CN110818033A - Preparation method and application of graphene gas diffusion electrode in electro-Fenton system - Google Patents
Preparation method and application of graphene gas diffusion electrode in electro-Fenton system Download PDFInfo
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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
- 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
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a preparation method and application of a graphene gas diffusion electrode in an electro-Fenton system, wherein a cathode material with high-efficiency catalytic performance on hydrogen peroxide generated by oxygen is researched, so that the electro-Fenton technology is put to practical use, and the energy consumption is well reduced. The preparation method and the application of the graphene gas diffusion electrode in the electro-Fenton system can improve the hydrogen peroxide yield of the cathode in the electro-Fenton system and greatly improve the degradation rate of organic matters, and the preparation method has the advantages of short reaction time, no toxic gas and high safety in the graphene preparation process; the electrode has the advantages of outstanding performance and energy saving compared with the like products, and the electrode prepared by the invention has good popularization and application values, thereby bringing good machine conversion for the treatment of the organic matters which are difficult to degrade in industrial wastewater.
Description
Technical Field
The invention relates to the technical field of industrial wastewater treatment by an electro-Fenton system, in particular to a preparation method and application of a graphene gas diffusion electrode in the electro-Fenton system.
Background
Refractory organic matters which cannot be removed by the traditional wastewater treatment technology in the industrial wastewater treatment can be treated by an advanced oxidation technology, oxidation groups with high oxidation potential in the advanced oxidation technology can react with the organic matters to degrade the organic matters, the Fenton method is one of the oxidation groups, the substance of the Fenton method is that H2O2 generates hydroxyl radicals under the catalytic action of Fe2+, the oxidation potential (2.8V) of the Fenton method is second to fluorine, and the hydroxyl radicals can react with the organic matters to degrade the organic matters non-selectively.
The conventional fenton method has the following disadvantages: 1. potential safety hazards exist in the transportation, storage and use processes of the H2O 2; 2. H2O2 added into the reactor can be decomposed into oxygen and water, and the cost of the medicament can be increased; 3. the Fe2+ and H2O2 have high reaction speed in the early reaction stage due to high concentration, and the degradation rate in the later stage can be rapidly reduced. Electro-fenton, which utilizes the generation of hydroxyl radicals by catalytically active electrodes, has the advantages of: 1. generating hydroxyl radicals directly or indirectly in situ by means of catalytically active electrodes; 2. only a small amount of catalyst is needed, and no chemical oxidant is needed to be added; 3. the equipment is relatively simple, and the process only needs to control current and voltage, thereby being convenient for realizing automation.
The graphene gas diffusion electrode has excellent conductivity, a special monoatomic layer plane two-dimensional structure and high specific surface area, so that the graphene gas diffusion electrode becomes an ideal cathode material with catalytic activity in an electro-Fenton system, and the graphene can generate harmful gases such as ClO2, NO2 or N2O4 and the like in the oxidation modification process and the reaction process of a Brodie method and a Staudenmier method, and has the characteristics of long reaction time and the like.
At present, the yield of hydrogen peroxide of a cathode in an electro-Fenton system is generally low, the degradation rate of organic matters is not high, and the key point of the practical electro-Fenton technology is to research a cathode material with high-efficiency catalytic performance for generating hydrogen peroxide by oxygen, so that the reduction of energy consumption becomes the current main attack direction.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method and application of a graphene gas diffusion electrode in an electro-Fenton system, and solves the problems that the yield of hydrogen peroxide of a cathode in the existing electro-Fenton system is generally low and the degradation rate of organic matters is not high.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method of a graphene gas diffusion electrode in an electro-Fenton system specifically comprises the following steps:
s1, firstly, adding 3-4.5 g of flake graphite and 7.6g of phosphoric acid into a 500ml reaction bottle, then placing the reaction bottle in an ice water bath, stirring the mixture in the ice water bath, adding 75-100 ml of concentrated sulfuric acid, stirring the mixture for 5 minutes under the conditions of keeping the temperature below 4 ℃ and 700rpm, then adding 8-12 g of potassium permanganate in three times, and continuing stirring the mixture for 10 minutes;
s2, heating in a water bath to 35 ℃, stirring for 1.5 hours, adding 170ml of hot distilled water after the solution becomes viscous, keeping the temperature for continuously reacting for 30 minutes, diluting the solution to 350ml of hot distilled water, adding 30% hydrogen peroxide to remove unreacted graphite, taking the upper layer liquid for high-speed centrifugation for 5 minutes, taking the lower layer precipitate, washing the upper layer liquid to be neutral by using 5% hydrochloric acid and distilled water, and performing vacuum drying at 60 ℃ for 1 hour to obtain a product GO;
s3, weighing 0.5g of the product obtained in the step S2 in 100ml of aqueous solution, adjusting the pH to 10 by using 28% ammonia water by mass fraction, and performing ultrasonic treatment for 30 minutes to obtain stable dispersion liquid without obvious particles;
s4, centrifuging the solution obtained in the step S3 at 3500r/min for 5 minutes, adding 0.5ml of hydrazine hydrate into the centrifuged dispersion liquid, and reacting at 85 ℃ for 3 hours to obtain graphene dispersion liquid;
s5, weighing 0.8g of graphite powder, adding the graphite powder into 15ml of 95% ethanol, carrying out ultrasonic treatment for 20 minutes, adding 20-40 ml of the graphene dispersion liquid obtained in the step S4 and 0.2g of polytetrafluoroethylene emulsion with the mass fraction of 60%, and continuing to carry out ultrasonic treatment for 20 minutes to obtain paste;
and S6, uniformly adhering the paste to two sides of a metal platinum mesh, cold-pressing for 10min under the pressure of 1.5Mpa for forming, and then calcining for 1h at 320 ℃ in a muffle furnace to obtain the graphene gas diffusion electrode.
Preferably, the time interval between each addition of potassium permanganate in step S1 is 10 minutes.
Preferably, the step S2 tells the rotation speed of the centrifuge to be 8000 r/min.
Preferably, the size of the platinum gauze in the step S6 can be customized according to the test requirements.
Preferably, the diffusion electrode prepared in step S6 is soaked in acetone solution for 12h before use, so as to remove residual ethanol and surface active substances, then repeatedly washed with distilled water until no acetone remains, and dried for standby.
Preferably, after the dilution with hot distilled water in step S2, 30% excess hydrogen peroxide is added until no bubbles are formed, and after cooling to room temperature, the solution is centrifuged at 1000r/min for 1 minute to remove unreacted graphite.
The invention also discloses an application of the graphene gas diffusion electrode in the electro-Fenton system, which is characterized by comprising the following steps: the application of the method in the degradation of organic matters in wastewater treatment specifically comprises the following steps:
t1, firstly, in an electrolytic cell, taking a graphene gas diffusion electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking metal platinum as an anode, and connecting the three electrodes with a constant potential rectifier;
t2, after the pH value of the solution is adjusted, ferrous sulfate heptahydrate is added, the plate spacing is controlled, and a certain amount of air is continuously introduced into the cathode through an aeration device;
t3, under the condition of the same voltage or current density, the degradation of the organic matters in the wastewater is examined by replacing different working electrodes.
(III) advantageous effects
The invention provides a preparation method and application of a graphene gas diffusion electrode in an electro-Fenton system. Compared with the prior art, the method has the following beneficial effects: the preparation method and the application of the graphene gas diffusion electrode in the electro-Fenton system specifically comprise the following steps: s1, firstly adding 3-4.5 g of flake graphite and 7.6g of phosphoric acid into a 500ml reaction bottle, then placing the mixture into an ice water bath, stirring the mixture, adding 75-100 ml of concentrated sulfuric acid, stirring the mixture for 5 minutes under the condition of keeping below 4 ℃ and 700rpm, then adding 8-12 g of potassium permanganate into the mixture for three times, continuing stirring the mixture for 10 minutes, S2, heating the mixture in the water bath to 35 ℃, stirring the mixture for 1.5 hours, adding 170ml of hot distilled water after the solution becomes viscous, keeping the temperature to continue reacting for 30 minutes, then diluting the mixture to 350ml by using the hot distilled