CN106966466A - A kind of method of utilization cupric oxide ceria Electrocatalysis Degradation phenol - Google Patents
A kind of method of utilization cupric oxide ceria Electrocatalysis Degradation phenol Download PDFInfo
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000015556 catabolic process Effects 0.000 title claims abstract description 25
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title description 15
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title description 3
- 229960004643 cupric oxide Drugs 0.000 title 1
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000005273 aeration Methods 0.000 claims abstract description 7
- 230000000593 degrading effect Effects 0.000 claims abstract description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 238000004458 analytical method Methods 0.000 claims 1
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 20
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种利用CuO‑CeO2电催化降解苯酚的方法。该方法采用CuO‑CeO2电极作为阴极、石墨片作为阳极、饱和甘汞电极作为参比电极构成三电极体系，苯酚溶液作为电解液，加入硫酸钠电解质，通电流，曝气环境下，电降解处理苯酚。所述方法利用CuO‑CeO2阴极原位产生过氧化氢，过程简便、环境友好、降解效率较高。本发明使用电化学催化氧化技术降解苯酚，避免了传统方法中产生的二次污染，因其成本低、操作简单、环境友好、快速高效，使得该方法在处理有机废水中拥有广阔的前景。
The invention relates to a method for electrocatalytically degrading phenol by using CuO -CeO2. The method uses CuO-CeO 2 electrode as cathode, graphite sheet as anode, saturated calomel electrode as reference electrode to form a three-electrode system, phenol solution as electrolyte, sodium sulfate electrolyte is added, current is passed, and under aeration environment, electrodegradation Handling of phenol. The method utilizes a CuO -CeO2 cathode to generate hydrogen peroxide in situ, and the process is simple, environmentally friendly and has high degradation efficiency. The invention uses the electrochemical catalytic oxidation technology to degrade phenol, avoiding the secondary pollution produced in the traditional method, and because of its low cost, simple operation, environmental friendliness, rapidity and high efficiency, the method has broad prospects in the treatment of organic wastewater.
Description
技术领域technical field
本发明属于电化学降解有机废水处理领域，具体涉及一种利用CuO-CeO2电催化降解苯酚的方法。The invention belongs to the field of electrochemical degradation organic wastewater treatment, and in particular relates to a method for electrocatalytically degrading phenol by using CuO -CeO2.
背景技术Background technique
近年来，随着我国工业的快速发展，随之而来的工业废水的排放在日益增多，不可避免地对环境造成的严重污染，且严重危害人类健康。酚类废水是常见工业废水中最重要的一类，也是危害最大、污染范围最广的难降解有机废水之一，被我国水污染控制列为重点解决的有害废水之一，主要来源于石油化工厂、煤气厂、焦化厂、绝缘材料厂等工业企业。对于酚类难降解有机废水的降解，我国已工业化投入使用的传统的降解方法主要有物理法、化学法和生物法等。但这些传统的技术有些只能使污染物转移，产生严重的二次污染；有些适应性差，当污染物浓度过高或过低时往往无能为力。因此，必须尽快采取切实可行的措施对存在的和潜在的环境污染和环境危害因子加以有效的治理。随着研究的深入，高级电催化氧化技术应运而生，逐渐受到研究者的青睐，已有显著的进展。In recent years, with the rapid development of my country's industry, the subsequent discharge of industrial wastewater is increasing, which inevitably causes serious pollution to the environment and seriously endangers human health. Phenolic wastewater is the most important type of common industrial wastewater. It is also one of the most harmful and most polluting refractory organic wastewater. It is listed as one of the key harmful wastewater by my country's water pollution control. It mainly comes from petrochemical industry. Plants, gas plants, coking plants, insulating material plants and other industrial enterprises. For the degradation of phenolic refractory organic wastewater, the traditional degradation methods that have been put into industrial use in my country mainly include physical, chemical and biological methods. However, some of these traditional technologies can only transfer pollutants and cause serious secondary pollution; some have poor adaptability, and are often powerless when the concentration of pollutants is too high or too low. Therefore, practical measures must be taken as soon as possible to effectively control the existing and potential environmental pollution and environmental hazards. With the deepening of research, advanced electrocatalytic oxidation technology has emerged as the times require, and has gradually been favored by researchers, and has made significant progress.
