CN110075922A - A kind of ferro-cobalt bimetallic catalytic material and the preparation method and application thereof based on MOF-74 - Google Patents
A kind of ferro-cobalt bimetallic catalytic material and the preparation method and application thereof based on MOF-74 Download PDFInfo
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- CN110075922A CN110075922A CN201910404334.8A CN201910404334A CN110075922A CN 110075922 A CN110075922 A CN 110075922A CN 201910404334 A CN201910404334 A CN 201910404334A CN 110075922 A CN110075922 A CN 110075922A
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- cobalt
- mof
- catalytic material
- ferro
- metal salt
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- 239000013118 MOF-74-type framework Substances 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000004913 activation Effects 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 5
- 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 description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 3
- 229960001180 norfloxacin Drugs 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960004306 sulfadiazine Drugs 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- WABMHCVYKWKAAH-UHFFFAOYSA-N dimethyl 2,5-dihydroxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC(O)=C(C(=O)OC)C=C1O WABMHCVYKWKAAH-UHFFFAOYSA-N 0.000 claims description 2
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 15
- 238000001994 activation Methods 0.000 description 12
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 7
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 208000031320 Teratogenesis Diseases 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940075933 dithionate Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
-
- 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
-
- 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
- B01J2531/845—Cobalt
-
- 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
-
- 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
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ferro-cobalt bimetallic catalytic material and the preparation method and application thereof based on MOF-74.The present invention by by metal salt, organic ligand in molar ratio (1~5): 1 is added in solvent, is transferred to ptfe autoclave after mixing evenly；Wherein, the metal salt is made of metal salt containing cobalt and ferrous metal salt, and the molar ratio of cobalt in the metal salt, iron is (1~9): (1~9)；Ptfe autoclave is put into baking oven and reacts 12~72h at 100~160 DEG C, obtains the ferro-cobalt bimetallic catalytic material based on MOF-74.The ferro-cobalt bimetallic catalytic material in conjunction with persulfate, can efficient various organic pollutants in depth degradation water body, should ferro-cobalt bimetallic catalytic material-persulfate catalyst system based on MOF-74 can be applied to deep purifying organic pollution sewage.
Description
Technical field
The invention belongs to technical field of sewage more particularly to a kind of ferro-cobalt bimetallic catalytic materials based on MOF-74
And the preparation method and application thereof.
Background technique
In recent years, synthetic organic chemistry product are increased with annual millions of, even over thousands of ten thousand kinds speed, these organic chemistry
Product enter in water body by all means.Organic matter accounts for the overwhelming majority in these organic chemicals, and these organic matters are general
All over there is big stable structure, Ecological Environment Risk, carcinogenic teratogenesis mutagenesis, be difficult to effectively remove in traditional water treatment technology
Characteristic.
Potentiometric titrations (SO is generated based on activation persulfate4 -The advanced oxidation of organic pollutants in water body) is handled
Technology is widely paid close attention in recent years.Compared with hydroxyl radical free radical (.OH), SO4 -Have under the conditions of neutral and alkali higher
Oxidation-reduction potential (2.5~3.1V), wider to the adaptation range of pH, oxidation selectivity is stronger, and has longer half-life period
The advantages that (30~40us).Theoretically, SO4 -It can be CO by most organic mineralising in waste water2And H2O。
SO4 -Generation mainly realizes that persulfate includes peroxy-monosulfate (PDS) and mistake by activation persulfate
Dithionate (PMS).Transition metal activation method has it is not necessary that activation can be realized under external heat source and light source, room temperature, repeat
The advantages such as use.Wherein, cobalt, two metal ion species of iron are proved to have best activation effect to persulfate.Transition metal is living
Change persulfate and is divided into homogeneous activation and heterogeneous two kinds of activation.In homogeneous activation system, metal in the form of ions,
Remaining a large amount of metal ions will cause new pollution in water body after the completion of reaction；And in heterogeneous catalytic oxidation system,
Metal exists usually by way of oxide, however traditional cobalt/cobalt oxide and ferriferous oxide imitates the activation of persulfate
Fruit is not so good as homogeneous system, and still has ion to spill into solution in activation process.
