CN114409052A - Preparation method and application of efficient and stable carbon-supported MnO @ C composite anode material - Google Patents
Preparation method and application of efficient and stable carbon-supported MnO @ C composite anode material Download PDFInfo
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- CN114409052A CN114409052A CN202210066216.2A CN202210066216A CN114409052A CN 114409052 A CN114409052 A CN 114409052A CN 202210066216 A CN202210066216 A CN 202210066216A CN 114409052 A CN114409052 A CN 114409052A
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 239000010405 anode material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229960003500 triclosan Drugs 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000013239 manganese-based metal-organic framework Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 14
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 14
- 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 14
- 229940099607 manganese chloride Drugs 0.000 claims description 14
- 235000002867 manganese chloride Nutrition 0.000 claims description 14
- 239000011565 manganese chloride Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical group O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 2
- 239000012924 metal-organic framework composite Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 claims 1
- 239000007832 Na2SO4 Substances 0.000 abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000002524 organometallic group Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- C02F1/46—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a preparation method and application of a high-efficiency stable carbon-supported MnO @ C composite anode material. Under normal temperature and normal pressure and in a single-chamber three-electrode system, the carbon-supported MnO @ C composite material prepared by the invention is used as an anode, and Na2SO4As an electrolyte, oxygen in the air is used as an oxidant, and the concentration of 240mL can be 50 mg.L under the external voltage of 1.0V (v.SEC)‑1The triclosan is completely mineralized within 120min and the cycling stability of the anode material is good.
Description
Technical Field
The invention relates to a preparation method and application of a high-efficiency stable carbon-supported MnO @ C composite anode material, in particular to a carbon-supported MnO @ C composite anode material which is obtained by taking Mn-MOF loaded on the surface of a carbon felt as a precursor through high-temperature heat treatment and can promote MnO loaded on the surface of the carbon felt and skeleton carbon to synergistically catalyze air to oxidize and degrade organic pollutants in a water body under the action of a lower external electric field.
Background
Metal organic framework Materials (MOFs) are a new class of organic-inorganic hybrid nanoporous materials assembled from inorganic components (metal ions or metal clusters) and organic components (organic or organometallic complexes), and have gained wide attention due to the diversity and adjustability of their structures. MOF precursor materials are often used as sacrificial templating agents to prepare various nanoporous metal or metal oxide @ carbon composites by pyrolysis under an inert atmosphere. Due to the periodic hybrid structure of the MOF material, metal elements in the MOF material can generate high-quality nanoparticles in the pyrolysis process and are uniformly dispersed in the porous carbon skeleton. Meanwhile, the porosity and specific surface area of the composite material obtained after the MOF precursor is subjected to heat treatment are large, contact between active sites and reactants is facilitated, electron transfer between an organic matter and a catalyst is accelerated, and mass transfer limitation in a catalysis process is reduced.
Despite the advantages of MOF-based composites, the MOF-based composites currently in use are mostly in the form of powder particles, which limits their applications in electrochemical catalysis, for example, mainly because the discontinuity between powder particles prevents the electron transfer between each other and the catalytic function of carbon skeleton surface functional groups.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-efficiency stable carbon-supported MnO @ C composite anode material.
According to the invention, a commercial carbon felt is taken as a substrate, manganese complex molecules are self-assembled on the surface of the carbon felt by a solvothermal method to form a Mn-MOF precursor in situ, and then the carbon-supported MnO @ C composite material is obtained by high-temperature heat treatment in an inert atmosphere. Under the action of a lower external electric field, MnO on the surface of the carbon felt and a carbon framework can be effectively promoted to synergistically catalyze air to oxidize and degrade organic pollutants in a water body.
The preparation method of the high-efficiency stable carbon-supported MnO @ C composite anode material comprises the following steps:
step 1: adding a certain amount of manganese chloride and trimesic acid into a mixed solvent which is N, N-dimethylformamide, ethanol and water as the mixed solvent to dissolve so as to form a colorless transparent solution; transferring the obtained transparent solution into a polytetrafluoroethylene inner container of a high-pressure reaction kettle, simultaneously putting a pretreated carbon felt and completely immersing the pretreated carbon felt in the solution, sealing the high-pressure reaction kettle, and then putting the high-pressure reaction kettle into an air-blast drying oven for solvothermal reaction to obtain a carbon-supported manganese MOF composite material (Mn-MOF/GF);
step 2: and drying the obtained Mn-MOF/GF composite material at 60 ℃ for 24h, then placing the dried composite material in a tubular furnace, and carrying out heat treatment for a certain time under the protection of nitrogen to obtain the carbon-supported MnO @ C composite material.
