CN116116393A - Cu-pPDA functionalized modification-based magnetic dendritic MOF material and preparation method and application thereof - Google Patents
Cu-pPDA functionalized modification-based magnetic dendritic MOF material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000004048 modification Effects 0.000 title claims description 24
- 238000012986 modification Methods 0.000 title claims description 24
- 239000002077 nanosphere Substances 0.000 claims abstract description 58
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 16
- 238000001179 sorption measurement Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 66
- 239000006185 dispersion Substances 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 150000003573 thiols Chemical class 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 claims description 3
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000001394 sodium malate Substances 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000012621 metal-organic framework Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- 239000010931 gold Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- -1 copper-p-Phenylenediamine Chemical compound 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- JLLMOYPIVVKFHY-UHFFFAOYSA-N Benzenethiol, 4,4'-thiobis- Chemical compound C1=CC(S)=CC=C1SC1=CC=C(S)C=C1 JLLMOYPIVVKFHY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000010793 electronic waste Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a Cu-pPDA functionalized modified magnetic dendritic MOF material, and a preparation method and application thereof, comprising magnetic Fe 3 O 4 Nanosphere synthesis, thiol-modified Fe 3 O 4 The nanospheres and Cu-pPDA perform functionalization to obtain the magnetic dendritic MOF material which is used for efficiently and selectively treating noble metals such as Au (III)/Pd (II). The Cu-pPDA functionalized modified magnetic dendritic MOF material is prepared by adopting dendritic MOF and Fe 3 O 4 The stable combination of the functional magnetic carrier of the nanospheres, the treatment of noble metal solution at 45 ℃ and pH value of 1-4, and the maximum adsorption capacity of Au (III) and Pd (II) reach more than 1400 mg/L; in the presence of other metal ions, the noble metal Au (III/Pd (II)) selectivity coefficient is more than 98%.
Description
Technical Field
The invention relates to the technical field of noble metal treatment, in particular to a Cu-pPDA functionalized modified magnetic dendritic MOF material, and a preparation method and application thereof.
Background
With industry development, noble metals (PMs) in commercial electronic parts have caused a serious series of environmental problems. The pretreatment of PMs in electrical and electronic equipment waste is critical, and the importance of subsequent recovery of precious metals as secondary resources is becoming more and more important. However, the treatment and recovery of PMs in electronic waste is always a difficult task, since electronic waste is often dissolved in a harsh acidic environment and is chemically disturbed by other metal ions, which may be detrimental to the absorption efficiency, the absorption selectivity and the stability of the absorbent material.
Metal-organic frameworks (MOFs) are a class of hybrid porous materials whose framework structure consists of inorganic metal clusters and organic-organic linkers, generally with high specific surface area, macroporosity, tunable porous structure, and high chemical and thermal stability, especially rich in organic functional groups, capable of interacting with objects (especially PMs) and thus can be used to treat PMs. However, one disadvantage of MOFs materials in terms of adsorption properties is the powder nature of MOFs, which to some extent limits the practical use of MOFs. Therefore, the MOF material is fixed on an effective carrier, so that the MOF material can be conveniently and efficiently recycled, and the method provides an optimistic prospect for the applicability of the MOF material. However, such composite/hybrid materials still encounter several difficulties associated with poor heterogeneous nucleation sites due to compatibility issues between the MOF and bare support surface.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art, and provides a magnetic dendritic MOF material (abbreviated as MDM hybrid) based on Cu-pPDA functionalization modification, which is prepared by dendritic MOP and Fe 3 O 4 The stable combination of the functional magnetic carrier of the nanospheres has extraordinary stability. The functionality of MDM hybrids derives from thiol functions of dendrite and amino functional frameworks, which show a significantly selective adsorption of Au (III) and Pd (II), especially in a harsh acidic environment, PMs are highly selective in the presence of the other ten metal ions.
