CN111992184A - Magnetic metal organic framework material and preparation method thereof - Google Patents
Magnetic metal organic framework material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title abstract description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 22
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 5
- 229910001430 chromium ion Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- -1 mercury ions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
Images
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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a metal-organic framework material and a preparation method thereof, belonging to the technical field of enrichment, purification and detection of heavy metals in an aqueous solution. The magnetic metal organic framework material is prepared by introducing 2, 3-dimercaptosuccinic acid (DMSA) molecules on an MOF-808 material through coordination substitution reaction and then introducing magnetic Fe3O4Synthesizing the novel magnetic metal organic framework material Fe3O4@ MOF-808-DMSA. Using magnetic metal organic frame material Fe3O4The @ MOF-808-DMSA has large heavy metal adsorption capacity, good selectivity and easy dissolutionThe characteristic of liquid separation provides a high-efficiency, rapid and selective method for enriching and purifying heavy metals in aqueous solution.
Description
Technical Field
The invention belongs to the technical field of enrichment, purification and detection of heavy metals in aqueous solution, and particularly relates to a novel magnetic metal-organic framework material and a preparation method thereof.
Background
The heavy metal pollutes the environment quite generally and has great harm to the human health, so the content of the heavy metal in the sample is accurately measured, and the method has important significance for evaluating the harm of the heavy metal to the human body. For the detection of heavy metals, the sample processing method determines the detection limit, precision and accuracy of the whole method, and is one of the most important steps in the analysis of heavy metals.
The magnetic solid phase extraction technology is a novel sample pretreatment technology developed in recent years. Magnetic solid phase extraction has some particularly significant advantages over solid phase extraction. The magnetic adsorbent can be easily separated from the sample solution by applying an external magnetic field without centrifugation or filtration; the magnetic adsorbent material is dispersed in the solution, which allows for more sufficient contact area between the sample and the magnetic adsorbent, faster mass transfer, and rapid equilibration.
Metal-Organic Frameworks (MOFs) have some advantageous structural features: the porous structure is provided, the specific surface area is large, and contact points for enrichment and adsorption are increased; the porous structure is more beneficial to the adsorption of a target object on the surface of metal organic framework Materials (MOFs); the extraction selectivity can be improved by optimizing the organic ligand structure and post-modification, thereby improving the enrichment effect. Therefore, metal organic framework Materials (MOFs) have wide application in the field of extraction and separation.
Disclosure of Invention
The invention aims to provide a magnetic metal-organic framework material (Fe) for adsorbing heavy metal ions in an aqueous solution3O4@ MOF-808-DMSA), another object of the present invention is to provide a method for preparing a magnetic metal-organic framework material.
According to the invention, 2, 3-dimercaptosuccinic acid (DMSA) molecules are introduced to a magnetic metal organic framework material MOF-808 material through coordination substitution reaction, and then magnetic ferroferric oxide (Fe)3O4) Synthesizing magnetic metal organic frame material (Fe)3O4@ MOF-808-DMSA). Magnetic metal organic framework material Fe3O4@ MOF-808-DMSA is black powder with particle size of 50-1000 nm.
The magnetic metal organic framework material is used for adsorbing heavy metal ions in an aqueous solution, and the adsorption recovery rate is more than 90%; the heavy metal ions are lead ions (Pb)2+) Mercury ion (Hg)2+) Cadmium ion (Cd)2+) And chromium ion (Cr)3+）。
The preparation method comprises the following specific preparation operation steps:
(1) dissolving 0.21g of organic ligand trimesic acid and 0.97g of zirconyl nitrate octahydrate in a mixed solvent of 35mL of N, N-dimethylformamide and 35mL of anhydrous formic acid; reacting for 48 hours in a reaction kettle at the temperature of 120 ℃; washing the solid precipitate with N, N-dimethylformamide, water and acetone in sequence to remove impurities; vacuum drying the obtained solid at 60 ℃ to obtain a metal organic framework material MOF-808;
(2) mixing metal organic framework materials MOF-808, 2, 3-dimercaptosuccinic acid (DMSA) and deionized water according to the mass ratio of 1 (5-50) to (100-250), and reacting for 24 hours at the temperature of 60 ℃; washing the obtained solid product with water and acetone in sequence to remove impurities; vacuum drying the obtained solid at 60 ℃ to obtain a metal-organic framework material MOF-808-DMSA;
(3) dissolving 0.21g of metal-organic framework material MOF-808-DMSA, 0.54g of ferric trichloride hexahydrate and 0.99g of sodium acetate in 20mL of ethylene glycol, and performing ultrasonic treatment for 1 hour; reacting for 24 hours in a reaction kettle at the temperature of 200 ℃; washing with water and ethanol in sequence to remove impurities; the obtained solid is dried in vacuum at 60 ℃ to obtain the magnetic metal organic framework material Fe3O4@MOF-808-DMSA。
The novel magnetic metal-organic framework material is used as an adsorbent and is used for simultaneously adsorbing various heavy metal ions in an aqueous solution.
