CN102600865B - Photocatalyst for degrading organic dye waste water pollutants and preparation method thereof - Google Patents
Photocatalyst for degrading organic dye waste water pollutants and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000000593 degrading effect Effects 0.000 title claims abstract description 7
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- 239000003403 water pollutant Substances 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 35
- 239000011777 magnesium Substances 0.000 claims abstract description 35
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- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical compound [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 238000003756 stirring Methods 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
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- 230000015556 catabolic process Effects 0.000 abstract description 9
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 11
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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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
本发明涉及用于降解有机染料废水污染物的光催化剂，该催化剂由铁酸镁和钒酸银纳米粒子复合而成；化学组成通式为：mMgFe2O4/Ag3VO4，m为MgFe2O4与Ag3VO4的质量比，0＜m≤0.005。其制备方法为：首先，分别用柠檬酸溶胶-凝胶法和化学沉淀法制备铁酸镁及钒酸银粉体，再按铁酸镁/钒酸银质量比，将铁酸镁与钒酸银粉体混合研磨10min，最后于200-500℃温度下焙烧4小时即得该催化剂成品。该催化剂制备方法简单，对染料废水中有机污染物的可见光降解性能较高，同时利于回收再利用。
The invention relates to a photocatalyst for degrading organic dye wastewater pollutants. The catalyst is composed of magnesium ferrite and silver vanadate nanoparticles; the general chemical composition formula is: mMgFe 2 O 4 /Ag 3 VO 4 , m is MgFe The mass ratio of 2 O 4 to Ag 3 VO 4 is 0<m≤0.005. The preparation method is as follows: firstly, magnesium ferrite and silver vanadate powders are prepared by citric acid sol-gel method and chemical precipitation method respectively, and then magnesium ferrite and vanadate are mixed according to the mass ratio of magnesium ferrite/silver vanadate The silver powder is mixed and ground for 10 minutes, and finally calcined at 200-500° C. for 4 hours to obtain the finished catalyst. The preparation method of the catalyst is simple, the visible light degradation performance of the organic pollutants in the dye wastewater is high, and the catalyst is beneficial to recycling and reuse.
Description
技术领域 technical field
本发明涉及可见光响应的复合光催化剂，特别涉及用于降解有机染料废水污染物的光催化剂及其制备方法。The invention relates to a composite photocatalyst responding to visible light, in particular to a photocatalyst for degrading organic dye wastewater pollutants and a preparation method thereof.
背景技术 Background technique
20世纪以来，随着经济的快速增长以及工业化大生产的助推，使人类的生活发生了翻天覆地的变化。但是于此同时也给人类赖以生存的环境造成了巨大的威胁与危害。目前，各国政府已经充分意识到环境污染问题的严重性，并且把环境净化与能源开发等问题一起提升到关系国家生存与发展的战略高度来对待，因此对该领域的研究与技术开发备受关注。其中染料废水污染尤为严重，染料废水的色度深、浓度高、致癌性高，难于在自然条件下降解或用微生物法降解。近年来随着研究的深入，人们发现光催化及其相关技术在环境污染治理技术、太阳能转换等诸多方面都显示出诱人的应用前景。且光催化氧化技术是一种全新的“绿色技术”，以其能耗低、操作简单、反应条件温和、氧化性强、成本低、无二次污染等特点，在环境治理方面日益受到人们的普遍重视，并成为各国产业界和学术界研究的热点。Since the 20th century, with the rapid economic growth and the promotion of industrialized production, human life has undergone earth-shaking changes. But at the same time, it has also caused huge threats and harm to the environment on which human beings depend for survival. At present, the governments of various countries have fully realized the seriousness of the environmental pollution problem, and raised the issues of environmental purification and energy development to a strategic height related to the survival and development of the country, so the research and technology development in this field have attracted much attention. . Among them, the pollution of dye wastewater is particularly serious. The dye wastewater has deep chroma, high concentration, and high carcinogenicity, and is difficult to degrade under natural conditions or by microbial methods. With the deepening of research in recent years, people have found that photocatalysis and its related technologies have shown attractive application prospects in many aspects such as environmental pollution control technology and solar energy conversion. Moreover, photocatalytic oxidation technology is a brand-new "green technology". It is increasingly popular in environmental governance due to its low energy consumption, simple operation, mild reaction conditions, strong oxidation, low cost, and no secondary pollution. It is widely valued and has become a research hotspot in the industry and academia of various countries.
