CN115594283A - Preparation method and application of iron-cobalt bimetal composite carbon felt electrode - Google Patents
Preparation method and application of iron-cobalt bimetal composite carbon felt electrode Download PDFInfo
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- CN115594283A CN115594283A CN202211350811.5A CN202211350811A CN115594283A CN 115594283 A CN115594283 A CN 115594283A CN 202211350811 A CN202211350811 A CN 202211350811A CN 115594283 A CN115594283 A CN 115594283A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 150000001721 carbon Chemical class 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 5
- 231100000719 pollutant Toxicity 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 55
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- 238000005406 washing Methods 0.000 claims description 42
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 34
- 229960002089 ferrous chloride Drugs 0.000 claims description 32
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 26
- 239000013110 organic ligand Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 230000007935 neutral effect Effects 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 239000007772 electrode material Substances 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000007810 chemical reaction solvent Substances 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 16
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 1
- 238000010525 oxidative degradation reaction Methods 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052742 iron Inorganic materials 0.000 abstract description 24
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 229910017061 Fe Co Inorganic materials 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 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 description 25
- 229940012189 methyl orange Drugs 0.000 description 25
- -1 hydroxyl free radical Chemical class 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 238000005273 aeration Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 150000004685 tetrahydrates Chemical class 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- 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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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- 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
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F2101/38—Organic compounds containing nitrogen
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- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention discloses a preparation method and application of an iron-cobalt bimetal composite carbon felt electrode, and belongs to the technical field of electrochemical advanced oxidation water treatment. The method takes a carbon felt as a substrate, prepares a modified carbon felt electrode with Fe-Co bimetal MOFs in-situ growth by a one-step hydrothermal synthesis method, and obtains the Fe-Co bimetal composite carbon felt electrode by carbonization treatment in a nitrogen atmosphere. Compared with the conventional electrode preparation method, the coating method and the tabletting method are simple and convenient to operate, and the stability of the electrode is excellent. When the composite material is used as a working cathode and applied to the heterogeneous electro-Fenton sewage treatment, the composite material shows high-efficiency catalytic degradation performance, a wide pH application range and low energy consumption, and compared with homogeneous Fenton and dispersed heterogeneous electro-Fenton treatment methods, the composite material avoids the generation of secondary pollutants of iron mud and avoids the separation and recovery of catalysts. Therefore, the iron-cobalt bimetal composite carbon felt electrode prepared by the method has better application potential in the aspect of sewage treatment.
Description
Technical Field
The present invention belongs to the field of electrochemical advanced oxidation water treatment technology. In particular to a preparation method of an iron-cobalt bimetal composite carbon felt electrode and application thereof in sewage treatment.
Background
The electro-Fenton technology is a novel advanced oxidation technology from Fenton reaction and adopts the principle that O is subjected to oxygen enrichment under the conditions of electrification and oxygen enrichment 2 In-situ generation of H by two-electron reduction reaction at cathode 2 O 2 H produced by the cathode 2 O 2 And metal catalytic ion Fe 2+ The Fenton reaction is carried out to generate hydroxyl free radical OH, the OH oxidizes and decomposes the organic pollutants difficult to degrade into small molecular substances with low toxicity or no toxicity by the strong oxidizing property of the OH, and further completely degrades into CO 2 And H 2 And O, thereby realizing the high-efficiency treatment of the organic pollutants which are difficult to degrade in the water. electro-Fenton technology relies on the cathode to generate H in situ 2 O 2 The step of adding hydrogen peroxide in the original Fenton reaction is avoided, and potential risks in the process of transporting and using the hydrogen peroxide are avoided. In addition, due to the high efficiency and environmental friendliness of electro-fenton technology, researchers have attracted considerable attention in recent years.
electro-Fenton's technique based on metal catalytic ions Fe 2+ The modes participating in the Fenton reaction can be roughly divided into three types, namely a homogeneous electro-Fenton technology, a dispersed heterogeneous electro-Fenton technology and an in-situ heterogeneous electro-Fenton technology. The in-situ heterogeneous electro-Fenton technology solves the problems that the homogeneous electro-Fenton technology is obviously limited by pH and iron mud secondary pollutants are generated in the treatment process, and the catalyst recovery of the dispersed heterogeneous electro-Fenton technology is complex. Therefore, in recent years, in-situ heterogeneous electro-Fenton technology is widely applied to the treatment research of organic pollutants difficult to degrade in water by researchers, wherein the research focus is on preparing a catalytic cathode with excellent performance, and how to prepare Fe loaded with catalytic metal ions 2+ Moreover, catalytic cathodes with excellent performance have become a focus of great attention of researchers.
