CN110548544B - Iron oxide doped iron metal organic framework, green macro preparation method and application - Google Patents
Iron oxide doped iron metal organic framework, green macro preparation method and application Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 114
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- 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 abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 29
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 27
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 22
- 230000015556 catabolic process Effects 0.000 claims abstract description 21
- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 229910021642 ultra pure water Inorganic materials 0.000 claims description 15
- 239000012498 ultrapure water Substances 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 13
- 230000003213 activating effect Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003344 environmental pollutant Substances 0.000 claims description 10
- 231100000719 pollutant Toxicity 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000000593 degrading effect Effects 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052939 potassium sulfate Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 20
- 230000015572 biosynthetic process Effects 0.000 abstract description 19
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 7
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- 238000002288 cocrystallisation Methods 0.000 abstract description 2
- 235000013980 iron oxide Nutrition 0.000 description 37
- 229960005404 sulfamethoxazole Drugs 0.000 description 19
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical compound OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical group NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000011010 flushing procedure Methods 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
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- 238000003911 water pollution Methods 0.000 description 2
- 101100184147 Caenorhabditis elegans mix-1 gene Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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]
-
- 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
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses an iron oxide doped iron metal organic framework material, a green macro preparation method and application, wherein the preparation method comprises the following steps: (1) grinding and uniformly mixing ferrous sulfate heptahydrate and trimesic acid, adding a sodium hydroxide solution, transferring the mixture into a microwave reaction kettle, performing ultrasonic treatment, heating, and cooling to room temperature to obtain a mixed liquid; (2) and (2) washing the mixed liquid obtained in the step (1), centrifuging to obtain a solid, washing the obtained solid, and drying in vacuum to obtain the iron oxide doped iron metal organic framework material. According to the invention, the synthesis of the heterogeneous catalyst is carried out by a microwave solid-phase co-crystallization method, the synthesis period is greatly shortened, the synthesis process is green, environment-friendly and efficient, and the synthesized iron oxide doped iron metal organic framework material can fully utilize unsaturated metal sites thereof to efficiently activate persulfate so as to degrade organic pollutants, thereby avoiding the generation of iron mud, reducing the synthesis cost of the heterogeneous catalytic material and the degradation cost of the organic pollutants, and improving the water environment quality.
Description
Technical Field
The invention belongs to the technical field of water pollution control, relates to a deep oxidation treatment and advanced oxidation technology of organic pollutants in water, and particularly relates to an iron oxide doped iron metal organic framework, a green macro preparation method and application.
Background
Global environmental challenges, particularly water pollution due to rapid economic and industrial growth, have become one of the most serious threats facing human beings at present. Organic contaminants such as industrial dyes, pesticides, Pharmaceuticals and Personal Care Products (PPCPs) are of increased interest due to their high toxicity and stability. Based on sulfate radicals (SO)4 ·-) Also gradually become a hot spot direction for organic pollutant treatment. Compared to the traditional advanced oxidation process based on hydroxyl radical. OH, SR-AOP has many advantages: SO (SO)4 ·-Has higher oxidation potential (SO)4 ·-，2.6-3.1V；·OH，1.8-2.7V)；SO4 ·-Can effectively react with target pollutants in a wide pH range; SO (SO)4 ·-Higher selectivity and longer half-life (SO)4 ·-30-40 mus; OH, < 1. mu.s). Therefore, the SR-AOP has wide application prospect in degrading pollutants, especially persistent organic pollutants.
