; effectively reduce the apparent band gap energy of the composite catalyst, broaden the spectral range, and improve the utilization efficiency of visible light; its dendritic shell can effectively avoid agglomeration, increase the contact area with the dye, and improve the catalytic performance. Efficiency; the excellent adsorption capacity of cross-linked chitosan can effectively adsorb dyes in wastewater to the catalyst surface, thereby improving the photocatalytic degradation efficiency of dyes; the three-dimensional network fixation of cross-linked chitosan to zinc ferrite and the shell The guiding and fixing effect of dendritic cuprous oxide growth makes the ternary composite visible light catalyst obtained in the present invention very stable and has no residue in wastewater; the magnetic zinc ferrite in the catalyst enables the catalyst to be recycled and reused conveniently and at low cost through an external magnetic field The waste water treatment process is simple, can greatly reduce the cost, and is a green, efficient new material and new method with industrial application prospects. The preparation method of this cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite core-shell type visible light catalyst and its products and applications are all pioneering works.
附图说明 Description of drawings
图1为本发明实施例1所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的SEM图。 Fig. 1 is the SEM image of the cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst obtained in Example 1 of the present invention.
图2为本发明中实施例1所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂、交联壳聚糖/铁酸锌复合物和原料壳聚糖的FT-IR谱图，其中1为原料壳聚糖，2为交联壳聚糖/铁酸锌复合物，3为氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。 Fig. 2 is the FT-IR spectrum of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, cross-linked chitosan/zinc ferrite composite and raw material chitosan obtained in embodiment 1 of the present invention Figure 1, wherein 1 is the raw material chitosan, 2 is the cross-linked chitosan/zinc ferrite complex, and 3 is the ternary composite visible light catalyst of cuprous oxide/cross-linked chitosan/zinc ferrite.
图3为本发明中实施例1所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂、铁酸锌和对比例1所得氧化亚铜的XRD图，其中1为铁酸锌，2为氧化亚铜，3为氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。 Fig. 3 is the XRD pattern of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, zinc ferrite and comparative example 1 gained cuprous oxide in the present invention, wherein 1 is zinc ferrite , 2 is cuprous oxide, and 3 is a ternary composite visible light catalyst of cuprous oxide/cross-linked chitosan/zinc ferrite.
图4为本发明中实施例1所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂、铁酸锌和对比例1所得氧化亚铜的UV-vis图谱，其中1为铁酸锌，2为氧化亚铜，3为氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。 Fig. 4 is the UV-vis spectrum of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, zinc ferrite and comparative example 1 gained cuprous oxide in the present invention, wherein 1 is iron zinc oxide, 2 is cuprous oxide, and 3 is a ternary composite visible light catalyst of cuprous oxide/cross-linked chitosan/zinc ferrite.
图5为本发明中实施例1～4所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂对罗丹明B废水的去除效果图，其中4为实施例3催化剂；3为实施例2催化剂；2为实施例1催化剂；1为实施例4催化剂。 Fig. 5 is the removal effect diagram of rhodamine B wastewater by cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst obtained in Examples 1 to 4 in the present invention, wherein 4 is the catalyst of embodiment 3; 3 is Embodiment 2 catalyst; 2 is embodiment 1 catalyst; 1 is embodiment 4 catalyst.
图6为本发明中实施例1～4所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂对亚甲基蓝废水的去除效果图，其中4为实施例3催化剂；3为实施例2催化剂；2为实施例1催化剂；1为实施例4催化剂。 Fig. 6 is the removal effect diagram of methylene blue wastewater by the cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst obtained in Examples 1 to 4 in the present invention, wherein 4 is the catalyst of Example 3; 3 is the embodiment 2 catalysts; 2 is the catalyst of Example 1; 1 is the catalyst of Example 4.