The invention researches a novel magnetic metal organic framework material Fe3O4The specific method for adsorbing the heavy metal by the @ MOF-808-DMSA comprises the following steps: 100 mL of primary water is added into a 100 mL centrifuge tube, and a heavy metal standard solution is added to prepare a mixed solution with the concentration of 1 ppm. 10 mg of magnetic metal organic framework material Fe is added3O4@ MOF-808-DMSA, adsorbing heavy metals by ultrasound for 10 minutes. Using a magnetic separation sample, the aqueous solution was decanted, 2mL of 5% L-cysteine solution was added, and the adsorbed heavy metals were eluted by vortexing for 30 seconds. And (4) measuring the heavy metal content of the eluent by using an inductively coupled plasma mass spectrometer. Research shows that the novel magnetic metal organic framework material Fe3O4@ MOF-808-DMSA on lead ion (Pb)2+) Mercury ion (Hg)2+) Cadmium ion (Cd)2+) And chromium ion (Cr)3 +) The adsorption recovery rate is more than 90%.
The beneficial technical effects of the invention are embodied in the following aspects:
1. the magnetic metal organic framework material Fe synthesized by the invention3O4The @ MOF-808-DMSA utilizes the strong complexation effect of 2, 3-dimercaptosuccinic acid (DMSA) on heavy metals, and the MOF material has the characteristics of porous structure and large specific surface area and can simultaneously carry out complexation on lead ions (Pb) in an aqueous solution2+) Mercury ion (Hg)2+) Cadmium ion (Cd)2+) And chromium ion (Cr)3+) The adsorption is carried out, and the adsorption recovery rate is more than 90 percent.
2. The magnetic metal organic framework material Fe synthesized by the invention3O4The @ MOF-808-DMSA realizes the efficient and rapid enrichment and purification of the heavy metals in the aqueous solution by utilizing the characteristic that the magnetic material is easy to separate from the solution.
Drawings
FIG. 1 shows the magnetic metal-organic framework material Fe in example 13O4Infrared spectrum of @ MOF-808-DMSA.
FIG. 2 shows the magnetic metal-organic framework material Fe in example 23O4Infrared spectrum of @ MOF-808-DMSA.
FIG. 3 shows the magnetic metal organic framework material Fe in example 33O4Infrared spectrum of @ MOF-808-DMSA.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The preparation operation steps of the magnetic metal organic framework material are as follows:
(1) dissolving 0.21g (1 mmol) of organic ligand trimesic acid and 0.97g (3 mmol) of zirconium oxychloride octahydrate in a mixed solvent of 35mL of N, N-dimethylformamide and 35mL of anhydrous formic acid, and reacting for 48 hours at 120 ℃ in a reaction kettle; washing the solid precipitate by sequentially using N, N-dimethylformamide, water and acetone to remove residual raw materials and impurities in the pore channel; and (3) drying the obtained solid product at 60 ℃ in vacuum to obtain the metal organic framework material MOF-808.
(2) Dissolving 0.2g of metal organic framework material MOF-808 and 1g of 2, 3-dimercaptosuccinic acid (DMSA) in 20mL of deionized water, wherein the mass ratio of the metal organic framework material MOF-808 to the 2, 3-dimercaptosuccinic acid is 1:5:100, and reacting for 24 hours at the temperature of 60 ℃; and washing the obtained solid product with water and acetone in sequence, and drying at 60 ℃ in vacuum to obtain the metal organic framework material MOF-808-DMSA.
