CN114308109B - ZnO/C-g-C 3 N 4 Photocatalyst, preparation method thereof and triclosan wastewater treatment method - Google Patents
ZnO/C-g-C 3 N 4 Photocatalyst, preparation method thereof and triclosan wastewater treatment method Download PDFInfo
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- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229960003500 triclosan Drugs 0.000 title claims abstract description 67
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
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- 238000001354 calcination Methods 0.000 claims abstract description 22
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims description 27
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 24
- 229940045872 sodium percarbonate Drugs 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 20
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- BHDAXLOEFWJKTL-UHFFFAOYSA-L dipotassium;carboxylatooxy carbonate Chemical compound [K+].[K+].[O-]C(=O)OOC([O-])=O BHDAXLOEFWJKTL-UHFFFAOYSA-L 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
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- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 76
- 239000011787 zinc oxide Substances 0.000 description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- WMWJCKBJUQDYLM-UHFFFAOYSA-N 2,8-dichlorodibenzo-p-dioxin Chemical compound C1=C(Cl)C=C2OC3=CC(Cl)=CC=C3OC2=C1 WMWJCKBJUQDYLM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-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
Description
技术领域Technical field
本发明属于水污染处理技术领域，具体涉及一种ZnO/C-g-C3N4光催化剂及其协同过碳酸盐降解三氯生的方法。The invention belongs to the technical field of water pollution treatment, and specifically relates to a ZnO/CgC 3 N 4 photocatalyst and a method for synergizing percarbonate to degrade triclosan.
背景技术Background technique
三氯生(TCS)作为一种高效抗菌剂广泛应用于个人护理产品和生活消费品中(例如：化妆品、除臭剂、牙膏、厨房用具和垃圾袋等)。随着社会经济的快速的发展，大量的TCS在污水处理厂的进水口中被检出，最高浓度可达8.62×10-2mg/L。有研究表明，TCS具有较强的生物体蓄积性，且在一定条件下可转化为毒性和生物体积累能力更强的2,8-二氯二苯并对二噁英(2,8-DCDD)。因此，研发一种高效处理废水中TCS的治理技术迫在眉睫。Triclosan (TCS), as a highly effective antibacterial agent, is widely used in personal care products and consumer products (such as cosmetics, deodorants, toothpaste, kitchen utensils and garbage bags, etc.). With the rapid development of social economy, a large amount of TCS has been detected in the water inlet of sewage treatment plants, with the highest concentration reaching 8.62×10 -2 mg/L. Studies have shown that TCS has strong bioaccumulation ability, and under certain conditions can be converted into 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD), which is more toxic and bioaccumulative. ). Therefore, it is urgent to develop a treatment technology that can efficiently treat TCS in wastewater.
石墨相氮化碳(g-C3N4)作为一种稳固的半导体，因其易合成、成本低、理化性质稳定和电子能带结构合适等优点，广泛应用于光催化领域的二氧化碳还原、制氢和环境修复应用。为了提高g-C3N4的光催化活性，使用构筑碳修饰合成的构筑碳/g-C3N4(C-g-C3N4)复合催化剂可显著提升材料的比表面积、孔隙率和结构稳定。然而，仅此一步改性过程并未有效解决光生电子-空穴的分离困难、寿命短和量子效率低等问题。因此，C-g-C3N4在实际中的应用受到了一定的限制。As a stable semiconductor, graphitic carbon nitride (gC 3 N 4 ) is widely used in carbon dioxide reduction and hydrogen production in the field of photocatalysis due to its advantages such as easy synthesis, low cost, stable physical and chemical properties, and suitable electronic band structure. and environmental remediation applications. In order to improve the photocatalytic activity of gC 3 N 4 , the built-carbon/gC 3 N 4 (CgC 3 N 4 ) composite catalyst synthesized using built-in carbon modification can significantly increase the specific surface area, porosity and structural stability of the material. However, this one-step modification process alone does not effectively solve the problems of difficult separation of photogenerated electrons and holes, short lifetime and low quantum efficiency. Therefore, the practical application of CgC 3 N 4 is subject to certain limitations.