The MOFs is a novel porous material formed by self-assembling inorganic metal nodes and organic ligands through coordination bonds. MOFs have the characteristics of porous structure, large surface area, ordered structure, adjustable chemical composition and the like, and have great potential in the application fields of adsorption separation, catalysis, gas storage, medical diagnosis and the like. However, MOFs have poor stability in water, which prevents their use in aqueous environments and long-term operation. Therefore, at present, researchers often use MOFs as a precursor and obtain a MOFs-derived carbon material through carbonization. The MOFs derived carbon material reserves the three-dimensional structure of the MOFs, has enhanced stability, and can be better applied to water treatment processes such as adsorption separation, catalytic degradation and the like, thereby widening the application range of the MOFs material.
The carbon fiber felt (carbon felt for short) has a highly developed microporous structure, a large adsorption capacity, a three-dimensional self-supporting structure and good conductivity, and is therefore often used as an electrode material in the field of electrochemical research. The invention utilizes carbon felt as a substrate electrode material, iron-cobalt MOF-74 is grown on the substrate carbon felt in situ by a one-step hydrothermal synthesis method to prepare a bimetal MOF composite electrode, and the iron-cobalt bimetal composite carbon felt electrode is obtained after carbonization in a tube furnace. And a heterogeneous electro-Fenton system is constructed and used for a cathode in the heterogeneous electro-Fenton system to carry out in-situ catalytic oxidation degradation on organic pollutants under a near-neutral condition, so that the high-efficiency degradation of the pollutants is realized, and the pH value range of the application is widened.
Disclosure of Invention
The invention provides a preparation method of an iron-cobalt bimetal composite carbon felt electrode, which comprises the following steps:
(1) Putting the carbon felt into a mixed solvent, washing and drying to constant weight;
(2) Under the conditions of heating and condensing reflux, oxidizing the cleaned carbon felt obtained in the step (1) by using concentrated nitric acid;
(3) Soaking and washing the carbon oxide felt obtained in the step (2) until the cleaning solution is neutral, and drying to constant weight to obtain a pretreated carbon felt;
(4) Adding metal salt into a reaction solvent according to a ratio, dissolving, and stirring to fully mix to obtain a stirring solution;
(5) Adding organic ligand 2, 5-dihydroxy terephthalic acid (DHTA) into the stirring solution obtained in the step (4) according to the ratio of the metal salt to the organic ligand, dissolving and stirring to obtain an MOF precursor solution;
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), stirring, then moving into a 100mL polytetrafluoroethylene lining hydro-thermal synthesis reaction kettle together, introducing nitrogen into the polytetrafluoroethylene lining for a period of time, discharging air, assembling the hydro-thermal synthesis reaction kettle, placing the hydro-thermal synthesis reaction kettle into a drying oven for hydro-thermal reaction, taking out the modified carbon felt, washing and drying;
(7) And (4) calcining the modified carbon felt obtained in the step (6) by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material.
Further, in the above technical solution, in the step (1), the mixed solvent is absolute ethyl alcohol and acetone, and the volume ratio is 1; the washing is firstly ultrasonic cleaning and then washing by deionized water.
Further, in the technical scheme, the heating in the step (2) adopts water bath heating, and the heating temperature is 90-95 ℃; carrying out oxidation treatment on the carbon felt obtained in the step (1) by concentrated nitric acid, and shaking once every 10-20min in the oxidation process for 3-4 h; and (4) soaking and washing the carbon oxide felt by deionized water in the step (3) until the washing liquid is neutral, wherein the drying temperature is 60-80 ℃.
Further, in the above technical solution, the metal salt in the step (4) is ferrous chloride tetrahydrate; in the step (4), the reaction solvent is N, N-Dimethylformamide (DMF), methanol and deionized water, and the volume ratio is 10.
Further, in the above technical solution, the metal salt in the step (4) is ferrous chloride tetrahydrate and cobalt nitrate hexahydrate, and when the metal salt is ferrous chloride tetrahydrate and cobalt nitrate hexahydrate, the ferrous chloride tetrahydrate accounts for more than 25% of the total mole of the metal salt; in the step (5), the molar ratio of the metal salt to the organic ligand is 1-3; the dissolving and stirring are carried out by magnetic stirring after ultrasonic dissolving.