In the presence of activating to produce SO4 ·-Among the various processes of (a) the use of heterogeneous catalysts for the activation of peroxymonosulfate or persulfate salts has proven to be a more desirable strategy. Therefore, the future development of SR-AOP depends on the development and synthesis of catalysts with high activity and stability. Metal-organic frameworks (MOFs) and derivatives thereof with large specific surface areas, ultra-high porosities and versatile designs have been studied in recent years as heterogeneous catalysts, thanks to the unsaturated metal sites abundant in MOFs, in particular iron-based MOFs, which activate persulfates to generate SO4 ·-Has higher efficiency and obvious effect in the degradation and removal of organic pollutants. However, because the traditional synthesis method of MOFs (water/solvent heat, etc.) requires high temperature and high pressure conditions, introduction of strong corrosive acids (hydrofluoric acid, concentrated nitric acid, etc.) easily causes potential safety hazards, and a large amount of toxic and harmful solvents (N, N-dimethylformamide, etc.) are required in the synthesis process to promote crystallization, so that waste liquid generated in synthesis causes secondary pollution. In addition to this, the present invention is,the traditional MOFs synthetic method has long synthetic period, low yield and other problems, and the popularization and application of the MOFs synthetic method in the environmental field are also limited. The invention provides a green macro-synthesis method of an iron oxide doped iron metal organic framework material, which can greatly shorten the synthesis period, improve the synthesis yield, reduce the use of chemical reagents, is green, environment-friendly, safe and reliable, and compared with an undoped iron metal organic framework material, the synthesized iron oxide doped iron metal organic framework material can anchor more unsaturated metal active sites, greatly improve the efficiency of activating persulfate to degrade organic pollutants, and has certain magnetism to be beneficial to separation and recovery.
Disclosure of Invention
The invention provides a green macro preparation method of iron oxide doped iron metal organic framework capable of effectively solving the problems and a method for activating persulfate to degrade organic pollutants by applying the green macro preparation method to activate persulfate, aiming at the problems that the prior ferrous ion (iron ion) homogeneous catalyst is easy to lose efficacy, cannot be recycled and generates iron mud, the energy consumption is high, the high-temperature and high-pressure conditions are harsh, the synthesis period is long, the secondary pollution is serious, the separation and recovery are difficult, the activation efficiency of the iron-containing heterogeneous catalyst is low and the like in the process of synthesizing a metal organic framework material. According to the invention, the heterogeneous catalyst is synthesized by a microwave solid-phase co-crystallization method, the synthesis period is greatly shortened, no acid/alkali with strong corrosivity is introduced, toxic and harmful solvents are not needed, the synthesis process is green, environment-friendly and efficient, the synthesized iron oxide doped with the iron metal organic framework material can fully utilize unsaturated metal sites thereof to efficiently activate persulfate to degrade organic pollutants, and the iron oxide doped with the iron metal organic framework material can be simply recycled through magnetic separation, so that the generation of iron mud can be avoided, the synthesis cost of the heterogeneous catalytic material and the degradation cost of the organic pollutants are reduced, and the water body environment quality is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a green macro-preparation method of iron oxide doped iron metal organic framework, which comprises the following steps:
(1) uniformly mixing ferrous sulfate heptahydrate and trimesic acid, adding a sodium hydroxide solution, transferring to a microwave reaction kettle, performing ultrasonic treatment, heating, and cooling to room temperature to obtain a mixed liquid;
(2) and (2) washing the mixed liquid obtained in the step (1), centrifuging to obtain a solid, washing the obtained solid, and drying in vacuum to obtain the iron oxide doped iron metal organic framework material, namely Fe-MOFs-MW.
Preferably, the molar ratio of the ferrous sulfate heptahydrate to the trimesic acid in the step (1) is (0.75-2): 1;
the molar weight ratio of the sodium hydroxide to the ferrous sulfate heptahydrate is (0.4-3) to 1;
the volume of the sodium hydroxide solution is 1/5-1/10 of the volume of the microwave reaction kettle.
Preferably, the microwave reaction kettle in the step (1) is provided with a polytetrafluoroethylene lining; respectively grinding and crushing ferrous sulfate heptahydrate and trimesic acid, and then uniformly mixing, wherein the grinding time is 20-30 min; the ultrasonic treatment time is 15-30 min; the cooling refers to ice water bath or natural cooling in air.
Preferably, the heating in the step (1) refers to putting the microwave reaction kettle into a microwave heater for heating; the microwave heater is a household adjustable microwave oven; the microwave power is 50-90w, and the microwave heating time is 50-120 min.
Preferably, the mixed liquid obtained in the washing step (1) in the step (2) is washed by deionized water or ultrapure water, the deionized water or ultrapure water is added into the mixed liquid, and the mixed liquid is magnetically stirred and centrifuged.
