CN111715261A - Application of G-C3N4 catalyst in degradation of organic dyes in high-salt wastewater - Google Patents

Application of G-C3N4 catalyst in degradation of organic dyes in high-salt wastewater Download PDF

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CN111715261A
CN111715261A CN202010616163.8A CN202010616163A CN111715261A CN 111715261 A CN111715261 A CN 111715261A CN 202010616163 A CN202010616163 A CN 202010616163A CN 111715261 A CN111715261 A CN 111715261A
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catalyst
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organic dyes
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张涛
罗才武
王中玮
姜宁
聂煜东
刘娅
李金春子
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University of South China
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2305/10Photocatalysts

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Abstract

The invention relates to the technical field of photocatalysis, and particularly discloses G-C3N4The application of the catalyst in degrading organic dye in high-salinity wastewater has the advantages of simple process, low cost and environmental protection, and the catalyst can efficiently remove the organic dye in water under a wide range of sodium chloride concentration and reduce environmental pollution.

Description

G-C3N4催化剂在降解高盐废水中有机染料中的应用Application of G-C3N4 catalyst in degradation of organic dyes in high-salt wastewater

技术领域technical field

本发明涉及光催化技术领域,具体公开一种G-C3N4催化剂在降解高盐废水中有机染料中的应用。The invention relates to the technical field of photocatalysis, and specifically discloses the application of a GC 3 N 4 catalyst in degrading organic dyes in high-salt wastewater.

背景技术Background technique

工业的高速发展,大大地促进了人类文明的进步,同时也引发了一系列的环境问题,如高盐有机废水中有机污染物,严重地威胁着人类的健康。高盐有机废水中有机污染物大多来源于海水用于生产生活的过程、工业生产等诸多领域,且水量逐年增加,将高盐有机废水中有机污染物直接排放到土壤和水体中,将造成严重的破坏。因此,高盐有机废水中有机污染物的治理已成为环保领域研究的重点和热点问题之一。高盐有机废水中有机污染物治理的方法有很多种,但是也存在不少问题,例如在高盐条件下采用芬顿或类芬顿技术去除有机染料,易产生毒性更大的卤素盐等。因此,适时研究开发去除高盐废水中有机染料的方法对解决其引起的污染环境问题以及回收盐有着重要的现实意义和经济价值。The rapid development of industry has greatly promoted the progress of human civilization, but also caused a series of environmental problems, such as organic pollutants in high-salt organic wastewater, which seriously threatens human health. Most of the organic pollutants in high-salt organic wastewater come from seawater used in production and living processes, industrial production and many other fields, and the amount of water is increasing year by year. The direct discharge of organic pollutants in high-salt organic wastewater into soil and water will cause serious problems. of destruction. Therefore, the treatment of organic pollutants in high-salt organic wastewater has become one of the key and hot issues in the field of environmental protection research. There are many ways to treat organic pollutants in high-salt organic wastewater, but there are also many problems. For example, using Fenton or Fenton-like technology to remove organic dyes under high-salt conditions is prone to produce more toxic halogen salts. Therefore, timely research and development of methods for removing organic dyes in high-salt wastewater has important practical significance and economic value for solving the environmental pollution problems caused by it and recovering salts.