图7为本发明中实施例1～4所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂对甲基橙废水的去除效果图，其中4为实施例3催化剂；3为实施例2催化剂；2为实施例1催化剂；1为实施例4催化剂。 Fig. 7 is the removal effect figure of methyl orange wastewater by cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst obtained in embodiments 1 to 4 of the present invention, wherein 4 is the catalyst of embodiment 3; 3 is Embodiment 2 catalyst; 2 is embodiment 1 catalyst; 1 is embodiment 4 catalyst.
图8为本发明实施例2和3所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂对亚甲基蓝废水去除效率和循环使用次数的关系图，其中1为实施例3催化剂，2为实施例2催化剂。 Fig. 8 is the relationship diagram of the removal efficiency of methylene blue wastewater and the number of recycle times of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst obtained in Examples 2 and 3 of the present invention, wherein 1 is the catalyst of Example 3, 2 is embodiment 2 catalyst.
具体实施方式 Detailed ways
下面结合实施例，对本发明作进一步说明，但本发明的应用不限于此。 The present invention will be further described below in conjunction with the examples, but the application of the present invention is not limited thereto.
实施例1 Example 1
本实施例是氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的制备。具体过程为：将10g壳聚糖加入到250g0.50mol/L的醋酸水溶液中，搅拌溶解，得壳聚糖醋酸溶液；向壳聚糖醋酸溶液中加入5g纳米铁酸锌，搅拌分散0.5h；向上述溶液中慢慢滴加10wt%稀氨水调节溶液的pH值为7，然后滴加40g25wt%的戊二醛水溶液进行交联反应，50℃下，反应3h，外加磁场分离，得到的球形产物依次用无水乙醇、去离子水充分洗涤，50℃真空干燥，得交联壳聚糖/铁酸锌复合物；将水合硫酸铜0.025mol加入到500mL去离子水中，搅拌至完全溶解，加入0.0625mmol聚乙二醇PEG-8000、31.2g交联壳聚糖/铁酸锌复合物，搅拌10min，分散均匀后，加入1mol/L的氢氧化钠水溶液50mL，搅拌30min，使Cu(OH)2沉淀完全；然后，边搅拌边滴加浓度为0.1mol/L的抗坏血酸水溶液125mL，室温、100rpm下，反应2h，外加磁场分离，分别用无水乙醇、去离子水各洗涤3次，50℃真空干燥，即得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的SEM图见图1，FT-IR红外光谱见图2，XRD见图3，UV-vis图谱见图4，由这些表征结果可知成功合成了氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。由图1可知，该催化剂为球形，表面为树枝状的氧化亚铜；由图4可知，本发明所制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂，较单独的铁酸锌、氧化亚铜光催化剂，吸光度大大提高，且在整个可见光区域均具有较强的吸收，大大拓宽了光谱范围；而最大吸收波长集中于500～600nm范围，正是太阳光能量集中的波长范围，因此对可见光有较高的利用效率。 This example is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst. The specific process is: add 10g of chitosan to 250g of 0.50mol/L acetic acid aqueous solution, stir and dissolve to obtain chitosan acetic acid solution; add 5g of nano-zinc ferrite to the chitosan acetic acid solution, stir and disperse for 0.5h; Slowly add 10wt% dilute ammonia water to the above solution to adjust the pH value of the solution to 7, then dropwise add 40g of 25wt% glutaraldehyde aqueous solution to carry out cross-linking reaction, react at 50°C for 3h, apply a magnetic field to separate, and obtain a spherical product Wash thoroughly with absolute ethanol and deionized water in sequence, and dry in vacuum at 50°C to obtain the cross-linked chitosan/zinc ferrite complex; add 0.025mol of copper sulfate hydrate into 500mL of deionized water, stir until completely dissolved, add 0.0625 mmol polyethylene glycol PEG-8000, 31.2g cross-linked chitosan/zinc ferrite complex, stirred for 10min, dispersed evenly, added 50mL of 1mol/L sodium hydroxide aqueous solution, stirred for 30min, to make Cu(OH) 2 The precipitation is complete; then, 125 mL of ascorbic acid aqueous solution with a concentration of 0.1 mol/L was added dropwise while stirring, reacted for 2 hours at room temperature and 100 rpm, separated by an external magnetic field, washed 3 times with absolute ethanol and deionized water respectively, and vacuumed at 50 °C After drying, the cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is obtained. The SEM figure of gained cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is shown in Fig. 1, the FT-IR infrared spectrum is shown in Fig. 2, the XRD is shown in Fig. 3, and the UV-vis collection of spectra is shown in Fig. 4, by these The characterization results show that the cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst was successfully synthesized. As can be seen from Fig. 1, the catalyst is spherical, and the surface is dendritic cuprous oxide; as can be seen from Fig. 4, the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is more effective than the single The zinc ferrite and cuprous oxide photocatalysts greatly increase the absorbance, and have strong absorption in the entire visible light region, which greatly broadens the spectral range; and the maximum absorption wavelength is concentrated in the range of 500-600nm, which is the concentration of sunlight energy. wavelength range, so it has a higher utilization efficiency for visible light.
