CN110482660B - Preparation method and application of etched graphite felt electrode applied to electro-Fenton system - Google Patents
Preparation method and application of etched graphite felt electrode applied to electro-Fenton system Download PDFInfo
- Publication number
- CN110482660B CN110482660B CN201910684805.5A CN201910684805A CN110482660B CN 110482660 B CN110482660 B CN 110482660B CN 201910684805 A CN201910684805 A CN 201910684805A CN 110482660 B CN110482660 B CN 110482660B
- Authority
- CN
- China
- Prior art keywords
- graphite felt
- temperature
- etched
- electro
- cobalt acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Abstract
A preparation method and application of an etched graphite felt electrode applied to an electro-Fenton system belong to the technical field of electrochemical water treatment. The method takes the graphite felt as a matrix, cobalt acetate is uniformly dispersed on the surface of the graphite felt fiber through ultrasonic impregnation, and the etched graphite felt can be obtained through high-temperature calcination under the condition of strong and continuous air introduction. Compared with the original graphite felt, when the etched graphite felt is used as a cathode material, the yield of hydrogen peroxide can be effectively improved, the degradation capability of organic pollutants is remarkably improved, and the cathode material has good stability. The method disclosed by the invention is simple to manufacture, convenient and controllable, can be used for large-scale production, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of electrochemical water treatment, and relates to a preparation method and application of an etched graphite felt electrode applied to an electro-Fenton system, which are mainly used for electrochemical oxidative degradation of organic pollutants in water.
Background
The electro-Fenton technology is a treatment method for quickly and efficiently degrading organic pollutants in water, and hydrogen peroxide generated in situ through a cathode Oxygen Reduction Reaction (ORR) and Fe in a solution2+The reaction generates hydroxyl free radical (OH) with strong oxidizing property, and the hydroxyl free radical can efficiently and nonselectively degrade organic pollutants in water. The electro-Fenton technology has a wide prospect in the aspects of environmental management, particularly water treatment as an environment-friendly electrochemical technology, and has attracted people's attention.
At present, a carbon material is an electrode material commonly used in the electro-fenton technology, wherein a graphite felt has a large specific surface area and good chemical stability, and is widely used in the field of water treatment, but the graphite felt has the disadvantages of poor hydrophilicity, low hydrogen peroxide yield, few active sites and the like, and at present, researchers at home and abroad make a great deal of research on modification and modification of the graphite felt, wherein the methods for modifying and modifying the graphite felt mainly comprise: chemical treatment, metal oxide modification, nonmetal modification and the like, but the methods have the problems of high manufacturing cost, complicated manufacturing process, unsuitability for large-scale production and the like. Therefore, the simple and efficient preparation method of the modified graphite felt electrode is developed, and the electrode prepared by the method is used for improving the degradation effect of organic pollutants in water in an electro-Fenton system, and has important significance.
Disclosure of Invention
Aiming at improving the degradation capability of the graphite felt cathode on organic pollutants in water, the invention provides a novel, efficient, simple and feasible preparation method and application of a modified graphite felt electrode applied to an electro-Fenton system, and the preparation method and application can improve the degradation rate and the degradation depth, improve the cyclicity and efficiency and the like.
A preparation method of an etched graphite felt electrode applied to an electro-Fenton system comprises the following steps:
(1) degreasing and high-temperature pretreatment:
soaking the graphite felt in an acetone solution for ultrasonic cleaning for 20-50min, ultrasonically cleaning with deionized water for several times to remove residual acetone, drying, and finally placing the graphite felt in a high-temperature atmosphere furnace for high-temperature treatment at 500 ℃ for 2-4 h;
(2) etching pretreatment:
soaking the graphite felt obtained in the step (1) after high-temperature treatment in an ethanol solution containing 0.5-1.5g/L of cobalt acetate, and performing ultrasonic treatment for 10-30min to ensure that the cobalt acetate ethanol solution fully infiltrates the graphite felt; then drying for 12h at room temperature to uniformly disperse the cobalt acetate crystals on the surface of the graphite felt fibers;
(3) high-temperature etching treatment:
placing the graphite felt loaded with the cobalt acetate crystals obtained in the step (2) in a high-temperature atmosphere furnace, heating to 200-300 ℃ at the speed of 3-6 ℃/min under the condition of strongly and continuously introducing air, and keeping the temperature for 0.5-1.5h to obtain the graphite felt loaded with the cobaltous trioxide crystals; then placing the graphite felt loaded with cobaltous oxide crystals in a high-temperature atmosphere furnace, heating to 400-600 ℃ at the speed of 3-6 ℃/min under the condition of strongly and continuously introducing air, and keeping the temperature for 0.5-1.5h to finally obtain the etched graphite felt.