The aim of the invention is achieved by the following technical scheme:
a preparation method of a magnetic dendritic MOF material based on Cu-pPDA functionalization modification comprises the following steps:
(1) Synthesis of magnetic Fe 3 O 4 Nanospheres:
ultrasonic dissolution of FeCl with ethylene glycol 3 ·6H 2 O, obtain FeCl 3 A dispersion;
dissolving organic salt by using glycol ultrasonic to obtain organic salt dispersion liquid;
dropwise addition of organic salt dispersion to FeCl 3 Mixing and stirring uniformly in the dispersion liquid, transferring to an autoclave for crystallization at 200 ℃ for 2 hours, cooling, washing with deionized water and ethanol, and vacuum drying to obtain the magnetic Fe 3 O 4 A nanosphere;
(2) Thiol-modified Fe 3 O 4 Nanospheres:
magnetic Fe 3 O 4 Ultrasonic dispersing the nanospheres in ethanol to obtain magnetic Fe 3 O 4 A nanosphere dispersion;
dissolving mercaptan in ethanol to obtain mercaptan solution;
dropwise addition of thiol solution to magnetic Fe 3 O 4 Stirring at 1000 rpm in nanosphere dispersion, maintaining at 40deg.C for 12 hr, centrifuging, washing with deionized water and ethanol, and vacuum drying to obtain the final productThiol-modified Fe 3 O 4 A nanosphere;
(3) Synthesis of MDM hybrid materials: modification of thiol to Fe 3 O 4 Dispersing nanospheres in a proper amount of deionized water, adding a connecting agent and copper chloride, vigorously stirring for 1h at 80 ℃, adding an ammonia water solution, continuously stirring for 16-24h, washing with deionized water and ethanol, centrifugally separating, and drying in vacuum to obtain the Cu-pPDA functionalized modified magnetic dendritic MOF material.
Further, the FeCl in step (1) 3 3-5mg FeCl is dissolved in 1mL ethanol in the dispersion 3 ·6H 2 O, 1mL of ethanol in the organic salt dispersion is used for dissolving 10-15mg of organic salt.
Further, the organic salt is one of sodium citrate, sodium acetate and sodium malate.
Further, the magnetic Fe in the step (2) 3 O 4 1mL of ethanol in the nanosphere dispersion is used for dispersing 10-15mg of magnetic Fe 3 O 4 A nanosphere; 1mL of ethanol in the mercaptan solution is mixed with 1-2mg of mercaptan, wherein the mercaptan is one of 1, 2-benzenedithiol, 1, 4-benzenedithiol and 4,4' -thiodiphenyl mercaptan.
Further, the thiol-modified Fe in the step (3) 3 O 4 The mass ratio of the nanospheres, the connecting agent and the copper chloride is 100:0.75:100.
Further, 100mg of thiol-modified Fe in the step (3) 3 O 4 The nanospheres require the addition of 0.8mL of an aqueous ammonia solution.
Further, the connecting agent is one of o-phenylenediamine, p-phenylenediamine and m-phenylenediamine.
The magnetic dendritic MOF material based on Cu-pPDA functional modification is prepared by the preparation method of the magnetic dendritic MOF material based on Cu-pPDA functional modification.
The magnetic dendritic MOF material based on Cu-pPDA functionalization modification is applied to adsorption treatment of Au (III) and Pd (II) noble metals, the maximum adsorption capacity of the Au (III) and the Pd (II) reaches 1400mg/L, and the selectivity coefficient of the Au (III) and the Pd (II) noble metals is more than 98% under the condition that other metal ions exist.
The invention has the beneficial effects that:
the final synthesis of the invention is MDM hybrid material (Cu-pPDAMOF-Fe) 3 O 4 ) The magnetic hybrid material is a magnetic hybrid material based on functional Cu-pPDA (copper-p-Phenylenediamine) MOF nanospheres, and basically comprises magnetic ferroferric oxide (core), thiol is connected in the middle, and copper amine MOF material is an outer layer. The method is used for efficiently adsorbing and treating noble metals such as gold Au (III), palladium Pd (II) and the like, the adsorption capacity reaches more than 1400mg/g, and the adsorption capacity of the noble metals such as Au (III)/Pd (II) and the like is only reduced by 5-20mg/g in the presence of more than ten transition metals, so that the method has remarkable efficient selectivity. The magnetic hybridization material of the Cu-pPDA (copper-p-phenylenediamine) MOF nanospheres provided by the invention has great environmental and social economic values due to the availability, excellent adsorption capacity and selectivity of the material and easiness in magnetic separation.
Drawings
FIG. 1a shows magnetic Fe in example 1 3 O 4 Nanosphere SEM image;
FIG. 1b is a thiol-modified Fe of example 1 3 O 4 Nanosphere SEM image;
FIG. 1c is an SEM image of the MDM hybrid material of example 1;
FIG. 1d shows magnetic Fe in example 1 3 O 4 A nanosphere TEM image;
FIG. 1e shows thiol-modified Fe in example 1 3 O 4 A nanosphere TEM image;
FIG. 1f is a TEM image of the MDM hybrid material of example 1;
FIG. 2 shows the adsorption amounts of Au (III) (a) and Pb (II) (b) of different materials in example 1;
FIG. 3 shows the adsorption amounts of Au (III) (a) and Pb (II) (b) of the MDM hybrid material in the presence of other metal ions in example 1.