Metal organic framework (MOF) is logical by inorganic metal center (metal ion or metal cluster) and the organic ligand of bridging
It crosses self assembly and connects the crystalline state porous material that the one kind to be formed has periodic network structure, regular orderly with cellular structure,
The features such as metal composition and aperture structure dimension adjustable, skeleton can be modified.Metallic cobalt and Tie Tong are crossed into MOF mode and are embedded in crystalline substance
The spilling of iron cobalt ions can be effectively prevented in internal portion, and the porous structure of MOF can make enriching pollutants in active catalytic
Near point, accelerate Catalysis Rate.Wherein, the duct MOF-74 class MOF is big, stable structure, and research shows that two kinds of elements of ferro-cobalt
MOF-74 crystalloid can be synthesized.It therefore, can by the regulatable ferro-cobalt bimetallic catalytic material of MOF-74 Opacity in lens ratio
With fast activating persulfate, efficient degradation organic pollutants in water body.
Summary of the invention
The purpose of the present invention is to provide a kind of ferro-cobalt bimetallic catalytic material based on MOF-74.
The preparation method of a further object of the present invention is to provide the above-mentioned ferro-cobalt bimetallic catalytic material based on MOF-74.
A further object of the present invention is to provide above-mentioned, and the ferro-cobalt bimetallic catalytic material based on MOF-74 is activating over cure
Application in terms of hydrochlorate or degradation Organic Pollutants In Water.
The invention is realized in this way a kind of preparation method of the ferro-cobalt bimetallic catalytic material based on MOF-74, the party
Method the following steps are included:
(1) in molar ratio (1~5) by metal salt, organic ligand: 1 is added in solvent, is transferred to poly- four after mixing evenly
Vinyl fluoride reaction kettle；Wherein, the metal salt is made of metal salt containing cobalt and ferrous metal salt, and cobalt in the metal salt, iron
Molar ratio is (1~9): (1~9)；
(2) ptfe autoclave is put into baking oven and reacts 12~72h at 100~160 DEG C, obtained based on MOF-74
Ferro-cobalt bimetallic catalytic material.
Preferably, in step (1), the metal salt containing cobalt is cobalt nitrate hexahydrate (Co (NO3)2.6H2O), four water acetic acid
Cobalt (Co (COOCH3)2.4H2O), CoCL2 6H2O (CoCl2.6H2O), cobalt sulfate (CoSO4.7H2One of O)；It is described
Ferrous metal salt is frerrous chloride (FeCl2), ferrous acetate (Fe (COOCH3)2), ferrous sulfate heptahydrate (FeSO4.7H2O in)
It is a kind of.
Preferably, in step (1), the organic ligand be 2,5-Dihydroxyterephthalic acid dimethyl ester (DHTA, CAS:
610-92-4)。
Preferably, in step (1), the solvent is deionized water (H2O), dimethylformamide (DMF), dimethyl second
One or more of amide (DMA), ethyl alcohol, tetrahydrofuran (THF).
The present invention further discloses the bimetallic catalytic materials that the above method is prepared.
The present invention further discloses application of the above-mentioned bimetallic catalytic material in terms of activating persulfate.
Preferably, the persulfate is one of potassium persulfate, potassium hydrogen peroxymonosulfate.
The present invention further discloses application of the above-mentioned bimetallic catalytic material in terms of Organic Pollutants In Water of degrading.
Preferably, bimetallic catalytic material degradation Organic Pollutants In Water in conjunction with activation persulfate.
Preferably, the organic pollutant includes sulphadiazine, rhodamine B, bisphenol-A, Norfloxacin, phthalic acid two
Methyl esters.
