CN115819789A - Method for rapidly synthesizing nanoscale hierarchical pore ZIF-93 material at room temperature in water phase - Google Patents
Method for rapidly synthesizing nanoscale hierarchical pore ZIF-93 material at room temperature in water phase Download PDFInfo
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Abstract
The invention discloses a method for rapidly synthesizing a ZIF-93 material with nanoscale hierarchical pores at room temperature in a water phase. Using deionized water as solvent, zn (CH) 3 COO) 2 ·2H 2 O and an organic ligand 4-methyl-5-imidazole formaldehyde are used as reactants, naOH is used as an inorganic deprotonation agent, low-cost methanol is used as a washing agent, and the ZIF-93 material with the nanoscale hierarchical pore is successfully prepared. Compared with the traditional solvothermal method, the method has the advantages of simple and convenient operation, mild conditions, greatly shortened reaction time, no need of activation and possibility of industrialization of materials. Meanwhile, the obtained product has rich micropores, mesopores and macropores, and has wide application prospect in the aspects of adsorption and catalysis with macromolecules.
Description
Technical Field
The invention belongs to the field of rapid preparation of metal organic frameworks, and particularly relates to a method for rapidly synthesizing a nanoscale hierarchical pore ZIF-93 material at room temperature in a water phase.
Background
Metal organic framework Materials (MOFs) are a novel functional porous material formed by coordination self-assembly of metal ions and organic ligands. The geometric configuration of the MOFs can be predicted according to the coordination manner of the metal ions and the organic ligands, and due to the different coordination manner of the metal ions and the organic ligands, the MOFs not only have ultra-high specific surface area and porosity, but also have modifiable surface characteristics and programmable pore structures. As a new functional material, MOFs show good prospects in various applications including adsorption, catalysis, separation, gas storage, and the like.
Zeolitic imidazolate framework materials (ZIFs) are a class of MOF materials having a zeolitic structural type formed by the copolymerization of metal ions with imidazolate ligands. ZIFs have better thermal and chemical stability than other MOFs, and are more suitable for practical adsorption capture. However, conventional ZIFs materials are mostly composed of micron-sized (size greater than 500 nm) crystal size and micro-porous (pore size less than 2 nm) pores. The larger crystal size can lead to longer diffusion path, slow diffusion speed and large mass transfer resistance of the guest molecules; in the application of separation, catalysis and the like with macromolecule participation, the micropores seriously hinder mass transfer and diffusion, so that the macromolecules cannot quickly reach active sites in the ZIFs, and the application of the ZIFs in the fields of catalysis, adsorption, sensing and the like with macromolecule participation is limited. Therefore, the crystal size and the pore size of the ZIFs are adjusted by adopting a simpler method, the respective structural characteristics of the nanoscale ZIFs and the hierarchical pore ZIFs are organically combined, and the design and synthesis of the nanoscale hierarchical pore ZIFs are urgent desires of people.
The water phase method is a new method for preparing MOFs materials, and the method is low in price, simple to operate and environment-friendly. The MOFs material with the nanoscale hierarchical pores can be synthesized by controlling the ratio of metal ions to ligands, the amount of water, the reaction time and the like. For example, manuel et al [ Yassin J M, taddesse AM, S a-nchez-S nchez M. From temperature synthesis of high-quality ce (iv) -based mofs in water [ J].Microporous and Mesoporous Materials,2021,324:111303.]Reports that the mixed solvent strategy (water as the solvent of Ce and N, N-dimethylformamide as the connecting agent) is adopted under the condition of room temperature and water phase, and the Ce (IV) -based MOF (UiO-66 (Ce) and Ce-MOF-808) with nanoscale hierarchical pores is successfully synthesized, wherein the crystal size of the UiO-66 (Ce) is 75-100nm, and abundant mesoporous and macroporous pore canals are shown. Foo et al [ Tan K L, foo K Y.preparation of mil-100via a novel water-based leather synthesis technique for the effective registration of phenolic acid-based pesticide [ J].Journal of Environmental Chemical Engineering,2021,9(1):104923.]The multi-stage pore MIL-100 (Fe) is successfully prepared under the condition of aqueous phase at room temperature and shows about 2000m 2 The specific surface area is huge per gram, and the adsorption capacity of the adsorbent is 858.11mg per gram for 2,4-D, and the adsorbent is rich in micropores and mesoporous channels.
ZIF-93 is a ZIF material with RHO type topology by self-assembly of zinc ions and organic ligand 4-methyl-5-imidazolecarboxaldehyde reported by The Yaghi topic group of U.S. A. William Morris, ning He, keith G.ray, et al. A. Combined experimental-functional study on The effect of a polar on carbon dioxide adsorption in a polar ionic imidazole structure [ J ]. The Journal of Physical Chemistry C,2012,116 (45): 24084-24090. The traditional ZIF-93 material is synthesized by a solvothermal method, the time consumption is long, the energy consumption is high, the crystal size of the synthesized ZIF-93 material is micron-sized, and the pore size is microporous. Therefore, the room temperature water phase method is adopted, the synthesis steps are simplified, the synthesis time is shortened, the pollution is reduced, and the method has important significance for the industrialization of materials.