Preferably, the solid obtained by washing in the step (2) is obtained by mixing deionized water or ultrapure water with the solid, magnetically stirring, centrifugally pouring out supernatant, repeating the washing operation for 2-3 times, and then washing with absolute ethyl alcohol for 2-3 times; the volume of deionized water, ultrapure water or absolute ethyl alcohol used for washing the solid each time is 5-30 times of the volume of the sodium hydroxide solution; the magnetic stirring time is 60-120 min; the centrifugal rotating speed is 8000-11000 r/min, and the centrifugal time is 8-15 min; the vacuum drying temperature is 60-75 deg.C, and the vacuum drying time is 16-24 h.
The invention also provides the iron oxide doped iron metal organic framework prepared by the preparation method.
The invention also provides application of the iron oxide doped iron metal organic framework material in activating persulfate to degrade organic pollutants, persulfate and the iron oxide doped iron metal organic framework material are added into organic wastewater, and the organic wastewater is placed in a constant-temperature oscillation incubator or a magnetic stirrer to be uniformly mixed and reacted.
Preferably, the persulfate is sodium persulfate, potassium persulfate, or ammonium persulfate; the molar ratio of persulfate to the degradation target pollutant in the organic wastewater is (80-800): 1;
the volume ratio of the mass of the iron oxide-doped iron metal organic framework material to the organic wastewater is 0.2-2 g/L.
Preferably, the rotation speed of the constant-temperature shaking incubator or the magnetic stirrer is 150-250 r/min, and the reaction temperature is 20-60 ℃.
Compared with the prior art, the invention has the following advantages that:
(1) according to the green macro-synthesis method of the iron oxide doped iron metal organic framework material, substances with strong corrosivity do not need to be added, a large amount of toxic and harmful solvents do not need to be added, waste liquid generated in the synthesis process is less, and secondary pollution is avoided;
(2) the green macro-synthesis method of the iron oxide doped iron metal organic framework material provided by the invention has the advantages of low energy input and high utilization efficiency. Simple operation, safety, reliability, mild condition, short synthesis period and high yield. The application prospect in the actual large-scale production and synthesis is wide;
(3) the iron oxide-doped iron metal organic framework material synthesized by the method can anchor more unsaturated metal active sites, the efficiency of activating persulfate to degrade pollutants is high, and meanwhile, the pore structure of the iron metal organic framework can enhance the mass transfer effect of the pollutants and increase the reaction sites of the material and the pollutants;
(4) the iron oxide-doped iron metal organic framework material synthesized by the method disclosed by the invention has low iron ion elution amount in the process of activating persulfate through heterogeneous catalysis, basically no iron mud is generated, and the problem of subsequent treatment can be effectively avoided;
(5) the application method of the synthesized iron oxide-doped iron metal organic framework material in degrading organic pollutants is simple, convenient and reliable, has wide application range, does not have the requirement of additional energy input, can carry out reaction spontaneously, has higher degradation efficiency, can effectively and thoroughly degrade pollutants, and has wide application prospect.
Drawings
FIG. 1 is an X-ray crystal diffraction pattern of iron oxide doped iron metal organic framework synthesized at different microwave heating times;
FIG. 2 is a graph of the efficiency of different materials in activating persulfate to degrade orange G;
FIG. 3 is an X-ray crystal diffraction pattern of iron oxide doped iron metal organic framework synthesized with microwave heating time of 90 min;
FIG. 4 shows the efficiency of doped iron metal organic frameworks of different iron oxides on the degradation of sulfamethoxazole by activated persulfate;
FIG. 5 shows the efficiency of degrading sulfamethoxazole by iron oxide doped with iron metal organic framework under different initial pH conditions;
FIG. 6 is a comparison of iron leaching amounts of PS-degraded sulfamethoxazole catalyzed and activated by iron metal organic framework doped with iron oxide at different initial pH values.
Detailed Description
The invention will now be described in further detail with reference to the following examples and figures, which illustrate the salient features and considerable developments of the invention, and which are intended to illustrate the invention and are in no way limited to the examples given below.
