CN115819789B - Method for rapidly synthesizing nanoscale hierarchical pore ZIF-93 material in room temperature water phase - Google Patents
Method for rapidly synthesizing nanoscale hierarchical pore ZIF-93 material in room temperature 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 in a room temperature water phase. Deionized water is used as solvent, zn (CH) 3 COO) 2 ·2H 2 O and an organic ligand 4-methyl-5-imidazole formaldehyde are taken as reactants, naOH is taken as an inorganic proton removing agent, and low-cost methanol is taken as a detergent, so that the ZIF-93 material with nanoscale hierarchical pores is successfully prepared. Compared with the traditional solvothermal method, the method has the advantages of simple operation, mild conditions, greatly shortened reaction time, no need of activation and possibility of industrialization of materials. Meanwhile, the obtained product has abundant micropores, mesopores and macropores, and has wide application prospect in the aspects of adsorption and catalysis with the participation of 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 nanoscale hierarchical pore ZIF-93 materials in a room-temperature water phase.
Background
Metal Organic Frameworks (MOFs) are a new class of functional porous materials formed by coordinated self-assembly of metal ions and organic ligands. The geometric configuration of MOFs can be predicted according to the coordination mode of metal ions and organic ligands, and MOFs not only have ultrahigh specific surface area and porosity, but also have modifiable surface characteristics and designable pore structures due to the different coordination modes of metal ions and organic ligands. MOFs, as a new functional material, show good promise in a variety of applications, including adsorption, catalysis, separation, gas storage, and the like.
Zeolitic Imidazolate Frameworks (ZIFs) are a class of MOF materials of the zeolite structure 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 crystal size in the micrometer scale (size greater than 500 nm) and micropores (pore size less than 2 nm) pores. The larger crystal size can lead to longer diffusion path of guest molecules, slow diffusion speed and large mass transfer resistance; in the applications of separation, catalysis and the like involving macromolecules, the micropores seriously obstruct mass transfer and diffusion, so that the macromolecules cannot quickly reach active sites in ZIFs, and the application of the ZIFs in the fields of catalysis, adsorption, sensing and the like involving macromolecules is limited. Therefore, in an attempt to adjust the crystal size and the pore size of the ZIFs by a simpler method, the structural characteristics of the nano-scale ZIFs and the hierarchical pore ZIFs are organically combined, and the design and synthesis of the nano-scale hierarchical pore ZIFs become urgent hopes.
The aqueous phase method is a novel method for preparing MOFs materials, and the method is low in cost, simple to operate and environment-friendly. MOFs material with nanoscale hierarchical pores can be synthesized by controlling the proportion of metal ions to ligands, the water consumption, the reaction time and the like. For example, manuel et al [ Yassin J M, taddess AM, S.cnhez-S.cnhez M.room temperature synthesis of high-quality (iv) -based mofs in water [ J)].Microporous and Mesoporous Materials,2021,324:111303.]The synthesis of Ce (IV) based MOFs (UIO-66 (Ce), ce-MOF-808) with nanoscale hierarchical pores was reported to be successful using a mixed solvent strategy (water as the solvent for Ce, N, N-dimethylformamide as the linker) under room temperature aqueous phase conditions, where the crystal size of UIO-66 (Ce) was 75-100nm and showed a abundance of mesoporous and macroporous channels. Foo et al [ Tan K L, foo K Y.preparation of mil-100via a novel water-based heatless synthesis technique for the effective remediation of phenoxyacetic acid-based peptide [ J ]].Journal of Environmental Chemical Engineering,2021,9(1):104923.]A hierarchical pore MIL-100 (Fe) was successfully prepared under room temperature aqueous conditions, exhibiting a concentration of about 2000m 2 Large specific surface area per gramThe product has abundant micropores and mesoporous channels, and the single-layer adsorption capacity of the catalyst for 2,4-D is 858.11mg/g.
ZIF-93 is a ZIF material with RHO type topology formed by self-assembly of zinc ions and the organic ligand 4-methyl-5-imidazolecarboxaldehyde reported by the U.S. Yaghi group of topics [ William Morris, ning He, keith G.ray, et al A combined experimental-computational study on the effect of topology on carbon dioxide adsorption in zeolitic imidazolate frameworks [ 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 and energy consumption are high, the crystal size of the synthesized ZIF-93 material is in the micron order, and the pore size is micropores. 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 industrialization of materials.