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，价带上的电子会被激发跃迁至导带，从而形成空穴电子对。这些具有很强氧化、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，在光催化领域中研究较为深入的是纳米TiO2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(3.2eV)过宽，仅可被太阳光中总能量不足4％的紫外光部分(波长小于387nm)激发，而对占太阳光谱中43％的可见光部分(波长范围，400-700nm)无法利用，限制了它的大规模应用。因此，为了更有效的利用太阳能，同时满足室内无紫外线环境光催化净化的需求，寻找高效的可见光响应的光催化剂势在必行。A photocatalyst is essentially a semiconductor material. When light with 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 carriers with strong oxidation and reduction capabilities 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-TiO 2 -based photocatalysts are more deeply studied in the field of photocatalysis. They have the characteristics of stable chemical properties, wear resistance, light corrosion resistance, low cost and non-toxicity. Photolysis of water and the preparation of solar cells also have a wide range of applications. However, the band gap (3.2eV) of titanium dioxide is too wide, and it can only be excited by the ultraviolet light part (wavelength less than 387nm) of less than 4% of the total energy in sunlight, and the visible light part (wavelength range, which accounts for 43% of the solar spectrum) 400-700nm) cannot be utilized, which limits its large-scale application. Therefore, in order to utilize solar energy more effectively and meet the demand for photocatalytic purification in indoor UV-free environments, it is imperative to find efficient photocatalysts that respond to visible light.
构筑新型、高效可见光响应光催化剂的方法主要有对半导体的掺杂(金属离子或非金属离子)、光敏化、半导体复合以及开发新型可见光响应催化剂等。但从目前研究结果看，它们在太阳光照射下的催化活性并不是很高，稳定性方面也存在一定的问题，光敏化催化剂则受到使用范围的限制。相对而言，半导体复合光催化剂更具开发潜力，半导体组合选择余地大，而且化学性质稳定，兼具两个半导体的物化性质，这些都有利于开发出高效的可见光响应催化剂。The methods for constructing new and efficient visible light-responsive photocatalysts mainly include semiconductor doping (metal ions or non-metal ions), photosensitization, semiconductor recombination, and the development of new visible-light-responsive catalysts. However, according to the current research results, their catalytic activity under sunlight irradiation is not very high, and there are also certain problems in terms of stability, and the photosensitized catalyst is limited by the scope of use. Relatively speaking, semiconductor composite photocatalysts have more potential for development, and the choice of semiconductor combinations is large, and the chemical properties are stable, and the physical and chemical properties of both semiconductors are combined, which are conducive to the development of efficient visible light-responsive catalysts.
近年来，Ag3VO4因其特殊的能带结构，使其在可见光下具有良好的催化活性，而受到了普遍关注。科研工作者们采用沉淀法、水热法等方法成功制备了纳米级Ag3VO4颗粒，然而其比表面积较小，影响催化剂的有效作用面积，对提升光催化剂的效率不利。因此需要对其进行复合改性，以期开发出在可见光下的高效光催化剂。In recent years, Ag 3 VO 4 has attracted widespread attention because of its special energy band structure, which makes it have good catalytic activity under visible light. Researchers have successfully prepared nanoscale Ag 3 VO 4 particles by precipitation method, hydrothermal method and other methods. However, their specific surface area is small, which affects the effective area of the catalyst and is not conducive to improving the efficiency of photocatalysts. Therefore, it needs to be compounded and modified in order to develop an efficient photocatalyst under visible light.
发明内容 Contents of the invention
本发明的目的为克服现有技术中的不足，提供制备方法简单、对染料废水中有机污染物的可见光降解性能较高，同时利于回收再利用的用于降解有机染料废水污染物的光催化剂及其制备方法及其应用。The purpose of the present invention is to overcome the deficiencies in the prior art, to provide a photocatalyst and a photocatalyst for degrading organic dye wastewater pollutants that is simple in preparation method, has high visible light degradation performance to organic pollutants in dye wastewater, and is beneficial to recycling and reuse. Its preparation method and application.