The present invention overcomes the deficiencies of the prior art and provide a kind of ferro-cobalt bimetallic catalytic material and its system based on MOF-74
Preparation Method and application.MOF-74 is based on the present invention relates to the ratio fabricated in situ by using two kinds of accurate adjusting cobalt, iron elements
Ferro-cobalt bimetallic catalytic material, and be applied to activation the efficient depth degradation organic pollutants in water body of persulfate.Wherein,
Ferro-cobalt bimetallic catalytic material based on MOF-74 the preparation method comprises the following steps: by containing cobalt and iron metal salt, organic ligand is according to one
Certainty ratio is added in solvent and stirs evenly, and is subsequently transferred to ptfe autoclave, and reaction is certain at a certain temperature
Time, finally obtain ferro-cobalt it is accurate in scale it is adjustable can the ferro-cobalt bimetallic based on MOF-74 of efficient degradation water pollutant urge
Change material.
Compared with the prior art the shortcomings that and deficiency, the invention has the following advantages:
(1) preparation method of the present invention is simple, and raw material is simple and easy to get, and reaction condition green is mild；
(2) catalysis material that is prepared of the present invention is with persulfate in conjunction with, can be various in efficient depth degradation water body
Organic pollutant, being somebody's turn to do ferro-cobalt bimetallic catalytic material-persulfate catalyst system based on MOF-74 can be applied to deep purifying
Organic pollution sewage.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1:
(1) by Co (NO3)2.6H2O(125mg,0.5mmol)、FeCl2(570mg,4.5mmol)、DHTA(1000mg,
5.0mmol) it is added to 200mL DMF/ ethyl alcohol/H2In the solvent of O (10/1/1), it is put into polytetrafluoro reaction kettle after mixing evenly；
(2) polytetrafluoro reaction kettle is put into baking oven, 120 DEG C of reactions are taken out afterwards for 24 hours, are cleaned with ethyl alcohol and are filtered afterwards three times
MOF-74 (Co/Fe) metal organic framework for being 1/9 to ferro-cobalt ratio.
The K of 2mM MOF-74 (Co/Fe) metal organic framework and 0.5mM2S2O8In conjunction with concentration being in 2 hours
The sulphadiazine of 1mM is degradable, and TOC removal rate is 80%.
Embodiment 2
(1) by CoCl2.6H2O(1200mg,5.0mmol)、FeSO4.7H2O(1400mg,5.0mmol)、DHTA(400mg,
2.0mmol) it is added to 200mL DMA/ ethyl alcohol/H2In the solvent of O (10/2/1), it is put into polytetrafluoro reaction kettle after mixing evenly；
(2) polytetrafluoro reaction kettle is put into baking oven, is taken out after 160 DEG C of reaction 12h, is cleaned with ethyl alcohol and filtered afterwards three times
MOF-74 (Co/Fe) metal organic framework for being 1/1 to ferro-cobalt ratio.
Concentration can be by 2mM MOF-74 (Co/Fe) metal organic framework in 1 hour in conjunction with the Oxone of 1mM
The rhodamine B of 2mM is degradable, and TOC removal rate is 76%.
Embodiment 3
(1) by Co (COOCH3)2.4H2O(2250mg,9.0mmol)、Fe(COOCH3)2(173mg,1.0mmol)、DHTA
(800mg, 4.0mmol) is added to 500mL DMF/ ethyl alcohol/H2In the solvent of O (10/2/1), it is put into polytetrafluoro after mixing evenly
Reaction kettle；
(2) polytetrafluoro reaction kettle is put into baking oven, is taken out after 100 DEG C of reaction 72h, is cleaned with ethyl alcohol and filtered afterwards three times
MOF-74 (Co/Fe) metal organic framework for being 9/1 to ferro-cobalt ratio.
Concentration can be by 2mM MOF-74 (Co/Fe) metal organic framework in 2 hours in conjunction with the Oxone of 1mM
The bisphenol-A of 1mM is degradable, and TOC removal rate is 82%.