实施例2 Example 2
本实施例是氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的制备。具体过程为：将10g壳聚糖加入到300g0.50mol/L的醋酸水溶液中，搅拌溶解，得壳聚糖醋酸溶液；向壳聚糖醋酸溶液中加入2.5g纳米铁酸锌，搅拌分散1h；向上述溶液中慢慢滴加10wt%稀氨水调节溶液的pH值为8，然后滴加70g25wt%的戊二醛水溶液进行交联反应，60℃下，反应5h，外加磁场分离，得到的球形产物依次用无水乙醇、去离子水充分洗涤，50℃真空干燥，得交联壳聚糖/铁酸锌复合物；将水合硫酸铜0.05mol加入到500mL去离子水中，搅拌至完全溶解，加入0.1111mmol聚乙二醇PEG-8000、87.5g交联壳聚糖/铁酸锌复合物，搅拌12min，分散均匀后，加入2mol/L的氢氧化钠水溶液63mL，搅拌40min，使Cu(OH)2沉淀完全；然后，边搅拌边滴加浓度为0.2mol/L的抗坏血酸水溶液125mL，室温、100rpm下，反应3h，外加磁场分离，分别用无水乙醇、去离子水各洗涤3次，50℃真空干燥，即得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的XRD(2θ)结果为：24.86o，30.31o，34.88o，38.14o，42.01o，44.81o，53.11o，61.24o，64.05o，74.26o，与图3所得结果吻合，可知成功合成了氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。 This example is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst. The specific process is: add 10g of chitosan to 300g of 0.50mol/L acetic acid aqueous solution, stir and dissolve to obtain chitosan acetic acid solution; add 2.5g nanometer zinc ferrite to the chitosan acetic acid solution, stir and disperse for 1 hour; Slowly add 10wt% dilute ammonia water dropwise to the above solution to adjust the pH of the solution to 8, then dropwise add 70g of 25wt% glutaraldehyde aqueous solution to carry out the crosslinking reaction, react at 60°C for 5h, apply a magnetic field to separate, and obtain a spherical product Wash thoroughly with absolute ethanol and deionized water in sequence, and dry in vacuum at 50°C to obtain the crosslinked chitosan/zinc ferrite complex; add 0.05mol of copper sulfate hydrate into 500mL of deionized water, stir until completely dissolved, add 0.1111 mmol polyethylene glycol PEG-8000, 87.5g cross-linked chitosan/zinc ferrite complex, stirred for 12min, dispersed evenly, added 63mL of 2mol/L sodium hydroxide aqueous solution, stirred for 40min, made Cu(OH) 2 The precipitation is complete; then, 125 mL of ascorbic acid aqueous solution with a concentration of 0.2 mol/L was added dropwise while stirring, reacted for 3 hours at room temperature and 100 rpm, separated by an external magnetic field, washed 3 times with absolute ethanol and deionized water respectively, and vacuumed at 50 °C After drying, the cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is obtained. The XRD (2θ) results of the obtained cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst are: 24.86 o , 30.31 o , 34.88 o , 38.14 o , 42.01 o , 44.81 o , 53.11 o , 61.24 o , 64.05 o , 74.26 o , consistent with the results in Figure 3, it can be known that cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst was successfully synthesized.