为解决该技术问题，本发明采用的技术方案为：For solving this technical problem, the technical scheme that the present invention adopts is:
用于降解有机染料废水污染物的光催化剂，其特征在于：该催化剂由铁酸镁和钒酸银纳米粒子复合而成；化学组成通式为：mMgFe2O4/Ag3VO4，其中铁酸镁的化学式为MgFe2O4，钒酸银的化学式为Ag3VO4；m为MgFe2O4与Ag3VO4质量比，0＜m≤0.005。较佳的是m为0.002。A photocatalyst for degrading organic dye wastewater pollutants, characterized in that the catalyst is composed of magnesium ferrite and silver vanadate nanoparticles; the general chemical composition formula is: mMgFe 2 O 4 /Ag 3 VO 4 The chemical formula of magnesium oxide is MgFe 2 O 4 , and the chemical formula of silver vanadate is Ag 3 VO 4 ; m is the mass ratio of MgFe 2 O 4 to Ag 3 VO 4 , 0<m≤0.005. Preferably, m is 0.002.
该催化剂的制备方法，包括以下步骤：The preparation method of this catalyst comprises the following steps:
(1)铁酸镁的制备(1) Preparation of Magnesium Ferrite
在搅拌的情况下，按摩尔比1∶2∶4.5将硝酸镁、硝酸铁、柠檬酸溶于去离子水中，往上述混合溶液中滴加30％的氨水调节其pH值等于7，继续搅拌直至形成绿色凝胶，将该绿色凝胶于120℃温度下干燥，研磨，再在700℃温度下焙烧3小时即得到红褐色铁酸镁粉体。While stirring, dissolve magnesium nitrate, ferric nitrate, and citric acid in deionized water at a molar ratio of 1:2:4.5, add 30% ammonia water dropwise to the above mixed solution to adjust its pH value to 7, and continue stirring until A green gel is formed, which is dried at 120° C., ground, and calcined at 700° C. for 3 hours to obtain reddish-brown magnesium ferrite powder.
(2)钒酸银的制备(2) Preparation of silver vanadate
在搅拌的情况下，按摩尔比1∶6将五氧化二钒溶于氢氧化钠溶液中，至溶液澄清透明；然后将硝酸银溶液缓慢滴加至上述溶液中，即生成黄色沉淀物；沉淀经搅拌陈化后，过滤除去多余离子，所得固体烘干，最后在400℃温度下焙烧2小时，冷却后即得钒酸银粉体。While stirring, dissolve vanadium pentoxide in sodium hydroxide solution at a molar ratio of 1:6 until the solution is clear and transparent; then slowly add silver nitrate solution to the above solution to form a yellow precipitate; After stirring and aging, filter to remove excess ions, dry the obtained solid, and finally roast it at 400°C for 2 hours, and obtain silver vanadate powder after cooling.
(3)铁酸镁-钒酸银纳米复合材料的制备(3) Preparation of magnesium ferrite-silver vanadate nanocomposites
按铁酸镁/钒酸银质量比，将铁酸镁与钒酸银粉体混合研磨10min，最后于200-500℃温度下焙烧4小时，即得该催化剂成品。According to the mass ratio of magnesium ferrite/silver vanadate, the magnesium ferrite and silver vanadate powders are mixed and ground for 10 minutes, and finally calcined at 200-500° C. for 4 hours to obtain the finished catalyst.
制备的催化剂为：铁酸镁-钒酸银纳米复合材料光催化剂。The prepared catalyst is: magnesium ferrite-silver vanadate nanocomposite photocatalyst.