电化学氧化技术原理是利用具有催化性能的金属或金属氧化物电极，在通电条件下，在电极表面直接或者间接地产生过氧化氢、羟基自由基等强氧化性物质，直接与废水中的有机污染物反应，将其降解为二氧化碳、水和简单的有机物，避免二次污染。电催化氧化技术是一种环境友好的高级氧化技术，正在取代传统方法，成为处理苯酚废水的一种有效手段。电催化氧化技术分为阳极氧化和阴极还原两种方法。阳极氧化是利用阳极发生氧化反应而使有机污染物转化为无害的物质；而阴极还原是利用阴极发生氧气还原反应生成具有氧化活性的过氧化氢或进一步转化为羟基自由基，对有机污染物进行氧化处理。目前，对于阳极的研究较为成熟，阴极材料的研究较少。据文献报道，使用较多的阴极材料主要是碳材料，但是生成过氧化氢的浓度不高。因此，选择正确有效的阴极材料，提高氧气的利用率，增强氧气的二电子还原反应生成过氧化氢至关重要。The principle of electrochemical oxidation technology is to use a metal or metal oxide electrode with catalytic properties to directly or indirectly generate strong oxidizing substances such as hydrogen peroxide and hydroxyl radicals on the surface of the electrode under the condition of electricity, and directly react with organic substances in wastewater. Pollutants react and degrade them into carbon dioxide, water and simple organic matter, avoiding secondary pollution. Electrocatalytic oxidation technology is an environmentally friendly advanced oxidation technology, which is replacing traditional methods and becoming an effective means of treating phenol wastewater. Electrocatalytic oxidation technology is divided into two methods: anodic oxidation and cathodic reduction. Anodic oxidation is to use the oxidation reaction at the anode to convert organic pollutants into harmless substances; while cathodic reduction is to use the oxygen reduction reaction at the cathode to generate hydrogen peroxide with oxidative activity or further convert it into hydroxyl radicals. Oxidation treatment is carried out. At present, the research on the anode is more mature, and the research on the cathode material is less. According to literature reports, the most widely used cathode materials are mainly carbon materials, but the concentration of hydrogen peroxide is not high. Therefore, it is very important to select the correct and effective cathode materials, improve the utilization rate of oxygen, and enhance the two-electron reduction reaction of oxygen to generate hydrogen peroxide.
贵金属催化剂是首选阴极材料，其具有较好的电催化活性，但由于其价格昂贵，使得其在废水处理领域受到限制。近年来，金属氧化物材料备受研究者们的关注。CuO-CeO2是一种高稳定性、高活性的一种新型催化剂。由于二氧化铈较强的氧化还原能力和储氧释氧能力，以及二氧化铈与氧化铜之间较强的相互作用，使得CuO-CeO2复合催化剂具有较高的催化活性，且该催化剂能够促进氧气的二电子还原反应产生过氧化氢。目前，将CuO-CeO2复合催化剂作为阴极材料，进行电化学降解苯酚废水的研究尚未有报道。Noble metal catalyst is the preferred cathode material, which has good electrocatalytic activity, but its high price limits its application in the field of wastewater treatment. In recent years, metal oxide materials have attracted the attention of researchers. CuO-CeO 2 is a new catalyst with high stability and high activity. Due to the strong redox ability, oxygen storage and release ability of ceria, and the strong interaction between ceria and copper oxide, the CuO-CeO 2 composite catalyst has a high catalytic activity, and the catalyst can Facilitates the two-electron reduction of oxygen to produce hydrogen peroxide. At present, there is no report on the electrochemical degradation of phenol wastewater using CuO-CeO 2 composite catalyst as cathode material.
