CN110387048B - Metal organic framework two-dimensional nanosheet and preparation method thereof - Google Patents
Metal organic framework two-dimensional nanosheet and preparation method thereof Download PDFInfo
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- CN110387048B CN110387048B CN201910763107.4A CN201910763107A CN110387048B CN 110387048 B CN110387048 B CN 110387048B CN 201910763107 A CN201910763107 A CN 201910763107A CN 110387048 B CN110387048 B CN 110387048B
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Abstract
The invention discloses a metal organic framework two-dimensional nanosheet and a preparation method thereof, wherein the two-dimensional nanocrystal is metal salt (ZnAc)2•2H2O) and an organic ligand (2-methylimidazole) are synthesized under the action of surfactant assistance (sodium dodecyl sulfate, namely SDS), zinc acetate dihydrate, 2-methylimidazole and SDS solution are prepared at normal temperature respectively, then the solutions are mixed uniformly, placed in a constant temperature box for standing for 24 hours and then centrifugally washed by methanol, and the 2D ZIF-8 nanosheet is obtained. The method is simple and easy to implement, is carried out at normal temperature, has low energy consumption, is green and environment-friendly, has controllable product appearance and has good application prospect.
Description
Technical Field
The invention relates to a metal organic framework two-dimensional nanosheet and a preparation method thereof, and belongs to the technical field of nanostructure synthesis.
Background
Metal organic framework compounds (MOFs) are crystalline porous materials with a periodic network structure formed by self-assembly of metals (single metal ions or metal clusters) and organic ligands through coordination bonds. MOFs, also known as coordination polymers (coordination polymers), are an organic-inorganic hybrid material that combines the rigidity of inorganic materials with the flexibility characteristics of organic materials. MOFs can form different framework pore structures because the arrangement of metals (single metal ions or metal clusters) and organic ligands has a distinct directionality. Therefore, the MOFs have the advantages of high porosity, high specific surface area, regular pore channels, adjustable pore diameters, diversity and tailorability of topological structures and the like, and have potential applications in catalysis, nonlinear optics, ion exchange, gas storage and separation. (Kitaura R, Kitagawa S, Kubota Y, et al, Formation of a one-dimensional array of oxygen in a microprous metal-organic solid. [ J ]. Science, 2002, 298(5602):2358-
In recent years, traditional bulk MOFs have not fully met the needs of many specific applications, particularly for bio-related applications, where smaller dimensions are required for MOFs to facilitate their entry into cells, such as biomedical imaging, drug delivery, and biosensing, and the like, and the synthesis of nanoscale MOF crystals with controlled size and morphology has become an emerging topic. The surface area of the nanoscale MOFs is larger than that of the bulk MOFs, resulting in improved performance in separation, catalysis, and sensing. (Furukawa S, Reboul J, Diring S, et al, structural of metal-organic frames at the meso/macromolecular scale [ J ]. Chemical Society Reviews, 2014, 43(16): 5700-5734.) thus, the synthesis of nanoscale MOFs is of major importance.
Two methods are mainly used for synthesizing 2D MOF nano sheets, namely a top-down synthesis method which is to strip from a block MOF; the other is a bottom-up synthesis method, which directly synthesizes 2D MOF nano-sheets by using metal and organic ligands. (ZHao M, Lu Q, Ma Q, et al. Two-Dimensional Metal-Organic Framework Nanosheets [ J ]. Small Methods, 2016, 1(1-2): 1600030.)