The air flow rate of the cavity with the strong and continuous air introduction volume of every 4.5 liters is 5-15L/min.
The etched graphite felt prepared by the method is used as an electro-Fenton system cathode material for removing organic pollutants, especially organic chlorine pollutants, in water.
Compared with the prior art, the invention has the following excellent effects:
1. the invention has simple manufacturing process, can be produced in large scale and is easy to popularize and apply.
2. The graphite felt prepared by the method has larger specific surface area, more surface defect structures and stronger hydrophilicity, thereby obviously improving the degradation effect of an electro-Fenton system on organic pollutants in water.
3. The graphite felt prepared by the method is used as an electro-Fenton system cathode for degrading organic pollutants, has high degradation rate and good degradation depth, can be degraded in percentage, and has good stability and repeatability.
4. The electrode can effectively improve the yield of hydrogen peroxide, obviously improve the degradation capability of organic pollutants, and the cathode material has good stability.
Drawings
Fig. 1(a) and fig. 1(B) are scanning electron micrographs of the surface of the graphite felt material before and after etching by the method of the present invention, respectively (comparative example in fig. 1(a), example 1 in fig. 1 (B)).
FIG. 2 shows N of the graphite felt before and after etching by the method of the present invention2Adsorption-desorption curve (77K). (Curve a: comparative example; Curve b: example 1)
FIG. 3 shows the degradation effect of diuron by using graphite felt as cathode material of electro-Fenton system before and after etching. (Curve a: comparative example; curve b: example 1; curve c: example 2; curve d: example 3)
FIG. 4 shows the reusability of the etched graphite felt as cathode material of electro-Fenton system.
Detailed Description
The method comprises the steps of uniformly loading cobalt acetate crystals on the surface of graphite felt fibers, and calcining at high temperature under the condition of continuously introducing air to obtain the etched graphite felt. The method for etching the graphite felt mainly comprises the following steps: degreasing, etching pretreatment and high-temperature etching treatment.
The graphite felt material adopted by the invention is purchased from Jiuhua carbon high-tech company Limited in Hunan, and the thickness is 5 mm.
The following examples and comparative examples will be described in further detail with reference to the accompanying drawings, but the present invention is not limited to the following examples.
Example 1
The preparation method of the etched graphite felt electrode comprises the following steps:
(1) degreasing and high-temperature pretreatment:
soaking the graphite felt in an acetone solution for ultrasonic cleaning for 30min, ultrasonically cleaning the graphite felt with deionized water for several times to remove residual acetone, drying, and finally placing the graphite felt in a high-temperature atmosphere furnace for high-temperature treatment at 500 ℃ for 3 h;
(2) etching pretreatment:
soaking the graphite felt obtained in the step (1) after high-temperature treatment in an ethanol solution containing 1g/L of cobalt acetate, and performing ultrasonic treatment for 15min to ensure that the cobalt acetate ethanol solution fully infiltrates the graphite felt; then drying for 12h at room temperature to uniformly disperse the cobalt acetate crystals on the surface of the graphite felt fibers;
(3) high-temperature etching treatment:
placing the graphite felt loaded with the cobalt acetate crystals obtained in the step (2) in a high-temperature atmosphere furnace, heating to 300 ℃ at a speed of 4 ℃/min under the condition of strongly and continuously introducing air (wherein the size of a hearth is 200mm multiplied by 150mm, and the air flow rate is 10L/min), and keeping the temperature for 1h to obtain the graphite felt loaded with the cobaltous oxide crystals; and then placing the graphite felt loaded with the cobaltous oxide crystals in a high-temperature atmosphere furnace, heating to 400 ℃ at a speed of 4 ℃/min under the condition of strongly and continuously introducing air (wherein the size of a hearth is 200mm multiplied by 150mm, and the air flow rate is 10L/min), and keeping the temperature for 1h to finally obtain the etched graphite felt.