发明内容Contents of the invention
本发明的目的是提供一种利用CuO-CeO2电催化氧化降解苯酚的方法，操作简单、效率高、环境友好，避免了传统方法带来的二次污染。该方法使用CuO-CeO2电极作为阴极，石墨片作为阳极，饱和甘汞电极作为参比电极，构成电解池，电化学降解苯酚。The purpose of the present invention is to provide a method for electrocatalytic oxidation degradation of phenol using CuO -CeO2, which is simple in operation, high in efficiency and environment-friendly, and avoids secondary pollution caused by traditional methods. The method uses CuO -CeO2 electrode as cathode, graphite sheet as anode, and saturated calomel electrode as reference electrode to constitute an electrolytic cell to electrochemically degrade phenol.
一种利用CuO-CeO2电催化降解苯酚的方法，CuO-CeO2电极作为阴极、石墨片作为阳极、饱和甘汞电极作为参比电极构成三电极体系，苯酚溶液作为电解液，加入电解质，通电流，曝气环境下，电降解处理苯酚。A method for electrocatalytically degrading phenol by using CuO -CeO2. The CuO -CeO2 electrode is used as the cathode, the graphite sheet is used as the anode, and the saturated calomel electrode is used as the reference electrode to form a three-electrode system. The phenol solution is used as the electrolyte. Electrodegradation of phenol under electric current and aeration environment.
进一步的，所述的CuO-CeO2电极的制备方法为：1)采取溶胶凝胶法制备催化剂CuO-CeO2：按Cu(NO3)2·3H2O与Ce(NO3)3·6H2O摩尔比为(1:10)-(3:1)的比例分别溶于2-10mL去离子水中，超声搅拌至完全溶解，将二者混合于圆底烧瓶中，置于40-100℃恒温水浴锅中搅拌10-30min，然后按硝酸铈与柠檬酸摩尔比为(1:1)-(1:5)的比例加入柠檬酸，继续搅拌加热至凝胶状，取出置于60-120℃烘箱干燥8-12h，再在300-800℃马弗炉中煅烧1-5h，得到催化剂CuO-CeO2；2)将50-100mg催化剂CuO-CeO2与8-15mg炭黑，5-15μL的浓度为10-60wt％的PTFE溶液分散于2-8mL无水乙醇中，然后均匀滴在泡沫镍上，80-110℃烘干，压片，置于200-300℃的马弗炉中煅烧0.5-2h，即制作成CuO-CeO2电极。Further, the preparation method of the CuO-CeO 2 electrode is as follows: 1) The catalyst CuO-CeO 2 is prepared by the sol-gel method: Cu(NO 3 ) 2 ·3H 2 O and Ce(NO 3 ) 3 ·6H The 2 O molar ratio is (1:10)-(3:1) respectively dissolved in 2-10mL deionized water, stirred ultrasonically until completely dissolved, mixed the two in a round-bottomed flask, and placed at 40-100°C Stir in a constant temperature water bath for 10-30min, then add citric acid according to the molar ratio of cerium nitrate to citric acid (1:1)-(1:5), continue to stir and heat until gel, take it out and place it in 60-120 ℃ oven drying for 8-12 hours, and then calcined in a muffle furnace at 300-800 ℃ for 1-5 hours to obtain the catalyst CuO-CeO 2 ; 2) mix 50-100mg catalyst CuO-CeO 2 with 8-15mg carbon black, The PTFE solution with a concentration of 10-60wt% is dispersed in 2-8mL of absolute ethanol, and then evenly dropped on the nickel foam, dried at 80-110°C, pressed into tablets, and calcined in a muffle furnace at 200-300°C 0.5-2h, that is, it is made into CuO-CeO 2 electrode.
进一步的，所述苯酚溶液浓度为25-300mg/L，优选100mg/L，体积100mL。Further, the concentration of the phenol solution is 25-300mg/L, preferably 100mg/L, and the volume is 100mL.
进一步的，所述电解质是浓度为0.01-1mol/L的硫酸钠溶液，优选0.1mol/L，加入体积为10-30mL。Further, the electrolyte is a sodium sulfate solution with a concentration of 0.01-1 mol/L, preferably 0.1 mol/L, and the added volume is 10-30 mL.
