CN107715843B - Method for rapidly synthesizing mesoporous and microporous ZIF-8 material at normal temperature - Google Patents
Method for rapidly synthesizing mesoporous and microporous ZIF-8 material at normal temperature Download PDFInfo
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Abstract
The invention discloses a method for rapidly synthesizing a mesoporous and microporous ZIF-8 material at normal temperature, which can successfully reduce the synthesis time to 20 min. The method comprises the following steps: firstly, dissolving zinc oxide in water; secondly, dissolving zinc acetate dihydrate in water; dissolving 2-methylimidazole in N, N-dimethylformamide; fourthly, mixing the zinc oxide solution with the zinc acetate solution, and fully stirring; fifthly, adding the 2-methylimidazole solution and bromohexadecane into the mixed solution of zinc oxide and zinc acetate, and fully stirring; and sixthly, carrying out suction filtration and drying on the obtained product to obtain the hierarchical pore ZIF-8 material. According to the invention, by adding zinc oxide and bromohexadecane as a template agent, the operation is simple and convenient, the conditions are mild, and the synthesis time is greatly shortened. The product has rich pore structure, high specific surface area, stable structure and good application prospect in the adsorption and catalysis of macromolecules.
Description
Technical Field
The invention belongs to the field of rapid preparation of hierarchical porous metal organic frameworks, and particularly relates to a method for rapidly synthesizing a mesoporous and microporous ZIF-8 material at normal temperature.
Background
In the last two decades, metal organic framework Materials (MOFs) have attracted considerable interest to researchers as emerging porous materials. The structural diversity, tunability and porosity of [ Zhou H C, Long J R, Yaghi O m.introduction to metal-organic frameworks [ J ].2012 ] make MOFs have great potential in multifunctional applications. Liu J, Chen L, Cui H, et al.applications of metal-organic framework catalysis [ J ]. Chemical Society Reviews,2014,43(16): 6011-. Although some mesoporous MOFs have been reported [ Li P Z, Wang X J, Tan S Y, et al. Clicked isospecific metals-organic structures and the upper high performance in the selective capture and deposition of large organic molecules [ J ]. Angewandte chemical International Edition 2015,54(43):12748-12752 ], experimental studies have shown that the pore size of MOFs is mainly tunable in the microporous state, which is actually disadvantageous for the application of the material. Since the small pore size slows the diffusion rate of the molecules and limits the movement of macromolecules. So the multigraded-hole MOFs are the key point of our research. The hierarchical porous MOFs not only inherits the characteristics of the traditional MOFs micropores, but also obtains innovation in the aspects of mesopores and macropores. Micropores create a relatively large specific surface area for the material, while mesopores and macropores facilitate the transport and diffusion of molecules. The synthesis of the multigraded-pore MOFs is our work focus.
Fang et al [ Fang Q R, Makal T A, Young M D, et al].Comments on InorganicChemistry,2010,31(5-6):165-195.]And Xuan et al [ Xuan W, Zhu C, Liu Y, et].Chemical Society Reviews,2012,41(5):1677-1695.]A more detailed review of mesoporous MOFs was made. In most reported mesoporous MOFs, the most important research is the control of pore size and the stability of the material. Multigraded-pore MOFs materials are generally prepared using a solvent process, the channels of the MOFs prepared are usually occupied by solvent molecules that must be removed to obtain permanent porosity without causing structural collapse. Generally, the larger the porosity of the material, the more easily its frame collapses. Although MOFs can be built from well-designed organic ligands (framework linkers) to create macropores, the frameworks often interpenetrate, leading to the appearance of interpenetrating structures in the material, which are also unstable. Thus, it is more difficult to achieve permanent porosity in mesoporous MOFs than in their microporous analogs. Strategies have been employed to construct mesoporous MOFs by using elongated organic ligands along with other ductile linkers, which facilitate the formation of stable bulky secondary building blocks (SBUs). Furthermore, post-synthesis modification remains a useful method to produce MOFs materials with tunable mesopores. In principle, the use of ligands capable of linear extension can introduce larger channels or pores during mesoporous MOF synthesis. However, by longer ligandsThe constructed MOFs tend to collapse rapidly after the ligand is removed, resulting in interpenetration among a plurality of pore channels, which greatly reduces the pore size, thereby limiting the entrance of macromolecules. It is one of our work to find suitable ligands and prepare mesoporous MOFs. In 2002, Eddaoudi et al [ Eddaoudi M, Kim J, Rosin, et al].Science,2002,295(5554):469-472.]Synthesis of the first mesoporous MOF (Zn) using the organic ligand trityl dicarboxylate (TPDC)4O(TPDC)3(DMF)12(H2O)2). The material has the expected topology of calcium hexaborate (CaB 6), a mesoporous MOF composed of octahedral-shaped SBUs. In 2010, Yaghi's topic group [ Furukawa H, Ko N, Go Y B, et al].Science,2010,329(5990):424-428.]The triphenyl formate is used for synthesizing the MOF-180, the volume of the MOF-180 is 2 times larger than that of a traditional MOF-177 unit cell, and the porosity of the crystal is more than 89%. Wang et al [ Wang X S, Ma S, Sun D, et al.A Mesoporous Metal-Organic Framework with Permanent Porosity [ J ]].Journal of the American Chemical Society,2006,128(51):16474-16475.]Mesoporous MOF-1, which is structurally not interpenetrating, is reported and the material exhibits good thermal stability.