Example 1
The embodiment provides a green macro-preparation method of an iron oxide doped iron metal organic framework, which is used for preparing the iron oxide doped iron metal organic framework by the preparation method of the embodiment with different microwave heating time, and comprises the following steps:
ferrous sulfate heptahydrate with the molar weight of 8mmol and trimesic acid with the molar weight of 8mmol are weighed, placed in an agate mortar and fully ground until the ferrous sulfate heptahydrate and the trimesic acid are completely and uniformly mixed, and transferred to a 50mL microwave reaction kettle with a polytetrafluoroethylene lining. And then adding 10mL of sodium hydroxide solution with the molar concentration of 1.6mol/L into the microwave reaction kettle, screwing a cover of the microwave reaction kettle, carrying out ultrasonic treatment for 30min, putting the microwave reaction kettle into a cavity of a common household microwave oven, setting the microwave power to be 70w, setting the microwave heating time to be 50min, 60min, 70min, 90min and 120min respectively, taking out the microwave reaction kettle after the microwave heating is finished, and placing the microwave reaction kettle in the air for cooling for 3 hours until the temperature of the microwave reaction kettle is reduced to the room temperature. Transferring the reacted mixture into a 150mL beaker, adding 50mL of ultrapure water, flushing a microwave reaction kettle, merging flushing liquid into the beaker, magnetically stirring for 60min, transferring the mixed liquid into a 50mL centrifugal tube, centrifuging for 10min at 10000r/min by a high-speed centrifuge, pouring supernatant, washing the centrifuged solid ultrapure water for 2 times according to the operation, ensuring that the unreacted ferrous sulfate heptahydrate is complete, removing centrifugation, and pouring the supernatant. Transferring the centrifuged solid into a 150mL beaker, adding 50mL of absolute ethyl alcohol, magnetically stirring for 60min, transferring the mixed solution into a 50mL centrifugal tube, centrifuging the mixed solution for 10min at 10000r/min by a high-speed centrifuge, pouring supernatant, repeatedly washing the centrifuged solid for 2 times by using the absolute ethyl alcohol according to the operation, and ensuring that trimesic acid which does not participate in coordination crystallization is completely removed. And centrifuging in a high-speed centrifuge, pouring supernatant, transferring the centrifuge tube filled with centrifuged solid into a vacuum drying oven, and vacuum drying at 65 ℃ for 24h to obtain orange solid which is the iron oxide-doped iron metal organic framework synthesized in different microwave heating times and marked as Fe-MOFs-MW-50min, Fe-MOFs-MW-60min, Fe-MOFs-MW-70min, Fe-MOFs-MW-90min and Fe-MOFs-MW-120 min.
An XRD spectrum of the iron oxide-doped iron metal organic framework material synthesized in example 1 with different microwave heating times is shown in fig. 1, which is an XRD crystal diffraction pattern at microwave times of 50min, 60min, 70min, 90min and 120min, respectively, and the iron oxide-doped iron metal organic framework has 6 characteristic diffraction peaks within the angular ranges of 2 θ ═ 9 °, 12 °, 15 °, 19 °, 24 ° and 28 °, which are relatively matched with the characteristic peaks of MIL-100 crystal, and also has characteristic peaks of ferroferric oxide at 2 θ ═ 27.4 ° and 36.5 °, which indicates that the synthesized iron oxide-doped iron metal organic framework material is. From fig. 1, it can be found that the materials synthesized by different microwave heating times have different diffraction peak intensities, the positions of diffraction peaks of the samples are highly consistent, and the iron oxide doped iron metal organic framework material with better crystallinity can be synthesized in shorter synthesis time, which further illustrates the stability and reliability of the synthesis method of the present invention.
