CN107739074B - Preparation method of nitrogen-doped graphene composite cathode with high catalytic activity and technology for degrading organic pollutants - Google Patents
Preparation method of nitrogen-doped graphene composite cathode with high catalytic activity and technology for degrading organic pollutants Download PDFInfo
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- CN107739074B CN107739074B CN201710815000.0A CN201710815000A CN107739074B CN 107739074 B CN107739074 B CN 107739074B CN 201710815000 A CN201710815000 A CN 201710815000A CN 107739074 B CN107739074 B CN 107739074B
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a preparation method of a nitrogen-doped graphene composite cathode with high catalytic activity and a technology for degrading organic pollutants. According to the invention, graphene prepared by electrochemical stripping is used as a carbon source, ammonium nitrate is used as a nitrogen source, nitrogen-doped graphene is prepared by a low-temperature calcination method, and the nitrogen-doped graphene, carbon black, polytetrafluoroethylene and the like are uniformly coated on a graphite felt electrode after being mixed according to a certain proportion, and then the composite cathode is obtained by calcination. Using DSA or metal oxide high oxygen evolution potential electrode as anode, degrading organic pollutant at voltage of 2.5-5V and aeration amount of 0.5-1L/min. The nitrogen-doped graphene provided by the invention can effectively improve the capability of the graphene for catalyzing hydrogen peroxide to generate hydroxyl radicals in situ. Compared with the traditional electro-Fenton technology, the method can effectively enlarge the pH application range and avoid the secondary pollution of the iron mud. In addition, the technology does not need to add oxidants such as hydrogen peroxide and the like, and the catalytic activity is easy to regenerate, so that the technology is a novel efficient, energy-saving, green and environment-friendly organic pollutant treatment technology.
Description
Technical Field
The invention belongs to the technical field of environmental engineering, and mainly relates to a preparation method of a nitrogen-doped graphene composite cathode with high catalytic activity and a pollutant degradation technology thereof.
Background
Electrochemical advanced oxidation technologies (EAOPs) are processes for degrading organic pollutants by generating radicals with strong oxidizing properties. Among them, the electro-Fenton technology is developed rapidly in recent years, and the treatment effect on the organic pollutants difficult to degrade is obvious by using a common electrochemical advanced oxidation technology. The technique is based on the reduction of molecular oxygen to hydrogen peroxide (H) at the cathode2O2) And reacts with added ferrous ions to generate hydroxyl radicals with strong oxidizing property, thereby realizing the process of degrading organic pollutants, and the reaction is as follows:
the research for developing cathode materials capable of efficiently generating hydrogen peroxide becomes a great research hotspot in the direction. But at the same time, the narrow pH applicability (2.5-3.5) and the secondary pollution of the iron mud become two major restrictive factors of the development of the traditional electro-Fenton technology. In recent years it has become possible to use,various carbon materials such as activated carbon, graphite felt, graphene and the like are reported to have excitation and addition of H2O2The reagent generates hydroxyl radicals to degrade the contaminants. Therefore, a carbon material cathode capable of efficiently producing hydrogen peroxide is developed, and H generated in situ by the carbon material cathode can be excited by the carbon material cathode2O2The method can generate hydroxyl free radicals, thereby forming a metal-free electrochemical advanced oxidation technology, is expected to realize the degradation of organic pollutants and simultaneously effectively overcome the defects of the traditional electro-Fenton technology, is an efficient, low-consumption, green and environment-friendly organic pollutant reduction technology, and has important significance for promoting the practical application of the treatment of refractory organic pollutants.