进一步的，电流密度为10-60mA/cm2，优选40mA/cm2；pH值范围为1-13，优选7。Further, the current density is 10-60mA/cm 2 , preferably 40mA/cm 2 ; the pH range is 1-13, preferably 7.
进一步的，所述泡沫镍的大小为2cm*2cm。Further, the size of the nickel foam is 2cm*2cm.
进一步的，调节pH值使用硫酸或氢氧化钠。Further, sulfuric acid or sodium hydroxide is used to adjust the pH value.
使用高效液相色谱分析上述方法的苯酚降解率，C18柱，甲醇：水的体积比为3:7，波长为270nm，柱温25℃，流速为1mL/min，保留时间6min。Use high performance liquid chromatography to analyze the phenol degradation rate of the above method, C18 column, methanol: water volume ratio is 3:7, wavelength is 270nm, column temperature is 25°C, flow rate is 1mL/min, retention time is 6min.
本发明的有益技术效果：采用了CuO-CeO2催化剂作为阴极电极，采用三电极体系，在曝气下，通过控制苯酚的初始浓度、电解质硫酸钠的浓度、pH值、电解的电流密度等，利用阴极发生氧气还原反应生成的过氧化氢，进一步实现了对苯酚的有效降解。本发明中的不需要外加过氧化氢，利用CuO-CeO2催化剂阴极原位产生过氧化氢，避免了过氧化氢的运输问题，操作简单、反应条件温和、环境友好，降解效率高，达91％以上，在废水处理领域具有良好的发展前景。Beneficial technical effect of the present invention: adopt CuO -CeO catalyzer as cathode electrode, adopt three-electrode system, under aeration, by controlling the initial concentration of phenol, the concentration of electrolyte sodium sulfate, pH value, the current density of electrolysis etc., The hydrogen peroxide generated by the oxygen reduction reaction at the cathode is used to further realize the effective degradation of phenol. In the present invention, hydrogen peroxide does not need to be added, and hydrogen peroxide is generated in situ by the cathode of CuO -CeO2 catalyst, which avoids the transportation problem of hydrogen peroxide, and has simple operation, mild reaction conditions, environmental friendliness, and high degradation efficiency of up to 91 More than %, it has a good development prospect in the field of wastewater treatment.
附图说明Description of drawings
图1是实施例1苯酚的初始浓度对苯酚去除率的影响示意图。Figure 1 is a schematic diagram of the influence of the initial concentration of phenol in Example 1 on the removal rate of phenol.
图2是实施例2电解质浓度对苯酚去除率的影响示意图。Figure 2 is a schematic diagram of the influence of the electrolyte concentration on the removal rate of phenol in Example 2.
图3是实施例3pH值对苯酚去除率的影响示意图。Fig. 3 is the schematic diagram of the effect of pH value on the removal rate of phenol in Example 3.
图4是实施例4电流密度对苯酚去除率的影响示意图。Figure 4 is a schematic diagram of the influence of current density on the removal rate of phenol in Example 4.
具体实施方式detailed description
为让本发明之上述和其他目的、特征、和优点能更明显易懂，下文特举出较佳实施例及对比例，并配合所附图式，作详细说明如下，但本发明的实施方式不限于此。In order to make the above-mentioned and other purposes, features, and advantages of the present invention more clearly and easily understood, the preferred embodiments and comparative examples are enumerated below, together with the accompanying drawings, and described in detail as follows, but the embodiment of the present invention It is not limited to this.