Disclosure of Invention
The invention aims to provide a method for rapidly synthesizing a nanoscale hierarchical pore ZIF-93 material at room temperature in a water phase, and aims to rapidly synthesize a ZIF-93 material with nanoscale hierarchical pores at room temperature in a water phase.
The raw material of the invention is Zn (CH) 3 COO) 2 ·2H 2 O, 4-methyl-5-imidazole formaldehyde, naOH, deionized water (self-made in a laboratory) and methanol, and the nanoscale multistage imidazole can be synthesized by only using the deionized water as a solventA porous ZIF-93 material.
The purpose of the invention is realized by the following technical scheme:
a method for rapidly synthesizing a nanoscale hierarchical pore ZIF-93 material at room temperature in a water phase comprises the following steps:
s01, at the room temperature of 25-30 ℃, deionized water is used as a solvent, zn (CH 3 COO) 2.2H 2O and an organic ligand 4-methyl-5-imidazole formaldehyde are used as reactants; the molar ratio of Zn (CH 3 COO) 2 & 2H2O, 4-methyl-5-imidazole formaldehyde and deionized water is (0.25-1): (0.75-2): (2000-3000); dissolving Zn (CH 3 COO) 2.2H 2O and an organic ligand 4-methyl-5-imidazole formaldehyde in deionized water;
s02, fully stirring the solution obtained in the step S01 for 5-10 min at the stirring speed of 500-1000 r/min to fully dissolve Zn (CH 3 COO) 2.2H 2O and the organic ligand 4-methyl-5-imidazole formaldehyde, and uniformly dispersing the solution into deionized water;
s03, adding an inorganic proton-removing agent NaOH into the mixed solution in the step SO2, wherein the molar ratio of Zn (CH 3 COO) 2.2H 2O to NaOH is (0.25-1): (1-2), stirring for 1-60 min at the stirring speed of 1000-1500 r/min;
s04, centrifuging the product obtained in the step S03 for 10-15 min at the centrifugation speed of 10000rpm to obtain solid powder;
s05, continuously centrifuging and washing the solid powder obtained in the step S04 for 2-3 times by the same centrifugal program of the step S04, wherein a washing agent is absolute methanol;
and S06, putting the solid powder washed in the step S05 into a vacuum drying oven, and carrying out vacuum drying for 6-12 h at the room temperature of 25-30 ℃ to obtain the ZIF-93 material with the nanoscale hierarchical holes.
The nanoscale hierarchical pore ZIF-93 material is obtained by the method for rapidly synthesizing the nanoscale hierarchical pore ZIF-93 material under the room-temperature water phase condition.
Compared with the prior art, the invention has the following advantages and effects:
(1) According to the invention, water is selected as a solvent, activation is not required, the nanoscale hierarchical pore ZIF-93 material can be rapidly synthesized at normal temperature, the operation is simple, the condition is mild, the energy is saved, the environment is protected, no pollution is caused, and the possibility is provided for the industrialization of the material.
(2) The synthesis method is rapid, simple and convenient, the time required by the traditional synthesis method is 16 hours, the synthesis method can synthesize the product within 1 minute, and simultaneously, the prepared sample contains abundant micropores, mesopores and macropores, is uniform in size and distribution, and has good application prospects in the aspects of macromolecule adsorption and catalysis.
Drawings
FIG. 1 is an X-ray diffraction pattern of a computer modeled ZIF-93 material and nanoscale, multi-graded-pore ZIF-93 materials prepared in examples 1-3.
FIG. 2 is a N of the nanoscale, hierarchical pore ZIF-93 material prepared in examples 1-3 2 Adsorption-desorption isotherm diagram.
FIG. 3 is a graph of the full pore size distribution of the nanoscale, multi-level pore ZIF-93 materials prepared in examples 1-3.
FIG. 4 is a scanning electron micrograph of the nanoscale hierarchical pore ZIF-93 material prepared in example 1.
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
0.4g of Zn (CH) 3 COO) 2 ·2H 2 O and 0.4g 4-methyl-5-imidazole formaldehyde are respectively dissolved in 45ml deionized water and stirred for 5 minutes; mixing the two solutions to obtain a mixed solution, and stirring for 5 minutes; adding 0.9g of NaOH into the mixed solution, stirring for 1 minute, and centrifuging the obtained product; and (4) placing the centrifuged product into a vacuum drying oven for drying at room temperature for 12 hours to obtain a nanoscale hierarchical pore ZIF-93 material which is marked as a sample A.
Example 2
0.4g of Zn (CH) 3 COO) 2 ·2H 2 O and 0.4g 4-methyl-5-imidazole formaldehyde are respectively dissolved in 45ml deionized water and stirred for 5 minutes; mixing the two solutions to obtain a mixed solution, and stirring for 5 minutes; to the resulting mixed solution was added 0.9g NaOH, and after stirring for 10 minutes, the resultant wasCentrifuging; and (4) placing the centrifuged product into a vacuum drying oven for drying at room temperature for 12 hours to obtain a nanoscale hierarchical pore ZIF-93 material which is marked as a sample B.