Now, we can start with MOFs with good chemical stability and introduce mesopores into MOFs materials by adding longer ligands. Zeolitic imidazolate framework materials (ZIFs) are a new class of MOFs. ZIFs not only have all the advantages of MOFs, but also possess excellent thermal stability and chemical resistance, but usually have only a pore size
Therefore, the synthesis of hierarchical porous ZIFs to improve its performance has received attention from researchers. We can consider the preparation of a hierarchical pore material by adding a ligand of a certain length during the synthesis process to make the material appear mesoporous structure units.
The invention adopts the bromohexadecane as the template agent to quickly synthesize the mesoporous and microporous metal-organic framework material.
Disclosure of Invention
The invention aims to provide a method for rapidly synthesizing a mesoporous and microporous ZIF-8 material at normal temperature, and aims to simply, conveniently and rapidly synthesize a ZIF-8 material simultaneously having a microporous pore passage and a mesoporous pore passage.
The raw materials of the invention are zinc oxide and Zn (CH)3COO)2·2H2O (zinc acetate dihydrate), 2-methylimidazole, bromohexadecane (purchased from carbofuran) serving as a template agent and N, N-dimethylformamide, zinc oxide and zinc acetate are used to form double metal salts, and the bromohexadecane is used as a structure guiding agent, so that the ZIF-8 material rich in various pore channel structures can be quickly synthesized.
The purpose of the invention is realized by the following technical scheme.
A method for rapidly synthesizing a hierarchical pore ZIF-8 material comprises the following steps:
(1) dissolving zinc oxide in water, and stirring to obtain a zinc oxide aqueous solution;
(2) dissolving zinc acetate dihydrate in water, and stirring to obtain a zinc acetate aqueous solution;
(3) dissolving 2-methylimidazole in N, N-dimethylformamide, and stirring to obtain a 2-methylimidazole solution;
(4) mixing the zinc oxide aqueous solution obtained in the step (1) with the zinc acetate aqueous solution obtained in the step (2), and stirring to obtain a mixed solution of zinc oxide and zinc acetate;
(5) adding the 2-methylimidazole solution and bromohexadecane in the step (3) into the mixed solution of zinc oxide and zinc acetate in the step (4), and fully stirring;
(6) and (5) carrying out suction filtration on the product obtained in the step (5), and then putting the product into a vacuum drying oven for drying to obtain the hierarchical pore ZIF-8 material.
Preferably, the stirring time in step (1) is 20 to 30 minutes in each case.
Preferably, the stirring time in steps (2) and (3) is 10-20 minutes.
Preferably, the stirring time in step (4) is 20 to 30 minutes.
Preferably, the stirring time in step (5) is 20 to 30 minutes, and more preferably 20 minutes.
Preferably, the drying temperature in the step (6) is 110-120 ℃, and the drying time is 10-12 h.
Preferably, step (1), step (2), step (3), step (4) and step (5) are all carried out at normal temperature.
Preferably, the Zn (CH)3COO)2·2H2The mol ratio of O, zinc oxide, 2-methylimidazole and bromohexadecane is (1-1.1): (0.7-0.8): (1.2-1.3): (0.7-0.8).
Compared with the prior art, the invention has the following advantages and effects:
(1) the method can synthesize the ZIF-8 material only in 20min, and the material has rich pore channel structures (micropores and mesopores), not only has a stable structure, but also has a high specific surface area, and has a good application prospect in the aspects of macromolecule adsorption and catalysis.