In the step 1, the volume ratio of the N, N-dimethylformamide to the ethanol to the water in the mixed solvent is 10: 1-4: 1 to 4.
In the step 1, the pretreated carbon felt is obtained by placing a commercial PAN-based carbon felt in a high-pressure reaction kettle containing an absolute ethanol solution and pretreating for 12 hours at 120 ℃. Further, the mass of the pretreated carbon felt was 1.2% of the mass of the mixed solvent.
In the step 1, the manganese chloride is tetrahydrate manganese chloride, and the adding mass of the manganese chloride is 50-150% of the mass of the carbon felt; the molar ratio of manganese chloride to trimesic acid is 1-3: 1.
in the step 1, the reaction temperature of the solvothermal reaction is 120-180 ℃, and the reaction time is 12-24 h.
In the step 2, the optimized temperature of the heat treatment is 700-900 ℃, and the time is 0.5-4 h.
The invention relates to an application of a high-efficiency stable carbon-supported MnO @ C composite anode material in catalyzing air to oxidize and degrade organic pollutants in a water body.
The organic contaminants include triclosan and the like.
Specifically, the carbon-supported MnO @ C composite material prepared by the method is used as an anode in a single-chamber three-electrode system at normal temperature and normal pressure, and Na is added2SO4As an electrolyte, oxygen in the air is used as an oxidant, and the concentration of 240mL can be 50 mg.L under the external voltage of 1.0V (v.SEC)-1The triclosan is completely mineralized within 120min and the cycling stability of the anode material is good.
Compared with the prior art, the invention has the beneficial effects that:
1. the carbon-supported MnO @ C composite anode material prepared by the invention can effectively promote the rapid degradation of organic pollutants by the synergistic catalysis of the nano MnO and the carbon skeleton surface functional groups and the oxygen through the driving of lower external voltage.
2. The carbon-supported MnO @ C composite material prepared by the invention greatly reduces the loading capacity of metal oxide, so that the metal oxide crystal grains are smaller and the surface distribution is more uniform, thereby being beneficial to exerting the catalytic activity of the metal oxide.
3. The carbon skeleton material in the carbon-supported MnO @ C composite material prepared by the invention has the effects of blocking, coating and the like on the metal oxide, so that the stability of the metal oxide is effectively improved, and the secondary pollution caused by leaching of metal ions on the surface of the electrode is reduced.
Drawings
FIG. 1 is an SEM photograph of the carbon supported MnO @ C composite material prepared in example 1, and it can be seen that MnO @ C particles are coated on the surface of carbon felt fibers in the form of small spheres, and the diameter of the MnO @ C particles is about 50 μm;
FIG. 2 is an EDS photograph of the carbon supported MnO @ C composite prepared in example 1, showing that Mn, C and O elements are uniformly distributed on the surface of MnO @ C beads;
FIG. 3 is XRD patterns of the carbon supported MnO @ C composite material prepared in example 1 before calcination (Mn-MOF/GF), after calcination (MnO @ C/GF) and after concentrated hydrochloric acid soaking to remove MnO (C/GF), respectively, and it can be seen that the XRD curve of the material before calcination shows characteristic peaks of Mn-MOF, after calcination mainly MnO and after hydrochloric acid soaking, MnO characteristic peaks disappear;
FIG. 4 is a graph of a comparison of MnO @ C/GF prepared in example 1 and TG for MnO/GF composites prepared by the dipping method, showing that the MnO content of the MnO @ C/GF is much less than the MnO/GF;
FIG. 5 is a graph showing the degradation effect of MnO @ C/GF prepared in example 1 on triclosan, MnO/GF prepared by an impregnation method, C/GF obtained after MnO is removed by soaking in concentrated hydrochloric acid, and blank GF, and it can be seen that MnO and framework carbon of MnO @ C/GF composite material have a concerted catalytic effect on triclosan degradation;
FIG. 6 is a graph of the removal rate of triclosan from the MnO @ C/GF composite material prepared in example 1 with the addition of various quenchers, and it can be seen that the catalytic oxidation mechanism is a non-radical mechanism.