(3) Dissolving 0.2g of metal organic framework material MOF-808-DMSA, 0.54g of ferric trichloride hexahydrate and 0.99g of sodium acetate in 20mL of ethylene glycol, and performing ultrasonic treatment for 1 hour; reacting for 24 hours in a reaction kettle at the temperature of 200 ℃; washing the obtained solid product with water and ethanol in sequence, and drying at 60 ℃ in vacuum to obtain the magnetic metal organic framework material Fe3O4@MOF-808- DMSA。
Magnetic metal organic framework material Fe3O4The @ MOF-808-DMSA is black powder with the particle size of 50-1000 nm; magnetic metal organic framework material Fe3O4Infrared spectrum of @ MOF-808-DMSA, see FIG. 1.
Magnetic metal organic framework material Fe3O4@ MOF-808-DMSA for use of lead ions (Pb) in aqueous solutions2+) The average recovery rate of adsorption is 95 percent; for mercury ions (Hg) in aqueous solutions2+) The average recovery rate of adsorption is 97 percent; for cadmium ion (Cd) in aqueous solution2+) The average recovery rate of adsorption is 93 percent; for chromium ion (Cr) in aqueous solution3+) The average recovery rate of adsorption of (1) was 91%.
Example 2
The preparation operation steps of the magnetic metal organic framework material are as follows:
(1) dissolving 0.21g (1 mmol) of organic ligand trimesic acid and 0.97g (3 mmol) of zirconium oxychloride octahydrate in a mixed solvent of 35mL of N, N-dimethylformamide and 35mL of anhydrous formic acid, and reacting for 48 hours at 120 ℃ in a reaction kettle; washing the solid precipitate by sequentially using N, N-dimethylformamide, water and acetone to remove residual raw materials and impurities in the pore channel; and (3) drying the obtained solid product at 60 ℃ in vacuum to obtain the metal organic framework material MOF-808.
(2) Dissolving 0.2g of metal organic framework material MOF-808 and 2g of 2, 3-dimercaptosuccinic acid (DMSA) in 40 mL of deionized water, wherein the mass ratio of the metal organic framework material MOF-808 to the 2, 3-dimercaptosuccinic acid is 1:10:200, and reacting for 24 hours at the temperature of 60 ℃; and washing the obtained solid product with water and acetone in sequence, and drying at 60 ℃ in vacuum to obtain the metal organic framework material MOF-808-DMSA.
(3) Dissolving 0.2g of metal organic framework material MOF-808-DMSA, 0.54g of ferric trichloride hexahydrate and 0.99g of sodium acetate in 20mL of ethylene glycol, and performing ultrasonic treatment for 1 hour; reacting for 24 hours in a reaction kettle at the temperature of 200 ℃; washing the obtained solid product with water and ethanol in sequence, and drying at 60 ℃ in vacuum to obtain the magnetic metal organic framework material Fe3O4@MOF-808- DMSA。
Magnetic metal organic framework material Fe3O4The @ MOF-808-DMSA is black powder with the particle size of 50-1000 nm; magnetic metal organic framework material Fe3O4Infrared spectrum of @ MOF-808-DMSA, see FIG. 2.
Example 3
The preparation operation steps of the magnetic metal organic framework material are as follows:
(1) dissolving 0.21g (1 mmol) of organic ligand trimesic acid and 0.97g (3 mmol) of zirconium oxychloride octahydrate in a mixed solvent of 35mL of N, N-dimethylformamide and 35mL of anhydrous formic acid, and reacting for 48 hours at 120 ℃ in a reaction kettle; washing the solid precipitate by sequentially using N, N-dimethylformamide, water and acetone to remove residual raw materials and impurities in the pore channel; vacuum drying the obtained solid product at 60 ℃ in a room to obtain the metal organic framework material MOF-808
(2) Dissolving 0.2g of metal organic framework material MOF-808 and 10 g of 2, 3-dimercaptosuccinic acid (DMSA) in 50 mL of deionized water, wherein the mass ratio of the metal organic framework material MOF-808 to the 2, 3-dimercaptosuccinic acid (DMSA) is 1:50:250, and reacting for 24 hours at the temperature of 60 ℃; and washing the obtained solid product with water and acetone in sequence, and drying at 60 ℃ in vacuum to obtain the metal organic framework material MOF-808-DMSA.