Disclosure of Invention
The invention aims to provide a method for preparing a nitrogen-doped graphene composite cathode with high catalytic activity and degrading pollutants by the nitrogen-doped graphene composite cathode, aiming at the defects of narrow pH applicability and secondary pollution of iron mud in the traditional electro-Fenton technology. The method comprises the steps of mixing graphene prepared by electrochemical stripping as a carbon source and ammonium nitrate as a nitrogen source according to the mass ratio of 1:1-1:10, calcining for 0.5-2h under the protection of nitrogen at the temperature of 300-400 ℃, cooling, washing, vacuum-filtering, and drying at the temperature of 55 ℃; mixing the nitrogen-doped graphene prepared by the method with carbon black according to the mass ratio of 1:1-1:5, adding 0.3-0.6 mL of polytetrafluoroethylene, 1-2 mL of ethanol and 1-2 mL of deionized water, shaking and mixing, uniformly coating the mixture on two sides of a graphite felt electrode pretreated by an acetone solution, and calcining the mixture at 360 ℃ for 30-40 min. Further, the nitrogen-doped graphene composite cathode prepared by the method is used as a cathode, a metal oxide high oxygen evolution potential electrode is used as an anode, the working voltage is controlled to be 2.5-5V, and the aeration amount is controlled to be 0.5-1L/min, so that organic pollutants are degraded.
The invention has the following outstanding characteristics and excellent effects:
(1) according to the method, the nitrogen-doped graphene can be obtained by taking ammonium nitrate as a nitrogen source and graphene prepared by electrochemical stripping as a carbon source and calcining at low temperature, and the preparation method is simple, low in consumption and environment-friendly;
(2) the nitrogen doping can effectively improve the capability of graphene for catalyzing and exciting hydrogen peroxide to generate hydroxyl radicals in situ without influencing the effect of efficiently generating hydrogen peroxide by a graphene cathode, so that the degradation rate of organic pollutants is greatly improved;
(3) the developed in-situ nonmetal electrochemical advanced oxidation technology has better organic pollutant degradation effect under both acidic and neutral conditions, and compared with the traditional electro-Fenton technology, the pH application range can be effectively enlarged, and secondary pollution of iron mud is avoided;
(4) the in-situ nonmetal electrochemical advanced oxidation technology does not need to add oxidants such as hydrogen peroxide and the like, has easy regeneration of catalytic activity, is a novel high-efficiency, energy-saving, green and environment-friendly organic pollutant treatment technology, and has wide application prospect.
Drawings
FIG. 1 is a comparison of hydroxyl radical production in an electrochemical advanced oxidation process for a nitrogen-doped graphene composite cathode (N-EEGr-GF) and a nitrogen-undoped graphene composite cathode (EEGr-GF);
FIG. 2 is a graph showing the comparison of the in-situ non-metal electrochemical advanced oxidation (in-situ metal free EAOPs) and the conventional electro-Fenton (EEGr-GE EF) technologies for contaminant removal at different pH values;
FIG. 3 shows the recycling stability of the in-situ non-metal electrochemical advanced oxidation technique.
Detailed Description
The present invention is further described in detail by the following examples in conjunction with the accompanying drawings.
FIG. 1 is a graph showing the comparison of hydroxyl radical production in the electrochemical advanced oxidation process of a nitrogen-doped graphene composite cathode (N-EEGr-GF) and an undoped nitrogen graphene composite cathode (EEGr-GF). As can be seen, the concentration of radicals generated by the N-EEGr-GF increases gradually with time, but the concentration of radicals generated by the N-EEGr-GF is twice as high as that of the radicals generated by the N-EEGr-GF.
FIG. 2 shows a comparison of the in-situ non-metal electrochemical advanced oxidation technique with the cathode of N-EEGr-GF and the conventional electro-Fenton technique with the cathode of EEGr-GE. When the pH =3, the difference between the two is not great, and the organic phenol can be completely degraded in 50 min; however, at pH =7, the in-situ non-metal electrochemical advanced oxidation technique has an organic removal rate more than 2 times that of electro-fenton and a removal rate 5 times that of the latter, which is a significant advantage.
FIG. 3 shows the recycling stability of the in-situ non-metal electrochemical advanced oxidation technique. The electrodes were regenerated with ethanol and run continuously for 5 times. The yield of hydrogen peroxide and the removal rate of organic matters are only slightly fluctuated, which shows that the nitrogen-doped graphene composite cathode electrode has better reusability.
