CN113896291A - Preparation and application of iron-copper bimetallic oxide composite electrode for heterogeneous electro-Fenton system - Google Patents
Preparation and application of iron-copper bimetallic oxide composite electrode for heterogeneous electro-Fenton system Download PDFInfo
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- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 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 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000011065 in-situ storage Methods 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003344 environmental pollutant Substances 0.000 claims description 6
- 231100000719 pollutant Toxicity 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims 1
- 238000010525 oxidative degradation reaction Methods 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 11
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000012924 metal-organic framework composite Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 229960005404 sulfamethoxazole Drugs 0.000 description 21
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000002351 wastewater Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000005273 aeration Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910002553 FeIII Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013246 bimetallic metal–organic framework Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 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
- C02F1/46—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic 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
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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Abstract
A preparation and application of an iron-copper bimetallic oxide composite electrode for a heterogeneous electro-Fenton system relate to the technical field of electrochemical water treatment. The invention takes graphite felt as a matrix, and dissolves ferrous sulfate heptahydrate, copper acetate monohydrate and 2-amino terephthalic acid in water: ethanol: taking a solution with DMF (dimethyl formamide) at a ratio of 1:1:8 as an MOF precursor solution, obtaining the iron-copper bimetal MOF composite electrode through a one-step hydrothermal synthesis method, and preparing the iron-copper bimetal oxide composite electrode after low-temperature pyrolysis in a nitrogen atmosphere. The preparation method is simple and controllable, the prepared composite self-supporting electrode has good stability, the separation and recovery of the catalyst are avoided, the secondary pollution caused by iron mud is avoided, the energy consumption is reduced, the organic pollutants can be efficiently degraded under the near-neutral condition, and the preparation method has good application potential.
Description
Technical Field
The invention relates to the technical field of electrochemical water treatment, in particular to a preparation method of an iron-copper bimetallic oxide composite electrode prepared by taking MOF as a precursor and application of the electrode in a heterogeneous electro-Fenton system.
Background
The electro-Fenton technique, one of the advanced oxidation techniques, is considered as a very potential technique due to its environmental friendliness and the characteristic of generating high concentration of hydroxyl radicals (. OH), and is applied to oxidation, degradation and mineralization of various organic compounds. The basic principle is O2The two electrons are reduced at the cathode to generate H2O2，Fe2+And H2O2OH is generated by the reaction, thereby the organic matter is oxidized and degraded into the organic matter with low or no toxicityToxic small molecular substances realize the high-efficiency treatment of the organic matters difficult to degrade.
The conventional heterogeneous electro-Fenton process has many limitations. Such as secondary sludge, the ferric and ferrous ions contained in the treated wastewater produce hydroxide precipitates that increase cost and reduce overall efficiency. To limit the occurrence of precipitates, the system must be operated under strict ph control. Since these hydroxides are soluble only at pH values below about 4, the pH of the wastewater should reach 2.0-3.0.
In recent years, heterogeneous electro-fenton technology has become a solution to the problem of ferric hydroxide precipitation. In heterogeneous electro-Fenton, the iron catalyst is present in solid form, and Fe is addedⅡ/FeⅢThe solid state is maintained, and the defects of iron mud generation, narrow pH application range and the like are overcome. But still has the defects of easy loss, difficult recovery, poor reusability and the like of the catalyst. The catalyst is combined with a proper electrode material to realize in-situ catalytic oxidation degradation of organic pollutants, so that the problems can be overcome, and Fe in the catalyst can be solvedⅡReduction to FeⅢThe process of (2) is slow, and the catalyst is recovered. In-situ catalysis in heterogeneous electro-Fenton technology has gradually become a research hotspot in advanced oxidation technology of water treatment.
Metal-organic framework (MOF) is a permanent microporous material with diverse topological structures, a highly ordered porous crystal structure synthesized from Metal ions/clusters and multidentate organic ligands. MOFs have the characteristics of large surface area, ordered structure, easy functionalization and the like, and are potential water treatment catalyst materials. However, MOFs have poor stability in water, preventing their widespread use and long-term operation. For this reason, strategies to thermally convert MOF materials into robust nanomaterials improve their stability, thereby widening the range of applications of MOF materials.