FIG. 7 is a graph showing the effect of different ethanol to water ratios in a mixed solvent on the catalytic oxidation of triclosan by a MnO @ C/GF composite anode under the conditions of example 1.
FIG. 8 is a graph of the effect of different heat treatment temperatures on the catalytic oxidation of triclosan by MnO @ C/GF composite anodes under the conditions of example 1.
Detailed Description
The following describes embodiments of the present invention in detail with reference to some embodiments.
Example 1:
dissolving manganese chloride and trimesic acid into a mixed solvent of N, N-dimethylformamide, ethanol and water according to a molar ratio of 3:1, wherein the mass of the manganese chloride is 150% of that of the carbon felt, and the volume ratio of the N, N-dimethylformamide to the ethanol to the water is 4: 1: stirring until the mixture is colorless and transparent, transferring the mixture into a polytetrafluoroethylene inner container of a high-pressure reaction kettle, and putting the pretreated carbon felt into the high-pressure reaction kettle to completely immerse the carbon felt into the solution. And (3) sealing the high-pressure reaction kettle, and then placing the high-pressure reaction kettle in an air-blast drying oven at 150 ℃ for solvothermal reaction for 20 hours to obtain Mn-MOF/GF. And drying the obtained Mn-MOF/GF at 60 ℃ for 24h, then placing the dried Mn-MOF/GF in a tubular furnace, and carrying out heat treatment at 700 ℃ for 1h under the protection of nitrogen to obtain the carbon-supported MnO @ C composite material.
Under normal temperature and normal pressure and in a single-chamber three-electrode system, the carbon-supported MnO @ C composite material prepared by the invention is used as an anode, and Na2SO4The electrolyte is oxygen in the air as oxidant, and the air is catalyzed to oxidize 240mL of air with the concentration of 50 mg.L under the external voltage of 1.0V (v.SEC)-1The removal rate of the triclosan in the triclosan solution within 80min reaches 100 percent, and the removal rate of the TOC within 120min reaches 100 percent. After 8 cycles, the removal rate of the triclosan in 120min can still reach 100 percent, and the removal rate of the TOC reaches 99 +/-0.3 percent.
Example 2:
dissolving manganese chloride and trimesic acid into a mixed solvent of N, N-dimethylformamide, ethanol and water according to a molar ratio of 1:1, wherein the mass of the manganese chloride is 50% of that of the carbon felt, and the volume ratio of the N, N-dimethylformamide to the ethanol to the water is 10: 1: 4, stirring until the mixture is colorless and transparent, transferring the mixture into a polytetrafluoroethylene inner container of a high-pressure reaction kettle, and putting the pretreated carbon felt into the high-pressure reaction kettle to completely immerse the carbon felt into the solution. And (3) sealing the high-pressure reaction kettle, and then placing the high-pressure reaction kettle in an air-blast drying oven at 120 ℃ for solvothermal reaction for 24 hours to obtain Mn-MOF/GF. And drying the obtained Mn-MOF/GF at 60 ℃ for 24h, then placing the dried Mn-MOF/GF in a tubular furnace, and carrying out heat treatment at 900 ℃ for 0.5h under the protection of nitrogen to obtain the carbon-supported MnO @ C composite material.
Under normal temperature and normal pressure and in a single-chamber three-electrode system, the carbon-supported MnO @ C composite material prepared by the invention is used as an anode, and Na2SO4The electrolyte is oxygen in the air as oxidant, and the air is catalyzed to oxidize 240mL of air with the concentration of 50 mg.L under the external voltage of 1.0V (v.SEC)-1The removal rate of the triclosan in 120min of the triclosan solution reaches 85 +/-0.2 percent, and the removal rate of the TOC reaches 81 +/-0.3 percent. After 8 cycles, the removal rate of the triclosan at 120min can still reach 84 +/-0.3 percent, and the removal rate of the TOC reaches 80 +/-0.4 percent.
Example 3:
dissolving manganese chloride and trimesic acid into a mixed solvent of N, N-dimethylformamide, ethanol and water according to a molar ratio of 1.8:1, wherein the mass of the manganese chloride is 100% of that of the carbon felt, and the volume ratio of the N, N-dimethylformamide to the ethanol to the water is 10: 4: stirring until the mixture is colorless and transparent, transferring the mixture into a polytetrafluoroethylene inner container of a high-pressure reaction kettle, and putting the pretreated carbon felt into the high-pressure reaction kettle to completely immerse the carbon felt into the solution. And sealing the high-pressure reaction kettle, and then placing the high-pressure reaction kettle in an air-blast drying box for carrying out solvothermal reaction for 12 hours at 180 ℃ to obtain Mn-MOF/GF. And drying the obtained Mn-MOF/GF at 60 ℃ for 24h, then placing the dried Mn-MOF/GF in a tubular furnace, and carrying out heat treatment at 800 ℃ for 4h under the protection of nitrogen to obtain the carbon-supported MnO @ C composite material.
