CN109896598B - Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water - Google Patents
Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water Download PDFInfo
- Publication number
- CN109896598B CN109896598B CN201910194920.4A CN201910194920A CN109896598B CN 109896598 B CN109896598 B CN 109896598B CN 201910194920 A CN201910194920 A CN 201910194920A CN 109896598 B CN109896598 B CN 109896598B
- Authority
- CN
- China
- Prior art keywords
- electro
- fenton
- cathode material
- carbon felt
- electrode
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000010406 cathode material Substances 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000015556 catabolic process Effects 0.000 title abstract description 17
- 238000006731 degradation reaction Methods 0.000 title abstract description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 16
- 239000004917 carbon fiber Substances 0.000 claims abstract description 14
- 238000004070 electrodeposition Methods 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 229920000767 polyaniline Polymers 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 9
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 9
- 229940012189 methyl orange Drugs 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000004043 dyeing Methods 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000007832 Na2SO4 Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000004688 heptahydrates Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a preparation method of an electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of the electro-Fenton cathode material in degradation of organic pollutants in water, and belongs to the technical field of preparation of the electro-Fenton cathode material and electro-Fenton water treatment. The technical scheme provided by the invention has the key points that: loading polyaniline on a pure carbon felt through electrochemical deposition, then loading iron particles to obtain an iron-carbon doped porous composite carbon fiber material, applying the carbon felt as a cathode material in an electro-Fenton water treatment device and exposing the carbon felt to air, and catalyzing the carbon felt at a cathode to generate hydroxyl radicals so as to degrade organic pollutants in water. The invention fully exerts the characteristic of large specific surface area of the carbon fiber, has the advantages of high treatment efficiency, environmental protection and the like, and can generate economic and social benefits in the field of industrial printing and dyeing wastewater and underground water treatment.
Description
Technical Field
The invention belongs to the technical field of preparation of electro-Fenton cathode materials and electro-Fenton water treatment, and particularly relates to a preparation method of an electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of the electro-Fenton cathode material in degradation of organic pollutants in water.
Background
In recent years, the major rivers and lakes in China are polluted by organic matters to different degrees, and the major polluted areas are the middle and lower reaches of Yangtze river, yellow river basin, Zhujiang river Delta and Songhua river basin. According to the years of monitoring results in China, 68 pollutants are preferentially controlled in water, wherein 58 toxic organic pollutants exist, and the water pollution in China is mainly organic pollution. The persistent organic pollutants are extremely harmful to the environment ecology, are difficult to degrade and have wide pollution sources. Wherein, a large amount of wastewater containing high-concentration dye is discharged by a printing and dyeing mill, the components are complex, and the degradation treatment is difficult to be carried out by using the traditional physical and chemical method. Meanwhile, soil pollution mainly caused by organic pollution gradually draws attention. The organic pollutants are of various types, have great influence on environmental ecology and human health, and have certain barrier effect on sustainable development. At present, the mode of treating industrial wastewater, domestic sewage and soil polluted water areas in China is single, the selectivity is not strong, the industrial wastewater, the domestic sewage and the soil polluted water areas are difficult to be widely used, the cost is high, the time and the labor are consumed, and the purification effect is not good. With the development of science and technology, Advanced Oxidation (AOP) technology is becoming more and more popular in the industry in water pollution treatment, has the characteristics of high energy efficiency, high automation degree, mild and safe operating environment and the like, and is considered to be one of the best choices for treating organic wastewater with complex components.
The electro-Fenton technology mainly depends on the purpose of oxidizing organic pollutants by generating hydrogen peroxide through the catalysis of metal ions and further generating hydroxyl radicals. The electro-Fenton technology is particularly excellent in degrading organic matters, shows good performance in the aspects of degradation rate and decontamination rate, and overcomes the defects that a large amount of deposited sludge is generated and hydrogen peroxide needs to be continuously added in the traditional Fenton. The main point of the difference between the electro-Fenton reaction system and other Fenton reaction-based water treatment processes is that the electro-Fenton reaction can be used for electrolyzing to generate hydrogen peroxide, so that the cost and risk of hydrogen peroxide production are avoided, and in addition, divalent iron ions are continuously regenerated in the cathode reduction process, so that the degradation continuity is ensured. A small amount of ferrous ions can enhance the activity of hydrogen peroxide during the electro-fenton reaction, thereby more efficiently generating ferric ions and hydroxyl radicals. From many aspects, the electro-Fenton technology has wide application prospect in the field of environmental electrochemistry.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of an electro-Fenton cathode material based on carbon felt loaded iron nanoparticles, which is simple in process and low in cost.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the electro-Fenton cathode material based on the carbon felt loaded iron nanoparticles is characterized by comprising the following specific steps of:
step S1: ultrasonically soaking the carbon fiber material for 20-40 min by using deionized water and ethanol respectively, and cleaning and drying the carbon fiber material for later use;
step S2: aniline hydrochloride solution is prepared by mixing aniline, concentrated hydrochloric acid and deionized water for later use, and ferrous sulfate solution is prepared by ferrous sulfate heptahydrate and deionized water for later use;
step S3: setting an electro-deposition device, wherein electrodes in the electro-deposition device comprise an anode, a cathode and a reference electrode, the anode is connected with the anode of an electrochemical workstation, the cathode is connected with the cathode of the electrochemical workstation, the reference electrode is an AgCl electrode, a prepared aniline hydrochloride solution is used as a deposition solution, the voltage of the electrochemical workstation is set to be 0.8V, electro-deposition is carried out by a constant voltage method, a deposition electrode loaded with polyaniline is obtained after electro-deposition reaction is carried out for 1-2 h, and then the deposition electrode is soaked in a prepared ferrous sulfate solution for 12-24 h to obtain an electro-Fenton cathode material loaded with polyaniline and iron nanoparticles;
step S4: and (3) placing the electro-Fenton cathode material loaded with polyaniline and iron nanoparticles into a tubular furnace, heating to 600-900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and calcining for 1-2 h to obtain the target product, namely the electro-Fenton cathode material loaded with iron nanoparticles in the carbon felt.
Preferably, the carbon fiber material of step S1 has a gauge of 3cm by 9cm by 0.5cm to 5cm by 12cm by 1 cm.
Preferably, in the aniline hydrochloride solution in the step S2, the mass ratio of aniline to concentrated hydrochloric acid to deionized water is 9:16:75, and the molar concentration of the ferrous sulfate solution is 0.08-0.12 mol/L.
Preferably, the calcination temperature in step S4 is 700 ℃.
The invention discloses an application of an electro-Fenton cathode material based on carbon felt supported iron nanoparticles in degradation of organic pollutants in water, which is characterized by comprising the following specific steps: in an electro-Fenton system, the prepared electro-Fenton cathode material based on carbon felt loaded iron nanoparticles is used as a cathode and connected with a working electrode of an electrochemical workstation, a common carbon felt electrode is connected with a counter electrode of the electrochemical workstation, ferrous sulfate heptahydrate particles are added into electrolyte, wherein the electrolyte is a 4-400 mmol/L sodium sulfate solution, the concentration of the ferrous sulfate heptahydrate in the electrolyte is 0.1mmol/L, the current of the electrochemical workstation is set to be 50-130 mA, electrolysis is carried out in a constant current mode for 60-150 min, magnetic stirring is started, the pH value of the solution system is adjusted to be 1-10 and the temperature is 10-50 ℃, oxygen is reduced on the surface of activated carbon fibers to generate hydrogen peroxide, the obtained hydrogen peroxide is further catalyzed to generate a large number of hydroxyl free radicals, organic pollutants in water are further oxidatively degraded, the reacted electrode is washed by deionized water, Drying and recycling.
Preferably, the electrolyte is a 40mmol/L sodium sulfate solution, the current of the electrochemical workstation is set to be 110mA, and the pH value of the solution system is adjusted to be 2-3.
Preferably, the organic pollutant is methyl orange, congo red or rhodamine B.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention gives full play to the characteristic of large specific surface area of the carbon felt, has the advantages of high treatment efficiency, environmental protection and the like, and can generate economic and social benefits in the field of industrial printing and dyeing wastewater and underground water treatment;
2. the reagents and electrode materials used in the method are low in price and easy to obtain, hydrogen peroxide consumed in the electrolysis process is automatically regenerated under the condition of introducing air, so that the continuous degradation of pollutants is ensured, and compared with the traditional Fenton method, any oxidant is not required to be added externally;
3. the electro-Fenton cathode material based on the carbon felt supported iron nanoparticles can be repeatedly recycled after being cleaned, and still keeps high degradation efficiency.
Drawings
Fig. 1 is a technical scheme of a preparation method of carbon felt supported iron nanoparticle-based electro-fenton cathode material and its water treatment application;
FIG. 2 is a scanning electron microscope image of the electro-Fenton cathode material based on carbon felt supported iron nanoparticles prepared in example 1;
FIG. 3 is a transmission electron microscope image of the electro-Fenton cathode material based on carbon felt supported iron nanoparticles prepared in example 1;
FIG. 4 is a graph showing the degradation effect of the electro-Fenton cathode material based on carbon felt supported iron nanoparticles prepared in example 1 as a cathode on methyl orange under different conditions;
fig. 5 is a graph showing the recycling effect of the carbon felt-supported iron nanoparticle-based electro-fenton cathode material prepared in example 1 as a cathode.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Preparing an electro-Fenton cathode material based on carbon felt supported iron nanoparticles:
(1) pretreatment: selecting a carbon fiber material with the specification of 3cm by 9cm by 0.5cm, respectively ultrasonically soaking the carbon fiber material for 30min by using deionized water and ethanol, and cleaning and drying the carbon fiber material for later use;
(2) preparing aniline hydrochloride solution and ferrous sulfate solution: the aniline hydrochloride solution is prepared by mixing aniline, concentrated hydrochloric acid and deionized water according to the mass ratio of 9:16:75, and then performing magnetic stirring for 30 min; the ferrous sulfate solution is prepared from heptahydrate, ferrous sulfate and deionized water, and the molar concentration is 0.1 mol/L;
(3) setting an electro-deposition device, wherein electrodes in the electro-deposition device comprise an anode, a cathode and a reference electrode, the anode is connected with the anode of an electrochemical workstation, the cathode is connected with the cathode of the electrochemical workstation, the reference electrode is an AgCl electrode, a prepared aniline hydrochloride solution is used as a deposition solution, the voltage of the electrochemical workstation is set to be 0.8V, electro-deposition is carried out by a constant voltage method, a deposition electrode loaded with polyaniline is obtained after 2h of electro-deposition reaction, and then the deposition electrode is soaked in a prepared ferrous sulfate solution for 18h to obtain an electro-Fenton cathode material loaded with polyaniline and iron nanoparticles;
(4) and (3) firing of the deposition electrode: and (3) placing the electro-Fenton cathode material loaded with polyaniline and iron nanoparticles into a tubular furnace, heating to 600-900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and calcining for 1h to obtain the carbon felt iron nanoparticle-loaded electro-Fenton cathode material.
Fig. 2 and fig. 3 are a scanning electron microscope picture and a transmission electron microscope picture of the electro-fenton cathode material with the carbon felt loaded with the iron nanoparticles, respectively, and it can be seen from the pictures that the iron nanoparticles are distributed on the surface of the smooth activated carbon fiber.
As shown in fig. 4 and 5, in an electro-fenton system, the active electro-fenton cathode material obtained by the present invention is used as a cathode, air is introduced, and under the magnetic stirring action, oxygen is reduced on the surface of active carbon fibers to generate hydrogen peroxide, and the obtained hydrogen peroxide further catalyzes to generate a large amount of hydroxyl radicals, so as to further oxidize and degrade organic pollutants in water.
Fig. 4 shows a comparative graph of the removal effect of the active electro-fenton cathode material on methyl orange under different firing temperatures (a), different current intensities (b), different ph (c) of the solution and different concentrations of the electrolyte (d). As can be seen from the graph (a), the electrode degradation effect is the best at the firing temperature of 700 ℃; as shown in the graph (b), the influence of the current level on the removal rate is small, and the solution efficiency is relatively high at a current of 110 mA. In the graph (c), the degradation effect is high under the condition that the pH value is 2-3; as can be seen from FIG. (d), the highest degradation efficiency was observed when 40mM sodium sulfate was added.
Fig. 5 shows a graph of the effect of cyclic degradation of the active electro-fenton cathode material as a cathode, and it can be found from the graph that the removal rate of methyl orange can still reach over 90% with the increase of the use times, and it can be seen that the stability of the electro-fenton cathode material based on carbon felt supported iron nanoparticles is better.
Example 2
Example 1 the removal effect of carbon felt supported iron nanoparticle based electro-fenton cathode material on different dye liquors was prepared:
volume of reaction solution: 100 mL;
temperature of the reaction solution: 25 +/-10 ℃;
initial pH of reaction solution: 3;
electrode area: 27cm2；
Electrolyte concentration: 40mM Na2SO4A solution;
oxygen flow rate: 100 mL/min;
current intensity: 100 mA;
reaction time: 60 min;
different dye solutions: methyl orange, congo red, rhodamine B;
concentration of the dye solution: 100 mg/L.
TABLE 1 Elimination rates of electro-Fenton cathode materials as cathodes for different dye liquors
As can be seen from example 2, the electro-Fenton cathode material based on carbon felt supported iron nanoparticles prepared in example 1 has particularly remarkable degradation efficiency as a cathode for different dye solutions with the concentration of 100 mg/L.
Example 3
Example 1 effect of carbon felt supported iron nanoparticle based electro-fenton cathode material on methyl orange removal at different pH conditions:
volume of reaction solution: 100 mL;
temperature of the reaction solution: 25 +/-10 ℃;
electrode area: 27cm2；
Electrolyte concentration: 40mM Na2SO4A solution;
oxygen flow rate: 100 mL/min;
current intensity: 100 mA;
reaction time: 120 min;
concentration of the dye solution: 100mg/L methyl orange solution;
initial pH of reaction solution: 2. 3, 4 and 5.
Table 2 effect of electro-fenton cathode material on methyl orange removal rate under different pH conditions
| |
2 | 3 | 4 | 5 |
| Removal rate | 97.8％ | 96.7％ | 91.3％ | 92.1％ |
As can be seen from example 3, the electro-fenton cathode material based on carbon felt supported iron nanoparticles prepared in example 1 under acidic conditions all have methyl orange removal rates of 90% or more, and the removal rates at pH 2 and 3 are most significant.
In summary, the invention utilizes an electro-Fenton cathode material based on carbon felt loaded iron nanoparticles, polyaniline is loaded on a pure carbon felt through electrodeposition, iron ions are loaded to obtain an iron-carbon doped porous composite carbon fiber material, the carbon felt is used as a cathode in an electro-Fenton reaction device, air is introduced under a condition of proper pH and magnetic stirring is carried out, oxygen is reduced on the surface of active carbon fibers to generate hydrogen peroxide, and the obtained hydrogen peroxide is further catalyzed to generate a large amount of hydroxyl radicals, so that organic pollutants in water are oxidized and degraded. The preparation method of the load type electro-Fenton cathode material is simple, the conditions are mild, the used reagents and electrode materials are low in price and easy to obtain, hydrogen peroxide consumed in the electrolysis process is automatically regenerated under the condition of introducing air, the continuous degradation of pollutants is ensured, and compared with the traditional Fenton method, any oxidant is not required to be added from an external source. The carbon felt has the characteristics of large specific surface area, and the active electrode can be recycled after being used, has high stability, has the advantages of high treatment efficiency, environmental protection and the like, and can create great economic and social benefits in the field of industrial printing and dyeing wastewater and underground water treatment.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (2)
1. The application of the electro-Fenton cathode material based on carbon felt supported iron nanoparticles in degrading organic pollutants in water is characterized by comprising the following specific steps: in an electro-Fenton system, the prepared electro-Fenton cathode material based on carbon felt loaded iron nanoparticles is used as a cathode and connected with a working electrode of an electrochemical workstation, a common carbon felt electrode is connected with a counter electrode of the electrochemical workstation, ferrous sulfate heptahydrate particles are added into electrolyte, the electrolyte is a 4-400 mmol/L sodium sulfate solution, the concentration of the ferrous sulfate heptahydrate in the electrolyte is 0.1mmol/L, the current of the electrochemical workstation is set to be 50-130 mA, electrolysis is carried out in a constant current mode for 60-150 min, magnetic stirring is started, the pH = 1-10 and the temperature of the solution system are adjusted to be 10-50 ℃, oxygen is reduced on the surface of activated carbon fibers to generate hydrogen peroxide, the obtained hydrogen peroxide further catalyzes and generates a large number of hydroxyl radicals to oxidize and degrade organic pollutants in water, the reacted electrode is washed by deionized water, Drying and recycling the materials;
the preparation method of the electro-Fenton cathode material based on the carbon felt supported iron nanoparticles comprises the following specific steps:
step S1: ultrasonically soaking the carbon fiber material for 20-40 min by using deionized water and ethanol respectively, and cleaning and drying the carbon fiber material for later use;
step S2: aniline hydrochloride solution is prepared by mixing aniline, concentrated hydrochloric acid and deionized water for later use, and ferrous sulfate solution is prepared by ferrous sulfate heptahydrate and deionized water for later use;
step S3: setting an electro-deposition device, wherein electrodes in the electro-deposition device comprise an anode, a cathode and a reference electrode, the anode is connected with the anode of an electrochemical workstation, the cathode is connected with the cathode of the electrochemical workstation, the reference electrode is an AgCl electrode, a prepared aniline hydrochloride solution is used as a deposition solution, the voltage of the electrochemical workstation is set to be 0.8V, electro-deposition is carried out by a constant voltage method, a deposition electrode loaded with polyaniline is obtained after electro-deposition reaction is carried out for 1-2 h, and then the deposition electrode is soaked in a prepared ferrous sulfate solution for 12-24 h to obtain an electro-Fenton cathode material loaded with polyaniline and iron nanoparticles;
step S4: placing the electro-Fenton cathode material loaded with polyaniline and iron nanoparticles in a tubular furnace, heating to 600-900 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and calcining for 1-2 h to obtain the target product, namely the electro-Fenton cathode material loaded with iron nanoparticles in the carbon felt;
the specification of the carbon fiber material in the step S1 is 3cm by 9cm by 0.5cm to 5cm by 12cm by 1 cm;
in the step S2, the mass ratio of aniline to concentrated hydrochloric acid to deionized water in the aniline hydrochloride solution is 9:16:75, and the molar concentration of the ferrous sulfate solution is 0.08-0.12 mol/L;
the calcination temperature in the step S4 is 700 ℃;
the organic pollutants are methyl orange, Congo red or rhodamine B.
2. Use according to claim 1, characterized in that: the electrolyte is a 40mmol/L sodium sulfate solution, the current of an electrochemical workstation is set to be 110mA, and the pH = 2-3 of a solution system is adjusted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910194920.4A CN109896598B (en) | 2019-03-14 | 2019-03-14 | Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910194920.4A CN109896598B (en) | 2019-03-14 | 2019-03-14 | Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109896598A CN109896598A (en) | 2019-06-18 |
| CN109896598B true CN109896598B (en) | 2022-02-25 |
Family
ID=66953650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910194920.4A Active CN109896598B (en) | 2019-03-14 | 2019-03-14 | Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109896598B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110801826A (en) * | 2019-11-12 | 2020-02-18 | 广东工业大学 | Photoelectrocatalysis graphite felt material and preparation method and application thereof |
| 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 |
| CN111668499A (en) * | 2020-04-20 | 2020-09-15 | 中山大学 | Polyaniline-derived nitrogen-doped carbon-supported multi-element alloy catalyst and preparation method and application thereof |
| CN111851058B (en) * | 2020-06-10 | 2022-11-29 | 广州大学 | Modified carbon fiber and application thereof in separation and recovery of oily wastewater |
| CN111969217B (en) * | 2020-09-02 | 2022-06-24 | 河南师范大学 | Preparation method and application of polyaniline cathode material for microbial electro-Fenton fuel cell |
| CN112408668B (en) * | 2020-11-27 | 2023-04-07 | 南京信息工程大学 | Iron-tannic acid derivative modified graphite felt heterogeneous electro-Fenton cathode material, preparation method and application |
| CN112803030B (en) * | 2020-12-29 | 2022-06-10 | 河北工业大学 | Preparation method and application method of electro-Fenton composite membrane cathode |
| CN113716653A (en) * | 2021-07-22 | 2021-11-30 | 中化学朗正环保科技有限公司 | Penetrating heterogeneous electro-Fenton water treatment device and application thereof |
| CN113526646B (en) * | 2021-08-20 | 2022-04-05 | 中南大学 | electro-Fenton system for in-situ production of hydrogen peroxide by cathode/anode and application of electro-Fenton system in strengthening degradation of organic pollutants |
| CN114481187B (en) * | 2022-02-15 | 2024-01-19 | 中国科学院赣江创新研究院 | electro-Fenton cathode material and preparation method and application thereof |
| CN115072839B (en) * | 2022-03-14 | 2023-08-08 | 南京理工大学 | Iron-containing composite magnetic material, preparation method and catalytic application thereof |
| CN115321646B (en) * | 2022-07-20 | 2023-08-15 | 湖北大学 | Method for electrocatalytic degradation of organic pollutants by externally applied magnetic field |
| CN115382551B (en) * | 2022-07-26 | 2023-10-13 | 湖南大学 | Three-dimensional carbonaceous functional cathode material based on potassium ferrate modification, and preparation method and application thereof |
| CN115893592B (en) * | 2022-11-03 | 2024-05-24 | 北京林业大学 | Rapid purification technology for electro-flocculation in-situ coupling electro-Fenton overflow pollution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641722A (en) * | 2012-04-24 | 2012-08-22 | 清华大学 | Arsenic removal material by adsorption of electrochemistry strengthened nano ferro-manganese loaded carbon fiberand arsenic removal method by using same |
| CN102674525A (en) * | 2011-03-15 | 2012-09-19 | 吉林师范大学 | Method for preparing cathode for cathode electro-fenton process |
| CN106400048A (en) * | 2016-09-10 | 2017-02-15 | 华南理工大学 | Electro-Fenton cathode material based on lignin and preparation method thereof |
| CN106757174A (en) * | 2017-02-23 | 2017-05-31 | 黄芃 | A kind of electro-deposition prepares the method and device of metal dust |
| CN108927228A (en) * | 2018-08-07 | 2018-12-04 | 哈尔滨工业大学 | A kind of preparation method of carbon cloth load type Fenton catalyst |
-
2019
- 2019-03-14 CN CN201910194920.4A patent/CN109896598B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674525A (en) * | 2011-03-15 | 2012-09-19 | 吉林师范大学 | Method for preparing cathode for cathode electro-fenton process |
| CN102641722A (en) * | 2012-04-24 | 2012-08-22 | 清华大学 | Arsenic removal material by adsorption of electrochemistry strengthened nano ferro-manganese loaded carbon fiberand arsenic removal method by using same |
| CN106400048A (en) * | 2016-09-10 | 2017-02-15 | 华南理工大学 | Electro-Fenton cathode material based on lignin and preparation method thereof |
| CN106757174A (en) * | 2017-02-23 | 2017-05-31 | 黄芃 | A kind of electro-deposition prepares the method and device of metal dust |
| CN108927228A (en) * | 2018-08-07 | 2018-12-04 | 哈尔滨工业大学 | A kind of preparation method of carbon cloth load type Fenton catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109896598A (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109896598B (en) | Preparation method of electro-Fenton cathode material based on carbon felt supported iron nanoparticles and application of electro-Fenton cathode material in degradation of organic pollutants in water | |
| Radi et al. | The comparison of sonochemistry, electrochemistry and sonoelectrochemistry techniques on decolorization of CI Reactive Blue 49 | |
| CN111196653A (en) | Electro-catalytic Fenton oxidation-electrochemical oxidation coupling process and device for efficient treatment of chemical wastewater | |
| CN102092820A (en) | Method and device for removing organic matters from water by using double-pool double-effect visible light in response to photo-electro-Fenton reaction | |
| CN107445244B (en) | Photoelectrocatalysis-chlorine free radical denitrification method | |
| CN108275777A (en) | A kind of cathode catalysis film coupling membraneless microbiological fuel cell is used for coking wastewater processing system | |
| CN111153470B (en) | Preparation method of electro-Fenton cathode material based on carbon felt loaded cobalt particles and application of electro-Fenton cathode material in sewage treatment | |
| CN201567249U (en) | Ultrasonic electrochemical wastewater treatment device | |
| CN210656331U (en) | Sewage treatment device of coupling microbial fuel cell and electro-Fenton system | |
| CN105084648A (en) | Treatment method for hardly biodegraded sewage | |
| CN102633322A (en) | Semi-coke waste water pretreatment method based on Electro-Fenton oxidization technology | |
| Xu et al. | The feasibility and mechanism of reverse electrodialysis enhanced photocatalytic fuel cell-Fenton system on advanced treatment of coal gasification wastewater | |
| CN106830467B (en) | Fenton method sewage treatment integrated device based on iron mud recycling and method thereof | |
| CN103435134A (en) | Method for improving biodegradability of semi-coking wastewater based on CNTs/Fe3O4 three-dimensional electric-Fenton | |
| CN211946615U (en) | Electrochemical coupling ozone micro-nano bubble processing system | |
| WO2012137992A1 (en) | Microbial fuel cell that produces electrical energy from wastewater containing organic matter | |
| CN106145483B (en) | Multiple oxidation treatment method and device for wastewater | |
| Liu et al. | Green degradation for ribavirin on sulfur-doped MnFe2O4 photoelectrocatalysis cathode electrode | |
| CN113683234A (en) | Tubular membrane electrode and heterogeneous ozone catalyst coupled degradation device and degradation method | |
| CN105198049A (en) | Method of sewage treatment | |
| WO2023098252A1 (en) | Photoelectric microbial coupling nitrogen and carbon removal system | |
| CN113800605B (en) | Method for treating aquaculture seawater tail water based on photoelectrocatalysis to generate free radicals | |
| CN102060419A (en) | Treating process of printing and dyeing waste water | |
| CN113511760B (en) | Mn (Mn) 2+ Method for electrocatalytic degradation of organic pollutants coupled with peroxodisulfate | |
| CN105776776A (en) | Treatment method of cotton fabric printing and dyeing wastewater |
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 |