Embodiment 4
(1) by CoSO4.7H2O(281mg,1.0mmol)、FeCl2(630mg,5mmol)、DHTA(800mg,4.0mmol)
It is added to 300mL DMF/ ethyl alcohol/H2In the solvent of O (10/1/1), it is put into polytetrafluoro reaction kettle after mixing evenly；
(2) polytetrafluoro reaction kettle is put into baking oven, is taken out after 140 DEG C of reaction 48h, is cleaned with ethyl alcohol and filtered afterwards three times
MOF-74 (Co/Fe) metal organic framework for being 1/5 to ferro-cobalt ratio.
The K of 2mM MOF-74 (Co/Fe) metal organic framework and 1mM2S2O8In conjunction with can be by concentration in 1 hour
The Norfloxacin of 1mM is degradable, and TOC removal rate is 70%.
Embodiment 5
(1) by Co (NO3)2.6H2O(250mg,1mmol)、FeSO4.7H2O(560mg,2.0mmol)、DHTA(400mg,
2.0mmol) it is added to 200mL DMF/ ethyl alcohol/H2In the solvent of O (10/1/0.5), it is put into polytetrafluoro reaction after mixing evenly
Kettle；
(2) polytetrafluoro reaction kettle is put into baking oven, 120 DEG C of reactions are taken out afterwards for 24 hours, are cleaned with ethyl alcohol and are filtered afterwards three times
MOF-74 (Co/Fe) metal organic framework for being 1/2 to ferro-cobalt ratio.
Concentration can be by 2mM MOF-74 (Co/Fe) metal organic framework in 1 hour in conjunction with the Oxone of 1mM
The repefral of 1mM is degradable, and TOC removal rate is 75%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of the ferro-cobalt bimetallic catalytic material based on MOF-74, which is characterized in that this method includes following
Step:
(1) in molar ratio (1~5) by metal salt, organic ligand: 1 is added in solvent, is transferred to polytetrafluoroethyl-ne after mixing evenly
Alkene reaction kettle；Wherein, the metal salt is made of metal salt containing cobalt and ferrous metal salt, and in the metal salt cobalt, iron mole
Than for (1~9): (1~9)；
(2) ptfe autoclave is put into baking oven and reacts 12~72h at 100~160 DEG C, obtain the cobalt based on MOF-74
Iron double metal catalysis material.
2. the preparation method of the ferro-cobalt bimetallic catalytic material based on MOF-74 as described in claim 1, which is characterized in that
In step (1), the metal salt containing cobalt is cobalt nitrate hexahydrate, Cobalt diacetate tetrahydrate, CoCL2 6H2O, one in cobalt sulfate
Kind；The ferrous metal salt is one of frerrous chloride, ferrous acetate, ferrous sulfate heptahydrate.
3. the preparation method of the ferro-cobalt bimetallic catalytic material based on MOF-74 as described in claim 1, which is characterized in that
In step (1), the organic ligand is 2,5-Dihydroxyterephthalic acid dimethyl ester.
4. the preparation method of the ferro-cobalt bimetallic catalytic material based on MOF-74 as described in claim 1, which is characterized in that
In step (1), the solvent is one of deionized water, dimethylformamide, dimethyl acetamide, ethyl alcohol, tetrahydrofuran
Or it is several.
5. the bimetallic catalytic material that any one of Claims 1 to 4 the method is prepared.
6. application of the bimetallic catalytic material described in claim 5 in terms of activating persulfate.
7. application as claimed in claim 6, which is characterized in that the persulfate is potassium persulfate, potassium hydrogen peroxymonosulfate
One of.
8. application of the bimetallic catalytic material described in claim 5 in terms of Organic Pollutants In Water of degrading.
9. application as claimed in claim 8, which is characterized in that the bimetallic catalytic material drops in conjunction with activation persulfate
Solve Organic Pollutants In Water.
10. application as claimed in claim 8, which is characterized in that the organic pollutant includes sulphadiazine, rhodamine B, double
Phenol A, Norfloxacin, repefral.