Example 2
The preparation method of the etched graphite felt electrode comprises the following steps:
the difference between the preparation process of the embodiment and the preparation process of the embodiment 1 is that in the step (3), the graphite felt loaded with cobaltous oxide crystals is placed in a high-temperature atmosphere furnace, and under the condition of strong and continuous air introduction (wherein the size of a hearth is 200mm multiplied by 150mm, and the air flow rate is 10L/min), the temperature is raised to 400 ℃ at the speed of 4 ℃/min, and the temperature is kept for 0.5h, so that the etched graphite felt is finally obtained.
Example 3
The preparation method of the etched graphite felt electrode comprises the following steps:
the difference between the preparation process of the embodiment and the preparation process of the embodiment 1 is that in the step (3), the graphite felt loaded with cobaltous oxide crystals is placed in a high-temperature atmosphere furnace, and under the condition of strong and continuous air introduction (wherein the size of a hearth is 200mm multiplied by 150mm, and the air flow rate is 10L/min), the temperature is raised to 600 ℃ at 4 ℃/min, and the temperature is kept for 1h, so that the etched graphite felt is finally obtained.
Comparative example
Soaking the graphite felt in acetone solution, ultrasonically cleaning for 30min, ultrasonically cleaning with deionized water for several times to remove residual acetone, and drying.
Examples of Effect application
The etched graphite felt prepared in example 1 above was tested for performance using the following method.
1. Etching surface characteristics and physical properties of graphite felt
As shown in the attached figure 1(B), the surface of the graphite felt fiber is subjected to high-temperature and strong air flow etching to generate a plurality of micropore structures and surface defect structures, so that the graphite felt fiber has more active sites.
As shown in figure 2, the specific surface area of the etched graphite felt is obviously increased, and the specific surface area of the graphite felt before and after etching is changed from the original 0.557m2The/g is increased to 5.506m2The specific surface area is increased by a factor of 10 per gram, which makes it possible to have more reaction sites.
2. And (3) the performance of the etched graphite felt applied to an electro-Fenton system.
The etched graphite felt obtained in this example 1 was applied to an electro-fenton system as a cathode material. The system adopts a three-electrode system, a reference electrode is a saturated calomel electrode, a counter electrode is a platinum sheet, a working electrode is a graphite felt, and Fe is additionally added2+The concentration is 0.5mM, the electrolyte is 0.05M Na2SO4The working potential is-0.7V (vs SCE), the initial pH is 3, and 300ml of diuron simulated pesticide wastewater containing 20mg/L is degraded.
As shown in figure 3, when the etched graphite felt is etched for 20min, the removal rate of the diuron is as high as 74.9%, and the removal rate of the unetched graphite felt to the diuron is only 25.6%; when the graphite felt is etched in 50min, the diuron removal rate reaches 100%, and the diuron removal rate of the graphite felt which is not etched is only 67.8%. This shows that the etching method can significantly improve the degradation capability of the graphite felt to organic pollutants.
As can be seen from FIG. 4, the number of times from 1 st to 25 th of repeated useThe apparent rate of the etched graphite felt electrode for degrading the diuron is gradually increased, which shows that the electrode has better and better degrading effect on the diuron; the apparent rates of the 35 th and 1 st etched graphite felt electrodes for diuron degradation are respectively 0.085 and 0.088min-1The result shows that the degradation effect of diuron is not obviously reduced after the etched graphite felt is repeatedly used for 35 times, which shows that the etched graphite felt has good stability and repeatability.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification of the above embodiment according to the technical spirit of the present invention is within the scope of the present invention, unless departing from the technical spirit of the present invention.