纳米氧化锌(ZnO)作为一种金属氧化物半导体，已表现出优越的增强光催化效率性能。ZnO禁带宽度约为3.37eV，高于g-C3N4，载流电荷的迁移路径可能为g-C3N4的导带处的光生电子向ZnO的导带处迁移，ZnO的价带处的空穴向g-C3N4的价带处迁移，形成异质结，二者带隙结构的相匹配可有效增强复合催化剂的光催化活性。Nanoscale zinc oxide (ZnO), as a metal oxide semiconductor, has shown superior performance in enhancing photocatalytic efficiency. The forbidden band width of ZnO is about 3.37eV, which is higher than that of gC 3 N 4. The migration path of the current-carrying charge may be that the photogenerated electrons at the conduction band of gC 3 N 4 migrate to the conduction band of ZnO, and the vacancies at the valence band of ZnO The holes migrate to the valence band of gC 3 N 4 to form a heterojunction. The matching of the band gap structures of the two can effectively enhance the photocatalytic activity of the composite catalyst.
近年来，基于过碳酸盐(如过碳酸钠2Na2CO3·3H2O2,SPC)的氧化工艺广泛应用于水污染的处理中，其作为过氧化氢的载体，具有稳定、廉价和安全等优点，可与过渡金属形成类芬顿体系进行污染物的降解。但其在应用过程中难免受到实际水体环境的限制，导致其作用效率降低，所以通过结合不同的处理体系(例如光催化体系)，提高处理***的效果并降低能耗日益成为研究主流。目前，鲜有将ZnO/C-g-C3N4应用于光催化协同的相关报道。该种光催化剂降解TCS的效率也尚未可知。In recent years, the oxidation process based on percarbonate (such as sodium percarbonate 2Na 2 CO 3 ·3H 2 O 2 , SPC) has been widely used in the treatment of water pollution. As a carrier of hydrogen peroxide, it is stable, cheap and It has advantages such as safety and can form a Fenton-like system with transition metals to degrade pollutants. However, its application is inevitably limited by the actual water environment, resulting in a reduction in its efficiency. Therefore, it has become increasingly mainstream to improve the effectiveness of the treatment system and reduce energy consumption by combining different treatment systems (such as photocatalytic systems). At present, there are few reports on the application of ZnO/CgC 3 N 4 in photocatalytic synergy. The efficiency of this photocatalyst in degrading TCS is also unknown.
发明内容Contents of the invention
针对上述的技术问题，本发明提供了一种ZnO/C-g-C3N4复合光催化剂，其利用纳米ZnO与C掺杂的g-C3N4，协同过碳酸盐作用进行TCS的降解，从而控制其对生态环境和人类健康构成的威胁。In view of the above technical problems, the present invention provides a ZnO/CgC 3 N 4 composite photocatalyst, which uses nano-ZnO and C-doped gC 3 N 4 to cooperate with percarbonate to degrade TCS, thereby controlling its threats to the ecological environment and human health.
第一方面，本发明提供了一种ZnO/C-g-C3N4光催化剂，其通过C-g-C3N4与锌的含氧酸盐共同煅烧得到。煅烧温度为250～650℃。C-g-C3N4为碳掺杂石墨相氮化碳的复合材料。In a first aspect, the present invention provides a ZnO/CgC 3 N 4 photocatalyst, which is obtained by co-calcining CgC 3 N 4 and zinc oxo acid salt. The calcination temperature is 250~650℃. CgC 3 N 4 is a composite material of carbon doped graphite phase carbon nitride.
作为优选，锌的含氧酸盐采用硝酸锌。Preferably, zinc nitrate is used as the oxygen-containing acid salt of zinc.
作为优选，所述的煅烧温度为550℃。Preferably, the calcination temperature is 550°C.
作为优选，所述的C-g-C3N4通过对g-C3N4前驱体、甲醛的低聚物与g-C3N4前驱体的混合物进行煅烧得到。Preferably, the CgC 3 N 4 is obtained by calcining a mixture of gC 3 N 4 precursor, formaldehyde oligomer and gC 3 N 4 precursor.