water, then adding 30% of hydrogen peroxide to remove unreacted graphite, taking the upper layer liquid for high-speed centrifugation for 5 minutes, taking the lower layer for precipitation, washing the lower layer to be neutral by using 5% hydrochloric acid and distilled water, carrying out vacuum drying for 1 hour at 60 ℃ to obtain a product GO, S3, weighing 0.5g of the product obtained in the step S2 into 100ml of aqueous solution, adjusting the pH to 10, performing ultrasonic treatment for 30 minutes to obtain stable dispersion liquid without obvious particles, S4, centrifuging the solution obtained in the step S3 for 5 minutes at 3500r/min, adding 0.5ml of hydrazine hydrate into the centrifuged dispersion liquid, reacting for 3 hours at 85 ℃ to obtain graphene dispersion liquid, S5, weighing 0.8g of graphite powder, adding 15ml of 95% ethanol, performing ultrasonic treatment for 20 minutes, adding 20-40 ml of the graphene dispersion liquid obtained in the step S4 and 0.2g of polytetrafluoroethylene emulsion with the mass fraction of 60%, continuing to perform ultrasonic treatment for 20 minutes to obtain paste, S6, uniformly adhering the paste to two sides of a metal platinum net, performing cold pressing for 10 minutes under the pressure of 1.5MPa, molding, and calcining for 1 hour at the temperature of 320 ℃ in a muffle furnace to obtain the graphene gas diffusion electrode, so that the yield of hydrogen peroxide of a cathode in an electro-Fenton system can be improved, the degradation rate of organic matters is greatly improved, and the invention has short reaction time in the preparation process of graphene, no toxic gas is generated, and the safety is high; the electrode has the advantages of outstanding performance and energy saving compared with the like products, and the electrode prepared by the invention has good popularization and application values, thereby bringing good machine conversion for the treatment of the organic matters which are difficult to degrade in industrial wastewater.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the embodiment of the present invention provides three technical solutions: a preparation method of a graphene gas diffusion electrode in an electro-Fenton system specifically comprises the following steps:
example 1
S1, adding 3g of flake graphite and 7.6g of phosphoric acid into a 500ml reaction bottle, placing the mixture into an ice water bath, stirring the mixture, adding 75ml of concentrated sulfuric acid, stirring the mixture for 5 minutes at the temperature of below 4 ℃ and at the speed of 700rpm, adding 8g of potassium permanganate in three times, stirring the mixture once every 10 minutes, and continuing to stir the mixture for 10 minutes;
s2, heating in a water bath to 35 ℃, stirring for 1.5 hours, adding 170ml of hot distilled water after the solution becomes viscous, keeping the temperature for continuously reacting for 30 minutes, diluting the solution to 350ml by using the hot distilled water, then adding slightly excessive 30% hydrogen peroxide until no bubbles are generated, cooling to normal temperature, centrifuging the solution for 1 minute at 1000r/min, removing unreacted graphite, taking the upper layer liquid for high-speed centrifugation for 5 minutes at the rotating speed of 8000r/min, taking the lower layer precipitate, washing the lower layer precipitate to be neutral by using 5% hydrochloric acid and distilled water, and performing vacuum drying for 1 hour at 60 ℃ to obtain a product GO;
s3, weighing 0.5g of the product obtained in the step S2 in 100ml of aqueous solution, adjusting the pH to 10 by using 28% ammonia water by mass fraction, and performing ultrasonic treatment for 30 minutes to obtain stable dispersion liquid without obvious particles;
s4, centrifuging the solution obtained in the step S3 at 3500r/min for 5 minutes, adding 0.5ml of hydrazine hydrate into the centrifuged dispersion liquid, and reacting at 85 ℃ for 3 hours to obtain graphene dispersion liquid;
s5, weighing 0.8g of graphite powder, adding the graphite powder into 15ml of 95% ethanol, carrying out ultrasonic treatment for 20 minutes, adding 40ml of graphene dispersion liquid obtained in the step S4 and 0.2g of polytetrafluoroethylene emulsion with the mass fraction of 60%, and continuing the ultrasonic treatment for 20 minutes to obtain paste;
and S6, uniformly adhering the paste to two sides of a metal platinum net, wherein the size of the metal platinum net can be customized according to test requirements, cold-pressing for 10min under the pressure of 1.5Mpa for molding, calcining for 1h at 320 ℃ in a muffle furnace to obtain the graphene gas diffusion electrode, soaking the electrode in an acetone solution for 12h before use, removing residual ethanol and surface active substances, repeatedly washing with distilled water until no acetone residue exists, and drying for later use, thus obtaining the No. 1 electrode.