Under normal temperature and normal pressure and in a single-chamber three-electrode system, the carbon-supported MnO @ C composite material prepared by the invention is used as an anode, and Na2SO4The electrolyte is oxygen in the air as oxidant, and the air is catalyzed to oxidize 240mL of air with the concentration of 50 mg.L under the external voltage of 1.0V (v.SEC)-1The removal rate of the triclosan in 120min of the triclosan solution reaches 95 +/-0.2 percent, and the removal rate of the TOC reaches 90 +/-0.1 percent. After 8 cycles, the removal rate of the triclosan in 120min can still reach 93 plus or minus 0.1 percent, and the removal rate of the TOC reaches over 88 plus or minus 0.3 percent.
Claims (10)
1. A preparation method of a high-efficiency stable carbon-supported MnO @ C composite anode material is characterized by comprising the following steps of:
firstly, taking a commercial carbon felt as a substrate, adopting a solvothermal method to enable manganese complex molecules to form a Mn-MOF precursor in situ through self-assembly on the surface of the carbon felt, and then carrying out high-temperature heat treatment under an inert atmosphere to obtain a carbon-supported MnO @ C composite material; the method comprises the following steps:
step 1: adding a certain amount of manganese chloride and trimesic acid into a mixed solvent which is N, N-dimethylformamide, ethanol and water as the mixed solvent to dissolve so as to form a colorless transparent solution; transferring the obtained transparent solution into a polytetrafluoroethylene inner container of a high-pressure reaction kettle, simultaneously putting a pretreated carbon felt and completely immersing the pretreated carbon felt in the solution, sealing the high-pressure reaction kettle, and then putting the high-pressure reaction kettle into an air-blast drying box for solvothermal reaction to obtain a carbon-supported manganese MOF composite material Mn-MOF/GF;
step 2: and drying the obtained Mn-MOF/GF composite material at 60 ℃ for 24h, then placing the dried composite material in a tubular furnace, and carrying out heat treatment for a certain time under the protection of nitrogen to obtain the carbon-supported MnO @ C composite material.
2. The method of claim 1, wherein:
in the step 1, the volume ratio of the N, N-dimethylformamide to the ethanol to the water in the mixed solvent is 10: 1-4: 1 to 4.
3. The method of claim 1, wherein:
in the step 1, the pretreated carbon felt is obtained by placing a commercial PAN-based carbon felt in a high-pressure reaction kettle containing an absolute ethanol solution and pretreating for 12 hours at 120 ℃.
4. The production method according to claim 3, characterized in that:
the mass of the pretreated carbon felt is 1.2 percent of the mass of the mixed solvent.
5. The method of claim 1, wherein:
in the step 1, the manganese chloride is tetrahydrate manganese chloride, and the adding mass of the manganese chloride is 50-150% of the mass of the carbon felt; the molar ratio of manganese chloride to trimesic acid is 1-3: 1.
6. the method of claim 1, wherein:
in the step 1, the reaction temperature of the solvothermal reaction is 120-180 ℃, and the reaction time is 12-24 h.
7. The method of claim 1, wherein:
in the step 2, the temperature of the heat treatment is 700-900 ℃, and the time is 0.5-4 h.
8. The application of the high-efficiency stable carbon-supported MnO @ C composite anode material prepared by the preparation method according to any one of claims 1-7 is characterized in that: the catalyst is used for catalyzing air to oxidize and degrade organic pollutants in water.
9. Use according to claim 8, characterized in that:
the organic contaminant comprises triclosan.
10. Use according to claim 8, characterized in that:
under normal temperature and pressure and in a single-chamber three-electrode system, the carbon-supported MnO @ C composite material is used as an anode, and Na is added2SO4The electrolyte is oxygen in the air as an oxidant, and the air is catalyzed to oxidize and degrade organic pollutants in the water body under the external voltage of 1.0V (v.SEC).
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