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| CN110591108A (en) * | 2019-09-24 | 2019-12-20 | 福州大学 | Preparation and application of bimetallic MOFs material |
| CN110841714A (en) * | 2019-10-17 | 2020-02-28 | 杭州电子科技大学 | Iron-cobalt bimetal-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand and preparation method and application thereof |
| CN111151303A (en) * | 2020-01-07 | 2020-05-15 | 东北师范大学 | Application of novel MIL-53(Fe) -based catalyst in removal of antibiotics in water |
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN111715298A (en) * | 2020-07-23 | 2020-09-29 | 广西师范大学 | Diamond-like bimetallic FeCo-MOF oxygen evolution electrocatalyst and preparation method thereof |
| CN111774038A (en) * | 2020-07-24 | 2020-10-16 | 山东建筑大学 | Preparation method and application of microporous/mesoporous/macroporous composite pore iron-cobalt bimetallic organic framework material |
| CN112076752A (en) * | 2020-10-13 | 2020-12-15 | 南京林业大学 | MOF-74 derived magnetic composite catalyst and preparation method and application thereof |
| CN113941332A (en) * | 2021-09-09 | 2022-01-18 | 华北电力大学 | Heterogeneous CoFe/Mg-LDO catalyst, preparation method and dimethylamine wastewater treatment method |
| CN114849788A (en) * | 2022-03-24 | 2022-08-05 | 华南理工大学 | Organic matter-cobalt-iron bimetallic composite catalyst and preparation method and application thereof |
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| CN110591108A (en) * | 2019-09-24 | 2019-12-20 | 福州大学 | Preparation and application of bimetallic MOFs material |
| CN110841714A (en) * | 2019-10-17 | 2020-02-28 | 杭州电子科技大学 | Iron-cobalt bimetal-organic framework material based on 2, 5-dihydroxy terephthalic acid ligand and preparation method and application thereof |
| CN111151303A (en) * | 2020-01-07 | 2020-05-15 | 东北师范大学 | Application of novel MIL-53(Fe) -based catalyst in removal of antibiotics in water |
| CN111302476A (en) * | 2020-02-27 | 2020-06-19 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN111302476B (en) * | 2020-02-27 | 2021-12-17 | 南京大学 | Preparation and application of magnetic material capable of activating persulfate and allowing MOF (metal-organic framework) in-situ growth of CNT (carbon nano tube) |
| CN111715298B (en) * | 2020-07-23 | 2022-12-30 | 广西师范大学 | Diamond-like bimetallic FeCo-MOF oxygen evolution electrocatalyst and preparation method thereof |
| CN111715298A (en) * | 2020-07-23 | 2020-09-29 | 广西师范大学 | Diamond-like bimetallic FeCo-MOF oxygen evolution electrocatalyst and preparation method thereof |
| CN111774038A (en) * | 2020-07-24 | 2020-10-16 | 山东建筑大学 | Preparation method and application of microporous/mesoporous/macroporous composite pore iron-cobalt bimetallic organic framework material |
| CN111774038B (en) * | 2020-07-24 | 2023-05-23 | 山东建筑大学 | Preparation method and application of micropore/mesopore/macropore composite pore iron-cobalt bimetallic organic framework material |
| CN112076752A (en) * | 2020-10-13 | 2020-12-15 | 南京林业大学 | MOF-74 derived magnetic composite catalyst and preparation method and application thereof |
| CN113941332A (en) * | 2021-09-09 | 2022-01-18 | 华北电力大学 | Heterogeneous CoFe/Mg-LDO catalyst, preparation method and dimethylamine wastewater treatment method |
| CN114849788A (en) * | 2022-03-24 | 2022-08-05 | 华南理工大学 | Organic matter-cobalt-iron bimetallic composite catalyst and preparation method and application thereof |
| CN114849788B (en) * | 2022-03-24 | 2023-02-14 | 华南理工大学 | Organic matter-cobalt-iron bimetallic composite catalyst and preparation method and application thereof |
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