(3) Dissolving 0.2g of metal-organic framework material MOF-808-DMSA, 0.54g of ferric trichloride hexahydrate and 0.99g of sodium acetate in 20mL of ethylene glycol, and performing ultrasonic treatment for 1 hour; reacting for 24 hours in a reaction kettle at the temperature of 200 ℃; washing the obtained solid product with water and ethanol in sequence, and drying at 60 ℃ in vacuum to obtain the magnetic metal organic framework material Fe3O4@MOF-808- DMSA。
Magnetic metal organic framework material Fe3O4The @ MOF-808-DMSA is black powder with the particle size of 50-1000 nm; magnetic metal organic framework material Fe3O4Infrared spectrum of @ MOF-808-DMSA, see FIG. 3.
Claims (2)
1. A magnetic metal organic framework material, characterized by:
2, 3-dimercaptosuccinic acid molecules are introduced to the magnetic metal organic framework material MOF-808 through coordination substitution reaction, and then magnetic ferroferric oxide is introduced to prepare the magnetic metal organic framework material Fe3O4@ MOF-808-DMSA; the magnetic metal organic framework material Fe3O4The @ MOF-808-DMSA is black powder with the particle size of 50-1000 nm;
the magnetic metal organic framework material is used for adsorbing heavy metal ions in an aqueous solution, and the adsorption recovery rate is more than 90%; the heavy metal ions are lead ions, mercury ions, cadmium ions and chromium ions.
2. The method for preparing a magnetic metal organic framework material according to claim 1, characterized by the following steps:
(1) dissolving 0.21g of organic ligand trimesic acid and 0.97g of zirconyl nitrate octahydrate in a mixed solvent of 35mL of N, N-dimethylformamide and 35mL of anhydrous formic acid; reacting for 48 hours in a reaction kettle at the temperature of 120 ℃; washing the solid precipitate with N, N-dimethylformamide, water and acetone in sequence to remove impurities; vacuum drying the obtained solid at 60 ℃ to obtain a metal organic framework material MOF-808;
(2) mixing metal organic framework materials MOF-808, 2, 3-dimercaptosuccinic acid and deionized water according to the mass ratio of 1 (5-50) to (100-250), and reacting for 24 hours at the temperature of 60 ℃; washing the obtained solid product with water and acetone in sequence to remove impurities; vacuum drying the obtained solid at 60 ℃ to obtain a metal-organic framework material MOF-808-DMSA;
(3) dissolving 0.21g of metal-organic framework material MOF-808-DMSA, 0.54g of ferric trichloride hexahydrate and 0.99g of sodium acetate in 20mL of ethylene glycol, and performing ultrasonic treatment for 1 hour; reacting for 24 hours in a reaction kettle at the temperature of 200 ℃; washing with water and ethanol in sequence to remove impurities; the obtained solid is dried in vacuum at 60 ℃ to obtain the magnetic metal organic framework material Fe3O4@MOF-808-DMSA。
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| DE102005039623A1 (en) * | 2005-08-22 | 2007-03-01 | Basf Ag | Process for the preparation of organometallic frameworks Main groups containing metal ions |
| WO2012144758A2 (en) * | 2011-04-18 | 2012-10-26 | 한국화학연구원 | Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst |
| CN104030389A (en) * | 2014-06-23 | 2014-09-10 | 东北林业大学 | Method for removing dyes in water by utilizing magnetic metal-organic framework material |
| CN105148852A (en) * | 2015-10-12 | 2015-12-16 | 武汉大学 | Thiohydroxy-modified magnetic MOFs adsorbent and preparation method and application thereof |
| CN107159128A (en) * | 2017-05-16 | 2017-09-15 | 北京化工大学 | A kind of novel metal organic framework material as well as preparation method and application thereof |
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| CN116813374A (en) * | 2022-12-14 | 2023-09-29 | 张锦彬 | Ceramic manufactured by fly ash of garbage power plant |
| CN116813374B (en) * | 2022-12-14 | 2024-04-09 | 张锦彬 | Ceramic manufactured by fly ash of garbage power plant |
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