The graphite felt is an electrode material which has a three-dimensional structure, is good in conductivity, high in tensile strength, large in specific surface area, and has obvious advantages for other carbon electrodes, so that the graphite felt is widely applied. According to the invention, graphite felt is used as a carbon-based electrode material, iron-copper MOF is directly loaded on the graphite felt electrode through a one-step hydrothermal synthesis method to prepare a bimetallic MOF composite electrode, the composite electrode is calcined in a nitrogen atmosphere to obtain an iron-copper bimetallic oxide electrode which is used for a cathode in a heterogeneous electro-Fenton body, in-situ catalytic oxidation degradation is carried out on organic pollutants under a near-neutral condition, the efficient degradation of the pollutants is realized, and the pH value range of the reaction is widened. The self-supporting electrode with the active component growing in situ not only improves the diffusivity to reactants, but also has lower internal resistance to accelerate the mass transfer speed.
Disclosure of Invention
The invention provides preparation and application of an iron-copper bimetallic oxide composite electrode prepared by taking MOF as a precursor in a heterogeneous electro-Fenton system. The composite electrode provided by the invention has the advantages of high catalytic efficiency, simple operation, convenient control and good catalytic effect under a near-neutral condition, overcomes the defects of narrow pH value range, easy generation of iron mud, difficult catalyst recovery and the like, reacts with hydrogen peroxide continuously generated on a cathode, and is subjected to in-situ catalysis to be converted into hydroxyl radicals with strong oxidizing property to efficiently degrade pollutants.
A preparation method of an iron-copper bimetallic oxide composite electrode for a heterogeneous electro-Fenton system comprises the following specific steps:
(1) soaking the graphite felt in acetone for ultrasonic treatment, washing with deionized water for several times, and drying;
(2) 0-50mM ferrous sulfate heptahydrate, 0-50mM copper acetate monohydrate and 50mM 2-amino terephthalic acid, terephthalic acid or trimesic acid are completely dissolved in water: ethanol: obtaining an MOF precursor solution in a solution with the volume ratio of DMF being 1:1: 8; ferrous sulfate and copper acetate are not 0 at the same time; preferably, the monohydrate of the copper acetate is 0-20mM, and further preferably, both the ferrous sulfate and the copper acetate are not 0;
(3) placing the pretreated graphite felt obtained in the step (1) into the MOF precursor solution obtained in the step (2), placing the pretreated graphite felt into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 90-150 ℃ for 24 hours, cleaning with deionized water and ethanol, and drying;
(4) and (4) placing the graphite felt electrode loaded with the iron-copper MOF obtained in the step (3) in a high-temperature atmosphere furnace, and pyrolyzing the graphite felt electrode at the temperature of 200-600 ℃ for 2h in the nitrogen atmosphere to obtain the iron-copper bimetallic oxide composite electrode material.
The iron-copper bimetallic oxide composite electrode obtained by the preparation method is used as a cathode, is applied to a heterogeneous electro-Fenton system, and is used for in-situ catalytic oxidation degradation of refractory pollutants under a near-neutral condition (pH is 5.6).
Compared with the prior art, the invention has the following excellent effects:
1. the invention does not need to add catalyst and has good stability.
2. Compared with the existing electro-Fenton cathode material, the bimetallic MOF is loaded on the pretreated graphite felt by a one-step hydrothermal method and pyrolyzed to obtain the bimetallic oxide composite electrode, and the preparation method is simple to operate, convenient and controllable.