该催化剂在降解有机染料废水污染物中的应用：降解罗丹明B染料的降解率几乎为100％Application of the catalyst in the degradation of organic dye wastewater pollutants: the degradation rate of rhodamine B dye is almost 100%
本发明采用研磨-焙烧法制备得到的铁酸镁-钒酸银纳米复合光催化剂，该催化剂催化活性高，可以吸收波长小于600nm的可见光，这使得本发明制备的催化剂具有很高的可见光吸收能力；且有比单一半导体催化剂更高的催化活性，能快速、有效地降解工业废水中的有机污染物。此外，本发明制备的催化剂还有制备方法简单、适用条件宽松、光催化降解性能稳定等优点，因此，具有较高的商业化应用前景。The magnesium ferrite-silver vanadate nanocomposite photocatalyst prepared by the grinding-roasting method in the present invention has high catalytic activity and can absorb visible light with a wavelength less than 600nm, which makes the catalyst prepared in the present invention have a high visible light absorption capacity ; And it has higher catalytic activity than a single semiconductor catalyst, and can quickly and effectively degrade organic pollutants in industrial wastewater. In addition, the catalyst prepared by the invention has the advantages of simple preparation method, loose application conditions, stable photocatalytic degradation performance, etc., therefore, it has a high commercial application prospect.
附图说明 Description of drawings
图1为实施例1～5及比较例1～3制备的催化剂在可见光下催化降解罗丹明B活性图。Fig. 1 is the catalytic degradation activity diagram of rhodamine B under visible light for the catalysts prepared in Examples 1-5 and Comparative Examples 1-3.
图2为实施例2、6～8制备的催化剂在可见光下催化降解罗丹明B活性图。Fig. 2 is the catalytic degradation activity graph of rhodamine B under visible light for the catalysts prepared in Examples 2, 6-8.
图3为实施例2及比较例1、2制备的催化剂的X射线粉末衍射(XRD)。Fig. 3 is the X-ray powder diffraction (XRD) of the catalyst prepared in Example 2 and Comparative Examples 1 and 2.
图4为实施例2及比较例1～3制备的催化剂的紫外可见吸收(UV-vis)光谱。Fig. 4 is the ultraviolet-visible absorption (UV-vis) spectrum of the catalyst prepared in Example 2 and Comparative Examples 1-3.
具体实施方式 Detailed ways
以下用实施例进一步阐明本发明，但本发明不局限于以下实施例。The following examples further illustrate the present invention, but the present invention is not limited to the following examples.
实施例1：Example 1:
(1)分别称取6.46g、2.05g和7.56g硝酸铁、硝酸镁及柠檬酸，在搅拌的情况下，溶于20ml去离子水中。在60℃温度下往上述混合溶液中滴加30％的氨水约20ml，调节其pH值等于7，继续搅拌直至形成绿色凝胶。将该绿色凝胶于120℃温度下干燥24小时，得到黑色前驱体，最后经研磨在700℃温度下焙烧3小时即得到红褐色铁酸镁粉体。(1) Weigh 6.46g, 2.05g and 7.56g of ferric nitrate, magnesium nitrate and citric acid respectively, and dissolve them in 20ml of deionized water while stirring. Add about 20 ml of 30% ammonia water dropwise to the above mixed solution at a temperature of 60° C., adjust its pH value to 7, and continue stirring until a green gel is formed. The green gel was dried at 120°C for 24 hours to obtain a black precursor, and finally ground and calcined at 700°C for 3 hours to obtain reddish-brown magnesium ferrite powder.
(2)称取2.40g氢氧化钠，30℃水浴搅拌溶于30ml去离子水中，得到氢氧化钠溶液。称取10.10g硝酸银，溶于30ml去离子水中，30℃水浴搅拌溶解，得到硝酸银溶液。然后在搅拌的情况下将硝酸银溶液缓慢滴加到氢氧化钠溶液中，生成黄色沉淀物，搅拌2小时后陈化24小时，分别用去离子水和无水乙醇冲洗除去多余离子，所得固体在烘箱中80℃下烘干，最后在马福炉中焙烧，升温速率1℃/min，于400℃下焙烧4小时。自然冷却后即得沉淀法制备的Ag3VO4催化剂。(2) Weigh 2.40 g of sodium hydroxide, dissolve in 30 ml of deionized water with stirring in a water bath at 30° C., to obtain a sodium hydroxide solution. Weigh 10.10 g of silver nitrate, dissolve it in 30 ml of deionized water, stir and dissolve in a water bath at 30° C., and obtain a silver nitrate solution. Then, the silver nitrate solution was slowly added dropwise to the sodium hydroxide solution while stirring to form a yellow precipitate, which was aged for 24 hours after being stirred for 2 hours, rinsed with deionized water and absolute ethanol to remove excess ions, and the obtained solid Dry in an oven at 80°C, and finally bake in a muffle furnace at a heating rate of 1°C/min, and bake at 400°C for 4 hours. After natural cooling, the Ag 3 VO 4 catalyst prepared by precipitation method was obtained.