光催化氧化技术,具有反应条件温和、矿化完全、绿色环保等优点,一直以来备受广大研究者们的青睐。至今为止,光催化技术处理高盐废水中有机污染物,所使用的光催化剂主要为金属基催化剂,例如中国专利(201910510947.X)公开了一种处理高盐废水中玫瑰红B的复合光催化剂及其制备方法和应用,其中,复合光催化剂由磷酸银、聚苯胺和铬掺杂钛酸锶构成;中国专利(201711046176.0)公开了多孔石墨相碳化氮负载碳酸氧铋作为光催化剂处理高盐废水中有机染料。但是,金属基催化剂存在二次污染的问题;且由于高盐溶液中氯离子被吸附在金属基催化剂的表面,形成氯自由基物种,氯自由基物种与反应物结合可以形成毒性大的次氯酸盐。另外,氯自由基物种能够与光生电子结合生成氯离子,消耗了部分光生空穴-电子对,影响金属基催化剂的光催化性能。与金属基光催化剂相比,非金属基光催化剂降解高盐条件下水中有机污染物更具有吸引力。文献(Appl.Catal.B:Environ.2014,158-159:321-328)报道了在不同钠盐(Na2SO3、NaCl和Na2SO4)条件下石墨相碳化氮(分子式:g-C3N4)可见光降解有机染料的研究,结果表明,这些钠盐在可见光下皆能促进水中有机染料的降解,但其反应速率较慢。除此之外,催化剂能否承受更高的氯化钠浓度的影响,以便于更广阔地应用于工业之中也是值得探索的。文献(Chem.Eng.J.2012,192:171-178)专题研究了氯离子浓度对TiO2光催化降解有机染料AO7的影响,研究表明,当氯离子浓度低于200mM时,氯离子能增强光催化剂的性能;当氯离子浓度高于200mM时,氯离子对光催化剂起着显著地抑制作用。由此可见,氯化钠浓度的高低是制约该技术发展的一个重要因素。总之,现有技术中使用的光催化剂在氯化钠条件下降解水中有机染料,存在易引起二次污染、反应速率慢、承受氯化钠浓度不高等缺点。因此,开发一种新的高效降解处理高盐废水中有机染料的方法是十分必要的。Photocatalytic oxidation technology has the advantages of mild reaction conditions, complete mineralization, and environmental protection, and has been favored by researchers for a long time. So far, photocatalytic technology has been used to treat organic pollutants in high-salt wastewater, and the photocatalysts used are mainly metal-based catalysts. For example, Chinese patent (201910510947.X) discloses a composite photocatalyst for the treatment of rose Bengal B in high-salt wastewater The preparation method and application thereof, wherein, the composite photocatalyst is composed of silver phosphate, polyaniline and chromium-doped strontium titanate; Chinese patent (201711046176.0) discloses porous graphite phase nitrogen-supported bismuth oxycarbonate as a photocatalyst to treat high-salt wastewater Medium organic dyes. However, metal-based catalysts have the problem of secondary pollution; and because chloride ions in high-salt solutions are adsorbed on the surface of metal-based catalysts to form chlorine radical species, chlorine radical species can combine with reactants to form highly toxic hypochlorite acid salt. In addition, chlorine radical species can combine with photogenerated electrons to generate chloride ions, which consumes part of the photogenerated hole-electron pairs and affects the photocatalytic performance of metal-based catalysts. Compared with metal-based photocatalysts, non-metal-based photocatalysts are more attractive to degrade organic pollutants in water under high-salt conditions. Literature (Appl.Catal.B:Environ.2014, 158-159:321-328) reported graphitic nitrogen carbide (molecular formula: gC 3 ) under the condition of different sodium salts (Na 2 SO 3 , NaCl and Na 2 SO 4 ). N 4 ) visible light degradation of organic dyes, the results show that these sodium salts can promote the degradation of organic dyes in water under visible light, but the reaction rate is slow. In addition, it is worth exploring whether the catalyst can withstand the influence of higher sodium chloride concentration for wider industrial application. The literature (Chem.Eng.J.2012,192:171-178) has studied the effect of chloride ion concentration on the photocatalytic degradation of organic dye AO7 by TiO2 . The study shows that when the chloride ion concentration is lower than 200mM, the chloride ion can enhance the The performance of the photocatalyst; when the chloride ion concentration is higher than 200mM, the chloride ion plays a significant inhibitory role on the photocatalyst. It can be seen that the level of sodium chloride concentration is an important factor restricting the development of this technology. In a word, the photocatalyst used in the prior art degrades organic dyes in water under the condition of sodium chloride, which has the disadvantages of easily causing secondary pollution, slow reaction rate, and low concentration of sodium chloride. Therefore, it is necessary to develop a new method for efficient degradation of organic dyes in high-salt wastewater.