Detailed Description
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
The reagents or apparatus used in the present invention are conventional products commercially available without identifying the manufacturer.
Example 1
(1) Synthesis of magnetic Fe 3 O 4 Nanospheres:
200mg FeCl 3 ·6H 2 O is dispersed in 40mL glycol for 1h by ultrasonic to obtain FeCl 3 A dispersion;
500mg NaAc.3H 2 O is ultrasonically dispersed in 40mL of glycol for 1h to obtain organic salt dispersion liquid;
dropwise addition of organic salt dispersion to FeCl 3 Mixing and stirring uniformly in the dispersion liquid, transferring into an autoclave, preserving heat at 200 ℃ for 2 hours, cooling, placing an external magnet below the solution, washing with deionized water and ethanol for 5 times, and drying in a vacuum oven at 100 ℃ for 12 hours to obtain the magnetic Fe 3 O 4 A nanosphere.
(2) Thiol-modified Fe 3 O 4 Nanospheres:
500mg of magnetic Fe 3 O 4 The nanospheres are dispersed in 50mL of ethanol for 2 hours by ultrasonic wave to obtain magnetic Fe 3 O 4 A nanosphere dispersion;
100mg of 4,4' -thiodiphenyl mercaptan is dissolved in 50mL of ethanol to obtain a mercaptan solution;
dropwise addition of thiol solution to magnetic Fe 3 O 4 Stirring at 1000 rpm in nanosphere dispersion, maintaining at 40deg.C for 12 hr, centrifuging, washing with deionized water and ethanol, and drying at 100deg.C in vacuum oven for 12 hr to obtain thiol-modified Fe 3 O 4 A nanosphere.
(3) Synthesis of MDM hybrid materials: 100mg of mercaptan modified Fe 3 O 4 Dispersing nanospheres in 100mL deionized water, adding 0.75mg of o-phenylenediamine connecting agent and 100mg of copper chloride, vigorously stirring for 1h at 80 ℃, then stirring for 24h with 0.8mL of ammonia water solution, washing with deionized water and ethanol, centrifuging, and drying for 24h in a vacuum oven at 80 ℃ to obtain a magnetic dendritic MOF material based on Cu-pPDA functionalization modification, namely an MDM hybrid material (Cu-pPDAMOF-Fe) 3 O 4 )。
Example 2
(1) Synthesis of magnetic Fe 3 O 4 Nanospheres:
120mg FeCl 3 ·6H 2 O is dispersed in 40mL glycol for 1h by ultrasonic to obtain FeCl 3 A dispersion;
dispersing 400mg of sodium citrate in 40mL of glycol for 1h by ultrasonic, so as to obtain an organic salt dispersion liquid;
dropwise addition of organic salt dispersion to FeCl 3 Mixing and stirring uniformly in the dispersion liquid, transferring into an autoclave, preserving heat at 200 ℃ for 2 hours, cooling, placing an external magnet below the solution, washing with deionized water and ethanol for 5 times, and drying in a vacuum oven at 100 ℃ for 12 hours to obtain the magnetic Fe 3 O 4 A nanosphere.
(2) Thiol-modified Fe 3 O 4 Nanospheres:
600mg of magnetic Fe 3 O 4 The nanospheres are dispersed in 50mL of ethanol for 2 hours by ultrasonic wave to obtain magnetic Fe 3 O 4 A nanosphere dispersion;
50mg of 1, 2-benzenedithiol is dissolved in 50mL of ethanol to obtain a mercaptan solution;
dropwise addition of thiol solution to magnetic Fe 3 O 4 Stirring at 1000 rpm in nanosphere dispersion, maintaining at 40deg.C for 12 hr, centrifuging, washing with deionized water and ethanol, and drying at 100deg.C in vacuum oven for 12 hr to obtain thiol-modified Fe 3 O 4 A nanosphere.