(3)分别称取0.001g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于300℃温度下焙烧4小时，自然冷却后即得300℃焙烧的MgFe2O4/Ag3VO4质量比为0.001的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.001g of magnesium ferrite and 1.0g of silver vanadate respectively, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally roast them at 300°C for 4 hours, and cool them naturally That is, the MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.001 calcined at 300° C. was obtained.
实施例2：Example 2:
(1)同实施例1中(1)的步骤。(1) With the step of (1) in embodiment 1.
(2)同实施例1中(2)的步骤。(2) With the step of (2) in embodiment 1.
(3)分别称取0.002g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于300℃温度下焙烧4小时，自然冷却后即得300℃焙烧的MgFe2O4/Ag3VO4质量比为0.002的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.002g of magnesium ferrite and 1.0g of silver vanadate, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally bake them at 300°C for 4 hours, and cool them naturally That is, a MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.002 calcined at 300° C. was obtained.
实施例3：Example 3:
(1)同实施例1中(1)的步骤。(1) With the step of (1) in embodiment 1.
(2)同实施例1中(2)的步骤。(2) With the step of (2) in embodiment 1.
(3)分别称取0.003g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于300℃温度下焙烧4小时，自然冷却后即得300℃焙烧的MgFe2O4/Ag3VO4质量比为0.003的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.003g of magnesium ferrite and 1.0g of silver vanadate respectively, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally roast them at 300°C for 4 hours, and cool them naturally That is, a MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.003 calcined at 300° C. was obtained.
实施例4：Example 4:
(1)同实施例1中(1)的步骤。(1) With the step of (1) in embodiment 1.
(2)同实施例1中(2)的步骤。(2) With the step of (2) in embodiment 1.
(3)分别称取0.004g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于300℃温度下焙烧4小时，自然冷却后即得300℃焙烧的MgFe2O4/Ag3VO4质量比为0.004的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.004g of magnesium ferrite and 1.0g of silver vanadate respectively, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally bake them at 300°C for 4 hours, and cool them naturally That is, a MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.004 calcined at 300° C. was obtained.
实施例5：Example 5:
(1)同实施例1中(1)的步骤。(1) With the step of (1) in embodiment 1.
(2)同实施例1中(2)的步骤。(2) With the step of (2) in embodiment 1.
(3)分别称取0.005g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于300℃温度下焙烧4小时，自然冷却后即得300℃焙烧的MgFe2O4/Ag3VO4质量比为0.005的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.005g of magnesium ferrite and 1.0g of silver vanadate respectively, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally bake them at 300°C for 4 hours, and cool them naturally That is, the MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.005 calcined at 300° C. was obtained.
实施例6：Embodiment 6:
(1)同实施例1中(1)的步骤。(1) With the step of (1) in embodiment 1.
(2)同实施例1中(2)的步骤。(2) With the step of (2) in embodiment 1.
(3)分别称取0.002g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于200℃温度下焙烧4小时，自然冷却后即得200℃焙烧的MgFe2O4/Ag3VO4质量比为0.002的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.002g of magnesium ferrite and 1.0g of silver vanadate respectively, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally roast them at 200°C for 4 hours, and cool them naturally That is, a MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.002 calcined at 200° C. was obtained.
实施例7：Embodiment 7:
(1)同实施例1中(1)的步骤。(1) With the step of (1) in embodiment 1.
(2)同实施例1中(2)的步骤。(2) With the step of (2) in embodiment 1.