第二方面，本发明提供前述的ZnO/C-g-C3N4复合光催化剂的制备方法，其具体步骤如下：In a second aspect, the present invention provides a method for preparing the aforementioned ZnO/CgC 3 N 4 composite photocatalyst. The specific steps are as follows:
步骤一、将g-C3N4前驱体与甲醛进行聚合反应，得到由g-C3N4前驱体-甲醛低聚物和g-C3N4前驱体组成的PHDM混合物。Step 1: Polymerize gC 3 N 4 precursor and formaldehyde to obtain a PHDM mixture composed of gC 3 N 4 precursor-formaldehyde oligomer and gC 3 N 4 precursor.
步骤二、将步骤一所得的PHDM混合物进行水热反应后煅烧。Step 2: The PHDM mixture obtained in Step 1 is subjected to hydrothermal reaction and then calcined.
步骤三、将步骤二所得的煅烧产物与刻蚀剂混合后进行振荡，分别用去离子水和乙醇洗涤后，得到C-g-C3N4。Step 3: Mix the calcined product obtained in Step 2 with the etchant, shake it, and wash it with deionized water and ethanol respectively to obtain CgC 3 N 4 .
步骤四、将步骤三所得的C-g-C3N4与Zn(NO3)2混合并充分搅拌至浆糊状后烘干，得到混合物固体。Step 4: Mix the CgC 3 N 4 and Zn(NO 3 ) 2 obtained in Step 3, stir thoroughly until they become paste-like, and then dry them to obtain a solid mixture.
步骤五、对步骤四所得的混合物固体进行煅烧，得到ZnO/C-g-C3N4光催化剂。Step 5: Calculate the solid mixture obtained in Step 4 to obtain a ZnO/CgC 3 N 4 photocatalyst.
作为优选，步骤一中所述的g-C3N4前驱体为三聚氰胺。Preferably, the gC 3 N 4 precursor described in step 1 is melamine.
作为优选，步骤一中所述的聚合反应条件为：三聚氰胺和甲醛的混合物溶于去离子水中，加热至70℃完全溶解，搅拌均匀后，调节溶液pH至2～3。Preferably, the polymerization reaction conditions described in step one are: dissolve the mixture of melamine and formaldehyde in deionized water, heat to 70°C to completely dissolve, stir evenly, and adjust the pH of the solution to 2-3.
作为优选，步骤二中所述的水热合成条件为：取PHDM混合物置于聚四氟乙烯内衬的高压反应釜中，180℃下反应20h。Preferably, the hydrothermal synthesis conditions described in step 2 are: place the PHDM mixture in a polytetrafluoroethylene-lined high-pressure reactor and react at 180°C for 20 hours.
作为优选，步骤二中所述的煅烧条件为：以10℃/min的加热速率加热至550℃，在550℃下煅烧2h后，自然冷却至室温。Preferably, the calcination conditions described in step 2 are: heating to 550°C at a heating rate of 10°C/min, calcining at 550°C for 2 hours, and then cooling to room temperature naturally.
作为优选，步骤三中所述的刻蚀剂为过氧化氢。Preferably, the etchant in step three is hydrogen peroxide.
作为优选，步骤四中所述的C-g-C3N4与Zn(NO3)2混合条件为：C-g-C3N4与0.15M的Zn(NO3)2水溶液，通过磁力搅拌混匀。C-g-C3N4相对于Zn(NO3)2水溶液的用量为0.1g/mL。Preferably, the mixing conditions of CgC 3 N 4 and Zn(NO 3 ) 2 described in step 4 are: CgC 3 N 4 and 0.15M Zn(NO 3 ) 2 aqueous solution are mixed evenly by magnetic stirring. The dosage of CgC 3 N 4 relative to the Zn(NO 3 ) 2 aqueous solution is 0.1g/mL.
作为优选，步骤五中所述的煅烧条件为：混合物固体置于管式炉内通50mL/min空气下分别在250℃～650℃下煅烧3h。Preferably, the calcination conditions described in step five are: the solid mixture is placed in a tubular furnace and calcined at 250°C to 650°C for 3 hours with air flowing at 50 mL/min.