Claims (5)
1. A preparation method of an etched graphite felt electrode applied to an electro-Fenton system is characterized by comprising the following steps:
(1) degreasing and high-temperature pretreatment:
soaking the graphite felt in an acetone solution for ultrasonic cleaning for 20-50min, ultrasonically cleaning with deionized water for several times to remove residual acetone, drying, and finally placing the graphite felt in a high-temperature atmosphere furnace for high-temperature treatment at 500 ℃ for 2-4 h;
(2) etching pretreatment:
soaking the graphite felt obtained in the step (1) after high-temperature treatment in an ethanol solution containing 0.5-1.5g/L of cobalt acetate, and performing ultrasonic treatment for 10-30min to ensure that the cobalt acetate ethanol solution fully infiltrates the graphite felt; then drying at room temperature to uniformly disperse the cobalt acetate crystals on the surface of the graphite felt fibers;
(3) high-temperature etching treatment:
placing the graphite felt loaded with the cobalt acetate crystals obtained in the step (2) in a high-temperature atmosphere furnace, heating to 200-300 ℃ at the speed of 3-6 ℃/min under the condition of strongly and continuously introducing air, and keeping the temperature for 0.5-1.5h to obtain the graphite felt loaded with the cobaltous trioxide crystals; then placing the graphite felt loaded with cobaltous oxide crystals in a high-temperature atmosphere furnace, heating to 400-600 ℃ at the speed of 3-6 ℃/min under the condition of strongly and continuously introducing air, and keeping the temperature for 0.5-1.5h to finally obtain an etched graphite felt;
the air flow rate of the cavity with the strong and continuous air introduction volume of every 4.5 liters is 5-15L/min.
2. An etched graphite felt electrode made according to the method of claim 1.
3. Use of an etched graphite felt electrode prepared according to the method of claim 1 as a cathode material in electro-Fenton systems.
4. Use according to claim 3 for removing organic contaminants from water.
5. Use according to claim 4 for the removal of organochlorine contaminants from water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910684805.5A CN110482660B (en) | 2019-07-26 | 2019-07-26 | Preparation method and application of etched graphite felt electrode applied to electro-Fenton system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910684805.5A CN110482660B (en) | 2019-07-26 | 2019-07-26 | Preparation method and application of etched graphite felt electrode applied to electro-Fenton system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110482660A CN110482660A (en) | 2019-11-22 |
| CN110482660B true CN110482660B (en) | 2022-02-08 |
Family
ID=68548393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910684805.5A Active CN110482660B (en) | 2019-07-26 | 2019-07-26 | Preparation method and application of etched graphite felt electrode applied to electro-Fenton system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110482660B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534456B (en) * | 2018-11-12 | 2021-04-30 | 北京工业大学 | Preparation method of Co3O 4/graphite felt composite electrode applied to anodic oxidation system |
| CN111153470B (en) * | 2020-02-12 | 2021-11-09 | 浙江师范大学 | Preparation method of electro-Fenton cathode material based on carbon felt loaded cobalt particles and application of electro-Fenton cathode material in sewage treatment |
| CN111883781B (en) * | 2020-06-05 | 2021-10-29 | 辽宁科技大学 | Activation method for nickel salt etched graphite felt electrode |
| CN112678924A (en) * | 2020-12-30 | 2021-04-20 | 北京工业大学 | Preparation method and application of hydrothermal modified graphite felt electrode applied to electro-Fenton system |
| 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 |
| CN113149155A (en) * | 2021-05-20 | 2021-07-23 | 北京工业大学 | Cu-doped Fe2O3Preparation and application of nano-particle/porous graphite felt cathode |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789154A (en) * | 2004-12-15 | 2006-06-21 | 中国科学院生态环境研究中心 | Method and apparatus for removing water organisms by utilizing inductive electric Fenton reaction |
| CN102887567A (en) * | 2012-10-11 | 2013-01-23 | 南开大学 | Method for modifying graphite felt material applied to electro-Fenton system |
| CN103170334A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Carbon-supported cobalt oxide catalyst and preparation and application thereof |
| CN104163474A (en) * | 2014-08-19 | 2014-11-26 | 中山大学 | Activation method of graphite felt applied to cathode of Electro-Fenton system |
| JP2017060942A (en) * | 2015-09-25 | 2017-03-30 | 国立大学法人京都大学 | Wastewater treatment device |