Example 2
The embodiment provides a preparation method of an iron oxide doped iron metal organic framework material, which comprises the following steps:
(1) weighing 8mmol ferrous sulfate heptahydrate and 5.33mmol trimesic acid, placing in an agate mortar, and fully grinding until the ferrous sulfate heptahydrate and the trimesic acid are completely and uniformly mixed to obtain a mixture-1;
(2) weighing 8mmol ferrous sulfate heptahydrate and 8mmol trimesic acid, and placing in an agate mortar for fully grinding until the ferrous sulfate heptahydrate and the trimesic acid are completely and uniformly mixed to obtain a mixture-2;
(3) weighing 8mmol ferrous sulfate heptahydrate and 10.66mmol trimesic acid, placing in an agate mortar, and fully grinding until the ferrous sulfate heptahydrate and the trimesic acid are completely and uniformly mixed to obtain a mixture-3;
(4) mix-1, mix-2 and mix-3 were each transferred to a 50mL teflon lined microwave reactor. And then adding 10mL of sodium hydroxide solution with the molar concentration of 1.6mol/L into the microwave reaction kettle, screwing a cover of the microwave reaction kettle, carrying out ultrasonic treatment for 30min, putting the microwave reaction kettle into a cavity of a common household microwave oven, setting the microwave power to be 70w, setting the microwave heating time to be 90min respectively, taking out the microwave reaction kettle after the microwave heating is finished, placing the microwave reaction kettle in air, cooling the microwave reaction kettle for 3 hours until the temperature of the microwave reaction kettle is reduced to the room temperature, and obtaining mixed liquid-1, mixed liquid-2 and mixed liquid-3 respectively. Transferring the reacted mixed liquid-1, the mixed liquid-2 and the mixed liquid-3 into a 150mL beaker, adding 50mL of ultrapure water, flushing a microwave reaction kettle, merging flushing liquid into the beaker, magnetically stirring for 60min, transferring the mixed liquid into a 50mL centrifugal tube, centrifuging for 10min at 10000r/min by a high-speed centrifuge, pouring supernatant, washing the centrifuged solid with ultrapure water for 2 times according to the operation, ensuring that unreacted ferrous sulfate heptahydrate is completely removed, and pouring the supernatant after centrifugation. Transferring the centrifuged solid into a 150mL beaker, adding 50mL of absolute ethyl alcohol, magnetically stirring for 60min, transferring the mixed solution into a 50mL centrifugal tube, centrifuging the mixed solution for 10min at 10000r/min by a high-speed centrifuge, pouring supernatant, repeatedly washing the centrifuged solid for 2 times by using the absolute ethyl alcohol according to the operation, and ensuring that trimesic acid which does not participate in coordination crystallization is completely removed. And (3) pouring supernatant after centrifuging in a high-speed centrifuge, transferring the centrifuge tube filled with centrifuged solid into a vacuum drying oven, and carrying out vacuum drying at 65 ℃ for 24h to obtain orange solid, wherein the orange solid is iron oxide doped iron metal organic frameworks synthesized by different trimesic acid adding amounts, namely a No. 1 sample, a No. 2 sample and a No. 3 sample.
Example 3
The embodiment provides a preparation method of an iron oxide doped iron metal organic framework material, which analyzes the preparation of iron oxide doped iron metal organic framework materials with different sodium hydroxide adding amounts, and the preparation method comprises the following steps:
weighing 8mmol ferrous sulfate heptahydrate and 8mmol trimesic acid, placing in an agate mortar, fully grinding until the mixture is completely and uniformly mixed, and respectively transferring the mixture to a 50mL polytetrafluoroethylene-lined microwave reaction kettle. Then respectively adding the mixture into a microwave reaction kettle
(1)10mL of ultrapure water;
(2)10mL of sodium hydroxide solution with the molar concentration of 1.6 mol/L;
(3)10mL of sodium hydroxide solution with the molar concentration of 2.4 mol/L;
and after ultrasonic treatment is carried out for 30min, the microwave reaction kettle is placed into a cavity of a common household microwave oven, the microwave power is set to be 70w, the microwave heating time is respectively set to be 90min, the microwave reaction kettle is taken out after the microwave heating is finished and is placed in the air to be cooled for 3 h until the temperature of the microwave reaction kettle is reduced to the room temperature, and mixed liquid-4, mixed liquid-5 and mixed liquid-6 are respectively obtained. Transferring the reacted mixed liquid-4, mixed liquid-5 and mixed liquid-6 into a 150mL beaker, adding 50mL of ultrapure water, flushing a microwave reaction kettle, merging flushing liquid into the beaker, magnetically stirring for 60min, transferring the mixed liquid into a 50mL centrifugal tube, centrifuging for 10min at 10000r/min by a high-speed centrifuge, pouring supernatant, washing the centrifuged solid with ultrapure water for 2 times according to the operation, ensuring that unreacted ferrous sulfate heptahydrate is complete, removing the centrifugation, and pouring the supernatant. Transferring the centrifuged solid into a 150mL beaker, adding 50mL of absolute ethyl alcohol, magnetically stirring for 60min, transferring the mixed solution into a 50mL centrifugal tube, centrifuging the mixed solution for 10min at 10000r/min by a high-speed centrifuge, pouring supernatant, repeatedly washing the centrifuged solid for 2 times by using the absolute ethyl alcohol according to the operation, and ensuring that trimesic acid which does not participate in coordination crystallization is completely removed. And (3) pouring supernatant after centrifuging in a high-speed centrifuge, transferring the centrifuge tube filled with centrifuged solid into a vacuum drying oven, and carrying out vacuum drying at 65 ℃ for 24h to obtain orange solid, namely iron oxide doped iron metal organic frameworks (No. 4 sample, No. 5 sample and No. 6 sample) synthesized by different sodium hydroxide adding amounts.