3. The composite electrode material prepared by the method is used as a cathode to be applied to a heterogeneous electro-Fenton system, and not only is used as cathode for generating H through electro-catalysis2O2The metal ion can be catalyzed in situ to be converted into hydroxyl radical with strong oxidizing property, simultaneously, the reduction rate of high-valence metal ions to low-valence metal ions is accelerated by fully utilizing the synergistic action of the reducibility of the cathode and the second metal, the sulfamethoxazole is efficiently degraded under the near-neutral condition, and the pH application range is widened (in the prior art, the acidity of a pollutant aqueous solution needs to be regulated and controlled, but the invention can be directly degraded under the acidic condition of the pollutant aqueous solution and can be degraded under the alkaline condition).
Drawings
Fig. 1 is a plot of cyclic voltammetry for the iron-copper bimetallic oxide electrode prepared in example 1 versus the pretreated graphite felt prepared in comparative example 1. (Curve a: comparative example 1; Curve b: example 1)
Fig. 2 is a linear cyclic voltammogram of the iron-copper bimetallic oxide electrode prepared in example 1 and the pretreated graphite felt prepared in comparative example 1. (Curve a: comparative example 1; Curve b: example 1)
FIG. 3 is an X-ray diffraction pattern of electrodes obtained under different preparation conditions. (Curve a: example 1; curve b: example 2; curve c: comparative example 2)
FIG. 4 shows the degradation effect of different molar ratios of bimetallic prepared electrodes on sulfamethoxazole in a heterogeneous electro-Fenton system. (Curve a: example 2; Curve b: example 3; Curve c: example 1)
FIG. 5 shows the degradation effect of sulfamethoxazole in a heterogeneous electro-Fenton system when electrodes are prepared at different hydrothermal temperatures. (Curve a: example 5; Curve b: example 4; Curve c: example 1)
FIG. 6 shows the degradation effect of sulfamethoxazole in a heterogeneous electro-Fenton system when electrodes are prepared under different pH conditions. (Curve a: example 6; Curve b: example 7; Curve c: example 1)
Detailed Description
The following detailed description is given in conjunction with the accompanying drawings and specific examples, but the present invention is not limited to the following examples.
Example 1
(1) Soaking the graphite felt in acetone for ultrasonic treatment, washing with deionized water for several times, and drying;
(2) completely dissolve 33.25mM ferrous sulfate heptahydrate, 16.67mM copper acetate monohydrate, 50mM 2-amino terephthalic acid in water: ethanol: obtaining MOF precursor solution in a solution with DMF at a ratio of 1:1: 8;
(3) putting the pretreated graphite felt obtained in the step (1) and the MOF precursor solution obtained in the step (2) into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 90 ℃ for 24 hours, cleaning with deionized water and ethanol, and drying;
(4) and (4) placing the graphite felt electrode loaded with the iron-copper MOF obtained in the step (3) in a high-temperature atmosphere furnace, and pyrolyzing the graphite felt electrode at 300 ℃ for 2 hours in a nitrogen atmosphere to obtain the iron-copper bimetallic oxide composite electrode material.
The electrode is used as a cathode, a platinum sheet 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 condition is that the pH is 5.6, the I is 150mA, the aeration rate is 0.6L/min, 200mL sulfamethoxazole wastewater with the concentration of 10mg/L is degraded, and when the time is 45min, the removal rate of sulfamethoxazole reaches 100% as shown by a curve c in figure 4.
Example 2
The specific preparation process is the same as (1) (3) (4) in example 1, and the difference of the (2) step is that 50mM ferrous sulfate heptahydrate and 50mM 2-amino terephthalic acid are completely dissolved in water: ethanol: and (3) in a solution with DMF (dimethyl formamide) being 1:1:8, obtaining an MOF precursor solution.
The obtained monometallic iron oxide electrode is used as a cathode, a platinum sheet 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 that the pH is 5.6, the I is 150mA, the aeration rate is 0.6L/min, 200mL sulfamethoxazole wastewater with the concentration of 10mg/L is degraded, and when the time is 45min, as shown by a curve a in figure 4, the removal rate of sulfamethoxazole reaches 88%.
Example 3
The specific preparation process was the same as (1) (3) (4) in example 1, and the difference in the (2) step was that 40M ferrous sulfate heptahydrate, 10mM copper acetate monohydrate, and 50mM 2-aminoterephthalic acid were completely dissolved in water: ethanol: and (3) in a solution with DMF (dimethyl formamide) being 1:1:8, obtaining an MOF precursor solution.