第三方面，本发明提供一种三氯生废水的方法，其具体过程为向三氯生废水中加入ZnO/C-g-C3N4复合光催化剂和过碳酸盐，并持续提供可见光条件。In a third aspect, the present invention provides a method for treating triclosan wastewater. The specific process is to add ZnO/CgC 3 N 4 composite photocatalyst and percarbonate to triclosan wastewater, and continuously provide visible light conditions.
作为优选，ZnO/C-g-C3N4复合光催化剂、过碳酸盐相对于三氯生废水的用量分别为1.0g/L、0.07g/L。Preferably, the dosages of ZnO/CgC 3 N 4 composite photocatalyst and percarbonate relative to triclosan wastewater are 1.0g/L and 0.07g/L respectively.
作为优选，所述过碳酸盐采用过碳酸钠和过碳酸钾中的一种或两种。Preferably, the percarbonate is one or both of sodium percarbonate and potassium percarbonate.
作为优选，被处理的三氯生废水中三氯生的质量浓度为1.0mg/L。Preferably, the mass concentration of triclosan in the treated triclosan wastewater is 1.0 mg/L.
本发明具有的有益效果是：The beneficial effects of the present invention are:
1、本发明使用ZnO/C-g-C3N4复合光催化剂，将g-C3N4的可见光响应性、ZnO较大的禁带宽度和碳材料的导电性和吸附性结合起来构建新型ZnO/C-g-C3N4催化剂，并将其用于光催化降解三氯生，实现了三氯生废水的快速降解。1. The present invention uses ZnO/CgC 3 N 4 composite photocatalyst to combine the visible light responsiveness of gC 3 N 4 , the large bandgap width of ZnO and the conductivity and adsorption of carbon materials to construct a new type of ZnO/CgC 3 N 4 catalyst, and used it for photocatalytic degradation of triclosan, achieving rapid degradation of triclosan wastewater.
2、本发明提供了以ZnO/C-g-C3N4复合光催化剂协同过碳酸盐对三氯生废水进行降解的技术；经测试，ZnO/C-g-C3N4复合光催化剂能够活化过碳酸盐，产生大量羟基自由基脱氯，同时可直接氧化分解三氯生，以及通过取代作用实现脱氯，提高过碳酸盐对三氯生的降解效果，实现了两种降解方式的相互促进，从而高能量利用率、高脱氯效率地降解水体中的三氯生。2. The present invention provides a technology for degrading triclosan wastewater using ZnO/CgC 3 N 4 composite photocatalyst in collaboration with percarbonate; after testing, the ZnO/CgC 3 N 4 composite photocatalyst can activate percarbonate, Generates a large amount of hydroxyl radicals for dechlorination, and can directly oxidize and decompose triclosan, as well as achieve dechlorination through substitution, improve the degradation effect of percarbonate on triclosan, and realize the mutual promotion of the two degradation methods, thus achieving high Degrade triclosan in water bodies with high energy utilization and high dechlorination efficiency.
附图说明Description of the drawings
图1为实施例2中不同煅烧温度下制得的ZnO/C-g-C3N4复合光催化剂对TCS去除率的对比图。Figure 1 is a comparison chart of the TCS removal rates of the ZnO/CgC 3 N 4 composite photocatalysts prepared at different calcination temperatures in Example 2.
图2为实施例3中ZnO/C-g-C3N4复合光催化剂在不同投加量下对TCS去除率随时间变化关系图。Figure 2 is a graph showing the relationship between the TCS removal rate of the ZnO/CgC 3 N 4 composite photocatalyst as a function of time under different dosages in Example 3.
图3为实施例4中ZnO/C-g-C3N4复合光催化剂协同过碳酸盐体系降解TCS期间产生羟基自由基的电子自旋共振谱图。Figure 3 is the electron spin resonance spectrum of hydroxyl radicals generated during the degradation of TCS by the ZnO/CgC 3 N 4 composite photocatalyst in cooperation with the percarbonate system in Example 4.