Analyzing the yield of the iron oxide doped iron metal organic framework material synthesized under different microwave-assisted solid phase synthesis conditions, analyzing the yield of the iron oxide doped iron metal organic framework prepared under different microwave-assisted solid phase synthesis conditions (a sample No. 1, a sample No. 2, a sample No. 3, a sample No. 4, a sample No. 5 and a sample No. 6) by using a one-ten-thousandth balance, and calculating the STY (space-time-yield) value of the iron oxide doped iron metal organic framework in unit time and unit space by using the yield, wherein the total volume of the synthesis reaction is calculated by 30 mL. As shown in Table 1, the ratio of STY (500-3D) the yield of the iron oxide doped with iron metal organic framework prepared in green macro by adopting the method is greatly improved, and the STY values are all over 1000kg/m3D, while the STY value in sample No. 4 without sodium hydroxide was greatly reduced, the effect of the method of the present invention on yield improvement was also highlighted. Comparing the No. 2 and No. 5 samples synthesized under the same synthesis condition, the method of the invention is further proved to be efficient and stable and can realize macro synthesis.
TABLE 1 yield of iron oxide doped iron metal organic framework material synthesized under different microwave-assisted solid phase synthesis conditions
Example 4
In the embodiment, iron oxide doped iron metal organic framework is used as a catalyst, and Orange G (OG) is used as simulated organic wastewater for degradation. And carrying out comparison by carrying out heterogeneous catalysis on OG degradation by persulfate through different materials.
Using a 250mL triangular flask as a reaction vessel, 100mL of OG solution with a molar concentration of 0.2mM was added as a simulated wastewater, and the following materials were added to the triangular flask, respectively:
(1) no material is added;
(2)0.05g of Fe-MOFs-MW-90min (prepared in example 1);
(3)0.05g of Fe-MOFs-MW-120min (prepared in example 1);
(4)0.05g of Fe3O4-1：Fe3O4(available from Aladdin, Shanghai) under the designation Fe3O4-1；
(5)0.05g of Fe3O4-2: the preparation of Fe-MOFs-MW-90min from example 1 was carried out without addition of 8mM trimesic acid, and the black solid powder obtained was marked Fe3O4-2；
The triangular flask is placed in constant temperature shaking culture to react at the rotating speed of 180r/min, and the temperature is set to be 25 ℃. Adding no sodium persulfate in the first 100min of the reaction stage, sampling and analyzing the OG adsorption effect of each material, adding 1.6mmol of sodium persulfate when reacting for 100min after adsorption saturation, and comparing the OG degradation efficiency of each material by activating the sodium persulfate, wherein as can be seen from figure 2, the single addition of the sodium persulfate hardly degrades the OG, the OG removal mainly passes through the degradation effect, the higher OG removal efficiency is that Fe-MOFs-MW-90min and Fe-MOFs-MW-120min which are iron oxidation doped iron metal organic framework materials synthesized in the embodiment 1 are utilized, the OG removal efficiency reaches more than 98% 2 hours after the sodium persulfate is added, and the OG removal efficiency is compared with Fe3O4-1 and Fe3O4-2, with limited OG degradation efficiency, of only about 25% after two hours of sodium persulfate additionAnd (4) degradation. This example further illustrates that the green macro-preparation of iron oxide doped with iron metal organic framework activated sodium persulfate in example 1 has a significant efficiency and a good degradation effect on OG.
Example 5
In this example, the removal rate of SMX by different catalyst addition amounts was investigated using Fe-MOFs-MW-90min prepared in example 1 as a persulfate heterogeneous catalyst and Sulfamethoxazole (SMX) as an antibiotic-contaminated simulated organic wastewater.
FIG. 3 is a crystal diffraction pattern of Fe-MOFs-MW-90 min.
