CN108993609B - Preparation method and application of high-dispersion metal catalyst - Google Patents
Preparation method and application of high-dispersion metal catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 239000006185 dispersion Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 title claims description 48
- 239000002184 metal Substances 0.000 title claims description 48
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 25
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 33
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 30
- 229960001699 ofloxacin Drugs 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 23
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000007605 air drying Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 12
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims 2
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 claims 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims 1
- 239000004100 Oxytetracycline Substances 0.000 claims 1
- 229960003760 florfenicol Drugs 0.000 claims 1
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 claims 1
- 229960000625 oxytetracycline Drugs 0.000 claims 1
- 235000019366 oxytetracycline Nutrition 0.000 claims 1
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 26
- 238000005303 weighing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012512 characterization method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
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- 239000011565 manganese chloride Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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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
- C02F1/722—Oxidation by peroxides
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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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention relates to the field of environmental catalytic materials, and provides a preparation method and application of a high-dispersion catalyst. The invention synthesizes a heterogeneous catalyst by taking a carbon nano tube as a carrier and a metal complex molecule as a load, is applied to an ultraviolet Fenton system, and catalyzes and degrades organic matters under visible light. The catalyst prepared by the invention has the advantages of simple preparation, stable structure, high catalytic activity and the like, and has a potential large-scale application prospect.
Description
Technical Field
The invention belongs to the field of environmental catalysis, and relates to a preparation method and application of a high-dispersion metal catalyst, which are suitable for ultraviolet light catalytic hydrogen peroxide oxidation degradation of organic pollutants in industrial wastewater.
Background
The shortage of water resources is a major problem which needs to be solved urgently in China at present, along with the development of economy, the industrial water consumption of China is increased year by year, and meanwhile, the industrial wastewater discharged to natural water is also increased continuously, so that the pollution of fresh water resources is caused. Among various pollutants in sewage, the organic pollutants account for the largest proportion, have long existence time and wide migration range in water, have great influence on animals and plants, and are difficult to degrade, so that how to efficiently treat organic wastewater on a large scale is always a hotspot of research in the field of environmental protection.
In industry, various technologies such as biochemical method, oxidation method, adsorption method and the like are commonly used for treating organic wastewater, but most of the technologies have the defects of low treatment efficiency, high degradation difficulty and the like, and cannot meet increasingly strict environmental standards. The advanced oxidation technology is one of the most effective methods for treating high-concentration refractory organic wastewater at present, and the principle of the advanced oxidation technology lies in that hydroxyl radicals with strong oxidizing property are generated by utilizing reaction conditions of light, electricity, catalysts and the like, and refractory organic matters in the wastewater are oxidized into nontoxic micromolecular substances. Among them, the Fenton method is very much noticed because of its simple operation, no need of high temperature and high pressure, and high oxidation efficiency.
The traditional homogeneous Fenton method uses Fe2+As catalyst, catalyze H2O2A large amount of hydroxyl radicals are generated, so that organic pollutants in wastewater are oxidatively degraded, but the existence form of Fe in a solution is limited by pH, so that a large amount of acid and alkali are consumed to adjust the pH in practical application, the overall reaction rate is reduced, meanwhile, iron mud which is difficult to treat is easily generated in the reaction, secondary pollution is caused to the environment, and the practical application of treating wastewater by a homogeneous Fenton method is limited. It has been found that H can likewise be reacted using heterogeneous catalysts2O2Generating hydroxyl free radicals, and avoiding the generation of refractory iron mud.
The optical Fenton oxidation technology is a novel advanced oxidation technology developed in recent years, overcomes the defects of the traditional Fenton method, and can improve H under the irradiation of ultraviolet light2O2The actual utilization rate of the catalyst is reduced, and the reaction time is shortened. However, the common heterogeneous light Fenton catalyst still has the problems of low catalytic activity, poor stability under ultraviolet light and the like. Therefore, the research of the heterogeneous light Fenton catalyst with strong catalytic activity and high stability has great application significance.
The transition metal catalyst is a metal complex taking transition metal as an active center, has higher catalytic activity and selectivity and simple preparation, and is a novel single-active-center catalyst. Research shows that under the condition of higher metal content, only a few metal active components play a catalytic role in the actual reaction, and when the active components are uniformly dispersed, the actual catalytic activity of the catalyst is higher. Therefore, increasing the dispersion of the metal has a greater effect on the improvement of the catalytic activity of the catalyst. In practical application, the existing transition metal catalyst has the problems of poor thermal stability, uneven dispersion of active components, easy inactivation of active centers and the like, the immobilization of the catalyst is one of effective ways for solving the problems, and the selection of a proper carrier is also the key for improving the activity of the catalyst.