(2) The method has the advantages of low raw material price, less environmental pollution and realization of industrialization.
(3) According to the invention, the zinc oxide and the template agent are added, so that the hierarchical pore ZIF-8 material can be rapidly synthesized at normal temperature, the operation is simple, the condition is mild, the steps of heating, ultrasound and the like are avoided, and the energy is saved.
Drawings
FIG. 1 is an X-ray diffraction pattern of a computer simulated ZIF-8 material and a meso-microporous ZIF-8 material prepared in example 1.
FIG. 2 is a N representation of a meso-microporous ZIF-8 material prepared in example 12Adsorption-desorption isotherm diagram.
FIG. 3 is a graph of the full pore size distribution calculated according to the DFT model for the meso-microporous ZIF-8 material prepared in example 1.
FIG. 4 is a scanning electron micrograph of a meso-microporous ZIF-8 material prepared according to example 1 of the present invention.
FIG. 5 is a TEM image of a meso-microporous ZIF-8 material prepared in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
Dissolving 0.285g of zinc oxide in 5mL of deionized water, and stirring for 20 minutes to obtain a zinc oxide solution; dissolving 1.097g of zinc acetate dihydrate in 5mL of deionized water, and stirring for 10 minutes to obtain a zinc acetate solution; dissolving 0.492g of 2-methylimidazole in 5mLN, N-dimethylformamide, and stirring for 10 minutes to obtain a 2-methylimidazole solution; mixing the zinc oxide solution with the zinc acetate solution, and stirring for 20 minutes to obtain a mixed solution of zinc oxide and zinc acetate; adding a 2-methylimidazole solution and 1.07g of bromohexadecane into a mixed solution of zinc oxide and zinc acetate, and stirring for 20 minutes; and (3) carrying out suction filtration on the obtained product, and drying the product in a vacuum drying oven at 110 ℃ for 10 hours to obtain a medium-micro double-pore ZIF-8 material which is marked as a sample A.
Example 2
Dissolving 0.296g of zinc oxide in 5mL of deionized water, and stirring for 30 minutes to obtain a zinc oxide solution; dissolving 1.097g of zinc acetate dihydrate in 5mL of deionized water, and stirring for 20 minutes to obtain a zinc acetate solution; dissolving 2-methylimidazole 0.485g in 5mLN, N-dimethylformamide, and stirring for 20 minutes to obtain a 2-methylimidazole solution; mixing the zinc oxide solution with the zinc acetate solution, and stirring for 30 minutes to obtain a mixed solution of zinc oxide and zinc acetate; adding a 2-methylimidazole solution and 1.11g of bromohexadecane into a mixed solution of zinc oxide and zinc acetate, and stirring for 30 minutes; and (3) carrying out suction filtration on the obtained product, and drying the product in a vacuum drying oven at the temperature of 120 ℃ for 12 hours to obtain a medium-micro diplopore ZIF-8 material which is marked as a sample B.
The medium and micro-double-hole ZIF-8 material prepared in the example 1 is taken as a representative for analysis, and the analysis results of the medium and micro-double-hole ZIF-8 material prepared in other examples are basically the same as those of the example 1 and are not provided.
(I) rapidly synthesizing crystal structure property of mesoporous and microporous ZIF-8 material at normal temperature
The crystal structure of example 1 according to the invention was characterized by means of an X-ray diffractometer model D8-ADVANCE from Bruker, Germany.
FIG. 1 is a wide angle X-ray diffraction pattern of a computer simulated ZIF-8 material and a hierarchical porous ZIF-8 material prepared in accordance with example 1 of the present invention. The ZIF-8 simulated by a computer is a perfect crystal formed by zinc ions and 2-methylimidazole, can fully embody the crystal structure of the zinc ions and can be compared with an experimental result. As can be seen from FIG. 1, sample A prepared in example 1 exhibited a stronger characteristic diffraction peak of the ZIF-8 metal-organic framework than the computer-simulated ZIF-8 material, indicating the presence of the highly crystalline ZIF-8 component in the product.
(II) rapidly synthesizing pore channel property of mesoporous and microporous ZIF-8 material at normal temperature
The pore structure of the samples prepared according to the invention was characterized using an ASAP2460 specific surface pore size distribution instrument, manufactured by U.S. Micro corporation, and the results are shown in Table 1. As can be seen from Table 1, the ZIF-8 material prepared by the invention has higher micropore and mesopore volume.