(3) Synthesis of MDM hybrid materials: 100mg of mercaptan modified Fe 3 O 4 Dispersing nanospheres in 100mL deionized water, adding 0.75mg of m-phenylenediamine connecting agent and 100mg of copper chloride, vigorously stirring for 1h at 80 ℃, then stirring for 16h with 0.8mL of ammonia water solution, washing with deionized water and ethanol, centrifugally separating, and drying for 24h in a vacuum oven at 80 ℃ to obtain the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, namely MDM hybrid material (Cu-pPDAMOF-Fe) 3 O 4 )。
Example 3
(1) Synthesis of magnetic Fe 3 O 4 Nanospheres：
160mg FeCl 3 ·6H 2 O is dispersed in 40mL glycol for 1h by ultrasonic to obtain FeCl 3 A dispersion;
dispersing 600mg of sodium malate in 40mL of glycol for 1h by ultrasonic treatment to obtain an organic salt dispersion liquid;
dropwise addition of organic salt dispersion to FeCl 3 Mixing and stirring uniformly in the dispersion liquid, transferring into an autoclave, preserving heat at 200 ℃ for 2 hours, cooling, placing an external magnet below the solution, washing with deionized water and ethanol for 5 times, and drying in a vacuum oven at 100 ℃ for 12 hours to obtain the magnetic Fe 3 O 4 A nanosphere.
(2) Thiol-modified Fe 3 O 4 Nanospheres:
750mg of magnetic Fe 3 O 4 The nanospheres are dispersed in 50mL of ethanol for 2 hours by ultrasonic wave to obtain magnetic Fe 3 O 4 A nanosphere dispersion;
75mg of 1, 4-benzenedithiol is dissolved in 50mL of ethanol to obtain a mercaptan solution;
dropwise addition of thiol solution to magnetic Fe 3 O 4 Stirring at 1000 rpm in nanosphere dispersion, maintaining at 40deg.C for 12 hr, centrifuging, washing with deionized water and ethanol, and drying at 100deg.C in vacuum oven for 12 hr to obtain thiol-modified Fe 3 O 4 A nanosphere.
(3) Synthesis of MDM hybrid materials: 100mg of mercaptan modified Fe 3 O 4 Dispersing nanospheres in 100mL deionized water, adding 0.75mg of p-phenylenediamine connecting agent and 100mg of copper chloride, vigorously stirring at 80 ℃ for 1h, then adding 0.8mL of ammonia water solution, continuously stirring for 18h, washing with deionized water and ethanol, centrifugally separating, and drying at 80 ℃ in a vacuum oven for 24h to obtain the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, namely an MDM hybrid material (Cu-pPDAMOF-Fe) 3 O 4 )。
The materials prepared in examples 1-3 were subjected to a noble metal adsorption procedure:
prior to performing the adsorption experiments, cu-pda functionalized modified magnetic dendritic MOF material based on was activated in a vacuum oven at 80 ℃ for 2 hours to remove moisture and adsorbAnd (5) an attached gas molecule. Using 0.1mol/L HNO 3 Aqueous solution of noble metal salt (HAuCl) 4 .6H 2 O/PdCl 2 ) Dissolving in deionized water to prepare a transparent solution of noble metal (Au (III)/Pd (II). The maximum adsorption amount was examined by treating a noble metal solution having an initial concentration of 10-2000mg/L at 45℃and a pH of 1-4. As shown in FIG. 2 and FIG. 3, the initial concentrations of the noble metals Au (III/Pd (II) and Pd (II) were 100mg/L in the presence of other metal ions, and the selectivity coefficients of Au (III) and Pd (II) were measured.
Those skilled in the art can also make appropriate changes and modifications to the above-described embodiments in light of the above disclosure. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. A preparation method of a magnetic dendritic MOF material based on Cu-pPDA functional modification is characterized by comprising the following steps: the method comprises the following steps:
(1) Synthesis of magnetic Fe 3 O 4 Nanospheres
Ultrasonic dissolution of FeCl with ethylene glycol 3 ·6H 2 O, obtain FeCl 3 A dispersion;
dissolving organic salt by using glycol ultrasonic to obtain organic salt dispersion liquid;
dropwise addition of organic salt dispersion to FeCl 3 Mixing and stirring uniformly in the dispersion liquid, transferring to an autoclave for crystallization at 200 ℃ for 2 hours, cooling, washing with deionized water and ethanol, and vacuum drying to obtain the magnetic Fe 3 O 4 A nanosphere;
(2) Thiol-modified Fe 3 O 4 Nanospheres
Magnetic Fe 3 O 4 Ultrasonic dispersing the nanospheres in ethanol to obtain magnetic Fe 3 O 4 A nanosphere dispersion;
dissolving mercaptan in ethanol to obtain mercaptan solution;
dropwise addition of thiol solution to magnetic Fe 3 O 4 Stirring at 1000 rpm in nanosphere dispersion, maintaining at 40deg.C for 12 hr, centrifuging, washing with deionized water and ethanol, and vacuum drying to obtain thiol-modified Fe 3 O 4 A nanosphere;
(3) Synthesis of MDM hybrid materials
Modification of thiol to Fe 3 O 4 Dispersing nanospheres in a proper amount of deionized water, adding a connecting agent and copper chloride, vigorously stirring for 1h at 80 ℃, adding an ammonia water solution, continuously stirring for 16-24h, washing with deionized water and ethanol, centrifugally separating, and drying in vacuum to obtain the Cu-pPDA functionalized modified magnetic dendritic MOF material.