The carbon nano tube has rich pore structure and stable surface chemical property, is suitable to be used as a carrier of a catalyst, improves the dispersibility of active components of the catalyst, can ensure that the prepared catalyst has higher stability and catalytic activity, and is convenient to recycle for secondary use in practical application.
The invention aims to use the carbon nano tube as a carrier to prepare the metal catalyst with high dispersibility for an ultraviolet Fenton system.
Disclosure of Invention
The invention aims to fully utilize the dispersibility of transition metals and rich pore structures of carbon nano tubes, use a transition metal complex as an active component, use the carbon nano tubes as a carrier of a catalyst, carry out the loading of the active component by a hydrothermal method, and then prepare a high-dispersion metal catalyst which is efficient, stable and easy to recover by roasting, wherein the high-dispersion metal catalyst is used for catalytically oxidizing refractory organic matters in wastewater under an ultraviolet Fenton system, and aims to overcome the defects of low hydrogen peroxide utilization rate, low catalytic activity and the like of the existing ultraviolet Fenton catalyst.
In order to achieve the aim, the invention prepares different high-dispersion light Fenton catalysts by changing the temperature and time of hydrothermal synthesis and calcination. Meanwhile, the experiment proves that the catalyst is applied to ultraviolet light and H2O2In the presence of the compound, the ofloxacin in the wastewater can be effectively catalytically degraded, and the compound has a large-scale application prospect.
The preparation method of the invention is as follows;
(1) taking a carbon nano tube and a metal complex precursor, and putting the carbon nano tube and the metal complex precursor into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(2) transferring the mixed solution in the step (1) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into an air-blowing drying oven, adjusting the temperature to be 60-180 ℃ (optimally to be 80-150 ℃), and standing for 12-48h (optimally to be 24-32 h);
(3) adjusting the temperature of the blast drying oven to 50-120 deg.C (most preferably 50-80 deg.C), and maintaining for 8-27h (most preferably 12-24 h);
(4) and taking out the mixed solution obtained after the hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and then putting the filter residue into a muffle furnace or a tubular furnace to calcine for 1-8h (most preferably for 1-4h) at 80-800 ℃ (most preferably for 100-500 ℃), thus obtaining the high-dispersion metal catalyst.
Wherein the mass ratio of the carbon nano tube taken in the step (1) to the metal complex precursor is 1:0.01-0.1 (most preferably 1: 0.02-0.05).
The preparation method of the metal complex precursor in the step (1) is as follows;
(1) and (3) putting the metal salt into the ethanol solution, slowly dripping the chelating agent into the ethanol solution, and stirring the mixture to obtain a mixed solution.
(2) And (2) putting the mixed solution in the step (1) into an oil bath pot, refluxing at a high temperature of 60-120 ℃ (optimally 60-90 ℃) for 2-8h (optimally 2-4h), washing, filtering and vacuumizing to obtain the metal complex.
In the preparation method of the metal complex precursor, the chelating agent is ethylenediamine, the metal salt is one of anhydrous copper chloride, anhydrous ferric chloride and anhydrous cobalt chloride, and the molar ratio of the metal salt to the chelating agent is 1: 1-3 (most preferably 1: 2).
The invention synthesizes a heterogeneous catalyst by taking a carbon nano tube as a carrier and a metal complex molecule as a load, is applied to an ultraviolet Fenton system, and catalyzes and degrades organic matters under visible light. The catalyst prepared by the invention has the advantages of simple preparation, stable structure, high catalytic activity and the like, and has a potential large-scale application prospect.
Drawings
FIG. 1 shows the removal rate of ofloxacin in 70min for the catalyst prepared in example 1.
Detailed Description
The invention will now be further described with reference to the following examples, but the scope of the invention is not limited to the following examples
Example 1;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the filter residue in a muffle furnace at 180 ℃ for 1h to obtain the M target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in example 1 was used to treat ofloxacin in an ultraviolet Fenton system, the treatment methods are shown in Table 1, and the treatment results are shown in FIG. 1 (with no catalyst added as a comparative group, and with other conditions with the catalyst added).
TABLE 1
Example 2;
preparing a high-dispersion metal catalyst;
(1) 1.0g of anhydrous copper chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous copper chloride and stirred to obtain a mixed solution, wherein the molar ratio of anhydrous ferric chloride to ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a muffle furnace at 180 ℃ for 1h to obtain the target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in the example 2 was used for treating ofloxacin in an ultraviolet Fenton system under the treatment conditions shown in Table 1, and after 70min of reaction, the removal rate of ofloxacin was 75%.