Further, in the above technical scheme, in the step (6), the MOF precursor solution and the carbon felt are together transferred into 100mL of polytetrafluoroethylene lining, and nitrogen is introduced into the polytetrafluoroethylene lining to exhaust air; the temperature of the hydrothermal reaction is 105-145 ℃, and the reaction time is 20-25h; the hydrothermal reaction temperature is provided by the temperature of an oven, the reaction kettle is assembled and put into the oven, and the temperature of the oven is adjusted; the washing is washing by sequentially adopting methanol and deionized water.
Further, in the above technical scheme, in the step (7), a tubular furnace is used for calcination, the calcination protective gas is nitrogen, the calcination temperature is 500-800 ℃, and the calcination time is 1-4 h.
The invention provides a preparation method of the self-supporting catalytic electrode, namely an MOFs in-situ growth method.
The invention also provides an application of the iron-cobalt bimetal composite carbon felt electrode, which is characterized in that the iron-cobalt bimetal composite carbon felt electrode is used as a cathode, the carbon oxide felt obtained in the step (3) is used as an anode, and a heterogeneous electro-Fenton system is constructed and applied to actual sewage treatment.
Further, in the technical scheme, the iron-cobalt bimetallic composite carbon felt electrode is used as a cathode to construct a heterogeneous electro-Fenton system to degrade pollutants which are difficult to degrade in water through in-situ catalytic oxidation under a neutral condition, wherein the neutral condition is that the pH value is 6-7.
The invention has the beneficial effects
1. The invention carries out concentrated nitric acid oxidation treatment on the carbon felt, and is beneficial to catalyzing the adhesion of metal ions and the in-situ growth of MOFs.
2. Compared with the existing electro-Fenton cathode preparation method, coating method and tabletting method, the preparation method of the self-supporting catalytic electrode, namely MOFs in-situ growth method, provided by the invention has the advantages of simplicity in operation, stable structure and excellent performance.
3. The iron-cobalt bimetallic composite carbon felt electrode prepared by the method is used as a cathode in a heterogeneous electro-Fenton system, and can generate H through two-electron reduction reaction of oxygen at the cathode 2 O 2 And H produced 2 O 2 Can directly generate Fenton reaction with catalytic metal ions on the electrode to generate hydroxyl radicals with strong oxidizing property. At the same time, it is fully beneficialThe reduction rate of the high-valence metal ions to the low-valence metal ions is accelerated by the synergistic action of the reducibility of the cathode and the second metal, the efficient degradation of methyl orange is realized under a neutral condition, and the pH application range is widened.
Drawings
FIG. 1 shows the degradation effect of different molar ratios of Fe-Co bimetallic prepared electrodes on methyl orange in a heterogeneous electro-Fenton system. ( Curve a: example 1; curve b: example 2; and c, curve c: example 3; curve d: example 4; curve e: example 5; curve f: example 6 )
FIG. 2 shows the degradation effect of different molar ratios of metal salt to organic ligand on methyl orange in a heterogeneous electro-Fenton system. ( Curve a: example 7; curve b: example 8; curve c: example 2 )
Fig. 3 shows the degradation effect of different hydrothermal synthesis temperatures for preparing electrodes on methyl orange in a heterogeneous electro-fenton system. ( Curve a: example 9; curve b: example 2; curve c: example 10 )
Fig. 4 shows the effect of different carbonization temperatures for preparing electrodes on the degradation of methyl orange in a heterogeneous electro-fenton system. ( Curve a: example 11; curve b: example 2; curve c: example 12 )
Detailed Description
The invention is further described with reference to the following figures and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claimed invention.
Example 1
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating the carbon felt after being cleaned obtained in the step (1) when the water bath temperature is 95 ℃, oxidizing the carbon felt by concentrated nitric acid for 3 hours, and shaking the carbon felt once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.75mmol of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 0.75mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely the ratio M of metal salt to organic ligand (O = 3);
(6) Placing the carbon felt pretreated in the step (3) in the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring the carbon felt into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24 hours, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1).
The removal rate of methyl orange reaches 95.85% at 60min, as shown by curve a in fig. 1, when C-Fe, co (1) -MOF-74@ OCF is used as a cathode, OCF is used as an anode, the distance between the anode and the cathode is 3cm, the concentration of sodium sulfate electrolyte is 0.05M, the reaction conditions are pH =7, I =40mA, the aeration rate is 0.4L/min, 200mL of simulated methyl orange wastewater with the concentration of 20mg/L is degraded.
Example 2
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.5mmol of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 1mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligating body 2, 5-dihydroxyterephthalic acid (DHTA), namely, the ratio M of metal salt to organic ligating body is (O = 3);
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1).