Claims (2)
1. A preparation method of a nitrogen-doped graphene composite cathode with high catalytic activity is characterized by comprising the following steps:
(1) preparing nitrogen-doped graphene: mixing graphene prepared by electrochemical stripping as a carbon source and ammonium nitrate as a nitrogen source according to the mass ratio of 1:1-1:10, calcining for 0.5-2h under the protection of nitrogen at the temperature of 300-;
(2) preparing a nitrogen-doped graphene composite electrode: mixing the nitrogen-doped graphene prepared by the method with carbon black according to the mass ratio of 1:1-1:5, adding 0.3-0.6 mL of polytetrafluoroethylene, 1-2 mL of ethanol and 1-2 mL of deionized water, shaking and mixing, uniformly coating the mixture on two sides of a graphite felt electrode pretreated by an acetone solution, and calcining the mixture at 360 ℃ for 30-40 min.
2. An organic pollutant degradation technology is characterized in that: the nitrogen-doped graphene composite cathode of claim 1 is used as a cathode, a metal oxide high oxygen evolution potential electrode is used as an anode, the working voltage is controlled to be 2.5-5V, and the aeration amount is controlled to be 0.5-1L/min, so that organic pollutants are degraded.
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| CN108751352B (en) * | 2018-05-25 | 2021-01-26 | 杭州电子科技大学 | Method for degrading cephalosporin through nitrogen-doped graphene aerogel electrode electrocatalysis |
| CN110117046B (en) * | 2019-05-15 | 2022-03-15 | 哈尔滨工业大学 | Preparation method and application of green electro-Fenton cathode |
| CN112723334B (en) * | 2019-10-28 | 2022-09-09 | 中国科学院上海硅酸盐研究所 | Method for preparing nitrogen-doped carbon material by using fluorine-containing polymer |
| CN111422953A (en) * | 2020-04-01 | 2020-07-17 | 北京林业大学 | In-situ flocculation-Fenton coupling electrochemical method for advanced treatment of high-salinity wastewater |
| CN112897645A (en) * | 2021-01-13 | 2021-06-04 | 中科院过程工程研究所南京绿色制造产业创新研究院 | Three-dimensional graphene-based electro-Fenton cathode and preparation method and application thereof |
| CN112897648B (en) * | 2021-01-22 | 2022-09-30 | 南开大学 | Boron-nitrogen co-doped carbon nanotube coated iron cathode heterogeneous electro-Fenton water treatment method |
| CN113023835B (en) * | 2021-03-12 | 2022-09-13 | 北京工业大学 | Preparation method of electro-Fenton cathode material based on sludge-based biomass carbon, product and application thereof |
| CN113072144A (en) * | 2021-04-26 | 2021-07-06 | 哈尔滨工业大学 | Preparation method and application of nitrogen-doped electro-Fenton cathode |
| CN113896298A (en) * | 2021-10-21 | 2022-01-07 | 北京工业大学 | electro-Fenton method for in-situ hydrogen peroxide generation or organic pollutant degradation of composite cathode by combining cathode aeration and cathode modification |
| CN115677012A (en) * | 2022-11-10 | 2023-02-03 | 四川大学 | Water treatment method for enhancing Fenton oxidation by nitrogen-doped reduced graphene oxide |
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| CN102306781A (en) * | 2011-09-05 | 2012-01-04 | 中国科学院金属研究所 | Doped graphene electrode material, macro preparation method and application of doped graphene electrode material |
| CN103896254A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN105609793A (en) * | 2015-12-31 | 2016-05-25 | 复旦大学 | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor |
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| KR101216052B1 (en) * | 2010-12-10 | 2012-12-27 | 국립대학법인 울산과학기술대학교 산학협력단 | Method of preparing nitrogen-doped graphene and nitrogen-doped graphene prepared thereby |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102306781A (en) * | 2011-09-05 | 2012-01-04 | 中国科学院金属研究所 | Doped graphene electrode material, macro preparation method and application of doped graphene electrode material |
| CN103896254A (en) * | 2012-12-26 | 2014-07-02 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN105609793A (en) * | 2015-12-31 | 2016-05-25 | 复旦大学 | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor |
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