图4为本发明实施例2与对比例1提供的三种作为对照的处理体系下TCS去除率随时间的变化关系图。Figure 4 is a graph showing the changes in TCS removal rate with time under three comparative treatment systems provided in Example 2 and Comparative Example 1 of the present invention.
具体实施方式Detailed ways
以下结合具体实施例，对本发明做进一步描述。The present invention will be further described below with reference to specific embodiments.
实施例1Example 1
一种ZnO/C-g-C3N4复合光催化剂的制备方法，具体步骤如下：A preparation method of ZnO/CgC 3 N 4 composite photocatalyst, the specific steps are as follows:
取10.0g三聚氰胺与5ml甲醛加入去离子水中，加热至70℃完全溶解，搅拌均匀后，调节溶液pH至2～3，得到由三聚氰胺-甲醛低聚物和三聚氰胺组成的混合物(PHDM)。取50mLPHDM置于100mL聚四氟乙烯内衬的高压反应釜中，180℃下反应20h后烘干，移入马弗炉中以10℃/min的加热速率加热至550℃，在550℃下煅烧2h后，自然冷却至室温备用。所得的煅烧产物与一定浓度刻蚀剂混合，在振荡器内振荡反应24h，分别用去离子水和乙醇洗涤数次，干燥后得到C-g-C3N4。Add 10.0g melamine and 5ml formaldehyde into deionized water, heat to 70°C to completely dissolve, stir evenly, adjust the pH of the solution to 2-3, and obtain a mixture (PHDM) composed of melamine-formaldehyde oligomer and melamine. Take 50mL of PHDM and place it in a 100mL polytetrafluoroethylene-lined high-pressure reactor. React at 180℃ for 20h and then dry. Move to a muffle furnace and heat to 550℃ at a heating rate of 10℃/min. Calculate at 550℃ for 2h. Then, cool to room temperature naturally and set aside. The obtained calcined product was mixed with a certain concentration of etchant, oscillated in a oscillator for 24 hours, washed several times with deionized water and ethanol, and dried to obtain CgC 3 N 4 .
取1.0g C-g-C3N4与10mL 0.15M的Zn(NO3)2混合，搅拌至浆糊状，随后在80℃烘箱中放置12小时烘干水分。固体混合物置于管式炉中，在50mL/min空气气氛下，分别在250℃、350℃、450℃、550℃和650℃煅烧3h，制备成一系列不同条件下的ZnO/C-g-C3N4。Mix 1.0g CgC 3 N 4 with 10mL 0.15M Zn(NO 3 ) 2 , stir until it becomes a paste, and then place it in an 80°C oven for 12 hours to dry the water. The solid mixture was placed in a tube furnace and calcined at 250°C, 350°C, 450°C, 550°C and 650°C for 3 hours respectively in an air atmosphere of 50mL/min to prepare ZnO/CgC 3 N 4 under a series of different conditions.
实施例2Example 2
使用实施例1中不同煅烧温度下制得的ZnO/C-g-C3N4复合光催化剂协同SPC(过碳酸钠)降解TCS的方法，具体过程如下：The ZnO/CgC 3 N 4 composite photocatalyst prepared at different calcination temperatures in Example 1 is used in conjunction with SPC (sodium percarbonate) to degrade TCS. The specific process is as follows:
取一定质量的TCS，室温下以异丙醇为牺牲剂和助溶剂(异丙醇:水＝30％:70％)，配制成1.0mg/L的TCS模拟废水。Take a certain mass of TCS and use isopropyl alcohol as the sacrificial agent and co-solvent (isopropyl alcohol: water = 30%: 70%) at room temperature to prepare 1.0 mg/L TCS simulated wastewater.