实施例1Example 1
采用三电极体系，参比电极为饱和甘汞电极，阴极为自制CuO-CeO2电极，阳极为石墨电极，阴阳两极电极大小均为2cm*2cm，电极间距2cm，分别取浓度为25，50，100，200和300mg/L苯酚溶液100mL于烧杯中，加入电解质0.1mol/L的Na2SO4溶液20mL，调溶液成中性，电流密度为40mA/cm2，持续曝气，使溶液处于氧气饱和状态，室温下电降解时间180min，每隔20min取样，通过高效液相色谱测定苯酚的降解情况。A three-electrode system is adopted, the reference electrode is a saturated calomel electrode, the cathode is a self-made CuO -CeO2 electrode, the anode is a graphite electrode, the size of the cathode and anode electrodes is 2cm*2cm, and the electrode spacing is 2cm. The concentrations are respectively 25, 50, Put 100mL of 100, 200 and 300mg/L phenol solution in a beaker, add 20mL of Na 2 SO 4 solution with 0.1mol/L electrolyte, adjust the solution to be neutral, set the current density to 40mA/cm 2 , and keep aerating to make the solution in oxygen Saturation state, the electrolytic degradation time at room temperature is 180min, samples are taken every 20min, and the degradation of phenol is determined by high performance liquid chromatography.
所述的CuO-CeO2电极的制备方法为：1)采取溶胶凝胶法制备催化剂CuO-CeO2：按Cu(NO3)2·3H2O与Ce(NO3)3·6H2O按摩尔比1:1的比例分别溶于5mL去离子水中，超声搅拌至完全溶解，将二者混合于圆底烧瓶中，置于80℃恒温水浴锅中搅拌20min，然后按硝酸铈与柠檬酸摩尔比为1:3的比例加入柠檬酸，继续搅拌加热至凝胶状，取出置于100℃烘箱干燥10h，再在500℃马弗炉中煅烧4h，得到催化剂CuO-CeO2；2)将50mg催化剂CuO-CeO2与10mg炭黑，10μL浓度为10wt％的PTFE溶液分散于4mL无水乙醇中，然后均匀滴在泡沫镍上，100℃烘干，压片，置于300℃的马弗炉中煅烧1h，即制作成CuO-CeO2电极。The preparation method of the CuO-CeO 2 electrode is as follows: 1) Prepare the catalyst CuO-CeO 2 by sol-gel method: massaging Cu(NO 3 ) 2 3H 2 O and Ce(NO 3 ) 3 6H 2 O Dissolve in 5mL deionized water at a molar ratio of 1:1, stir ultrasonically until completely dissolved, mix the two in a round bottom flask, place them in a constant temperature water bath at 80°C and stir for 20min, then Add citric acid at a ratio of 1:3, continue to stir and heat until it becomes gelatinous, take it out and place it in an oven at 100°C for 10 hours, and then calcinate it in a muffle furnace at 500°C for 4 hours to obtain the catalyst CuO-CeO 2 ; 2) 50 mg Catalyst CuO-CeO 2 and 10mg carbon black, 10μL PTFE solution with a concentration of 10wt% were dispersed in 4mL of absolute ethanol, and then evenly dropped on the foamed nickel, dried at 100°C, pressed into tablets, and placed in a muffle furnace at 300°C Calcined for 1h, that is, made into CuO-CeO 2 electrodes.
实施例2Example 2
采用三电极体系，参比电极为饱和甘汞电极，阴极为实施例1制得的CuO-CeO2电极，阳极为石墨电极，阴阳两极电极大小均为2cm*2cm，电极间距2cm，分别取100mg/L苯酚溶液100mL于烧杯中，分别加入电解质0.01，0.05,0.1，0.5和1mol/L的Na2SO4溶液20mL体积，调溶液成中性，电流密度为40mA/cm2，持续曝气，使溶液处于氧气饱和状态，室温下电降解时间180min，每隔20min取样，通过高效液相色谱测定苯酚的降解情况。Adopt a three-electrode system, the reference electrode is a saturated calomel electrode, the cathode is the CuO -CeO electrode prepared in Example 1, the anode is a graphite electrode, the size of the cathode and anode electrodes is 2cm*2cm, and the electrode spacing is 2cm, take 100mg respectively /L phenol solution 100mL in a beaker, respectively add electrolyte 0.01, 0.05, 0.1, 0.5 and 1mol/L Na 2 SO 4 solution 20mL volume, adjust the solution to be neutral, the current density is 40mA/cm 2 , continuous aeration, The solution was saturated with oxygen, and the electrolysis time was 180 minutes at room temperature. Samples were taken every 20 minutes, and the degradation of phenol was determined by high performance liquid chromatography.