实施例3 Example 3
本实施例是氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的制备。具体过程为：将10g壳聚糖加入到400g0.50mol/L的醋酸水溶液中，搅拌溶解，得壳聚糖醋酸溶液；向壳聚糖醋酸溶液中加入1.7g纳米铁酸锌，搅拌分散1.5h；向上述溶液中慢慢滴加10wt%稀氨水调节溶液的pH值为9，然后滴加120g25wt%的戊二醛水溶液进行交联反应，70℃下，反应7h，外加磁场分离，得到的球形产物依次用无水乙醇、去离子水充分洗涤，50℃真空干燥，得交联壳聚糖/铁酸锌复合物；将水合硫酸铜0.15mol加入到500mL去离子水中，搅拌至完全溶解，加入0.3000mmol聚乙二醇PEG-8000、337.5g交联壳聚糖/铁酸锌复合物，搅拌18min，分散均匀后，加入3mol/L氢氧化钠水溶液140mL，搅拌50min，使Cu(OH)2沉淀完全；然后，边搅拌边滴加浓度为0.3mol/L的抗坏血酸水溶液250mL，室温、100rpm下，反应4h，外加磁场分离，分别用无水乙醇、去离子水各洗涤3次，50℃真空干燥，即得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的XRD(2θ)结果为：24.86o，30.31o，34.88o，38.14o，42.01o，44.81o，53.11o，61.24o，64.05o，74.26o，与图3所得结果吻合，可知成功合成了氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。 This example is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst. The specific process is: add 10g chitosan to 400g 0.50mol/L acetic acid aqueous solution, stir and dissolve to obtain chitosan acetic acid solution; add 1.7g nanometer zinc ferrite to the chitosan acetic acid solution, stir and disperse for 1.5h Slowly add 10wt% dilute ammonia water to the above solution to adjust the pH value of the solution to 9, then dropwise add 120g25wt% glutaraldehyde aqueous solution to carry out cross-linking reaction, react for 7h at 70°C, and apply a magnetic field to separate, the obtained spherical The product was thoroughly washed with absolute ethanol and deionized water in turn, and dried in vacuum at 50°C to obtain a cross-linked chitosan/zinc ferrite complex; add 0.15 mol of copper sulfate hydrate into 500 mL of deionized water, stir until completely dissolved, and add 0.3000mmol polyethylene glycol PEG-8000, 337.5g cross-linked chitosan/zinc ferrite complex, stirred for 18min, dispersed evenly, added 140mL of 3mol/L sodium hydroxide aqueous solution, stirred for 50min, to make Cu(OH) 2 The precipitation is complete; then, 250 mL of ascorbic acid aqueous solution with a concentration of 0.3 mol/L was added dropwise while stirring, reacted for 4 hours at room temperature and 100 rpm, separated by an external magnetic field, washed 3 times with absolute ethanol and deionized water respectively, and vacuumed at 50 °C After drying, the cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is obtained. The XRD (2θ) results of the obtained cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst are: 24.86 o , 30.31 o , 34.88 o , 38.14 o , 42.01 o , 44.81 o , 53.11 o , 61.24 o , 64.05 o , 74.26 o , consistent with the results in Figure 3, it can be known that cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst was successfully synthesized.