A250 mL triangular flask is used as a reaction container, 100mL of SMX solution with the mass concentration of 20mg/L (the molar concentration is about 0.08mmol/L) is added as simulated wastewater, then sodium persulfate with the molar quantity of 6mmol is added, and Fe-MOFs-MW-90min with the mass as follows is respectively added into the triangular flask:
(1) adding no Fe-MOFs-MW-90 min;
(2)0.01g of Fe-MOFs-MW-90 min;
(3)0.05g of Fe-MOFs-MW-90 min;
(4)0.1g of Fe-MOFs-MW-90 min;
(5)0.15g of Fe-MOFs-MW-90 min;
the reaction was stirred on a magnetic stirrer at a speed of 220r/min, and samples were taken at intervals to determine the SMX concentration. FIG. 4 shows that the SMX degradation efficiency is activated by persulfate with different Fe-MOFs-MW-90min addition amounts, when only sodium persulfate is added, SMX has almost no degradation effect, the SMX degradation efficiency is remarkably improved along with the increase of the Fe-MOFs-MW-90min addition amount, after the Fe-MOFs-MW-90min addition amount is increased to 0.05g, the SMX degradation efficiency reaches 98% after the reaction is carried out for two hours, the degradation efficiency can be maintained at about 98% when the Fe-MOFs-MW-90min addition amount is continuously increased, and the optimal Fe-MOFs-MW-90min addition amount is 0.05g in consideration of the treatment cost and the degradation efficiency. The embodiment fully shows that the iron oxide-doped iron metal organic framework prepared in a green and macro scale manner can effectively activate persulfate to degrade SMX-type new pollutants, and has a wide application prospect in actual organic wastewater treatment.
Example 6
In this example, Fe-MOFs-MW-90min prepared in example 1 was used as a persulfate heterogeneous catalyst, Sulfamethoxazole (SMX) was used as an antibiotic-contaminated simulated organic wastewater, and the removal rate of SMX and the leaching amount analysis of iron ions in the system under different initial pH conditions were studied.
A250 mL triangular flask is used as a reaction vessel, 100mL of SMX solution with the mass concentration of 20mg/L (the molar concentration is about 0.08mmol/L) is added as simulated wastewater, and the initial pH value of the solution is adjusted by using 0.1mol/L sulfuric acid and 0.1mol/L sodium hydroxide solution, and the pH values are respectively:
(1) the initial pH was not adjusted and was 5.62;
(2) adjusting the initial pH to 2.92;
(3) adjusting the initial pH value to 6.08;
(4) adjusting the initial pH to 6.49;
(5) adjusting the initial pH value to 9.13;
then, sodium persulfate with the molar weight of 6mmol is respectively added into the solution after the initial pH is adjusted, 0.1g of Fe-MOFs-MW-90min prepared in the example 1 is respectively added into the triangular flask, the triangular flask is placed in a constant temperature shaking culture to react at the rotating speed of 180r/min, the temperature is set to be 25 ℃, and the sampling, measuring and analyzing are carried out for the set time: FIG. 5 shows the efficiency of degrading sulfamethoxazole by catalyzing and activating persulfate through the iron oxide doped with the iron metal organic framework under different initial pH values, and FIG. 6 shows the comparison of the iron leaching amount of degrading sulfamethoxazole by catalyzing and activating PS through the iron oxide doped with the iron metal organic framework under different initial pH values. The initial pH value is gradually changed from acidity to alkalinity, the removal rate of sulfamethoxazole can be kept at a higher level, and the iron oxide doped iron metal organic framework can activate persulfate to efficiently degrade organic pollutants under a wider initial pH condition. Meanwhile, in the whole reaction stage, the iron leaching amount is always kept at a low level no matter under acidic or neutral or even alkaline conditions, and the iron leaching amount is only less than 10mg/L under the acidic initial condition, so that the generation of iron mud can be greatly reduced, and the method has important significance in the treatment and application of degradation pollutants in the future.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any equivalent alterations, modifications or improvements made by those skilled in the art to the above-described embodiments using the technical solutions of the present invention are still within the scope of the technical solutions of the present invention.