The obtained bimetallic oxide electrode is used as a cathode, a platinum sheet 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 condition is that the pH is 5.6, the I is 150mA, the aeration rate is 0.6L/min, 200mL sulfamethoxazole wastewater with the concentration of 10mg/L is degraded, and when the time is 45min, the removal rate of sulfamethoxazole reaches 96% as shown by a curve b in figure 4.
Example 4
The specific preparation process is the same as (1), (2) and (4) in example 1, and the difference of the step (3) is that the hydrothermal reaction temperature is 120 ℃, the hydrothermal time is 24 hours, and the mixture is washed by deionized water and ethanol and dried.
The obtained bimetallic oxide electrode is used as a cathode, a platinum sheet 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 condition is that the pH is 5.6, the I is 150mA, the aeration rate is 0.6L/min, 200mL sulfamethoxazole wastewater with the concentration of 10mg/L is degraded, and when the time is 45min, as shown by a curve b in figure 5, the removal rate of sulfamethoxazole reaches 95%.
Example 5
The specific preparation process is the same as (1), (2) and (4) in example 1, and the difference of the (3) step is that the hydrothermal reaction temperature is 150 ℃ and the hydrothermal time is 24 h.
The obtained bimetallic oxide electrode is used as a cathode, a platinum sheet 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 condition is that the pH is 5.6, the I is 150mA, the aeration rate is 0.6L/min, 200mL sulfamethoxazole wastewater with the concentration of 10mg/L is degraded, and when the time is 45min, as shown by a curve a in figure 5, the removal rate of sulfamethoxazole reaches 100%.
Example 6
The preparation process was the same as that of (1), (2), (3) and (4) in example 1, except that the reaction pH was 7.
The obtained bimetallic oxide electrode is used as a cathode, a platinum sheet 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 condition is that the pH is 7, the I is 150mA, the aeration rate is 0.6L/min, 200mL sulfamethoxazole wastewater with the concentration of 10mg/L is degraded, and when the time is 45min, the removal rate of sulfamethoxazole reaches 96% as shown by a curve a in figure 6.
Example 7
The preparation process was the same as that of (1), (2), (3) and (4) in example 1, except that the reaction pH was set to 9.
The obtained bimetallic oxide electrode is used as a cathode, a platinum sheet 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 condition is that the pH is 9, the I is 150mA, the aeration rate is 0.6L/min, 200mL sulfamethoxazole wastewater with the concentration of 10mg/L is degraded, and when the time is 45min, the removal rate of sulfamethoxazole reaches 95% as shown by a curve b in figure 6.
Comparative example 1
Soaking the graphite felt in acetone for ultrasonic treatment, washing with deionized water for several times, and drying.
Comparative example 2
(1) Soaking the graphite felt in acetone for ultrasonic treatment, washing with deionized water for several times, and drying;
(2) completely dissolve 33.25mM ferrous sulfate heptahydrate, 16.67mM copper acetate monohydrate, 50mM 2-amino terephthalic acid in water: ethanol: obtaining MOF precursor solution in a solution with DMF at a ratio of 1:1: 8;
(3) and (3) putting the pretreated graphite felt obtained in the step (1) and the MOF precursor solution obtained in the step (2) into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 90 ℃ for 24 hours, cleaning with deionized water and ethanol, and drying.
The results of the examples and the comparative examples show that the 45min removal rate of sulfamethoxazole is only 44% when the graphite felt electrode without catalyst loading is used in the heterogeneous electro-Fenton system, while the 45min removal rate of sulfamethoxazole reaches 100% when the composite electrode prepared by the invention is used in the heterogeneous electro-Fenton system. The degradation effect comparison before and after doping the second metal shows that the synergistic effect of the second metal accelerates the reduction rate of the high valence metal ions to the low valence metal ions, and the degradation efficiency is greatly improved.