Example 2
S1, adding 3.8g of flake graphite and 7.6g of phosphoric acid into a 500ml reaction bottle, placing the mixture into an ice water bath, stirring the mixture in the ice water bath, adding 88ml of concentrated sulfuric acid, stirring the mixture for 5 minutes under the conditions of keeping the temperature below 4 ℃ and 700rpm, adding 10g of potassium permanganate in three times, stirring the mixture once every 10 minutes, and continuing to stir the mixture for 10 minutes;
s2, heating in a water bath to 35 ℃, stirring for 1.5 hours, adding 170ml of hot distilled water after the solution becomes viscous, keeping the temperature for continuously reacting for 30 minutes, diluting the solution to 350ml by using the hot distilled water, then adding slightly excessive 30% hydrogen peroxide until no bubbles are generated, cooling to normal temperature, centrifuging the solution for 1 minute at 1000r/min, removing unreacted graphite, taking the upper layer liquid for high-speed centrifugation for 5 minutes at the rotating speed of 8000r/min, taking the lower layer precipitate, washing the lower layer precipitate to be neutral by using 5% hydrochloric acid and distilled water, and performing vacuum drying for 1 hour at 60 ℃ to obtain a product GO;
s3, weighing 0.5g of the product obtained in the step S2 in 100ml of aqueous solution, adjusting the pH to 10 by using 28% ammonia water by mass fraction, and performing ultrasonic treatment for 30 minutes to obtain stable dispersion liquid without obvious particles;
s4, centrifuging the solution obtained in the step S3 at 3500r/min for 5 minutes, adding 0.5ml of hydrazine hydrate into the centrifuged dispersion liquid, and reacting at 85 ℃ for 3 hours to obtain graphene dispersion liquid;
s5, weighing 0.8g of graphite powder, adding the graphite powder into 15ml of 95% ethanol, carrying out ultrasonic treatment for 20 minutes, adding 30ml of graphene dispersion liquid obtained in the step S4 and 0.2g of polytetrafluoroethylene emulsion with the mass fraction of 60%, and continuing the ultrasonic treatment for 20 minutes to obtain paste;
and S6, uniformly adhering the paste to two sides of a metal platinum net, wherein the size of the metal platinum net can be customized according to test requirements, cold-pressing for 10min under the pressure of 1.5Mpa for molding, calcining for 1h at 320 ℃ in a muffle furnace to obtain the graphene gas diffusion electrode, soaking the electrode in an acetone solution for 12h before use, removing residual ethanol and surface active substances, repeatedly washing with distilled water until no acetone residue exists, and drying for later use, thus obtaining the 2# electrode.
Example 3
S1, adding 4.5g of flake graphite and 7.6g of phosphoric acid into a 500ml reaction bottle, placing the mixture into an ice water bath, stirring the mixture in the ice water bath, adding 100ml of concentrated sulfuric acid, stirring the mixture for 5 minutes under the conditions of keeping the temperature below 4 ℃ and 700rpm, adding 12g of potassium permanganate in three times, stirring the mixture once every 10 minutes, and continuing to stir the mixture for 10 minutes;
s2, heating in a water bath to 35 ℃, stirring for 1.5 hours, adding 170ml of hot distilled water after the solution becomes viscous, keeping the temperature for continuously reacting for 30 minutes, diluting the solution to 350ml by using the hot distilled water, then adding slightly excessive 30% hydrogen peroxide until no bubbles are generated, cooling to normal temperature, centrifuging the solution for 1 minute at 1000r/min, removing unreacted graphite, taking the upper layer liquid for high-speed centrifugation for 5 minutes at the rotating speed of 8000r/min, taking the lower layer precipitate, washing the lower layer precipitate to be neutral by using 5% hydrochloric acid and distilled water, and performing vacuum drying for 1 hour at 60 ℃ to obtain a product GO;
s3, weighing 0.5g of the product obtained in the step S2 in 100ml of aqueous solution, adjusting the pH to 10 by using 28% ammonia water by mass fraction, and performing ultrasonic treatment for 30 minutes to obtain stable dispersion liquid without obvious particles;
s4, centrifuging the solution obtained in the step S3 at 3500r/min for 5 minutes, adding 0.5ml of hydrazine hydrate into the centrifuged dispersion liquid, and reacting at 85 ℃ for 3 hours to obtain graphene dispersion liquid;
s5, weighing 0.8g of graphite powder, adding the graphite powder into 15ml of 95% ethanol, carrying out ultrasonic treatment for 20 minutes, adding 20ml of graphene dispersion liquid obtained in the step S4 and 0.2g of polytetrafluoroethylene emulsion with the mass fraction of 60%, and continuing the ultrasonic treatment for 20 minutes to obtain paste;
6. uniformly adhering the paste to two sides of a metal platinum net, wherein the size of the metal platinum net can be customized according to test requirements, cold pressing for 10min under the pressure of 1.5Mpa for molding, calcining for 1h at 320 ℃ in a muffle furnace to obtain the graphene gas diffusion electrode, soaking the electrode in an acetone solution for 12h before use, removing residual ethanol and surface active substances, repeatedly washing with distilled water until no acetone residue exists, and drying for later use, wherein the electrode is a No. 3 electrode.