发明内容SUMMARY OF THE INVENTION

有鉴于此,本发明提供一种G-C3N4催化剂在降解高盐废水中有机染料中的应用,使用该催化剂降解高盐废水中有机染料具有使用简单、成本低和绿色环保的优点,且能够在范围较宽的氯化钠浓度下高效去除水中有机染料,减少环境污染。In view of this, the present invention provides an application of a GC 3 N 4 catalyst in degrading organic dyes in high-salt wastewater, and using the catalyst to degrade organic dyes in high-salt wastewater has the advantages of simple use, low cost and environmental protection, and can be used. It can efficiently remove organic dyes in water under a wide range of sodium chloride concentrations, reducing environmental pollution.

本发明提供的G-C3N4催化剂在降解高盐废水中有机染料中的应用,所述G-C3N4催化剂是通过如下方法制备得到的多孔纳米片结构催化剂:The application of the GC 3 N 4 catalyst provided by the present invention in degrading organic dyes in high-salt wastewater, the GC 3 N 4 catalyst is a porous nano-sheet structure catalyst prepared by the following method:

将g-C3N4前驱物在550-600℃下焙烧2-4h,得g-C3N4固体;接着将所述g-C3N4固体在160-200℃下水热处理2-8h,冲洗,干燥,研磨成g-C3N4粉末;最后将所述g-C3N4粉末置于加盖坩埚中,在500-550℃下焙烧2-8h,快速冷却,即得所述G-C3N4催化剂。The gC 3 N 4 precursor was calcined at 550-600 ° C for 2-4 h to obtain gC 3 N 4 solid; then the gC 3 N 4 solid was hydrothermally treated at 160-200 ° C for 2-8 h, rinsed, dried, and ground gC 3 N 4 powder is formed; finally, the gC 3 N 4 powder is placed in a covered crucible, calcined at 500-550° C. for 2-8 hours, and rapidly cooled to obtain the GC 3 N 4 catalyst.

优选地,所述g-C3N4粉末的质量与所述坩埚的体积比为0.10-0.14g:50mL。Preferably, the mass ratio of the gC 3 N 4 powder to the volume of the crucible is 0.10-0.14 g:50 mL.

优选地,所述g-C3N4前驱物为三聚氰胺。Preferably, the gC 3 N 4 precursor is melamine.

优选地,采用所述G-C3N4催化剂降解高盐废水中有机染料的具体过程如下:将所述G-C3N4催化剂投加至含有机染料的高盐废水中,在黑暗条件下剧烈搅拌,平衡30min后,在光照条件下进行降解处理。Preferably, the specific process of using the GC 3 N 4 catalyst to degrade organic dyes in high-salt wastewater is as follows: adding the GC 3 N 4 catalyst to the high-salt wastewater containing organic dyes, stirring vigorously under dark conditions, After equilibration for 30 min, degradation treatment was carried out under light conditions.

更优选地,所述G-C3N4催化剂的加入量为0.1-1.0g/L。More preferably, the added amount of the GC 3 N 4 catalyst is 0.1-1.0 g/L.

更优选地,所述有机染料为罗丹明B、亚甲基蓝、甲基橙中的一种。More preferably, the organic dye is one of Rhodamine B, methylene blue and methyl orange.

更优选地,所述光照为LED、Xe灯、太阳光中的一种。More preferably, the illumination is one of LED, Xe lamp and sunlight.

与现有技术相比,本发明具有以下有益的技术效果:Compared with the prior art, the present invention has the following beneficial technical effects:

1、在范围较宽的氯化钠浓度下高效去除废水中有机染料,且无明显的抑制作用;1. Efficiently remove organic dyes in wastewater under a wide range of sodium chloride concentrations, and there is no obvious inhibitory effect;

2、在整个废水处理过程中不会产生二次污染;2. There will be no secondary pollution during the entire wastewater treatment process;

3、使用的催化剂具有制备简单、绿色环保和低成本的特点,且该催化剂易回收,可重复再利用。3. The used catalyst has the characteristics of simple preparation, green environmental protection and low cost, and the catalyst is easy to recover and can be reused.

附图说明Description of drawings

图1是实施例1和对比例1提供的催化剂的扫描电镜(SEM)图,其中,图a是g-C3N4电镜图,图b是G-C3N4电镜图;Fig. 1 is the scanning electron microscope (SEM) image of the catalyst provided by Example 1 and Comparative Example 1, wherein, Fig. a is the electron microscope image of gC 3 N 4 , and Fig. b is the electron microscope image of GC 3 N 4 ;

图2是实施例1和对比例1提供的有机染料处理方法中RhB的去除率图;Fig. 2 is the removal rate figure of RhB in the organic dye processing method that embodiment 1 and comparative example 1 provide;

图3是实施例4提供的不同氯化钠浓度下RhB的去除率图;Fig. 3 is the removal rate figure of RhB under the different sodium chloride concentrations that embodiment 4 provides;

图4是实施例5提供的催化剂不同投加量下RhB的去除率图。4 is a diagram showing the removal rate of RhB under different dosages of the catalyst provided in Example 5.

具体实施方式Detailed ways

下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于本发明而不用于限制本发明的范围。The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only for the present invention and are not intended to limit the scope of the present invention.

本发明提供的G-C3N4催化剂在降解高盐废水中有机染料中的应用,所述G-C3N4催化剂是通过如下方法制备得到的多孔纳米片结构催化剂;The application of the GC 3 N 4 catalyst provided by the present invention in degrading organic dyes in high-salt wastewater, the GC 3 N 4 catalyst is a porous nano-sheet structure catalyst prepared by the following method;

将g-C3N4前驱物在550-600℃下焙烧2-4h,得g-C3N4固体;接着将所述g-C3N4固体在160-200℃下水热处理2-8h,冲洗,干燥,研磨成g-C3N4粉末;最后将所述g-C3N4粉末置于加盖坩埚中,在500-550℃下焙烧2-8h,快速冷却,即得所述G-C3N4催化剂。The gC 3 N 4 precursor was calcined at 550-600 ° C for 2-4 h to obtain gC 3 N 4 solid; then the gC 3 N 4 solid was hydrothermally treated at 160-200 ° C for 2-8 h, rinsed, dried, and ground gC 3 N 4 powder is formed; finally, the gC 3 N 4 powder is placed in a covered crucible, calcined at 500-550° C. for 2-8 hours, and rapidly cooled to obtain the GC 3 N 4 catalyst.

下面结合具体实施例进行说明。The following description will be given in conjunction with specific embodiments.

实施例1Example 1

在室温下,配制50mL含10mg/L罗丹明B(标记为RhB)和500mM NaCl的混合溶液,置入到光催化反应器中,加入1.0g/L G-C3N4,在黑暗条件下剧烈搅拌30min,目的是在避光条件下,反应物能够在催化剂表面达到吸附-脱附平衡;接着在LED辐射下进行光催化反应,每隔一段时间取出反应液,分离,测定其吸光度,计算RhB降解率;At room temperature, prepare 50 mL of a mixed solution containing 10 mg/L Rhodamine B (labeled as RhB) and 500 mM NaCl, put it into a photocatalytic reactor, add 1.0 g/L GC 3 N 4 , and stir vigorously in the dark 30min, the purpose is that the reactants can reach the adsorption-desorption equilibrium on the catalyst surface under the condition of dark light; then the photocatalytic reaction is carried out under the LED radiation, the reaction solution is taken out at regular intervals, separated, measured its absorbance, and calculated RhB degradation Rate;

其中,G-C3N4的制备过程为:Wherein, the preparation process of GC 3 N 4 is:

在加盖的坩埚里放入前驱物三聚氰胺,于550℃下焙烧三聚氰胺4h,得到浅黄色g-C3N4固体,研磨备用,坩埚加盖能够防止三聚氰胺因升华而挥发;称取0.3g研磨后的g-C3N4粉末置入到50mL晶化釜中,添加25mL高纯水,于180℃水热处理4h,冲洗,干燥,研磨得到样品粉末;在50mL加盖的坩埚中,加入0.10g样品粉末,于550℃下再次焙烧4h,即得到所需的催化剂,标记为G-C3N4Put the precursor melamine into the covered crucible, roast the melamine at 550°C for 4 hours to obtain a light yellow gC 3 N 4 solid, which is ground for use, and the crucible is covered to prevent the melamine from volatilizing due to sublimation; weigh 0.3 g of the ground The gC 3 N 4 powder was placed in a 50 mL crystallization kettle, 25 mL of high-purity water was added, hydrothermally treated at 180 °C for 4 h, rinsed, dried, and ground to obtain the sample powder; in a 50 mL covered crucible, 0.10 g of the sample powder was added, and the sample powder was heated at 550 After calcining again at ℃ for 4h, the desired catalyst is obtained, which is marked as GC 3 N 4 .

在以上G-C3N4的制备过程中,将水热处理后的样品研磨成样品粉末,能使高温焙烧下的样品与空气充分接触。加盖焙烧的目的是使样品不至于完全地燃烧掉。样品质量与坩埚体积比有着严格的要求,这是由于在一定体积的坩埚中,待加热样品的量过多,很难获得所需的目标催化剂,而待加热样品的量过少,无任何样品残留。In the above preparation process of GC 3 N 4 , the sample after hydrothermal treatment is ground into sample powder, which can fully contact the sample under high temperature calcination with air. The purpose of the covered roasting is to prevent the sample from burning out completely. The ratio of sample mass to crucible volume has strict requirements. This is because in a crucible of a certain volume, the amount of the sample to be heated is too much, and it is difficult to obtain the desired target catalyst, while the amount of the sample to be heated is too small, and there is no sample. residue.

制备原理:对三聚氰胺进行高温焙烧得到g-C3N4纳米片,继续对g-C3N4纳米片进行水热处理,将g-C3N4纳米片进行部分剥离;第二次高温焙烧能够将部分剥离的g-C3N4进一步进行剥离。同时,部分g-C3N4纳米片被分解成气体,穿过g-C3N4纳米片形成大量的气孔,从而使g-C3N4呈现出多孔的纳米片结构。制备得到的G-C3N4催化剂的电镜图如图1所示,图1(a)是对比例1提供的g-C3N4电镜图,图1(b)是实施例1提供的G-C3N4电镜图。g-C3N4由纳米片聚集的颗粒构成,G-C3N4呈现出多孔的纳米片结构。由图1可见,与对照催化剂相比,最终制备的催化剂的结构发生很大的变化。Preparation principle: calcining melamine at high temperature to obtain gC 3 N 4 nanosheets, continue to perform hydrothermal treatment on gC 3 N 4 nanosheets, and partially exfoliate the gC 3 N4 nanosheets; the second high temperature calcination can exfoliate the partially exfoliated gC 3 N 4 nanosheets. 3 N 4 was further exfoliated. At the same time, part of the gC3N4 nanosheets were decomposed into gas, and a large number of pores were formed through the gC3N4 nanosheets , so that the gC3N4 presented a porous nanosheet structure. The electron microscope image of the prepared GC 3 N 4 catalyst is shown in Figure 1, Figure 1 (a) is the electron microscope image of gC 3 N 4 provided by Comparative Example 1, and Figure 1 (b) is the GC 3 N 4 provided by Example 1. Electron micrograph. gC3N4 is composed of particles aggregated by nanosheets , and GC3N4 exhibits a porous nanosheet structure. It can be seen from Fig. 1 that the structure of the finally prepared catalyst changed greatly compared with the control catalyst.

将RhB、NaCl的混合溶液与该G-C3N4催化剂混合后RhB的降解结果如图2所示。由图2可知,在30min内,RhB即被完全降解。Figure 2 shows the degradation results of RhB after mixing the mixed solution of RhB and NaCl with the GC 3 N 4 catalyst. It can be seen from Figure 2 that RhB was completely degraded within 30 min.

光降解反应原理:在光激发作用下,催化剂表面上产生光生空穴-电子对,其中,光生空穴具有氧化性,能够直接用于氧化有机染料。除此之外,光生电子可以与水中溶解氧结合生成过氧自由基物种,同样可以降解有机染料。在NaCl存在的情况下,Na+被吸附于催化剂表面上而Cl-处于反应液中,这样一来,光生空穴不与Cl-结合形成Cl·物种,进而不会形成毒性更大的次氯酸盐。The principle of photodegradation reaction: under the action of light excitation, photogenerated hole-electron pairs are generated on the surface of the catalyst. Among them, the photogenerated holes are oxidative and can be directly used to oxidize organic dyes. In addition, photogenerated electrons can combine with dissolved oxygen in water to generate peroxy radical species, which can also degrade organic dyes. In the presence of NaCl, Na + is adsorbed on the catalyst surface and Cl - is in the reaction solution, so that the photogenerated holes do not combine with Cl - to form Cl species, which will not form more toxic hypochlorite acid salt.

实施例2Example 2

与实施例1的不同之处仅在于:The only difference from Example 1 is:

在G-C3N4的制备过程中加入0.12g经水热处理的样品粉末,于550℃下再次焙烧4h,制备得到G-C3N4催化剂。During the preparation of GC 3 N 4 , 0.12 g of the hydrothermally treated sample powder was added, and calcined again at 550° C. for 4 h to prepare a GC 3 N 4 catalyst.

将该G-C3N4催化剂与50mL含10mg/L RhB和500mM NaCl的混合溶液光催化反应30min,RhB降解率达到99%。The GC 3 N 4 catalyst was photocatalytically reacted with 50 mL of a mixed solution containing 10 mg/L RhB and 500 mM NaCl for 30 min, and the RhB degradation rate reached 99%.

实施例3Example 3

与上述实施例的不同之处仅在于:The only difference from the above-mentioned embodiment is:

在G-C3N4的制备过程中加入0.14g经水热处理的样品粉末,于550℃下再次焙烧4h,制备得到G-C3N4催化剂。During the preparation of GC 3 N 4 , 0.14 g of the hydrothermally treated sample powder was added and calcined again at 550° C. for 4 h to prepare a GC 3 N 4 catalyst.

将该G-C3N4催化剂与50mL含10mg/L RhB和500mM NaCl的混合溶液光催化反应30min,RhB降解率达到99%。The GC 3 N 4 catalyst was photocatalytically reacted with 50 mL of a mixed solution containing 10 mg/L RhB and 500 mM NaCl for 30 min, and the RhB degradation rate reached 99%.

实施例4Example 4

在不同浓度氯化钠下光降解高盐废水中RhBPhotodegradation of RhB in high-salt wastewater under different concentrations of sodium chloride

在室温下,配制50mL含10mg/L RhB和NaCl的混合溶液,其中,NaCl浓度分别为1mM、10mM、100mM、300mM和500mM,置入到光催化反应器中,加入1.0g/L G-C3N4(制备方法同实施例1中G-C3N4的制备方法),在黑暗条件下剧烈搅拌30min;接着在LED辐射下进行光催化反应,每隔一段时间取出反应液,分离,测定其吸光度,计算RhB降解率,结果如图3所示。At room temperature, prepare 50 mL of a mixed solution containing 10 mg/L RhB and NaCl, wherein the NaCl concentrations are 1 mM, 10 mM, 100 mM, 300 mM and 500 mM, respectively, put into the photocatalytic reactor, and add 1.0 g/L GC 3 N 4 (the preparation method is the same as the preparation method of GC 3 N 4 in Example 1), stir vigorously for 30min under dark conditions; then carry out photocatalytic reaction under LED radiation, take out the reaction solution at intervals, separate, measure its absorbance, The RhB degradation rate was calculated and the results are shown in Figure 3.