C-Fe, co (1 2) -MOF-74@ OCF was used as a cathode, OCF was used as an anode, the distance between the anode and the cathode was 3cm, the sodium sulfate electrolyte concentration was 0.05M, the reaction conditions were pH =7, i =40ma, the aeration amount was 0.4L/min, 200mL of simulated methyl orange wastewater having a concentration of 20mg/L was degraded, and at 60min, the removal rate of methyl orange reached 97.55% as shown by curve b in fig. 1.
Example 3
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight when the temperature of the drying oven is 70 ℃ until the cleaning solution is neutral;
(4) 1mmol of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 0.5mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely the ratio M of metal salt to organic ligand (O = 3);
(6) Placing the carbon felt pretreated in the step (3) in the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring the carbon felt into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24 hours, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (2.
C-Fe, co (2).
Example 4
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.375mmol of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 1.125mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely the ratio M of metal salt to organic ligand (O = 3);
(6) Placing the carbon felt pretreated in the step (3) in the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring the carbon felt into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24 hours, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1.
The removal rate of methyl orange reaches 96.66% at 60min, as shown by curve d in fig. 1, when C-Fe, co (1 3) -MOF-74@ OCF is used as a cathode, OCF is used as an anode, the distance between the anode and the cathode is 3cm, the concentration of sodium sulfate electrolyte is 0.05M, the reaction conditions are pH =7, I =40mA, the aeration rate is 0.4L/min, 200mL of simulated methyl orange wastewater with the concentration of 20mg/L is degraded.
Example 5
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 1.125mmol of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 0.375mmol cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligating body 2, 5-dihydroxyterephthalic acid (DHTA), namely, the ratio M of metal salt to organic ligating body is (O = 3);
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material, which is recorded as C-Fe, co (3).
C-Fe, co (3).
Example 6
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 1.5mmol of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely the ratio M of metal salt to organic ligand (O = 3);
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (4) calcining the modified carbon felt obtained in the step (6) for 2 hours at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain a modified carbon felt electrode material, and marking the modified carbon felt electrode material as C-Fe-MOF-74@ OCF.
C-Fe-MOF-74@ OCF is used as a cathode, OCF is used as an anode, the distance between the anode and the cathode is 3cm, the concentration of sodium sulfate electrolyte is 0.05M, the reaction conditions are pH =7, I =40mA, the aeration rate is 0.4L/min, 200mL of simulated methyl orange wastewater with the concentration of 20mg/L is degraded, and the removal rate of methyl orange reaches 95.05% at 60min as shown by a curve f in FIG. 1.
Example 7
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.5mmol of ferrous chloride (FeCl) tetrahydrate 2 ·4H 2 O) and 1mmol cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 1.5mmol of organic ligating body 2, 5-dihydroxyterephthalic acid (DHTA), namely, the ratio M of metal salt to organic ligating body is (O = 1);
(6) Placing the carbon felt pretreated in the step (3) in the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring the carbon felt into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24 hours, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1).
C-Fe, co (1 2) -MOF-74@ OCF was used as a cathode, OCF was used as an anode, the distance between the anode and the cathode was 3cm, the sodium sulfate electrolyte concentration was 0.05M, the reaction conditions were pH =7, i =40ma, the aeration amount was 0.4L/min, 200mL of simulated methyl orange wastewater having a concentration of 20mg/L was degraded, and at 60min, the removal rate of methyl orange reached 97.67%, as shown by curve a in fig. 2.
Example 8
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.5mmol of ferrous chloride (FeCl) tetrahydrate 2 ·4H 2 O) and 1mmol cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.75mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely a metal salt and organic ligand in a ratio M: O = 2;
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1).
C-Fe, co (1 2) -MOF-74@ OCF was used as a cathode, OCF was used as an anode, the distance between the anode and the cathode was 3cm, the sodium sulfate electrolyte concentration was 0.05M, the reaction conditions were pH =7, i =40ma, the aeration amount was 0.4L/min, 200mL of simulated methyl orange wastewater having a concentration of 20mg/L was degraded, and at 60min, as shown by curve b in fig. 2, the removal rate of methyl orange reached 98.00%.
Example 9
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating the carbon felt after being cleaned obtained in the step (1) when the water bath temperature is 95 ℃, oxidizing the carbon felt by concentrated nitric acid for 3 hours, and shaking the carbon felt once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.5mmol of ferrous chloride (FeCl) tetrahydrate 2 ·4H 2 O) and 1mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely the ratio M of metal salt to organic ligand (O = 3);
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 115 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1.