实施例4 Example 4
本实施例是氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的制备。具体过程为：将10g壳聚糖加入到500g0.50mol/L的醋酸水溶液中，搅拌溶解，得壳聚糖醋酸溶液；向壳聚糖醋酸溶液中加入1.25g纳米铁酸锌，搅拌分散2h；向上述溶液中慢慢滴加10wt%稀氨水调节溶液的pH值为9，然后滴加150g25wt%的戊二醛水溶液进行交联反应，80℃下，反应8h，外加磁场分离，得到的球形产物依次用无水乙醇、去离子水充分洗涤，50℃真空干燥，得交联壳聚糖/铁酸锌复合物；将水合硫酸铜0.25mol加入到500mL去离子水中，搅拌至完全溶解，加入0.4167mmol聚乙二醇PEG-8000、624.0g交联壳聚糖/铁酸锌复合物，搅拌20min，分散均匀后，加入5mol/L的氢氧化钠水溶液150mL，搅拌60min，使Cu(OH)2沉淀完全；然后，边搅拌边滴加浓度为0.5mol/L的抗坏血酸水溶液250mL，室温、100rpm下，反应4h，外加磁场分离，分别用无水乙醇、去离子水各洗涤3次，50℃真空干燥，即得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。所得氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的XRD(2θ)结果为：24.86o，30.31o，34.88o，38.14o，42.01o，44.81o，53.11o，61.24o，64.05o，74.26o，与图3所得结果吻合，可知成功合成了氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂。 This example is the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst. The specific process is as follows: add 10g of chitosan to 500g of 0.50mol/L acetic acid aqueous solution, stir and dissolve to obtain chitosan acetic acid solution; add 1.25g of nanometer zinc ferrite to the chitosan acetic acid solution, stir and disperse for 2 hours; Slowly add 10wt% dilute ammonia water dropwise to the above solution to adjust the pH value of the solution to 9, then dropwise add 150g of 25wt% glutaraldehyde aqueous solution to carry out cross-linking reaction, react at 80°C for 8h, apply a magnetic field to separate, and obtain a spherical product Wash thoroughly with absolute ethanol and deionized water in sequence, and dry in vacuum at 50°C to obtain a cross-linked chitosan/zinc ferrite complex; add 0.25mol of hydrated copper sulfate to 500mL of deionized water, stir until completely dissolved, and add 0.4167 mmol polyethylene glycol PEG-8000, 624.0g cross-linked chitosan/zinc ferrite complex, stirred for 20min, dispersed evenly, added 150mL of 5mol/L sodium hydroxide aqueous solution, stirred for 60min, made Cu(OH) 2 The precipitation is complete; then, add dropwise 250 mL of ascorbic acid aqueous solution with a concentration of 0.5 mol/L while stirring, react for 4 hours at room temperature and 100 rpm, separate with an external magnetic field, wash with absolute ethanol and deionized water for 3 times, and vacuum at 50 °C After drying, the cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is obtained. The XRD (2θ) results of the obtained cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst are: 24.86 o , 30.31 o , 34.88 o , 38.14 o , 42.01 o , 44.81 o , 53.11 o , 61.24 o , 64.05 o , 74.26 o , consistent with the results in Figure 3, it can be known that cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst was successfully synthesized.
实施例5 Example 5
本实施例为制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的应用，重点考察该可见光催化剂对罗丹明B染料废水的处理效果。具体过程为：某印染厂废水样，pH为8，罗丹明B含量为150mg/L，常温下加入制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂，用量为：0.5g/L，以300W的氙灯为光源，用滤光片滤去紫外光部分。用紫外可见分光光度法测量染料废水的吸光度随光照时间的变化，计算有机染料的去除率，结果见图5。由图5可知：本发明所制备的三元复合催化剂可高效利用可见光，降解染料效率高，实施例1～4所得催化剂均在60min内达90%以上的去除率，其中实施例3所得催化剂更是在50min时，即达到了100%去除率。 This example is the application of the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, focusing on the treatment effect of the visible light catalyst on rhodamine B dye wastewater. The specific process is: a wastewater sample from a printing and dyeing factory has a pH of 8 and a rhodamine B content of 150 mg/L. Add the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst at room temperature. The dosage is: 0.5g/L, with a 300W xenon lamp as the light source, filter out the ultraviolet light with a filter. The change of absorbance of dye wastewater with light time was measured by ultraviolet-visible spectrophotometry, and the removal rate of organic dye was calculated. The results are shown in Figure 5. As can be seen from Fig. 5: the ternary composite catalyst prepared by the present invention can efficiently utilize visible light, and the dye degradation efficiency is high. The catalysts obtained in Examples 1 to 4 all reach a removal rate of more than 90% within 60 minutes, and the catalysts obtained in Example 3 are even higher. It was at 50 minutes that the removal rate of 100% was reached.