TABLE 1
FIG. 2 is a N representation of a meso-microporous ZIF-8 material prepared in accordance with example 1 of the present invention2Adsorption-desorption isotherm plot at P/P0<The adsorption isotherm is shown as type I adsorption under the pressure of 0.01, and the adsorption quantity is increased sharply, which indicates that the sample has a microporous structure. The IV-type adsorption hysteresis loop appears at the relative pressure of about 0.85, which is that the mesoporous material is in N2Typical characteristics in the adsorption and desorption curves indicate that the material contains mesopores.
The DFT full pore size distribution plot of fig. 3 shows that the hierarchical pore ZIF-8 material prepared in example 1 possesses a large number of mesoporous channels around 1nm, while possessing a large number of mesoporous and larger macroporous channels around 40 nm. The macropores are not inherent in the material itself, but are formed by the packing of material particles to form the packing pores. The method is shown to be capable of rapidly synthesizing the mesoporous and microporous ZIF-8 material.
(III) SEM image of rapidly synthesizing mesoporous and microporous ZIF-8 material at normal temperature
The product was characterized by using JSM-6330F scanning electron microscope (JEOL, Japan, Ltd.). As shown in fig. 4, it can be seen that the prepared sample a is in the shape of a pellet, the surface of the material is rich in micropores and mesopores, and the small particles are stacked together to form stacked pores.
(IV) TEM image of medium-and-micro-double-pore ZIF-8 material rapidly synthesized at normal temperature
The product was characterized by means of a JEM-2100HR transmission electron microscope (JEOL, Japan, Ltd.). As a result, as shown in fig. 5, it can be seen that the prepared sample has abundant micropores and mesopores.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the scope of the present invention.
Claims (8)
1. A method for rapidly synthesizing a mesoporous and microporous ZIF-8 material at normal temperature is characterized by comprising the following steps:
(1) dissolving zinc oxide in water, and stirring to obtain a zinc oxide aqueous solution;
(2) dissolving zinc acetate dihydrate in water, and stirring to obtain a zinc acetate aqueous solution;
(3) dissolving 2-methylimidazole in N, N-dimethylformamide, and stirring to obtain a 2-methylimidazole solution;
(4) mixing the zinc oxide aqueous solution obtained in the step (1) with the zinc acetate aqueous solution obtained in the step (2), and stirring to obtain a mixed solution of zinc oxide and zinc acetate;
(5) adding the 2-methylimidazole solution and bromohexadecane in the step (3) into the mixed solution of zinc oxide and zinc acetate in the step (4), and fully stirring;
(6) carrying out suction filtration on the product obtained in the step (5), and then putting the product into a vacuum drying oven for drying to obtain a medium-micro double-hole ZIF-8 material;
the molar ratio of the zinc acetate dihydrate to the zinc oxide to the 2-methylimidazole to the bromohexadecane is (1-1.1): (0.7-0.8): (1.2-1.3): (0.7-0.8).
2. The method of claim 1, wherein: the stirring time in the step (1) is 20-30 minutes.
3. The method of claim 1, wherein: the stirring time of the step (2) and the step (3) is 10-20 minutes.
4. The method of claim 1, wherein: the stirring time in the step (4) is 20-30 minutes.
5. The method of claim 1, wherein: the stirring time in the step (5) is 20-30 minutes.
6. The method of claim 5, wherein: the stirring time was 20 minutes.
7. The method of claim 1, wherein: the drying temperature in the step (6) is 110-120 ℃, and the drying time is 10-12 h.
8. The method of claim 1, wherein: the step (1), the step (2), the step (3), the step (4) and the step (5) are all carried out at normal temperature.
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| CN113171754B (en) * | 2021-04-27 | 2022-09-27 | 郑州大学 | Hierarchical porous metal organic framework material ZIF-8 and preparation method and application thereof |
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| MA56279A1 (en) * | 2022-03-29 | 2023-09-27 | Univ Mohammed Vi Polytechnique | PROCESS FOR PRODUCING ZIF-8, ITS COMPOSITE CHITOSAN@ZIF-8 AND THEIR APPLICATION |
| CN116173286B (en) * | 2023-04-19 | 2024-01-16 | 清泽医疗科技(广东)有限公司 | Medical adhesive, preparation method and application thereof |
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