将不同煅烧温度下制得的ZnO/C-g-C3N4复合光催化剂以1.0g/L加入100mL模拟废水，SPC的浓度为0.07g/L，置于暗处，在通入氮气的条件下振荡30min达到平衡。以300W氙灯为模拟太阳光光源，磁力搅拌转速设置为300rpm，在氙灯照射下进行光催化协同SPC脱氯反应120min。取反应后模拟废水样品，通过UPLC-MS-MS测定所取样品中TCS的浓度计算TCS去除效率T。Add the ZnO/CgC 3 N 4 composite photocatalyst prepared at different calcination temperatures to 100 mL of simulated wastewater at 1.0 g/L. The concentration of SPC is 0.07 g/L. Place it in a dark place and shake for 30 minutes under the condition of flowing nitrogen. Achieve balance. A 300W xenon lamp was used as the simulated sunlight source, the magnetic stirring speed was set to 300 rpm, and the photocatalytic synergistic SPC dechlorination reaction was carried out under xenon lamp irradiation for 120 min. Take simulated wastewater samples after the reaction, and measure the concentration of TCS in the samples by UPLC-MS-MS to calculate the TCS removal efficiency T.
不同煅烧温度下制得的ZnO/C-g-C3N4复合光催化剂对TCS去除率的结果如图1所示。结果表明，五种不同煅烧条件下制得的材料均表现出良好的脱氯与氧化分解性能；特别是经550℃煅烧后的ZnO/C-g-C3N4复合光催化剂在反应120min后，降解效果最佳，为最佳煅烧温度，相对于其他温度条件具有显著的优益性。The results of the TCS removal rate of ZnO/CgC 3 N 4 composite photocatalysts prepared at different calcination temperatures are shown in Figure 1. The results show that the materials prepared under five different calcination conditions all show good dechlorination and oxidative decomposition properties; especially the ZnO/CgC 3 N 4 composite photocatalyst calcined at 550°C has the best degradation effect after 120 minutes of reaction. It is the optimal calcination temperature and has significant advantages over other temperature conditions.
实施例3Example 3
对不同投加量、不同处理时间情况下使用ZnO/C-g-C3N4复合光催化剂协同SPC降解TCS的效果进行对比，具体过程如下：The effect of using ZnO/CgC 3 N 4 composite photocatalyst to cooperate with SPC to degrade TCS under different dosages and different treatment times was compared. The specific process is as follows:
取一定质量的TCS，室温下以异丙醇为牺牲剂和助溶剂(异丙醇:水＝30％:70％)，配制成1.0mg/L的TCS模拟废水。Take a certain mass of TCS and use isopropyl alcohol as the sacrificial agent and co-solvent (isopropyl alcohol: water = 30%: 70%) at room temperature to prepare 1.0 mg/L TCS simulated wastewater.
将ZnO/C-g-C3N4复合光催化剂以不同初始投加量加入100mL模拟废水，SPC的浓度为0.07g/L，置于暗处，在通入氮气的条件下振荡30min达到平衡。以300W氙灯为模拟太阳光光源，磁力搅拌转速设置为300rpm，在氙灯照射下进行光催化反应。定时取样，通过UPLC-MS-MS测定所取样品中TCS的浓度并计算TCS去除效率T。The ZnO/CgC 3 N 4 composite photocatalyst was added to 100 mL of simulated wastewater at different initial dosages. The concentration of SPC was 0.07g/L. It was placed in a dark place and oscillated for 30 minutes under the condition of nitrogen to reach equilibrium. A 300W xenon lamp was used as the simulated sunlight source, the magnetic stirring speed was set to 300 rpm, and the photocatalytic reaction was carried out under the xenon lamp irradiation. Samples were taken regularly, the concentration of TCS in the samples was measured by UPLC-MS-MS, and the TCS removal efficiency T was calculated.
各投加量下的ZnO/C-g-C3N4复合光催化剂对应的TCS去除率随时间的变化关系如图2所示。结果表明，随着复合催化剂投加量为从0g/L增加至1.0g/L时，SPC的初始投加量不改变，在反应进行120min的过程中，TCS的去除率逐渐增高。同时，在0min至90min内，光催化降解TCS的速率能够保持在较高的水平。当初始投加量增加至2.0g/L时，TCS的去除效率有所降低，最终去除率为90％左右，分析其原因可能为过量的固体材料导致体系中悬浮物浓度过高，影响了复合材料对光照的利用效果。The relationship between the TCS removal rate and time of the ZnO/CgC 3 N 4 composite photocatalyst at each dosage is shown in Figure 2. The results show that as the dosage of composite catalyst increases from 0g/L to 1.0g/L, the initial dosage of SPC does not change, and the removal rate of TCS gradually increases during the reaction for 120 minutes. At the same time, the rate of photocatalytic degradation of TCS can be maintained at a high level from 0 min to 90 min. When the initial dosage is increased to 2.0g/L, the removal efficiency of TCS decreases, and the final removal rate is about 90%. The reason may be that excessive solid materials cause the concentration of suspended solids in the system to be too high, which affects the composite effect. The material's use of light.