实施例6 Example 6
本实施例为制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的应用，重点考察该可见光催化剂对亚甲基蓝染料废水的处理效果。具体过程为：某印染厂废水样，pH为6，加氢氧化钠调pH至7，亚甲基蓝含量为50mg/L，常温下加入制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂，用量为：1.5g/L，以300W的氙灯为光源，用滤光片滤去紫外光部分。用紫外可见分光光度法测量染料废水的吸光度随光照时间的变化，计算有机染料的去除率，结果见图6。由图6可知：本发明所制备的三元复合催化剂可高效利用可见光，降解染料效率高，实施例1～4所得催化剂均在45min内达90%以上的去除率，其中实施例3所得催化剂更是在30min时，即达到了100%去除率。 This example is the application of the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, focusing on the treatment effect of the visible light catalyst on methylene blue dye wastewater. The specific process is: the wastewater sample of a printing and dyeing factory has a pH of 6, adding sodium hydroxide to adjust the pH to 7, the content of methylene blue is 50mg/L, and adding the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary at room temperature Composite visible light catalyst, the dosage is: 1.5g/L, with a 300W xenon lamp as the light source, and filter out the ultraviolet light part with a filter. The change of absorbance of dye wastewater with light time was measured by ultraviolet-visible spectrophotometry, and the removal rate of organic dye was calculated. The results are shown in Figure 6. As can be seen from Fig. 6: the ternary composite catalyst prepared by the present invention can efficiently utilize visible light, and the dye degradation efficiency is high. The catalysts obtained in Examples 1 to 4 all reach a removal rate of more than 90% within 45 minutes, and the catalysts obtained in Example 3 are even higher. It was at 30 minutes that the removal rate of 100% was reached.
实施例7 Example 7
本实施例为制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的应用，重点考察该可见光催化剂对甲基橙染料废水的处理效果。具体过程为：配制150mg/L甲基橙水溶液，pH约为7，常温下加入制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂，用量为：1.0g/L，以300W的氙灯为光源，用滤光片滤去紫外光部分。用紫外可见分光光度法测量染料废水的吸光度随光照时间的变化，计算有机染料的去除率，结果见图7。由图7可知：本发明所制备的三元复合催化剂可高效利用可见光，降解染料效率高，实施例1～4所得催化剂均在60min内达90%以上的去除率，其中实施例3所得催化剂更是在50min时，即达到了100%去除率。 This example is the application of the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, focusing on the treatment effect of the visible light catalyst on methyl orange dye wastewater. The specific process is: prepare 150mg/L methyl orange aqueous solution, the pH is about 7, add the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst at room temperature, the dosage is: 1.0g/L, Use a 300W xenon lamp as the light source, and use a filter to filter out the ultraviolet light. The change of absorbance of dye wastewater with light time was measured by ultraviolet-visible spectrophotometry, and the removal rate of organic dye was calculated. The results are shown in Figure 7. As can be seen from Fig. 7: the ternary composite catalyst prepared by the present invention can efficiently utilize visible light, and the dye degradation efficiency is high. The catalysts obtained in Examples 1 to 4 all reach a removal rate of more than 90% within 60 minutes, and the catalysts obtained in Example 3 are even higher. It was at 50 minutes that the removal rate of 100% was reached.