C-Fe, co (1 2) -MOF-74@ OCF was used as a cathode, OCF was used as an anode, the distance between the anode and the cathode was 3cm, the sodium sulfate electrolyte concentration was 0.05M, the reaction conditions were pH =7, i =40ma, the aeration amount was 0.4L/min, 200mL of simulated methyl orange wastewater having a concentration of 20mg/L was degraded, and at 60min, the removal rate of methyl orange reached 90.35% as shown by curve a in fig. 3.
Example 10
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.5mmol of ferrous chloride (FeCl) tetrahydrate 2 ·4H 2 O) and 1mmol cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligating body 2, 5-dihydroxyterephthalic acid (DHTA), namely, the ratio M of metal salt to organic ligating body is (O = 3);
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 135 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 600 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1.
The removal rate of methyl orange at 60min, as shown by curve C in fig. 3, was 97.56% when C-Fe, co (1) -MOF-74@ OCF was used as the cathode, OCF was used as the anode, the inter-anode-cathode distance was 3cm, the sodium sulfate electrolyte concentration was 0.05M, the reaction conditions were pH =7, i =40ma, the aeration rate was 0.4L/min, 200mL of simulated methyl orange wastewater with a concentration of 20mg/L was degraded.
Example 11
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating the carbon felt after being cleaned obtained in the step (1) when the water bath temperature is 95 ℃, oxidizing the carbon felt by concentrated nitric acid for 3 hours, and shaking the carbon felt once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.5mmol of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) and 1mmol of cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely the ratio M of metal salt to organic ligand (O = 3);
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 500 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1).
C-Fe, co (1 2) -MOF-74@ OCF was used as a cathode, OCF was used as an anode, the distance between the anode and the cathode was 3cm, the sodium sulfate electrolyte concentration was 0.05M, the reaction conditions were pH =7, i =40ma, the aeration amount was 0.4L/min, 200mL of simulated methyl orange wastewater having a concentration of 20mg/L was degraded, and at 60min, the removal rate of methyl orange reached 98.00% as shown by curve a in fig. 4.
Example 12
(1) Putting the cut carbon felt into a conical flask, adding absolute ethyl alcohol and acetone (volume ratio is 1;
(2) Building a condensation reflux device, heating when the water bath temperature is 95 ℃ to oxidize the cleaned carbon felt concentrated nitric acid obtained in the step (1) for 3 hours, and shaking once every 15min in the oxidation process to fully oxidize the carbon felt;
(3) And (3) soaking and washing the carbon oxide felt obtained in the step (2) by using deionized water, and recording the carbon oxide felt as OCF. Drying the cleaning solution to constant weight at 70 ℃ by using an oven until the cleaning solution is neutral;
(4) 0.5mmol of ferrous chloride (FeCl) tetrahydrate 2 ·4H 2 O) and 1mmol cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O) is added into 39mL of reaction solvent consisting of N, N-Dimethylformamide (DMF), methanol and deionized water (volume ratio 10;
(5) Adding 0.5mmol of organic ligand 2, 5-dihydroxyterephthalic acid (DHTA), namely the ratio M of metal salt to organic ligand (O = 3);
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), magnetically stirring for a period of time, then transferring into a 100mL polytetrafluoroethylene lining reaction kettle together, introducing nitrogen into the reaction kettle for a period of time to discharge air, carrying out hydrothermal reaction at 125 ℃ for 24h, taking out the carbon felt, washing with deionized water and methanol, and drying;
(7) And (3) calcining the modified carbon felt obtained in the step (6) for 2h at 700 ℃ in a nitrogen environment by using a tubular furnace to obtain the iron-cobalt bimetal composite carbon felt electrode material which is marked as C-Fe, co (1.
C-Fe, co (1 2) -MOF-74@ OCF was used as a cathode, OCF was used as an anode, the distance between the anode and the cathode was 3cm, the sodium sulfate electrolyte concentration was 0.05M, the reaction conditions were pH =7, i =40ma, the aeration amount was 0.4L/min, 200mL of simulated methyl orange wastewater having a concentration of 20mg/L was degraded, and at 60min, the removal rate of methyl orange reached 97.45% as shown by curve C in fig. 4.