由图3可知,在30min内,RhB即被完全降解。It can be seen from Figure 3 that RhB was completely degraded within 30 min.

实施例5Example 5

在不同催化剂投加量下光降解高盐废水中RhBPhotodegradation of RhB in high-salt wastewater under different catalyst dosages

在室温下,配制50mL含10mg/L RhB和500mM NaCl的混合溶液,置入到光催化反应器中,加入G-C3N4催化剂(制备方法同实施例1中G-C3N4的制备方法),其中,G-C3N4催化剂投加量分别为0.1g/L、0.3g/L、0.5g/L、0.7g/L和1.0g/L,在黑暗条件下剧烈搅拌30min;接着在LED辐射下进行光催化反应,每隔一段时间取出反应液,分离,测定其吸光度,计算RhB降解率,结果如图4所示。At room temperature, prepare 50 mL of a mixed solution containing 10 mg/L RhB and 500 mM NaCl, put it into a photocatalytic reactor, and add a GC 3 N 4 catalyst (the preparation method is the same as the preparation method of GC 3 N 4 in Example 1), Among them, the dosage of GC 3 N 4 catalyst was 0.1 g/L, 0.3 g/L, 0.5 g/L, 0.7 g/L and 1.0 g/L, respectively, and vigorously stirred for 30 min under dark conditions; then under LED radiation The photocatalytic reaction was carried out, the reaction solution was taken out at regular intervals, separated, its absorbance was measured, and the RhB degradation rate was calculated. The results are shown in Figure 4.

由图4可知,在30min内,RhB即被完全降解。As can be seen from Figure 4, RhB was completely degraded within 30 min.

对比例1Comparative Example 1

与实施例1-3的不同之间仅在于:The only difference from Examples 1-3 is:

催化剂的制备过程为:The preparation process of the catalyst is as follows:

在加盖的坩埚里加入前驱物三聚氰胺,于550℃下焙烧三聚氰胺4h,得到浅黄色g-C3N4固体,研磨备用。The precursor melamine was added to the covered crucible, and the melamine was calcined at 550° C. for 4 h to obtain a light yellow gC 3 N 4 solid, which was ground for use.

将该浅黄色g-C3N4固体与50mL含10mg/L RhB和500mM NaCl的混合溶液光催化反应30min,结果如图2所示。The light yellow gC 3 N 4 solid was photocatalytically reacted with 50 mL of a mixed solution containing 10 mg/L RhB and 500 mM NaCl for 30 min. The results are shown in FIG. 2 .

由图2可知,在30min内,g-C3N4上RhB降解率仅有30%。It can be seen from Figure 2 that the degradation rate of RhB on gC 3 N 4 is only 30% within 30 min.

与g-C3N4相比,G-C3N4的催化活性得到显著地提高,主要源自于其结构发生较大变化的缘故,比如,形貌发生较大变化,见图1所示。形貌的变化导致材料的比表面积大幅度增加,进而影响其吸附RhB的能力大小。Compared with gC 3 N 4 , the catalytic activity of GC 3 N 4 is significantly improved, mainly due to the large changes in its structure, such as the large changes in morphology, as shown in Figure 1. The change of morphology leads to a substantial increase in the specific surface area of the material, which in turn affects its ability to adsorb RhB.

需要说明的是,本发明权利要求书中涉及数值范围时,应理解为每个数值范围的两个端点以及两个端点之间任何一个数值均可选用,由于采用的步骤方法与实施例相同,为了防止赘述,本发明描述了优选的实施例,但本领域内的技术人员一旦得知了基本创造性概念,则可对这些实施例作出另外的变更和修改。所以,所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。It should be noted that when the claims of the present invention relate to the numerical range, it should be understood that the two endpoints of each numerical range and any value between the two endpoints can be selected, because the steps and methods used are the same as the examples, To avoid repetition, the present invention describes preferred embodiments, but those skilled in the art may make additional changes and modifications to these embodiments once the basic inventive concepts are known. Therefore, the appended claims are intended to be construed to include the preferred embodiment and all changes and modifications that fall within the scope of the present invention.