(3)分别称取0.002g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于400℃温度下焙烧4小时，自然冷却后即得400℃焙烧的MgFe2O4/Ag3VO4质量比为0.002的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.002g of magnesium ferrite and 1.0g of silver vanadate respectively, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally roast them at 400°C for 4 hours, and cool them naturally That is, the MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.002 calcined at 400° C. was obtained.
实施例8Example 8
(1)同实施例1中(1)的步骤。(1) With the step of (1) in embodiment 1.
(2)同实施例1中(2)的步骤。(2) With the step of (2) in embodiment 1.
(3)分别称取0.002g的铁酸镁和1.0g的钒酸银，按铁酸镁/钒酸银质量比，将其混合研磨10min，最后于500℃温度下焙烧4小时，自然冷却后即得500℃焙烧的MgFe2O4/Ag3VO4质量比为0.002的MgFe2O4/Ag3VO4复合催化剂。(3) Weigh 0.002g of magnesium ferrite and 1.0g of silver vanadate respectively, mix and grind them for 10min according to the mass ratio of magnesium ferrite/silver vanadate, and finally roast them at 500°C for 4 hours, and cool them naturally That is, the MgFe 2 O 4 /Ag 3 VO 4 composite catalyst with a MgFe 2 O 4 /Ag 3 VO 4 mass ratio of 0.002 calcined at 500° C. was obtained.
比较例1：Comparative example 1:
MgFe2O4。制备方法同实施例1中步骤(1)。MgFe 2 O 4 . The preparation method is the same as step (1) in Example 1.
比较例2：Comparative example 2:
Ag3VO4。制备方法同实施例1中步骤(2)。Ag 3 VO 4 . The preparation method is the same as step (2) in Example 1.
比较例3：Comparative example 3:
N掺杂TiO2(N-TiO2)。该光催化剂的制备方法如下：取钛酸四丁酯10ml，加入5ml冰乙酸，保持溶液温度在25℃左右，磁力搅拌10min后，缓慢滴加30％的浓氨水，至反应液pH值为9。将白色沉淀物用去离子水冲洗5次，85℃下烘干、研细，最后在400℃温度下焙烧2小时，冷却后即得到黄色的N-TiO2粉体催化剂。N-doped TiO 2 (N—TiO 2 ). The preparation method of the photocatalyst is as follows: take 10ml of tetrabutyl titanate, add 5ml of glacial acetic acid, keep the temperature of the solution at about 25°C, and after magnetic stirring for 10min, slowly add 30% concentrated ammonia water dropwise until the pH value of the reaction solution is 9 . Rinse the white precipitate with deionized water five times, dry it at 85°C, grind it finely, and finally roast it at 400°C for 2 hours, and obtain a yellow N-TiO 2 powder catalyst after cooling.
光催化活性的评价方法为：称取一定量的罗丹明B染料，配成浓度为1×10-5mol/L的溶液，pH约为7。量取100ml罗丹明B溶液于直径为5cm的石英反应管中，以一个500W的氙灯为光源，氙灯与反应管间距10cm，且之间置一420nm的滤光片以滤去紫外光部分，同时风扇用于风冷降温，反应时温度在30-40℃。每次反应时催化剂用量均为0.2g，反应前反应液均于黑暗条件下搅拌1h，以达到吸脱附平衡。根据反应一段时间后染料的脱色率来衡量催化剂的活性。当罗丹明B溶液的浓度在合适的范围内时，罗丹明B溶液的最大吸收波长处的吸光度A与浓度C之间的关系遵循朗伯-比尔定律，即A＝εbC，则罗丹明B溶液的脱色率η＝(A0-At)/A0。At为每隔5min抽取5ml左右的反应液，通过离心分离，然后用紫外-可见分光光度计测定上层清液的吸光度。所有催化剂活性均为反应30min后的数据。The evaluation method of photocatalytic activity is as follows: weigh a certain amount of rhodamine B dye, and prepare a solution with a concentration of 1×10 -5 mol/L, and the pH is about 7. Measure 100ml of rhodamine B solution in a quartz reaction tube with a diameter of 5 cm, use a 500W xenon lamp as the light source, and place a 420nm filter between the xenon lamp and the reaction tube to filter out the ultraviolet light. The fan is used for air cooling, and the temperature is 30-40°C during the reaction. The amount of catalyst used in each reaction was 0.2 g, and the reaction solution was stirred for 1 h in the dark before the reaction to achieve adsorption-desorption equilibrium. The activity of the catalyst is measured according to the decolorization rate of the dye after a period of reaction. When the concentration of rhodamine B solution is in the appropriate range, the relationship between the absorbance A at the maximum absorption wavelength of the rhodamine B solution and the concentration C follows the Lambert-Beer law, that is, A=εbC, then the rhodamine B solution The decolorization rate η=(A 0 -A t )/A 0 . At every 5min about 5ml of the reaction solution was extracted, separated by centrifugation, and then the absorbance of the supernatant was measured with an ultraviolet-visible spectrophotometer. All catalyst activities are data after 30 min of reaction.