Example 3;
preparing a high-dispersion metal catalyst;
(1) 1.0g of anhydrous cobalt chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of anhydrous ferric chloride to ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.3g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a muffle furnace at 180 ℃ for 1h to obtain the target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in example 3 was used to treat ofloxacin in an ultraviolet Fenton system under the treatment conditions shown in Table 1, and after 70min of reaction, the removal rate of ofloxacin was 73%.
Example 4;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 160 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a muffle furnace at 180 ℃ for 1h to obtain the target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in example 4 was used to treat ofloxacin in an ultraviolet Fenton system under the treatment conditions shown in Table 1, and after 70min of reaction, the removal rate of ofloxacin was 77%.
Example 5;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 12 h;
(6) and taking out the mixed solution obtained after the hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a muffle furnace at 180 ℃ for 8 hours to obtain the target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in example 5 was used to treat ofloxacin in an ultraviolet Fenton system under the treatment conditions shown in Table 1, and after 70min of reaction, the removal rate of ofloxacin was 81%.
Example 6;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a tubular furnace at 500 ℃ for 1h to obtain the target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in this example 6 was used to treat ofloxacin in an ultraviolet Fenton system under the treatment conditions shown in Table 1, and after 70min of reaction, the removal rate of ofloxacin was 85%.
Example 7;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) 1.0g of anhydrous copper chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous copper chloride and stirred to obtain a mixed solution, wherein the molar ratio of anhydrous ferric chloride to ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 150 ℃, and standing for 24 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a tubular furnace at 500 ℃ for 1h to obtain the target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in this example 7 was used to treat ofloxacin in an ultraviolet Fenton system under the treatment conditions shown in Table 1, and after 70min of reaction, the removal rate of ofloxacin was 77%.
Example 8;
preparing a high-dispersion metal catalyst;
(1) 1.0g of anhydrous cobalt chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of anhydrous ferric chloride to ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.3g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 32 hours;
(5) adjusting the temperature of the blast drying oven to 80 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a muffle furnace at 180 ℃ for 1h to obtain the target high-dispersion metal catalyst. The target highly dispersed metal catalyst was identified by SEM and XRD characterization.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in this example 8 was used to treat ofloxacin in an ultraviolet Fenton system under the treatment conditions shown in Table 1, and after 70min of reaction, the removal rate of ofloxacin was 75%.
Comparative example 1;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) adding 1.0g of anhydrous manganese chloride into 30mL of anhydrous ethanol, slowly dripping ethylenediamine and stirring to obtain a mixed solution, wherein the molar ratio of anhydrous ferric chloride to ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 12 h;
(6) and taking out the mixed solution obtained after the hydrothermal synthesis, carrying out suction filtration under reduced pressure, drying the filter residue, and calcining the dried filter residue in a muffle furnace at 180 ℃ for 8 hours to obtain the target catalyst.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in the comparative example 6 is used for treating ofloxacin in an ultraviolet Fenton system, the treatment conditions are shown in the table 1, and after 70min of reaction, the removal rate of ofloxacin is 29%.
Comparative example 2;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, citric acid is slowly added and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the citric acid is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out suction filtration under reduced pressure, drying the filter residue, and calcining the dried filter residue in a tubular furnace at 500 ℃ for 1h to obtain the target catalyst.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in the comparative example 5 is used for treating ofloxacin in an ultraviolet Fenton system, the treatment conditions are shown in the table 1, and after reaction for 70min, the removal rate of ofloxacin is 35%.
Comparative example 3;
preparing a high-dispersion metal catalyst;
(1) adding 1.0g of anhydrous copper chloride into 30mL of anhydrous ethanol, slowly dripping ethylenediamine and stirring to obtain a mixed solution, wherein the molar ratio of the anhydrous copper chloride to the ethylenediamine is 1: 1;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 80 ℃, and standing for 24 hours;
(5) and taking out the mixed solution obtained after the hydrothermal synthesis, carrying out suction filtration under reduced pressure, and drying the filter residue to obtain the target catalyst.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in the comparative example 1 is used for treating ofloxacin in an ultraviolet Fenton system, the treatment conditions are shown in the table 1, and after 70min of reaction, the removal rate of ofloxacin is 53%.