Disclosure of Invention
The invention aims to provide a method for rapidly synthesizing a nanoscale hierarchical pore ZIF-93 material in a room temperature water phase, which aims to rapidly synthesize the ZIF-93 material with nanoscale hierarchical pores in a room temperature 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 only deionized water is used as a solvent, so that the ZIF-93 material with nanoscale hierarchical pores can be synthesized.
The aim of the invention is achieved by the following technical scheme:
a method for rapidly synthesizing nanoscale hierarchical pore ZIF-93 material in room temperature water phase comprises the following steps:
s01, under the condition of room temperature of 25-30 ℃, deionized water is used as a solvent, zn (CH 3 COO) 2.2H2O and an organic ligand 4-methyl-5-imidazole formaldehyde are used as reactants; the mole 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) 2.2H2O and an organic ligand 4-methyl-5-imidazole formaldehyde in deionized water;
s02, fully stirring the solution in the step S01 for 5-10 min, wherein the stirring speed is 500-1000 r/min, so that Zn (CH 3 COO) 2.2H2O and the organic ligand 4-methyl-5-imidazole formaldehyde are fully dissolved and uniformly dispersed into deionized water;
s03, adding an inorganic proton removing agent NaOH into the mixed solution in the step SO2, wherein the mol ratio of Zn (CH 3 COO) 2.2H2O to NaOH is (0.25-1): (1-2), stirring for 1-60 min, wherein the stirring speed is 1000-1500 r/min;
s04, centrifuging the product obtained in the step S03 for 10-15 min at a centrifugation speed of 10000rpm to obtain solid powder;
s05, continuously centrifugally washing the solid powder obtained in the step S04 for 2-3 times by using the same centrifugal program in the step S04, wherein the detergent is anhydrous methanol;
s06, placing the solid powder washed in the step S05 into a vacuum drying oven, and vacuum drying for 6-12 h at the temperature of 25-30 ℃ to obtain the ZIF-93 material with nanoscale hierarchical pores.
The nanoscale hierarchical pore ZIF-93 material is obtained by the method for rapidly synthesizing the nanoscale hierarchical pore ZIF-93 material under the condition of room temperature and water phase.
Compared with the prior art, the invention has the following advantages and effects:
(1) The invention selects water as solvent, does not need to be activated, can rapidly synthesize the nanoscale hierarchical pore ZIF-93 material at normal temperature, has simple operation, mild condition, energy conservation, environmental protection and no pollution, and provides possibility for industrialization of the material.
(2) The synthesis method is quick and simple, the time required by the traditional synthesis method is 16 hours, the synthesis can be performed within 1 minute, and meanwhile, the prepared sample contains abundant micropores, mesopores and macropores, is uniform in size and uniform in 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 ZIF-93 material simulated by a computer and a nanoscale hierarchical pore ZIF-93 material prepared in examples 1-3.
FIG. 2 is an N-ray diagram of a nanoscale hierarchical pore ZIF-93 material prepared in examples 1-3 2 Adsorption-desorption isothermicityA line graph.
FIG. 3 is a graph of the full pore size distribution of nanoscale, hierarchical pore ZIF-93 materials prepared in examples 1-3.
FIG. 4 is a scanning electron microscope photograph of the nanoscale hierarchical pore ZIF-93 material prepared in example 1.
Detailed Description
The invention will be further described with reference to the drawings and examples, but the scope of the invention claimed is not limited to the examples.
Example 1
0.4g of Zn (CH) 3 COO) 2 ·2H 2 O and 0.4g of 4-methyl-5-imidazole formaldehyde are respectively dissolved in 45ml of deionized water and stirred for 5 minutes; mixing the two solutions to obtain a mixed solution, and stirring for 5 minutes; 0.9g of NaOH is added into the obtained mixed solution, and after stirring for 1 minute, the obtained product is centrifuged; and (3) drying the centrifuged product in a vacuum drying oven at room temperature for 12 hours to obtain the nanoscale hierarchical pore ZIF-93 material, and marking the nanoscale hierarchical pore ZIF-93 material as a sample A.