实施例8 Example 8
本实施例为制备的氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂的应用，重点考察该可见光催化剂的重复使用性能及残留。具体过程为：每次均以30mg/L的甲基蓝溶液100mL作为测试液，加入0.1g氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂，光照30min后，外加磁场分离催化剂，紫外分光光度法测定亚甲基蓝的去除率，原子吸收光谱法测金属残留，结果见图8。由图8可知：本发明所制备的三元复合催化剂重复使用20次，性能基本保持不变，且20次均未检测到金属在废水样中的残留，故本发明所制备的三元复合可见光催化剂性质稳定、效率高，可方便地通过外加磁场回收循环使用，大大降低成本。 This example is the application of the prepared cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, focusing on the repeated use performance and residue of the visible light catalyst. The specific process is as follows: 100 mL of 30 mg/L methylene blue solution is used as the test solution each time, and 0.1 g of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst is added, and after 30 minutes of light irradiation, an external magnetic field is applied to separate the samples. Catalyst, the removal rate of methylene blue was measured by ultraviolet spectrophotometry, and the metal residue was measured by atomic absorption spectrometry. The results are shown in Figure 8. It can be seen from Figure 8 that the ternary composite catalyst prepared by the present invention is reused 20 times, and its performance remains basically unchanged, and no metal residue in the wastewater sample is detected for 20 times, so the ternary composite catalyst prepared by the present invention The catalyst has stable properties and high efficiency, and can be conveniently recovered and recycled by an external magnetic field, greatly reducing the cost.
对比例1 Comparative example 1
本例作为对比例，在制备氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂相同的水热条件下制备氧化亚铜，与氧化亚铜/交联壳聚糖/铁酸锌三元复合可见光催化剂做性能对比。具体过程为：将水合硫酸铜0.025mol加入到500mL去离子水中，搅拌至完全溶解，加入0.0625mmol聚乙二醇PEG-8000，搅拌10min，分散均匀后，加入1mol/L的氢氧化钠水溶液50mL，搅拌30min，使Cu(OH)2沉淀完全；然后，边搅拌边滴加浓度为0.1mol/L的抗坏血酸水溶液125mL，室温、100rpm下，反应2h，离心分离固体，分别用无水乙醇、去离子水各洗涤3次，50℃真空干燥，即得氧化亚铜可见光催化剂。所得氧化亚铜的XRD(2θ)结果为：37.24o，43.05o，61.58o，73.11o，见图3。 In this example, as a comparative example, cuprous oxide was prepared under the same hydrothermal conditions as the preparation of cuprous oxide/cross-linked chitosan/zinc ferrite ternary composite visible light catalyst, and cuprous oxide/cross-linked chitosan/ferric acid Zinc ternary composite visible light catalyst for performance comparison. The specific process is: add 0.025mol of copper sulfate hydrate into 500mL of deionized water, stir until completely dissolved, add 0.0625mmol of polyethylene glycol PEG-8000, stir for 10min, after the dispersion is uniform, add 50mL of 1mol/L sodium hydroxide aqueous solution , stirred for 30min, so that Cu(OH) 2 precipitated completely; then, while stirring, 125mL of ascorbic acid aqueous solution with a concentration of 0.1mol/L was added dropwise, at room temperature and at 100rpm, reacted for 2h, centrifuged to separate the solid, and dehydrated with absolute ethanol, respectively. Each was washed three times with deionized water, and vacuum-dried at 50°C to obtain a cuprous oxide visible light catalyst. The XRD (2θ) results of the obtained cuprous oxide are: 37.24 o , 43.05 o , 61.58 o , 73.11 o , see Figure 3.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围内。 The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be considered Within the protection scope of the present invention.
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| CN107649151A (en) * | 2017-09-22 | 2018-02-02 | 常州大学 | A kind of preparation method of sulfur doping ferrous acid Co catalysts |
| CN108680625A (en) * | 2018-05-07 | 2018-10-19 | 杭州电子科技大学 | The preparation method and applications of cuprous oxide/cobalt acid nickel hollow-core construction composite nano-microsphere |
| CN111715277B (en) * | 2020-06-22 | 2021-06-25 | 江南大学 | Easily-recycled magnetic visible-light-driven photocatalyst and preparation method thereof |
| CN114054028B (en) * | 2021-12-09 | 2024-03-08 | 重庆化工职业学院 | Cu (copper) alloy 2 O/CoFe 2 O 4 Preparation method and application of magnetic composite catalyst |
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