实施例3Example 3
检验ZnO/C-g-C3N4复合光催化剂协同SPC降解TCS过程中自由基的产生情况，探究该TCS降解体系中实现快速脱氯和氧化分解的机理，具体过程如下：Examine the generation of free radicals during the degradation of TCS by the ZnO/CgC 3 N 4 composite photocatalyst in collaboration with SPC, and explore the mechanism of rapid dechlorination and oxidative decomposition in the TCS degradation system. The specific process is as follows:
取一定质量的TCS，室温下以异丙醇为牺牲剂和助溶剂(异丙醇:水＝30％:70％)，配制成1.0mg/L的TCS模拟废水。Take a certain mass of TCS and use isopropyl alcohol as the sacrificial agent and co-solvent (isopropyl alcohol: water = 30%: 70%) at room temperature to prepare 1.0 mg/L TCS simulated wastewater.
分别加入光催化剂及SPC母液，使各模拟废水中光催化剂的浓度为1.0g/L，SPC的浓度为0.07g/L，置于暗处，在通入氮气的条件下振荡30min达到平衡。以300W氙灯为模拟太阳光光源，磁力搅拌转速设置为300rpm，在氙灯照射下进行协同脱氯反应120min。取反应后模拟废水样品，测定ZnO/C-g-C3N4复合光催化剂协同SPC体系的电子自旋共振(ESR)谱。Add photocatalyst and SPC mother liquor respectively so that the concentration of photocatalyst in each simulated wastewater is 1.0g/L and the concentration of SPC is 0.07g/L. Place in a dark place and oscillate for 30 minutes under the condition of nitrogen to reach equilibrium. A 300W xenon lamp was used as the simulated sunlight source, the magnetic stirring speed was set to 300 rpm, and the collaborative dechlorination reaction was carried out under xenon lamp irradiation for 120 min. Take the simulated wastewater sample after the reaction and measure the electron spin resonance (ESR) spectrum of the ZnO/CgC 3 N 4 composite photocatalyst cooperative SPC system.
ZnO/C-g-C3N4复合光催化剂协同过碳酸盐体系降解TCS过程中产生羟基自由基(·OH)的ESR谱如图3所示。通过ESR光谱进一步鉴定了·OH生成，在暗条件下没有发现特征峰，而在可见光照射下的ZnO/C-g-C3N4复合光催化剂协同过碳酸盐体系则检测到·OH的特征ESR信号，表明该体系在降解TCS过程中产生大量·OH，揭示了反应机理。The ESR spectrum of hydroxyl radicals (·OH) generated during the degradation of TCS by the ZnO/CgC 3 N 4 composite photocatalyst in collaboration with the percarbonate system is shown in Figure 3. The generation of ·OH was further identified through ESR spectrum. No characteristic peak was found under dark conditions. However, the characteristic ESR signal of ·OH was detected by the ZnO/CgC 3 N 4 composite photocatalyst synergistic percarbonate system under visible light irradiation. It shows that this system produces a large amount of ·OH during the degradation of TCS, revealing the reaction mechanism.