The iron-copper bimetallic oxide composite electrode prepared by the invention has metal/metal oxide nanoparticles with high activity and strong stability, and widens the reaction pH value range. The self-supporting electrode with the active component growing in situ not only improves the diffusivity to reactants, but also accelerates the mass transfer speed due to lower internal resistance. In addition, the self-supporting electrode can simplify the operation, avoid the steps of separating and recovering the catalyst, avoid the secondary pollution generated by the iron mud and reduce the energy consumption. The invention is applied to an electro-Fenton system and can efficiently degrade sulfamethoxazole.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification of the above embodiment according to the technical spirit of the present invention is within the scope of the present invention, unless departing from the technical spirit of the present invention.
Claims (6)
1. The preparation method of the iron-copper bimetal oxide composite electrode is characterized by comprising the following specific steps of:
(1) soaking the graphite felt in acetone for ultrasonic treatment, washing with deionized water for several times, and drying;
(2) 0-50mM ferrous sulfate heptahydrate, 0-50mM copper acetate monohydrate and 50mM 2-amino terephthalic acid, terephthalic acid or trimesic acid are completely dissolved in water: ethanol: obtaining an MOF precursor solution in a solution with the volume ratio of DMF being 1:1: 8; ferrous sulfate and copper acetate are not 0 at the same time;
(3) placing the pretreated graphite felt obtained in the step (1) into the MOF precursor solution obtained in the step (2), placing the pretreated graphite felt into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 90-150 ℃ for 24 hours, cleaning with deionized water and ethanol, and drying;
(4) and (4) placing the graphite felt electrode loaded with the iron-copper MOF obtained in the step (3) in a high-temperature atmosphere furnace, and pyrolyzing the graphite felt electrode at the temperature of 200-600 ℃ for 2h in the nitrogen atmosphere to obtain the iron-copper bimetallic oxide composite electrode material.
2. The method for preparing an iron-copper bimetal oxide composite electrode according to claim 1, wherein the copper acetate in the step (2) is 0 to 20 mM.
3. The method for preparing an iron-copper bimetal oxide composite electrode according to claim 1, wherein the ferrous sulfate and the copper acetate in the step (2) are not 0.
4. An iron-copper bimetallic oxide composite electrode prepared according to the method of any one of claims 1 to 3.
5. Use of an iron-copper bimetallic oxide composite electrode prepared according to the method of any one of claims 1 to 3 as a cathode in a heterogeneous electro-Fenton system.
6. Use according to claim 5 for the in situ catalytic oxidative degradation of recalcitrant pollutants under near neutral conditions (pH 5.6).
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| CN115594283A (en) * | 2022-10-31 | 2023-01-13 | 大连海事大学（Cn） | Preparation method and application of iron-cobalt bimetal composite carbon felt electrode |
| CN116161754A (en) * | 2023-03-16 | 2023-05-26 | 北京工业大学 | Preparation and application of copper-aluminum-loaded layered double metal oxide modified graphite felt electrode for heterogeneous electro-Fenton system |
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| CN113149155A (en) * | 2021-05-20 | 2021-07-23 | 北京工业大学 | Cu-doped Fe2O3Preparation and application of nano-particle/porous graphite felt cathode |
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| CN111392821A (en) * | 2020-04-01 | 2020-07-10 | 同济大学 | Preparation method and application of graphite felt-loaded metal organic framework compound cathode material |
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| CN115594283A (en) * | 2022-10-31 | 2023-01-13 | 大连海事大学（Cn） | Preparation method and application of iron-cobalt bimetal composite carbon felt electrode |
| CN115594283B (en) * | 2022-10-31 | 2024-08-23 | 大连海事大学 | Preparation method and application of iron-cobalt bimetal composite carbon felt electrode |
| CN116161754A (en) * | 2023-03-16 | 2023-05-26 | 北京工业大学 | Preparation and application of copper-aluminum-loaded layered double metal oxide modified graphite felt electrode for heterogeneous electro-Fenton system |
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