以上实施例1～5以及对比例1～3所述的催化剂的光催化降解罗丹明B的活性见图1。实施例2和实施例6～8制得的催化剂的可见光催化降解罗丹明B的活性见图2。a1～a8分别对应实施例1～8制得的催化剂，b1～b3则分别对应比较例1～3制得的催化剂。由评价结果可知，采用本发明的制备方法制备的用于可见光下降解染料废水中有机污染物的光催化剂具有很高的光催化活性和使用寿命。在可见光照射下实施例2制得的催化剂降解罗丹明B染料的降解率几乎为100％。The activity of photocatalytic degradation of rhodamine B of the catalysts described in Examples 1-5 and Comparative Examples 1-3 above is shown in FIG. 1 . The activities of the catalysts prepared in Example 2 and Examples 6-8 for visible light catalytic degradation of Rhodamine B are shown in FIG. 2 . a1-a8 respectively correspond to the catalysts prepared in Examples 1-8, and b1-b3 respectively correspond to the catalysts prepared in Comparative Examples 1-3. It can be seen from the evaluation results that the photocatalyst prepared by the preparation method of the present invention for degrading organic pollutants in dye wastewater under visible light has high photocatalytic activity and service life. The degradation rate of the catalyst prepared in Example 2 to degrade Rhodamine B dye under visible light irradiation is almost 100%.
实施例2和比较例1～2制得的催化剂的X射线粉末衍射(XRD)表征结果见图3，实施例2和比较例1～3制得的催化剂的紫外可见漫反射吸收(UV-vis)表征结果见图4。从图3中可以看出，催化剂中只存在MgFe2O4和Ag3VO4相，由于两半导体间的协同耦合作用，使得光生电子-空穴对在这两相间能够定向迁移，从而有效的促进了电子-空穴对的分离，因此大大提高了其光催化活性。紫外可见漫反射吸收光谱表征结果表明实施例2在小于600nm可见光区范围内具有很强的吸收能力，且吸收能力远远大于N-TiO2。这与上述的催化性能评价结果是一致的，即实施例2制得的催化剂具有很高的可见光降解废水染料有机污染物性能。The X-ray powder diffraction (XRD) characterization result of the catalyst that embodiment 2 and comparative examples 1～2 makes is shown in Fig. 3, and the ultraviolet-visible diffuse reflection absorption (UV-visible) of the catalyst that embodiment 2 and comparative examples 1～3 makes is absorbed. ) characterization results are shown in Figure 4. It can be seen from Figure 3 that there are only MgFe 2 O 4 and Ag 3 VO 4 phases in the catalyst, and due to the synergistic coupling between the two semiconductors, the photogenerated electron-hole pairs can migrate directionally between the two phases, thus effectively The separation of electron-hole pairs is facilitated, thus greatly enhancing its photocatalytic activity. The ultraviolet-visible diffuse reflectance absorption spectrum characterization results show that Example 2 has a strong absorption capacity in the range of visible light less than 600nm, and the absorption capacity is much greater than that of N-TiO 2 . This is consistent with the above-mentioned catalytic performance evaluation results, that is, the catalyst prepared in Example 2 has a very high performance of visible light degradation of organic pollutants in wastewater dyes.
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