对比例1Comparative example 1
分别使用仅光照的体系1、单独利用SPC的体系2(仅加入SPC并光照)、仅利用ZnO/C-g-C3N4光催化的体系3(仅加入550℃煅烧得到的ZnO/C-g-C3N4光催化剂并光照)降解TCS体系。具体过程如下：System 1 using only illumination, system 2 using SPC alone (only adding SPC and lighting), and system 3 using only ZnO/CgC 3 N 4 photocatalysis (only adding ZnO/CgC 3 N 4 light obtained by calcining at 550°C) were used respectively. Catalyst and light) degrade the TCS system. The specific process is as follows:
取一定质量的TCS，室温下以异丙醇为牺牲剂和助溶剂(异丙醇:水＝30％:70％)，配制成1.0mg/L的TCS模拟废水。以上述3个处理体系，分别加入SPC母液；体系2中加入光催化剂，使得光催化剂的浓度为1.0g/L；体系3中加入SPC，使得SPC的浓度为0.07g/L；三个体系均置于暗处，在通入氮气的条件下振荡30min达到平衡。之后，以300W氙灯为模拟太阳光光源，磁力搅拌转速设置为300rpm，在氙灯照射下进行对三个体系分别进行脱氯反应120min。取反应后模拟废水样品，通过UPLC-MS-MS测定所取样品中TCS浓度的计算TCS去除效率T。Take a certain mass of TCS and use isopropyl alcohol as the sacrificial agent and co-solvent (isopropyl alcohol: water = 30%: 70%) at room temperature to prepare 1.0 mg/L TCS simulated wastewater. With the above three treatment systems, SPC mother liquor was added respectively; photocatalyst was added to system 2 so that the concentration of photocatalyst was 1.0g/L; SPC was added to system 3 so that the concentration of SPC was 0.07g/L; all three systems were Place in a dark place and shake for 30 minutes to reach equilibrium under the condition of nitrogen gas. Afterwards, a 300W xenon lamp was used as the simulated sunlight source, the magnetic stirring speed was set to 300 rpm, and the dechlorination reactions of the three systems were carried out under xenon lamp irradiation for 120 min. Take the simulated wastewater sample after the reaction, and measure the TCS concentration in the sample by UPLC-MS-MS to calculate the TCS removal efficiency T.
TCS去除率T通过测量实验前后模拟废水的TCS含量计算得到，具体计算公式如下：The TCS removal rate T is calculated by measuring the TCS content of the simulated wastewater before and after the experiment. The specific calculation formula is as follows:
其中，C0为模拟废水中的初始TCS浓度；C1为模拟废水在反应后的TCS浓度。Among them, C 0 is the initial TCS concentration in the simulated wastewater; C 1 is the TCS concentration of the simulated wastewater after the reaction.
实施例2(使用550℃煅烧得到的复合光催化剂进行处理)与本对比例中三个体系所得到的TCS去除率结果如图1所示，结果表明相比于单独利用SPC体系和ZnO/C-g-C3N4光催化体系，将二者协同的新型脱氯体系在相同时间内显著提高了TCS的降解效率；其中，光催化协同SPC体系在反应进行120min后，TCS去除率可达98％以上，去除效果最佳，且远高于体系1和2在相同处理条件下TCS去除率的加和，展现出ZnO/C-g-C3N4光催化协同SPC体系的显著高效性。该体系将ZnO/C-g-C3N4光催化剂本身优秀的稳定性、光催化性与SPC活化工艺有效结合，通过快速产生大量羟基自由基实现TCS的高效脱氯与氧化分解。The TCS removal rate results obtained by the three systems in Example 2 (processed using a composite photocatalyst calcined at 550°C) and this comparative example are shown in Figure 1. The results show that compared with the SPC system and ZnO/CgC alone 3 N 4 photocatalytic system, a new dechlorination system that synergizes the two, significantly improves the degradation efficiency of TCS in the same time; among them, the photocatalytic synergistic SPC system can achieve a TCS removal rate of more than 98% after 120 minutes of reaction. The removal effect is the best and is much higher than the sum of the TCS removal rates of systems 1 and 2 under the same treatment conditions, demonstrating the significant efficiency of the ZnO/CgC 3 N 4 photocatalytic synergistic SPC system. This system effectively combines the excellent stability and photocatalytic properties of the ZnO/CgC 3 N 4 photocatalyst with the SPC activation process to achieve efficient dechlorination and oxidative decomposition of TCS by rapidly generating a large amount of hydroxyl radicals.
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