本领域的技术人员应理解,以上所述仅为本发明的若干个具体实施方式,本发明并不仅限于此。应当指出,对于本领域的普通技术人员来说,还可以做出许多变形和改进,所有未超出权利要求所述的变形或改进均应视为本发明的保护范围。Those skilled in the art should understand that the above descriptions are only several specific embodiments of the present invention, and the present invention is not limited thereto. It should be pointed out that for those of ordinary skill in the art, many modifications and improvements can also be made, and all modifications or improvements that do not exceed the claims should be regarded as the protection scope of the present invention.

Claims (7)

1.G-C3N4催化剂在降解高盐废水中有机染料中的应用,所述G-C3N4催化剂是通过如下方法制备得到的多孔纳米片结构催化剂;1. Application of a GC 3 N 4 catalyst in degrading organic dyes in high-salt wastewater, the GC 3 N 4 catalyst is a porous nanosheet structure catalyst prepared by the following method; 将g-C3N4前驱物在550-600℃下焙烧2-4h,得g-C3N4固体;接着将所述g-C3N4固体在160-200℃下水热处理2-8h,冲洗,干燥,研磨成g-C3N4粉末;最后将所述g-C3N4粉末置于加盖坩埚中,在500-550℃下焙烧2-8h,快速冷却,即得所述G-C3N4催化剂。The gC 3 N 4 precursor was calcined at 550-600 ° C for 2-4 h to obtain gC 3 N 4 solid; then the gC 3 N 4 solid was hydrothermally treated at 160-200 ° C for 2-8 h, rinsed, dried, and ground gC 3 N 4 powder is formed; finally, the gC 3 N 4 powder is placed in a covered crucible, calcined at 500-550° C. for 2-8 hours, and rapidly cooled to obtain the GC 3 N 4 catalyst. 2.根据权利要求1所述的应用,其特征在于,所述g-C3N4粉末的质量与所述坩埚的体积比为0.10-0.14g:50mL。2 . The application according to claim 1 , wherein the mass ratio of the gC 3 N 4 powder to the volume of the crucible is 0.10-0.14 g: 50 mL. 3 . 3.根据权利要求1所述的应用,其特征在于,所述g-C3N4前驱物为三聚氰胺。3. The application according to claim 1 , wherein the gC3N4 precursor is melamine. 4.根据权利要求1所述的应用,其特征在于,采用所述G-C3N4催化剂降解高盐废水中有机染料的具体过程如下:将所述G-C3N4催化剂投加至含有机染料的高盐废水中,在黑暗条件下剧烈搅拌,平衡30min后,在光照条件下进行降解处理。4. application according to claim 1 is characterized in that, the concrete process that adopts described GC 3 N 4 catalyst to degrade organic dyes in high-salt waste water is as follows: described GC 3 N 4 catalyst is added to containing organic dyestuffs In the high-salt wastewater, vigorously stirred under dark conditions, equilibrated for 30 min, and then degraded under light conditions. 5.根据权利要求4所述的应用,其特征在于,所述G-C3N4催化剂的加入量为0.1-1.0g/L。5 . The application according to claim 4 , wherein the GC 3 N 4 catalyst is added in an amount of 0.1-1.0 g/L. 6 . 6.根据权利要求4所述的应用,其特征在于,所述有机染料为罗丹明B、亚甲基蓝、甲基橙中的一种。6. application according to claim 4, is characterized in that, described organic dye is a kind of in Rhodamine B, methylene blue, methyl orange. 7.根据权利要求4所述的应用,其特征在于,所述光照为LED、Xe灯、太阳光中的一种。7. The application according to claim 4, wherein the illumination is one of LED, Xe lamp, and sunlight.
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Application publication date: 20200929