Comparative example 4;
preparing a high-dispersion metal catalyst;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) and (4) filling the mixed solution in the step (3) into a hydrothermal synthesis kettle, and performing ultrasonic treatment for 6 hours at the temperature of 60 ℃. And obtaining the target catalyst.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in the comparative example 3 is used for treating ofloxacin in an ultraviolet Fenton system, the treatment conditions are shown in the table 1, and after reaction for 70min, the removal rate of ofloxacin is 39%.
Comparative example 5;
preparing a high-dispersion metal catalyst;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the ethylenediamine is 1: 2;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.4g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 100 ℃, and standing for 24 hours;
(5) adjusting the temperature of the blast drying oven to 60 ℃, and keeping for 14 h;
(6) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out suction filtration under reduced pressure, drying the filter residue, and calcining the dried filter residue in a tubular furnace at 140 ℃ for 1h to obtain the target catalyst.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in the comparative example 2 is used for treating ofloxacin in an ultraviolet Fenton system, the treatment conditions are shown in the table 1, and after reaction for 70min, the removal rate of ofloxacin is 47%.
Comparative example 6;
preparing a high-dispersion metal catalyst, which comprises the following steps;
(1) 1.0g of anhydrous ferric chloride is put into 30mL of anhydrous ethanol, ethylenediamine is slowly dripped into the anhydrous ethanol and stirred to obtain a mixed solution, wherein the molar ratio of the anhydrous ferric chloride to the ethylenediamine is 1: 0.5;
(2) and (3) placing the mixed solution in the step (1) into an oil bath pot, refluxing for 3 hours at a high temperature of 80 ℃, washing, filtering and vacuumizing to obtain the target metal complex.
(3) Weighing 1.0g of carbon nano tube and 0.2g of metal complex in the step (2), and putting into 30mL of absolute ethyl alcohol to obtain a mixed solution;
(4) transferring the mixed solution in the step (3) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 120 ℃, and standing for 27 hours;
(5) and taking out the mixed solution obtained after hydrothermal synthesis, carrying out suction filtration under reduced pressure, drying the filter residue, and calcining the dried filter residue in a tubular furnace at 500 ℃ for 1h to obtain the target catalyst.
Finally, the obtained catalyst is stored under the temperature of below 40 ℃ and under the dry condition in the dark.
The catalyst prepared in the comparative example 4 is used for treating ofloxacin in an ultraviolet Fenton system, the treatment conditions are shown in the table 1, and after reaction for 70min, the removal rate of ofloxacin is 35%.
Claims (5)
1. High-dispersion metal catalyst in photocatalytic wet H2O2The application of oxidation treatment in organic wastewater is characterized in that;
the preparation method of the catalyst comprises the following steps:
(1) putting the carbon nano tube and the metal complex precursor into absolute ethyl alcohol to obtain a mixed solution;
(2) transferring the mixed solution in the step (1) to a hydrothermal synthesis kettle, putting the hydrothermal kettle into a forced air drying oven, adjusting the temperature to 60-180 ℃, and standing for 12-48 h;
(3) adjusting the temperature of the blast drying oven to 50-120 ℃, and keeping for 8-27 h;
(4) taking out the mixed solution obtained after hydrothermal synthesis, carrying out vacuum filtration, drying the filter residue, and calcining the dried filter residue in a muffle furnace or a tubular furnace at the temperature of 80-800 ℃ for 1-8h to obtain the high-dispersion metal catalyst;
the preparation steps of the metal complex precursor are as follows;
(1) putting metal salt into an ethanol solution, slowly dripping a chelating agent into the solution and stirring the solution to obtain a mixed solution; the metal salt is one of anhydrous copper chloride, anhydrous ferric chloride and anhydrous cobalt chloride;
(2) refluxing the mixed solution in the step (1) at a high temperature of 60-120 ℃ for 2-8h, washing, filtering and vacuumizing to obtain the metal complex;
the organic wastewater is one or more than two of o-chlorophenol, ofloxacin, oxytetracycline and florfenicol.
2. The application of claim 1, wherein the mass ratio of the carbon nanotubes to the metal complex precursor in the step (1) is 1: 0.01-0.1.
3. Use according to claim 1, wherein the chelating agent is ethylenediamine.
4. Use according to claim 1, wherein the molar ratio of metal salt to chelating agent is 1: 1-3.
5. Use according to claim 1, wherein the catalyst is used for photocatalytic wet H2O2The intermittent reaction conditions for the oxidation treatment of the organic wastewater are as follows:
normal pressure, initial pH of wastewater: 3 to 7, the reaction temperature is 10 to 80 ℃, the ultraviolet light intensity is 50 to 5000W, and the adding amount of the catalyst is 0.01 to 1.0 g/L.
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