ZIFs are MOFs materials with zeolite-like framework structures generated by the reaction of divalent metal salts such as Zn and Co and imidazole ester or derivative ligands thereof in an organic solvent. The imidazole ester is a five-membered ring with conjugated property, and forms a connection mode just corresponding to a Si-O-Si structure in a zeolite material and M-IM-M (M: transition metal ion; IM: imidazole ester) with a bond angle close to 145 degrees by losing a proton and coordination with metal ions, so that the ZIFs material combines the dual advantages of a metal organic framework material and zeolite, and has the high porosity, large specific surface area and structural adjustability of the MOFs material and the high stability of inorganic zeolite. (Park K S, Ni Z, C ô t A P, et al From the Cover: empirical chemical and thermal stability of zeolitic imidiazolate frameworks [ J ]. Proc Natl Acad Sci U S A, 2006, 103(27): 10186-.
ZIF-8, is made of metal Zn2+ZnN formed by bonding to N atom in MIM4A tetrahedral structural unit. ZIF-8 Aperture 034 nm, cage diameter 11.6 nm, features large specific surface area and small pore size large pore cage. For electrical energy storage devices, excellent electrode materials have high surface area, high conductivity and good structural stability during discharge-charge, which can be achieved by ZIF-8 as a template and precursor. In addition, porous ZIF-8 derived carbide materials with controlled pore distribution can be synthesized by in situ ammonia treatment during annealing. Accordingly, ZIF-8 was successfully applied to anodes of Lithium Ion Batteries (LIBs), cathodes of Lithium Sulfur Batteries (LSBs), and components of other battery systems and supercapacitors.
Although ZIF-8 has regular pore canals, large specific surface area, small pore diameter, open skeleton structure, adjustable structure and various structures, the ZIF-8 cannot enter cells due to large size, and the specific surface area and the pore diameter cannot meet the requirements in certain applications, while 2D ZIF-8 nanosheets have the advantages of easiness in film formation, large specific surface area, exposure of active sites and the like, and have development prospects.
The bottom-up approach is used in the present invention. A key issue with this approach is the need to limit MOF growth in the vertical direction while growth in the lateral direction is not affected. We used a simple anionic surfactant-assisted synthesis method, the surfactant not only limited the growth of MOFs in the vertical direction, but also helped to disperse the synthesized MOF nanosheets.
Disclosure of Invention
The invention aims to: aiming at the defects in the prior art, the metal organic framework ZIF-8 two-dimensional nanosheet and the preparation method thereof are provided, the method is simple and easy to implement, is carried out at normal temperature, is low in energy consumption, is green and environment-friendly, and has a good application prospect, and the product appearance is controllable.
In order to achieve the purpose, the technical scheme of the invention is as follows: a metal organic framework two-dimensional nanosheet, characterized in that: the chemical formula is Zn [ MeIM ]2 (MeIM = 2-methylimidazole), and a basic unit is formed by 2-methylimidazole and metal atom Zn. The metal organic framework two-dimensional nanosheet is square, the length and width of the nanosheet are 200-500 nm, and the thickness of the nanosheet is 2-5 nm.
A preparation method of a metal organic framework two-dimensional nanosheet comprises the following steps:
a. zinc acetate dihydrate (ZnAC) in a mass ratio of 2:1 to 2:202•2H2O) solid medicine, Sodium Dodecyl Sulfate (SDS) solid medicine and 2-methylimidazole solid medicine are respectively dissolved in deionized water and are subjected to ultrasonic homogenization for later use;
b. slowly pouring the SDS aqueous solution into the zinc acetate dihydrate aqueous solution, and uniformly performing ultrasonic treatment for later use;
c. dropwise adding the 2-MIM solution into the mixed solution obtained in the step (2), stirring for 20-40 s after dropwise adding, and then standing for 20-30 h in a constant temperature oven at 30 ℃;
d. and (4) centrifugally washing the mixture for three times by using methanol, and freeze-drying the mixture for 10 hours to obtain a solid powdery sample for later use.
Furthermore, the mass concentration ratio of zinc acetate dihydrate, 2-methylimidazole and SDS in respective aqueous solutions is 2:20: 1-2.
Furthermore, in the step 3, the standing time is more than or equal to 20 hours, less than or equal to 48 hours, preferably about 24 hours.