| CN109534456A (en) * | 2018-11-12 | 2019-03-29 | 北京工业大学 | A kind of Co3O4/ graphite felt method for preparing composite electrode applied to anodic oxidation system |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102299307B (en) * | 2011-09-03 | 2014-01-01 | 深圳市贝特瑞新能源材料股份有限公司 | Electrode anode material and preparation method thereof |
| CN107442123B (en) * | 2017-08-10 | 2020-06-26 | 南京理工大学 | Preparation method of cobaltosic oxide/carbon catalyst |
-
2019
- 2019-07-26 CN CN201910684805.5A patent/CN110482660B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789154A (en) * | 2004-12-15 | 2006-06-21 | 中国科学院生态环境研究中心 | Method and apparatus for removing water organisms by utilizing inductive electric Fenton reaction |
| CN103170334A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Carbon-supported cobalt oxide catalyst and preparation and application thereof |
| CN102887567A (en) * | 2012-10-11 | 2013-01-23 | 南开大学 | Method for modifying graphite felt material applied to electro-Fenton system |
| CN104163474A (en) * | 2014-08-19 | 2014-11-26 | 中山大学 | Activation method of graphite felt applied to cathode of Electro-Fenton system |
| JP2017060942A (en) * | 2015-09-25 | 2017-03-30 | 国立大学法人京都大学 | Wastewater treatment device |
| CN109534456A (en) * | 2018-11-12 | 2019-03-29 | 北京工业大学 | A kind of Co3O4/ graphite felt method for preparing composite electrode applied to anodic oxidation system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110482660A (en) | 2019-11-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110482660B (en) | Preparation method and application of etched graphite felt electrode applied to electro-Fenton system | |
| CN110143647B (en) | Preparation method and application of carbon nanotube-nafion/foam metal gas diffusion electrode | |
| CN107601624B (en) | Preparation and application of electro-Fenton cathode material based on supported activated carbon fibers | |
| CN108615901B (en) | Treatment method for improving activity of graphite felt electrode of vanadium battery | |
| CN105040041B (en) | A kind of Pd/Co3O4The preparation method of/foamed nickel electrode material | |
| CN113277601B (en) | Foamed nickel/MXene-Co3O4Composite electrode and preparation method thereof | |
| CN112408555A (en) | Preparation and application of cuprous oxide/carbon nanotube/copper foam composite electrode for heterogeneous electro-Fenton system | |
| CN112973653B (en) | Preparation method of Mxene membrane adsorbing material based on polyamidoxime and uranium extraction method | |
| CN103435134A (en) | Method for improving biodegradability of semi-coking wastewater based on CNTs/Fe3O4 three-dimensional electric-Fenton | |
| CN108565475A (en) | A kind of method of modifying of graphite felt electrode | |
| CN110862128B (en) | Preparation method of iron disulfide composite graphite felt electrode | |
| CN104163474A (en) | Activation method of graphite felt applied to cathode of Electro-Fenton system | |
| CN112678924A (en) | Preparation method and application of hydrothermal modified graphite felt electrode applied to electro-Fenton system | |
| CN113149155A (en) | Cu-doped Fe2O3Preparation and application of nano-particle/porous graphite felt cathode | |
| CN112794413B (en) | Preparation method and application of graphite felt electrode applied to electro-active PDS system modified bimetal | |
| CN106630116A (en) | Method for strengthening micro-bioelectrochemistry denitrification and continuous flow bioelectrochemistry reaction device with large cathode chamber | |
| CN113441013A (en) | Preparation method of conductive nanofiltration membrane for water treatment | |
| CN112142168A (en) | Anode material for improving membrane pollution of converter valve external cold water system and electrochemical method | |
| CN112062230A (en) | Electrode material, preparation method thereof, electrode for capacitive deionization and application | |
| CN110980889A (en) | Electrode and preparation method thereof | |
| CN110801826A (en) | Photoelectrocatalysis graphite felt material and preparation method and application thereof | |
| CN113998760B (en) | Copper-cobalt oxide/carbon nano tube/foam nickel composite electrode for heterogeneous electro-Fenton system and application | |
| CN110386645A (en) | A kind of also original H of the electrocatalytic oxidation of high oxygen transmission2O2Gas-diffusion electrode preparation method | |
| CN116259772A (en) | Modified graphite felt electrode and preparation method and application thereof | |
| CN113788515B (en) | Heterogeneous electro-Fenton cathode material for industrial wastewater treatment, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |