CN112570029A - Preparation method of aluminum ion doped modified iron oxide catalyst with metal organic framework structure - Google Patents
Preparation method of aluminum ion doped modified iron oxide catalyst with metal organic framework structure Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 34
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 239000013206 MIL-53 Substances 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 6
- 231100000719 pollutant Toxicity 0.000 claims abstract description 6
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 5
- 238000004729 solvothermal method Methods 0.000 claims abstract description 5
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
- C02F2101/30—Organic compounds
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention relates to an Al with a metal-organic framework structure3+The preparation method of the doped modified iron oxide catalyst is to adopt a solvothermal method to prepare Al3+The MIL-53(Fe) is added to inhibit the decomposition of the MIL-53(Fe) in water, so as to enhance the stability of the MIL-53(Fe) in water. By means of H2Reduction in Ar atmosphereAnd (2) treatment, namely the MIL-53(Fe) framework is reserved, and meanwhile, part of amorphous carbon is generated, so that the specific surface area of the catalyst can be further increased, abundant catalytic activity sites are provided, the adsorption quantity of pollutants on the surface of the catalyst is effectively increased, and the efficient catalytic degradation of organic pollutants in water is promoted. In addition, the catalyst has good magnetism, effectively solves the problem of difficult recovery in practical application, realizes the high-efficiency recycling of the powder catalyst, and has a great practical application prospect.
Description
Technical Field
The invention relates to an aluminum ion (Al) with a metal organic framework structure3+) The preparation method of the doped modified iron oxide catalyst can effectively retain the metal organic framework structure and larger specific surface area of the catalyst, improves the water stability and simultaneously enhances the catalytic efficiency, and is used in the field of sewage treatment.
Background
Metal organic framework Materials (MOFs) are a kind of microporous-mesoporous hybrid materials with 3D network structure, not only have the advantages of high specific surface area, lower crystal density, adjustable pores, etc., but also are widely used in the fields of gas adsorption and storage, molecular separation, catalysis, etc.
Because Fe is an environment-friendly, low-cost and non-toxic metal, and the surface area of Fe-based MOFs is large, the Fe-based MOFs attracts wide attention in catalysis and adsorption. But the stability is relatively poor, and the polymer is easy to hydrolyze in water to cause skeleton collapse so as to lose the original porosity. Therefore, the problem to be solved urgently is to improve the water stability and expand the application range of the water-based paint. There are many factors affecting the stability of MOFs, and in order to solve the disadvantage of poor stability of MOFs, researchers have devoted themselves to obtaining stable MOFs through synthesis methods and post-modification, which are summarized as four approaches: (1) changing the strength of a metal-ligand bond, (2) changing the chemical function of a linker, (3) adjusting the structural architecture, and (4) surface modification of the backbone. Generally, the increased charge of the metal cation can lead to enhanced stability of the resulting MOFs, inhibiting the hydrolysis of the metal ion to cause the destruction of the base of the metal-ligand bond, thereby constructing a stable MOFs material.
Disclosure of Invention
Aiming at the problems of small specific surface area, poor catalytic activity and the like of the existing catalytic material, the invention aims to provide a preparation method of an Al3+ doped modified iron oxide catalyst with a metal-organic framework structure.
Yet another object of the present invention is to: an Al3+ doped modified iron oxide catalyst product having a metal-organic framework structure prepared by the above method is provided.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: al with metal organic frame structure3+Preparation method of doped modified iron oxide catalyst, adopting solvothermal method to make Al3+Adding MIL-53(Fe) into the mixture to inhibit the decomposition of MIL-53(Fe) in water, so as to enhance the stability of the mixture in water; by means of H2The method comprises the following steps of A, performing reduction treatment in an Ar atmosphere, generating partial amorphous carbon while keeping an MIL-53(Fe) framework, further increasing the specific surface area of a catalyst, providing abundant catalytic activity sites, effectively increasing the adsorption quantity of pollutants on the surface of the catalyst, and promoting the efficient catalytic degradation of organic pollutants in water, wherein the reduction treatment comprises the following steps:
(1) under the condition of magnetic stirring, aluminum nitrate nonahydrate Al (NO) is added according to the mol ratio of nAl: nFe of (10-100): 13)3·9H2O and ferric nitrate hexahydrate Fe (NO)3)3·6H2Adding O into DMF solvent for dissolving, after completely dissolving, dropwise adding terephthalic acid solution into the mixed solution, and adding Fe (NO)3)3·6H2The molar ratio of O to terephthalic acid is 2:1, the solution is transferred to a polytetrafluoroethylene reaction kettle after ultrasonic treatment is carried out for 30min, and solution thermal reaction is carried out;
(2) naturally cooling after the reaction is finished, centrifuging, washing and drying the product, and placing the product in 5% H2Heat treatment in an Ar atmosphere, and controlling the gas flow rate, the reaction temperature and the reaction time;
(3) transferring the product in the step (2) to a muffle furnace for roasting treatment for a period of time after reduction treatment to obtain Al with a metal-organic framework structure3+Doping a modified iron oxide catalyst.
In the step (1), the solvothermal reaction temperature is 150 ℃, and the reaction time is 12-24 h.
Step (2)In (b), the above H2The flow rate of the/Ar gas is 50-200 ml/min, the reaction temperature is 350-500 ℃, and the reaction time is 4-6 h.
And (3) roasting in a muffle furnace at the roasting temperature of 300-400 ℃ for 2-4 h.
The invention provides Al with a metal organic framework structure3+Method for preparing doped modified iron oxide catalyst by mixing Al3+Adding into MIL-53(Fe) and adding into H2Reduction treatment is carried out under the Ar atmosphere, the contact area of the catalyst and organic pollutants in water is increased by utilizing the large specific surface area of the metal organic framework structure, the adsorption quantity of the pollutants on the surface of the catalyst is effectively increased, and the efficient catalytic degradation of the organic pollutants in the water is promoted. Utilizes the oxidation of elementary Fe in the air atmosphere to promote Fe2+With Fe3 +The inter-charge transfer further promotes the improvement of the catalytic activity of the catalyst, which has important practical significance for applying the MOFs material to the degradation of organic matters in sewage.
The invention also provides Al with the metal organic framework structure3+Doped modified iron oxide catalyst, prepared according to any of the methods described above.
The invention also provides Al with a metal-organic framework structure3+The application of doped modified iron oxide catalyst in the degradation of oxalic acid solution.
Al with metal-organic framework structure3+Doping modified Fe2O3The evaluation of the catalytic performance of the catalyst is carried out in a beaker, a certain amount of oxalic acid solution is taken, a certain amount of peroxymonosulfate is added into the oxalic acid solution, a proper amount of catalyst is added after the pH is regulated, the oxalic acid solution is stirred and mixed, the sampling is carried out at regular time, after 30min of treatment, the supernatant is centrifugally separated, the concentration of the residual oxalic acid in the solution is measured, and the degradation efficiency of the oxalic acid solution is calculated.
The large specific surface area of the metal organic framework structure is utilized to increase the active sites, and cation doping modification is provided for solving the problem of poor water stability, so that the framework structure is prevented from collapsing, and the improvement of the catalytic efficiency is effectively promoted.
Hair brushThe Al with the metal-organic framework structure3+Doping modified Fe2O3The preparation method of the catalyst can effectively improve the water stability of the material, solve the problem of recovery of the powder catalyst and effectively expand the application of the powder catalyst in the field of catalysis.
Can effectively improve the water stability of the material, solve the problem of recovering the powder catalyst and effectively expand the application of the material in the field of catalysis. The invention has the following advantages:
(1) the invention provides Al with a metal organic framework structure3+Doping modified Fe2O3Method for preparing a catalyst by introducing Al into the MIL-53(Fe) framework3+And is in H2Reduction treatment is carried out under the Ar atmosphere, the contact area of the catalyst and organic pollutants in water is increased by utilizing the large specific surface area of the metal organic framework structure, the adsorption quantity of the pollutants on the surface of the catalyst is effectively increased, and the efficient catalytic degradation of the organic pollutants in the water is promoted.
(2) Al provided by the invention3+Doping modified Fe2O3Catalyst of H2The specific surface area of the catalyst can be further increased by forming simple substance Fe through reduction treatment in the Ar atmosphere and reserving an MIL-53(Fe) framework and generating part of amorphous carbon, abundant catalytic activity sites are provided, and Fe is promoted by utilizing oxidation in the simple substance Fe air atmosphere2+With Fe3+And the transition of charges further promotes the catalyst to catalyze the activation of peroxymonosulfate to generate sulfate radicals, thereby realizing the high-efficiency catalytic degradation of organic pollutants.
(3) The catalyst prepared by the invention has good magnetism, effectively solves the problem of difficult recovery in practical application, realizes the high-efficiency recycling of the powder catalyst, and has a larger practical application prospect.
Detailed Description
The present invention is further illustrated by examples.
Example 1:
al with metal organic frame structure3+Doping modified iron oxide catalyst by solvothermal methodMixing Al3+Adding MIL-53(Fe) into the mixture to inhibit the decomposition of MIL-53(Fe) in water, so as to enhance the stability of the mixture in water; by means of H2The method comprises the following steps of A, performing reduction treatment in an Ar atmosphere, generating partial amorphous carbon while keeping an MIL-53(Fe) framework, further increasing the specific surface area of a catalyst, providing abundant catalytic activity sites, effectively increasing the adsorption quantity of pollutants on the surface of the catalyst, and promoting the efficient catalytic degradation of organic pollutants in water, wherein the method comprises the following steps:
(1) aluminum nitrate nonahydrate Al (NO) is added according to the mol ratio of nAl: nFe of 10:1 under the magnetic stirring3)3·9H2O and ferric nitrate hexahydrate Fe (NO)3)3·6H2Adding O into DMF solvent for dissolving, and adding Fe (NO) after completely dissolving3)3·6H2Dropwise adding a terephthalic acid solution into the mixed solution with the molar ratio of O to terephthalic acid being 2:1, carrying out ultrasonic treatment for 30min, transferring the solution into a polytetrafluoroethylene reaction kettle, and carrying out thermal reaction on the solution at 150 ℃ for 24 h;
(2) naturally cooling after the reaction is finished, centrifuging, washing and drying the product, and placing the product in 5% H2Carrying out heat treatment in an Ar atmosphere, controlling the gas flow rate to be 200ml/min, and reacting for 4 hours at 350 ℃;
(3) transferring the product in the step (2) to a muffle furnace at 300 ℃ after reduction treatment for roasting treatment for 2h, thus obtaining Al with a metal-organic framework structure3+Doping a modified iron oxide catalyst.
The degradation rate of the prepared catalyst to oxalic acid solution is 73%.
Example 2:
al with metal organic frame structure3+The doped modified iron oxide catalyst is prepared by the following steps similar to the steps of the example 1:
(1) first, Al (NO) was added in a molar ratio of 10:1 nAl: nFe under magnetic stirring3)3·9H2O and Fe (NO)3)3·6H2Adding O into DMF solvent for dissolving, and adding Fe (NO) after completely dissolving3)3·6H2Dissolving terephthalic acid in a molar ratio of O to terephthalic acid of 2:1Dropwise adding the solution into the mixed solution, carrying out ultrasonic treatment for 30min, transferring the solution into a polytetrafluoroethylene reaction kettle, and regulating and controlling the reaction temperature and the reaction time to be 150 ℃ and 12h respectively;
(2) secondly, after the reaction is finished, the reaction product is naturally cooled, centrifuged, washed and dried, and then the product is placed in 5 percent H2Heat treatment in the Ar atmosphere, wherein the gas flow rate, the reaction temperature and the reaction time are respectively controlled to be 50ml/min, 500 ℃ and 2 hours;
(3) transferring the product in the step (2) to a muffle furnace at 350 ℃ after reduction treatment for roasting treatment for 2h to obtain Al with a metal-organic framework structure3+Doping modified Fe2O3A catalyst.
The degradation rate of the prepared catalyst to oxalic acid solution is 81%.
Example 3:
al with metal organic frame structure3+The doped modified iron oxide catalyst is prepared by the following steps similar to the steps of the example 1:
(1) first, Al (NO) was added in a molar ratio of nAl: nFe of 100:1 under magnetic stirring3)3·9H2O and Fe (NO)3)3·6H2Adding O into DMF solvent for dissolving, and adding Fe (NO) after completely dissolving3)3·6H2Dropwise adding a terephthalic acid solution into the mixed solution with the molar ratio of O to terephthalic acid being 2:1, carrying out ultrasonic treatment for 30min, transferring the solution into a polytetrafluoroethylene reaction kettle, and regulating and controlling the reaction temperature and the reaction time to be 150 ℃ and 24h respectively;
(2) secondly, after the reaction is finished, the reaction product is naturally cooled, centrifuged, washed and dried, and then the product is placed in 5 percent H2Heat treatment in the Ar atmosphere, wherein the gas flow rate, the reaction temperature and the reaction time are respectively controlled to be 100ml/min, 500 ℃ and 4 hours;
(3) transferring the product in the step (2) to a muffle furnace at 300 ℃ after reduction treatment for roasting treatment for 4h to obtain Al with a metal-organic framework structure3+Doping modified Fe2O3A catalyst.
The degradation rate of the prepared catalyst to oxalic acid solution is 64%.
Example 4:
al with metal organic frame structure3+The doped modified iron oxide catalyst is prepared by the following steps similar to the steps of the example 1:
(1) first, Al (NO) was added in a molar ratio of 10:1 nAl: nFe under magnetic stirring3)3·9H2O and Fe (NO)3)3·6H2Adding O into DMF solvent for dissolving, and adding Fe (NO) after completely dissolving3)3·6H2Dropwise adding a terephthalic acid solution into the mixed solution with the molar ratio of O to terephthalic acid being 2:1, carrying out ultrasonic treatment for 30min, transferring the solution into a polytetrafluoroethylene reaction kettle, and regulating and controlling the reaction temperature and the reaction time to be 150 ℃ and 24h respectively;
(2) secondly, after the reaction is finished, the reaction product is naturally cooled, centrifuged, washed and dried, and then the product is placed in 5 percent H2Heat treatment in the Ar atmosphere, wherein the gas flow rate, the reaction temperature and the reaction time are respectively controlled to be 100ml/min, 500 ℃ and 4 hours;
(3) transferring the product in the step (2) to a muffle furnace at 350 ℃ after reduction treatment for roasting treatment for 2h to obtain Al with a metal-organic framework structure3+Doping modified Fe2O3A catalyst.
The degradation rate of the prepared catalyst to the oxalic acid solution is 83 percent.
Claims (6)
1. Al with metal organic frame structure3+The preparation method of the doped modified iron oxide catalyst is characterized in that Al is subjected to solvothermal method3+Adding MIL-53(Fe) into the mixture to inhibit the decomposition of MIL-53(Fe) in water, so as to enhance the stability of the mixture in water; by means of H2The method comprises the following steps of A, performing reduction treatment in an Ar atmosphere, generating partial amorphous carbon while keeping an MIL-53(Fe) framework, further increasing the specific surface area of a catalyst, providing abundant catalytic activity sites, effectively increasing the adsorption quantity of pollutants on the surface of the catalyst, and promoting the efficient catalytic degradation of organic pollutants in water, wherein the reduction treatment comprises the following steps:
(1) the molar ratio according to nAl: nFe is (10) under magnetic stirring1 part of aluminum nitrate nonahydrate Al (NO)3)3·9H2O and ferric nitrate hexahydrate Fe (NO)3)3·6H2Adding O into DMF solvent for dissolving, after completely dissolving, dropwise adding terephthalic acid solution into the mixed solution, and adding Fe (NO)3)3·6H2The molar ratio of O to terephthalic acid is 2:1, the solution is transferred to a polytetrafluoroethylene reaction kettle after ultrasonic treatment is carried out for 30min, and solution thermal reaction is carried out;
(2) naturally cooling after the reaction is finished, centrifuging, washing and drying the product, and placing the product in 5% H2Heat treatment in an Ar atmosphere, and controlling the gas flow rate, the reaction temperature and the reaction time;
(3) transferring the product in the step (2) to a muffle furnace for roasting treatment for a period of time after reduction treatment to obtain Al with a metal-organic framework structure3+Doping a modified iron oxide catalyst.
2. Al with metal-organic framework structure according to claim 13+The preparation method of the doped modified iron oxide catalyst is characterized in that in the step (1), the solvothermal reaction temperature is 150 ℃, and the reaction time is 12-24 hours.
3. Al with metal-organic framework structure according to claim 13+The preparation method of the doped modified iron oxide catalyst is characterized in that in the step (2), the H is2The flow rate of the/Ar gas is 50-200 ml/min, the reaction temperature is 350-500 ℃, and the reaction time is 4-6 h.
4. Al with metal-organic framework structure according to claim 13+The preparation method of the doped modified iron oxide catalyst is characterized in that in the step (3), the roasting temperature is 300-400 ℃ in a muffle furnace, and the roasting time is 2-4 h.
5. Al with metal organic frame structure3+Doped modified iron oxide catalyst, characterized by being according toThe compound is prepared by the method of any one of claims 1 to 5.
6. Al according to claim 5 with a metal-organic framework structure3+The application of the doped modified iron oxide catalyst in the degradation of oxalic acid solution.
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