Application test example
Summary of the method: in an electrolytic cell, a graphene gas diffusion electrode is used as a working electrode, a saturated calomel electrode is used as a reference electrode, metal platinum is used as a counter electrode (anode), the three electrodes are connected with a constant potential rectifier, ferrous sulfate heptahydrate with certain molar concentration is added after the pH value of the solution is adjusted, the plate spacing is controlled, a certain amount of air is continuously introduced into the cathode through an aeration device, and the degradation condition of organic matters in the wastewater is inspected by replacing different working electrodes under the condition of the same voltage or current density. The degradation of organic matters is expressed by detecting the COD content in a water sample, namely the smaller the COD value after the experiment is, the higher the efficiency of the working electrode is, the better the performance of the electrode is, and the larger the COD value after the experiment is, the lower the efficiency of the working electrode is, and the worse the performance of the electrode is.
Experimental apparatus and equipment: a platinum electrode (type 213), a saturated calomel electrode (type 232), an intelligent acidimeter, a double-display potentiostat, a low-temperature constant-temperature tank, an air pump, a 250ml electrolytic cell, self-made graphene gas diffusion electrodes 1#, 2#, 3#, a commercially available carbon fiber electrode A, a commercially available graphite electrode B and a graphene gas diffusion electrode C in certain institutions (the A, B, C electrodes are all the optimal electrodes for experimental screening).
Medicament: ferrous sulfate heptahydrate (analytically pure).
Water for experiment: printing and dyeing wastewater.
The experimental conditions are as follows: firstly, under the conditions of determining that the initial pH value of the solution is 3, the aeration rate is 0.3L/min, the distance between a cathode plate and an anode plate is 3 cm, and the electrolysis time is 60 minutes, through a gradient test of respectively changing the voltage, the current density and the molar concentration of the ferrous sulfate heptahydrate, the conditions of the optimal voltage, the optimal current density and the molar concentration of the ferrous sulfate heptahydrate are found.
Then, different working electrodes were examined under these conditions, and relatively excellent graphene gas diffusion electrodes were selected. The results of the experiments are shown in table 1 below.
TABLE 1 analysis of the results
Under the experimental conditions that the pH value of a solution is 3, the aeration quantity is 0.3L/min, the plate spacing is 3 cm, the electrolysis time is 60 minutes, the voltage is 4 volts, the current density is 20mA/cm2, and the molar concentration of ferrous sulfate heptahydrate is 7.5mmol/L, the self-made electrode has the best 3# electrode test effect, the degradation rate is 68 percent, the 2# electrode is the worst, the degradation rate is 62 percent, in the commercially available electrode, the degradation rate of the electrode A is 41 percent, the degradation rate of the electrode B is 50 percent, and the degradation rate of the electrode C is 59 percent, compared with the self-made 3# electrode ①, the degradation rate of the self-made 3# electrode is 9 percent higher than that of the electrode C, the self-made 2# electrode is 3 percent higher than that of the electrode C, and the self-made 3# electrode ② saves about 13 percent of energy consumption compared with the electrode C, ① graphene gas diffusion electrode is much better than that of a graphite electrode and a carbon fiber electrode, ② prepared by the similar method is better than that of the ③ electrode of the same type.
Because the method has the advantages of short reaction time, no generation of toxic gas, higher safety, more outstanding performance of the electrode compared with the like products and energy conservation compared with the like products in the graphene preparation process, the electrode prepared by the method has good popularization and application values, and can bring good machine conversion for the treatment of industrial wastewater organic matters difficult to degrade.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A preparation method of a graphene gas diffusion electrode in an electro-Fenton system is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, firstly, adding 3-4.5 g of flake graphite and 7.6g of phosphoric acid into a 500ml reaction bottle, then placing the reaction bottle in an ice water bath, stirring the mixture in the ice water bath, adding 75-100 ml of concentrated sulfuric acid, stirring the mixture for 5 minutes under the conditions of keeping the temperature below 4 ℃ and 700rpm, then adding 8-12 g of potassium permanganate in three times, and continuing stirring the mixture for 10 minutes;
s2, heating in a water bath to 35 ℃, stirring for 1.5 hours, adding 170ml of hot distilled water after the solution becomes viscous, keeping the temperature for continuously reacting for 30 minutes, diluting the solution to 350ml of hot distilled water, adding 30% hydrogen peroxide to remove unreacted graphite, taking the upper layer liquid for high-speed centrifugation for 5 minutes, taking the lower layer precipitate, washing the upper layer liquid to be neutral by using 5% hydrochloric acid and distilled water, and performing vacuum drying at 60 ℃ for 1 hour to obtain a product GO;
s3, weighing 0.5g of the product obtained in the step S2 in 100ml of aqueous solution, adjusting the pH to 10 by using 28% ammonia water by mass fraction, and performing ultrasonic treatment for 30 minutes to obtain stable dispersion liquid without obvious particles;
s4, centrifuging the solution obtained in the step S3 at 3500r/min for 5 minutes, adding 0.5ml of hydrazine hydrate into the centrifuged dispersion liquid, and reacting at 85 ℃ for 3 hours to obtain graphene dispersion liquid;
s5, weighing 0.8g of graphite powder, adding the graphite powder into 15ml of 95% ethanol, carrying out ultrasonic treatment for 20 minutes, adding 20-40 ml of the graphene dispersion liquid obtained in the step S4 and 0.2g of polytetrafluoroethylene emulsion with the mass fraction of 60%, and continuing to carry out ultrasonic treatment for 20 minutes to obtain paste;
and S6, uniformly adhering the paste to two sides of a metal platinum mesh, cold-pressing for 10min under the pressure of 1.5Mpa for forming, and then calcining for 1h at 320 ℃ in a muffle furnace to obtain the graphene gas diffusion electrode.
2. The method for preparing the graphene gas diffusion electrode in the electro-Fenton system according to claim 1, wherein the method comprises the following steps: the time interval between each addition of potassium permanganate in step S1 was 10 minutes.
3. The method for preparing the graphene gas diffusion electrode in the electro-Fenton system according to claim 1, wherein the method comprises the following steps: the step S2 tells the rotating speed of the centrifuge to be 8000 r/min.
4. The method for preparing the graphene gas diffusion electrode in the electro-Fenton system according to claim 1, wherein the method comprises the following steps: the size of the platinum mesh in the step S6 can be customized according to the test requirements.
5. The method for preparing the graphene gas diffusion electrode in the electro-Fenton system according to claim 1, wherein the method comprises the following steps: before the diffusion electrode prepared in the step S6 is used, the electrode is soaked in an acetone solution for 12 hours, residual ethanol and surface active substances are removed, then the diffusion electrode is repeatedly washed by distilled water until no acetone remains, and the diffusion electrode is dried for standby.
6. The method for preparing the graphene gas diffusion electrode in the electro-Fenton system according to claim 1, wherein the method comprises the following steps: after diluting with hot distilled water in the step S2, 30% excess hydrogen peroxide was added until no bubbles were generated, and after cooling to room temperature, the solution was centrifuged at 1000r/min for 1 minute to remove unreacted graphite.
7. An application of a graphene gas diffusion electrode preparation method in an electro-Fenton system is characterized in that: the application of the method in the degradation of organic matters in wastewater treatment specifically comprises the following steps:
t1, firstly, in an electrolytic cell, taking a graphene gas diffusion electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking metal platinum as an anode, and connecting the three electrodes with a constant potential rectifier;
t2, after the pH value of the solution is adjusted, ferrous sulfate heptahydrate is added, the plate spacing is controlled, and a certain amount of air is continuously introduced into the cathode through an aeration device;
t3, under the condition of the same voltage or current density, the degradation of the organic matters in the wastewater is examined by replacing different working electrodes.
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| CN112723496A (en) * | 2021-01-11 | 2021-04-30 | 华南理工大学 | Flow type electrochemical system for generating double oxidants by double electrodes in cooperation for organic wastewater treatment and application |
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| CN104229949A (en) * | 2014-09-18 | 2014-12-24 | 西安建筑科技大学 | Preparation and application of iron ion and manganese ion loaded activated carbon fiber composite cathode |
| CN104528707A (en) * | 2015-01-23 | 2015-04-22 | 青岛科技大学 | Preparation method of high-conductivity graphene membrane |
| CN105836855A (en) * | 2016-06-13 | 2016-08-10 | 西安工业大学 | Preparation method and application of graphene gas diffusion electrode |
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| CN112723496A (en) * | 2021-01-11 | 2021-04-30 | 华南理工大学 | Flow type electrochemical system for generating double oxidants by double electrodes in cooperation for organic wastewater treatment and application |
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