Claims (10)
1. The preparation method of the iron-cobalt bimetal composite carbon felt electrode is characterized in that the electrode is prepared by the following steps:
(1) Putting the carbon felt into a mixed solvent, washing and drying to constant weight;
(2) Under the conditions of heating and condensing reflux, carrying out oxidation treatment on the carbon felt obtained in the step (1) by using concentrated nitric acid;
(3) Soaking and washing the carbon oxide felt obtained in the step (2) until the cleaning solution is neutral, and drying to constant weight to obtain a pretreated carbon felt;
(4) Adding metal salt into a reaction solvent, dissolving, and stirring to fully mix to obtain a stirring solution;
(5) Adding 2, 5-dihydroxy terephthalic acid of the organic ligand into the stirring liquid obtained in the step (4) according to the proportion of the metal salt to the organic ligand, dissolving and stirring to obtain an MOF precursor solution;
(6) Placing the carbon felt obtained after pretreatment in the step (3) into the MOF precursor solution obtained in the step (5), stirring, performing hydrothermal reaction, taking out the modified carbon felt, washing and drying;
(7) And (4) calcining the modified carbon felt obtained in the step (6) to obtain the iron-cobalt bimetal composite carbon felt electrode material.
2. The preparation method of the iron-cobalt bimetal composite carbon felt electrode according to claim 1, characterized in that in the step (1), the mixed solvent is absolute ethyl alcohol and acetone, and the volume ratio is 1; the washing is firstly ultrasonic cleaning and then washing by deionized water.
3. The preparation method of the iron-cobalt bimetal composite carbon felt electrode according to claim 1, wherein the heating in the step (2) is carried out by water bath heating, and the water bath heating temperature is 90-95 ℃; carrying out oxidation treatment on the carbon felt obtained in the step (1) by concentrated nitric acid, and shaking once every 10-20min in the oxidation process for 3-4 h; and (4) soaking and washing the carbon oxide felt by deionized water in the step (3) until the washing liquid is neutral, wherein the drying temperature is 60-80 ℃.
4. The method for preparing the iron-cobalt bimetal composite carbon felt electrode according to claim 1, wherein the metal salt in the step (4) is ferrous chloride tetrahydrate; the reaction solvent is N, N-dimethylformamide, methanol and deionized water, and the volume ratio is 10.
5. The method for preparing the iron-cobalt bimetal composite carbon felt electrode according to claim 1, wherein the metal salts in the step (4) are ferrous chloride tetrahydrate and cobalt nitrate hexahydrate, and when the metal salts are the ferrous chloride tetrahydrate and the cobalt nitrate hexahydrate, the ferrous chloride tetrahydrate accounts for more than 25% of the total mol of the metal salts; the molar ratio of the metal salt to the organic ligand in the step (5) is 1-3; the dissolving and stirring are performed by magnetic stirring after ultrasonic dissolving.
6. The preparation method of the iron-cobalt bimetal composite carbon felt electrode according to claim 1, wherein the hydrothermal reaction in the step (6) is carried out in a polytetrafluoroethylene-lined hydrothermal synthesis reaction kettle; the temperature of the hydrothermal reaction is 105-145 ℃, and the reaction time is 20-25h; the washing is washing by sequentially adopting methanol and deionized water.
7. The preparation method of the iron-cobalt bimetal composite carbon felt electrode according to claim 1, wherein in the step (7), a tubular furnace is adopted for calcination, the calcination protective gas is nitrogen, the calcination temperature is 500-800 ℃, and the calcination time is 1-4 h.
8. The iron-cobalt bimetal composite carbon felt electrode prepared by the method of any one of claims 1 to 7, which is characterized in that a preparation method of a self-supporting catalytic electrode, namely an MOFs in-situ growth method, is provided.
9. The use of the iron-cobalt bimetallic composite carbon felt electrode prepared according to any one of claims 1 to 7, characterized in that a heterogeneous electro-Fenton system is constructed to degrade pollutants in a water body by using the iron-cobalt bimetallic composite carbon felt electrode as a cathode and the carbon oxide felt obtained in the step (3) in claim 1 as an anode.
10. The use of a composite carbon felt electrode according to claim 9, wherein the heterogeneous electro-Fenton system is used for in situ catalytic oxidative degradation of recalcitrant contaminants in water under neutral conditions.
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| CN113896291A (en) * | 2021-11-01 | 2022-01-07 | 北京工业大学 | Preparation and application of iron-copper bimetallic oxide composite electrode for heterogeneous electro-Fenton system |
| CN114247444A (en) * | 2021-12-31 | 2022-03-29 | 南京大学 | electro-Fenton catalyst derived from iron-cobalt bimetallic organic framework and preparation method and application thereof |
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