Example 3
0.4g of Zn (CH) 3 COO) 2 ·2H 2 O and 0.4g 4-methyl-5-imidazole formaldehyde are respectively dissolved in 45ml deionized water and stirred for 5 minutes; mixing the two solutions to obtain a mixed solution, and stirring for 10 minutes; adding 0.9g of NaOH into the mixed solution, stirring for 60 minutes, and centrifuging the obtained product; and (4) placing the centrifuged product into a vacuum drying oven for drying at room temperature for 12 hours to obtain a nanoscale hierarchical pore ZIF-93 material which is marked as a sample C.
The nanoscale hierarchical pore ZIF-93 material prepared according to the examples was analyzed, and the analysis results are shown in the figure.
(I) crystal structure property of ZIF-93 material with nanoscale hierarchical pores rapidly synthesized in aqueous phase at room temperature
The crystal structure of ZIF-93 prepared in examples 1-3 of the present invention was characterized by using an X-ray diffractometer model D8-ADVANCE manufactured by Bruker, germany.
As shown in FIG. 1, it can be seen that the characteristic diffraction peak of the crystals of examples 1 to 3 prepared by the present invention is identical to the simulated characteristic diffraction peak of ZIF-93, indicating that the ZIF-93 material can be synthesized using the synthesis conditions of examples 1 to 3.
(II) pore channel Properties
The pore structure of the samples prepared according to the present invention was characterized using ASAP2020 specific surface pore size distribution apparatus manufactured by U.S. Micro corporation, and the results are shown in Table 1.
TABLE 1
FIG. 2 is a N-layer diagram of a nanoscale, multi-level pore ZIF-93 material prepared in examples 1-3 of the present invention 2 An adsorption-desorption isotherm diagram, wherein under lower pressure, the material has larger acting force with nitrogen, which proves that more micropores exist; at higher pressures, the adsorbate undergoes capillary condensationAnd (4) polymerizing to form a hysteresis loop, and proving that a mesoporous structure exists in the material.
The DFT full-aperture distribution diagram of FIG. 3 shows that besides micropores, mesoporous structures exist in the material, and the mesoporous volume is mainly and intensively distributed at about 20-100nm, which confirms that the N passes through 2 Conclusion of adsorption-desorption isotherms.
(III) SEM image of water phase rapid synthesis of ZIF-93 material with nanoscale hierarchical pores at room temperature
The product obtained in example 1 was characterized by a JSM-6330F scanning electron microscope (JEOL, japan, ltd.). The results are shown in fig. 4, and it can be seen that example 1 prepared by the present invention shows that nanoparticles are stacked into more uniform microporous, mesoporous, and macroporous channels.
Finally, it should be noted that the above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above-mentioned 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 substitutions and are included in the protection scope of the present invention.
Claims (2)
1. A method for rapidly synthesizing a nanoscale hierarchical pore ZIF-93 material at room temperature in a water phase is characterized by comprising the following steps:
s01, at the room temperature of 25-30 ℃, deionized water is used as a solvent, and Zn (CH) 3 COO) 2 ·2H 2 O and an organic ligand 4-methyl-5-imidazole formaldehyde as reactants; the molar ratio of Zn (CH 3 COO) 2 & 2H2O, 4-methyl-5-imidazole formaldehyde and deionized water is (0.25-1): (0.75-2): (2000-3000); adding Zn (CH) 3 COO) 2 ·2H 2 Dissolving O and organic ligand 4-methyl-5-imidazole formaldehyde in deionized water;
s02, fully stirring the solution in the step S01 for 5-10 min at the stirring speed of 500-1000 r/min to ensure that Zn (CH) 3 COO) 2 ·2H 2 Fully dissolving O and organic ligand 4-methyl-5-imidazole formaldehyde, and uniformly dispersing into deionized water;
s03, adding an inorganic proton removing agent NaOH into the step SIn a mixed solution of O2, zn (CH) 3 COO) 2 ·2H 2 The molar ratio of O to NaOH is (0.25-1): (1-2), stirring for 1-60 min at the stirring speed of 1000-1500 r/min;
s04, centrifuging the product obtained in the step S03 for 10-15 min at the centrifugation speed of 10000rpm to obtain solid powder;
s05, continuously centrifuging and washing the solid powder obtained in the step S04 for 2-3 times by the same centrifugal program of the step S04, wherein a washing agent is absolute methanol;
and S06, putting the solid powder washed in the step S05 into a vacuum drying oven, and carrying out vacuum drying for 6-12 h at the room temperature of 25-30 ℃ to obtain the ZIF-93 material with the nanoscale hierarchical holes.
2. The nanoscale hierarchical pore ZIF-93 material obtained by the method for rapidly synthesizing the nanoscale hierarchical pore ZIF-93 material under the room-temperature aqueous phase condition according to claim 1.
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