Compared with the prior art, the invention adopting the technical scheme has the following technical effects: the preparation method provided by the invention is simple and feasible, is carried out at normal temperature, has low energy consumption, is green and environment-friendly, has controllable product appearance, and has good application prospect.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is an SEM image of two-dimensional Metal Organic Framework (MOF) -8 prepared in example 1.
FIG. 2 is a TEM image of a two-dimensional nanocrystal ZIF-8 of the metal organic framework prepared in example 1.
FIG. 3 is a highly cross-sectional view of a two-dimensional nanocrystal ZIF-8 of the metal organic framework prepared in example 1.
FIG. 4 is a diagram showing the result of XRD test of two-dimensional nanocrystals ZIF-8 of metal organic framework prepared in example 1.
FIG. 5 is a BET test result of the two-dimensional metal organic framework ZIF-8 prepared in example 1 (a) after freeze-drying treatmentZIF-8 nanosheet N2And (b) carrying out adsorption-desorption isotherm (b) and carrying out freeze drying treatment on the ZIF-8 nanosheet aperture distribution map.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, these examples are for illustrative purposes only and do not limit the present invention.
The invention aims to provide a synthesis method of a metal organic framework two-dimensional nanocrystal ZIF-NS, wherein the operation without temperature indication is completed at room temperature.
The two-dimensional nanocrystal is a metal salt (ZnAc)2•2H2O) and an organic ligand (2-methylimidazole) are synthesized under the action of surfactant assistance (sodium dodecyl sulfate, namely SDS), zinc acetate dihydrate, 2-methylimidazole and SDS solution are prepared at normal temperature respectively, then the solutions are mixed uniformly, placed in a constant temperature box for standing for 24 hours and then centrifugally washed by methanol, and the 2D ZIF-8 is obtained.
Example 1
1. 0.6g of ZnAC was added to a 50mL beaker2•2H2Adding 10mL of deionized water and carrying out ultrasonic homogenization;
2. adding 0.394 g SDS into a 25 mL beaker, adding 10mL deionized water, and performing ultrasonic homogenization;
3. adding the 2 into the 1 and uniformly mixing by ultrasonic waves for later use;
4. 2.24g of 2-MIM is added into a 25 mL beaker, 10mL of deionized water is added, and the mixture is subjected to ultrasonic homogenization;
5. dropwise adding the 4 into the 1, stirring for 20 s after dropwise adding, and standing in a constant temperature oven at 30 ℃;
6. standing for 24 h, and then centrifugally washing with methanol for three times; centrifugally washing the mixture for three times by deionized water, and freeze-drying the mixture for 10 hours for later use.
Wherein, the nano-sheet shown in FIG. 1 is square, the length and width are between 200-500 nm, and a small hole is arranged in the middle.
The nanosheets shown in fig. 2 are relatively thin, have few pores, and have incomplete morphology.
The thickness of the nanosheets as shown in fig. 3 is 2-3 nm.
As shown in FIG. 4, the same as the standard card, indicating that the product is ZIF-8, some increase in diffraction intensity on the (200) plane, indicating that the ZIF-8 nanosheets grew along the (200) crystal plane.
As shown in FIG. 5, the BET specific surface area of the ZIF-8 nanosheets after freeze-drying was determined to be 658.772477 m2G, specific surface area of Langmuir 879.278175 m2The pore diameter is 2-3 nm.
Example 2
1. 0.6g of ZnAC was added to a 50mL beaker2•2H2Adding 10mL of deionized water and carrying out ultrasonic homogenization;
2. adding 0.788 g of SDS into a 25 mL beaker, adding 10mL of deionized water, and performing ultrasonic homogenization;
3. adding the 2 into the 1 and uniformly mixing by ultrasonic waves for later use;
4. 2.24g of 2-MIM is added into a 25 mL beaker, 10mL of deionized water is added, and the mixture is subjected to ultrasonic homogenization;
5. dropwise adding the 4 into the 1, stirring for 20 s after dropwise adding, and standing in a constant temperature oven at 30 ℃;
6. standing for 24 h, and then centrifugally washing with methanol for three times; centrifugally washing the mixture for three times by deionized water, and freeze-drying the mixture for 10 hours for later use.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiment, but equivalent modifications or changes made by those skilled in the art according to the present disclosure should be included in the scope of the present invention as set forth in the appended claims.