实施例3Example 3
采用三电极体系，参比电极为饱和甘汞电极，阴极为实施例1制得的CuO-CeO2电极，阳极为石墨电极，阴阳两极电极大小均为2cm*2cm，电极间距2cm，分别取浓度为100mg/L苯酚溶液100mL于烧杯中，加入电解质0.1mol/L的Na2SO4溶液20mL，电流密度为40mA/cm2，用稀硫酸或氢氧化钠调节pH值分别为1，3，5，7，10和13，持续曝气，使溶液处于氧气饱和环境下，室温下电降解时间180min，每隔20min取样，通过高效液相色谱测定苯酚的降解情况。Adopt a three-electrode system, the reference electrode is a saturated calomel electrode, the cathode is the CuO -CeO electrode prepared in Example 1, the anode is a graphite electrode, the size of the cathode and anode electrodes is 2cm*2cm, and the electrode spacing is 2cm. Put 100mL of 100mg/L phenol solution in a beaker, add 20mL of electrolyte 0.1mol/L Na 2 SO 4 solution, the current density is 40mA/cm 2 , adjust the pH value to 1, 3, 5 respectively with dilute sulfuric acid or sodium hydroxide , 7, 10 and 13, continuous aeration, so that the solution is in an oxygen-saturated environment, the electrolytic degradation time is 180min at room temperature, sampling every 20min, and the degradation of phenol is determined by high performance liquid chromatography.
实施例4Example 4
采用三电极体系，参比电极为饱和甘汞电极，阴极为实施例1制得的CuO-CeO2电极，阳极为石墨电极，阴阳两极电极大小均为2cm*2cm，电极间距2cm，分别取浓度为100mg/L苯酚溶液100mL于烧杯中，加入电解质0.1mol/L的Na2SO4溶液20mL，调溶液成中性，电流密度分别为10，20，30，40，50和60mA/cm2，持续曝气，使溶液处于氧气饱和状态，室温下电降解时间180min，每隔20min取样，通过高效液相色谱测定苯酚的降解情况。Adopt a three-electrode system, the reference electrode is a saturated calomel electrode, the cathode is the CuO -CeO electrode prepared in Example 1, the anode is a graphite electrode, the size of the cathode and anode electrodes is 2cm*2cm, and the electrode spacing is 2cm. Put 100mL of 100mg/L phenol solution in a beaker, add 20mL of electrolyte 0.1mol/L Na 2 SO 4 solution, adjust the solution to be neutral, and the current densities are 10, 20, 30, 40, 50 and 60mA/cm 2 , The aeration was continued to make the solution saturated with oxygen, and the electrolytic degradation time was 180 minutes at room temperature. Samples were taken every 20 minutes, and the degradation of phenol was determined by high performance liquid chromatography.
本发明披露的利用CuO-CeO2电催化降解苯酚的方法，过程简便、环境友好、降解效率较高。本发明使用电化学催化氧化技术降解苯酚，避免了传统方法中产生的二次污染，因其成本低、操作简单、环境友好、快速高效，使得该方法在处理有机废水中拥有广阔的前景。The method for electrocatalytically degrading phenol by using CuO -CeO2 disclosed in the present invention has the advantages of simple process, environmental friendliness and high degradation efficiency. The invention uses the electrochemical catalytic oxidation technology to degrade phenol, avoiding the secondary pollution produced in the traditional method, and because of its low cost, simple operation, environmental friendliness, rapidity and high efficiency, the method has broad prospects in the treatment of organic wastewater.
可以理解的是，以上是为了阐述本发明的原理和可实施性的示例，本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本发明的保护范围。It can be understood that the above is an example for explaining the principles and practicability of the present invention, and the present invention is not limited thereto. For those skilled in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also regarded as the protection scope of the present invention.
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