Claims (8)
1. The green macro preparation method of the iron oxide doped iron metal organic framework is characterized by comprising the following steps of:
(1) uniformly mixing ferrous sulfate heptahydrate and trimesic acid through solid-phase grinding, adding a sodium hydroxide solution, transferring to a microwave reaction kettle, performing ultrasonic microwave heating, and cooling to room temperature to obtain a mixed liquid; the molar ratio of the ferrous sulfate heptahydrate to the trimesic acid is (0.75-2): 1;
the molar weight ratio of the sodium hydroxide to the ferrous sulfate heptahydrate is (0.4-3) to 1; the volume of the sodium hydroxide solution is 1/5-1/10 of the volume of the microwave reaction kettle; the heating means that the microwave reaction kettle is put into a microwave heater for heating; the microwave heater is a household microwave oven with adjustable power; the microwave power is 50-90w, and the microwave heating time is 60-120 min;
(2) and (2) washing the mixed liquid obtained in the step (1), centrifuging to obtain a solid, washing the obtained solid, and drying in vacuum to obtain the iron oxide doped iron metal organic framework, namely Fe-MOFs-MW.
2. The green macro-preparation method of the iron oxide doped iron metal organic framework as claimed in claim 1, wherein in the step (1), the microwave reaction kettle is provided with a polytetrafluoroethylene lining; respectively grinding and crushing ferrous sulfate heptahydrate and trimesic acid, and then uniformly mixing, wherein the grinding time is 20-30 min; the ultrasonic treatment time is 15-30 min; the cooling refers to ice water bath or natural cooling in air.
3. The green macro-preparation method of iron oxide doped with iron metal organic framework as claimed in claim 1, wherein the mixed liquid obtained in the washing step (1) in the step (2) is washed with deionized water or ultrapure water, the deionized water or ultrapure water is added into the mixed liquid, and the mixed liquid is magnetically stirred and centrifuged.
4. The method for preparing the iron oxide doped iron metal organic framework material according to claim 1, wherein the solid obtained by washing in the step (2) is prepared by mixing deionized water or ultrapure water with the solid, magnetically stirring, centrifugally pouring a supernatant, repeating the washing operation for 2-3 times, and then washing with absolute ethyl alcohol for 2-3 times; the volume of deionized water, ultrapure water or absolute ethyl alcohol used for washing the solid each time is 5-30 times of the volume of the sodium hydroxide solution; the magnetic stirring time is 60-120 min; the centrifugal rotating speed is 8000-11000 r/min, and the centrifugal time is 8-15 min; the vacuum drying temperature is 60-75 deg.C, and the vacuum drying time is 16-24 h.
5. Iron oxide doped with an iron metal organic framework prepared by the preparation method of any one of claims 1 to 4.
6. The application of the iron oxide doped iron metal organic framework in degrading organic pollutants by activating persulfate as claimed in claim 5, characterized in that persulfate and the iron oxide doped iron metal organic framework material are added into the organic wastewater, and the mixture is placed in a constant-temperature shaking incubator or a magnetic stirrer to be uniformly mixed and reacted.
7. The use of an iron oxide doped iron metal organic framework as claimed in claim 6 wherein the persulfate is sodium, potassium or ammonium persulfate; the molar ratio of persulfate to the degradation target pollutant in the organic wastewater is (80-800): 1;
the volume ratio of the mass of the iron oxide-doped iron metal organic framework material to the organic wastewater is 0.2-2 g/L.
8. The application of the iron oxide doped iron metal organic framework in degrading organic pollutants by activating persulfate according to claim 6, wherein the rotation speed of a constant-temperature shaking incubator or a magnetic stirrer is 150-250 r/min, and the reaction temperature is 20-60 ℃.
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| CN114656648B (en) * | 2022-04-29 | 2023-05-26 | 南开大学 | Rapid preparation method of metal organic framework material and metal organic framework composite material |
| CN115745134B (en) * | 2022-11-23 | 2024-03-08 | 南京大学 | Method for catalyzing efficient selective oxidation of peroxymonosulfate by utilizing iron complex |
| CN115888775A (en) * | 2022-11-25 | 2023-04-04 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Catalyst for oxidative degradation of antibiotic wastewater based on microwave rapid activation of periodate and preparation and application methods thereof |
| CN116282465B (en) * | 2022-11-25 | 2024-06-18 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Method for rapidly oxidizing and degrading PPCPs wastewater by using microwave-activated periodate |
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