Claims (5)
1. A preparation method of a metal organic framework two-dimensional nanosheet is characterized by comprising the following steps: the method comprises the following steps:
a. respectively dissolving a zinc acetate dihydrate solid medicine, a sodium dodecyl sulfate solid medicine and a 2-methylimidazole solid medicine in the mass ratio of 2: 1-2: 20 into deionized water, and uniformly mixing by ultrasonic waves for later use;
b. dropwise adding the aqueous solution of sodium dodecyl sulfate into the aqueous solution of zinc acetate dihydrate, and uniformly mixing by ultrasonic waves for later use;
c. dropwise adding the 2-methylimidazole solution into the mixed solution obtained in the step b, stirring for 20-40 s after dropwise adding, and then standing for 20-30 h at constant temperature in a 30 ℃ constant temperature box;
d. centrifuging the solid product, washing the solid product with methanol for three times, and freeze-drying the solid product for 10 hours to obtain a solid powdery sample for later use, wherein the chemical formula of the finally obtained metal organic framework two-dimensional nanosheet is Zn [ MeIM ]]2I.e. MeIM = 2-methylimidazole, the basic unit is composed of 2-methylimidazole and the metal ion Zn.
2. The method for preparing metal organic framework two-dimensional nanoplates as in claim 1, wherein: the metal organic framework two-dimensional nanosheet is square, the length and width of the nanosheet are 200-500 nm, and the thickness of the nanosheet is 2-5 nm.
3. The method for preparing metal organic framework two-dimensional nanoplates as in claim 1, wherein: the mass concentration ratio of zinc acetate dihydrate, 2-methylimidazole and sodium dodecyl sulfate in respective aqueous solution is 2:20: 1-2.
4. The method for preparing metal organic framework two-dimensional nanoplates as in claim 1, wherein: in the step c, the standing time is more than or equal to 20 hours, and the standing time is less than or equal to 48 hours.
5. The method for preparing metal organic framework two-dimensional nanoplates as in claim 4, wherein: the standing time was 24 hours.
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| CN111326745B (en) * | 2020-02-12 | 2021-07-27 | 北京化工大学 | Two-dimensional zinc monoatomic/carbon nitrogen composite material and preparation method and application thereof |
| CN111533921A (en) * | 2020-05-28 | 2020-08-14 | 南京工业大学 | Preparation method of ZIF-8 nano platelet and ultrathin film thereof |
| CN111592661B (en) * | 2020-06-16 | 2022-03-04 | 南京邮电大学 | Preparation method of high-dispersity organic metal framework nano material |
| CN113387889B (en) * | 2021-06-17 | 2023-05-09 | 湖南文理学院 | Preparation method of porous imidazole metal compound nano-powder |
| CN113527707B (en) * | 2021-08-06 | 2022-03-29 | 南通大学 | Normal-temperature rapid preparation method of copper-based MOF |
| CN113648977A (en) * | 2021-09-10 | 2021-11-16 | 大连理工大学 | Modified zeolite-like imidazole framework adsorption material and preparation method and application thereof |
| CN114632943B (en) * | 2022-03-21 | 2023-10-03 | 中国科学院苏州纳米技术与纳米仿生研究所 | Two-dimensional metal nano sheet and preparation method and application thereof |
| CN116926616B (en) * | 2023-09-16 | 2024-01-02 | 山东海化集团有限公司 | Preparation method and application of flaky Cu-ZIF-8 material |
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