2. The method for preparing the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, according to claim 1, is characterized in that: the FeCl in step (1) 3 3-5mg FeCl is dissolved in 1mL ethanol in the dispersion 3 ·6H 2 O, 1mL of ethanol in the organic salt dispersion is used for dissolving 10-15mg of organic salt.
3. The method for preparing the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, according to claim 1, is characterized in that: the magnetic Fe in step (2) 3 O 4 1mL of ethanol in the nanosphere dispersion is used for dispersing 10-15mg of magnetic Fe 3 O 4 A nanosphere; 1mL of ethanol in the mercaptan solution is mixed with 1-2mg of mercaptan.
4. The method for preparing the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, according to claim 1, is characterized in that: the mercaptan modified Fe in the step (3) 3 O 4 The mass ratio of the nanospheres, deionized water, the connecting agent and the copper chloride is 100:100:0.75:100。
5. The method for preparing the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, according to claim 1, is characterized in that: 100mg of thiol-modified Fe in step (3) 3 O 4 The nanospheres require the addition of 0.8mL of an aqueous ammonia solution.
6. The method for preparing the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, according to claim 2, is characterized in that: the organic salt is one of sodium citrate, sodium acetate and sodium malate.
7. The method for preparing the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, according to claim 3, wherein the method comprises the following steps: the mercaptan is one of 1, 2-benzene dithiol, 1, 4-benzene dithiol and 4,4' -thio-benzene dithiol.
8. The method for preparing the magnetic dendritic MOF material based on Cu-pPDA functionalization modification, according to claim 4, is characterized in that: the connecting agent is one of o-phenylenediamine, p-phenylenediamine and m-phenylenediamine.
9. A magnetic dendritic MOF material based on Cu-pPDA functionalization modification is characterized in that: which is prepared by the preparation method of the magnetic dendritic MOF material based on Cu-pPDA functionalization modification as claimed in any one of claims 1 to 8.
10. The Cu-pda functionalization-modified magnetic dendritic MOF material of claim 9, wherein: the method is applied to adsorption treatment of Au (III) and Pd (II) noble metals, the maximum adsorption quantity of the Au (III) and the Pd (II) reaches 1400mg/L, and the selectivity coefficient of the Au (III) and the Pd (II) noble metals is more than 98% in the presence of other metal ions.
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| CN110604946A (en) * | 2019-11-04 | 2019-12-24 | 中国科学院大学 | Polyethylene glycol functionalized Fe3O4Method for selectively separating and enriching Au (III) from nanoparticles |
| CN113477220A (en) * | 2021-07-02 | 2021-10-08 | 北京科技大学 | Noble metal ion adsorption material based on magnetic metal organic framework and preparation method thereof |
| CN115023284A (en) * | 2019-11-26 | 2022-09-06 | 埃克森美孚技术与工程公司 | Metal-organic material extrudates, methods of making and methods of using |
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| CN110604946A (en) * | 2019-11-04 | 2019-12-24 | 中国科学院大学 | Polyethylene glycol functionalized Fe3O4Method for selectively separating and enriching Au (III) from nanoparticles |
| CN115023284A (en) * | 2019-11-26 | 2022-09-06 | 埃克森美孚技术与工程公司 | Metal-organic material extrudates, methods of making and methods of using |
| CN113477220A (en) * | 2021-07-02 | 2021-10-08 | 北京科技大学 | Noble metal ion adsorption material based on magnetic metal organic framework and preparation method thereof |
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