Example 2
0.4g of Zn (CH) 3 COO) 2 ·2H 2 O and 0.4g of 4-methyl-5-imidazole formaldehyde are respectively dissolved in 45ml of deionized water and stirred for 5 minutes; mixing the two solutions to obtain a mixed solution, and stirring for 5 minutes; 0.9g of NaOH is added into the obtained mixed solution, and after stirring for 10 minutes, the obtained product is centrifuged; and (3) drying the centrifuged product in a vacuum drying oven at room temperature for 12 hours to obtain the nanoscale hierarchical pore ZIF-93 material, and marking the nanoscale hierarchical pore ZIF-93 material as a sample B.
Example 3
0.4g of Zn (CH) 3 COO) 2 ·2H 2 O and 0.4g of 4-methyl-5-imidazole formaldehyde are respectively dissolved in 45ml of deionized water and stirred for 5 minutes; mixing the two solutions to obtain a mixed solution, and stirring for 10 minutes; 0.9g of NaOH was added to the resulting mixed solution, and after stirring for 60 minutes, the resulting product was centrifuged; and (3) drying the centrifuged product in a vacuum drying oven at room temperature for 12 hours to obtain the nanoscale hierarchical pore ZIF-93 material, and marking the nanoscale hierarchical pore ZIF-93 material as a sample C.
The nanoscale hierarchical pore ZIF-93 material prepared according to the embodiment is analyzed, and the analysis result is shown in the attached drawing.
(one) the crystal structure property of ZIF-93 material with nanoscale hierarchical pores is rapidly synthesized in room temperature water phase
The crystal structure of ZIF-93 prepared in examples 1-3 of the present invention was characterized using a D8-ADVANCE model X-ray diffractometer manufactured by Bruker, germany.
As shown in FIG. 1, it can be seen that the characteristic diffraction peaks of the crystals of examples 1-3 prepared by the present invention are consistent with the characteristic diffraction peaks simulated by ZIF-93, indicating that ZIF-93 materials can be synthesized using the synthesis conditions of examples 1-3.
(II) channel Property
The pore structure of the samples prepared according to the present invention was characterized using an ASAP2020 specific surface pore size distribution instrument manufactured by Micro corporation, usa, and the results are shown in table 1.
TABLE 1
FIG. 2 is a graph showing N of a nano-scale hierarchical pore ZIF-93 material prepared in examples 1-3 of the present invention 2 The adsorption-desorption isothermal diagram shows that under lower pressure, the material has larger acting force with nitrogen, so that more micropores exist; under higher pressure, the adsorbate is subjected to capillary condensation, a hysteresis loop appears, and the existence of a mesoporous structure in the material is proved.
The DFT full pore size distribution diagram of FIG. 3 shows that mesoporous structure exists in the material besides micropores, and the mesoporous volume is mainly concentrated and distributed at about 20-100nm, which proves that the material passes N 2 Adsorption-desorption isotherms.
(III) SEM image of ZIF-93 material with nanoscale hierarchical pores rapidly synthesized in room temperature water phase
The product obtained in example 1 was characterized by using a JSM-6330F scanning electron microscope (JEOL, japan). The results are shown in FIG. 4, and it can be seen that example 1 prepared according to the present invention exhibits relatively uniform packing of nanoparticles into micropores, mesopores and macropores.
Finally, it should be noted that the foregoing examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the foregoing examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made and all equivalent substitutions are intended to be included in the scope of the present invention.
Claims (2)
1. A method for rapidly synthesizing nanoscale hierarchical pore ZIF-93 material in room temperature water phase is characterized by comprising the following steps:
s01, under the condition of room temperature of 25-30 ℃, deionized water is used as a solvent, zn (CH) 3 COO) 2 ·2H 2 O and an organic ligand 4-methyl-5-imidazole formaldehyde are used as reactants; zn (CH) 3 COO) 2 ·2H 2 The mol ratio of O, 4-methyl-5-imidazole formaldehyde and deionized water is (0.25-1): (0.75-2): (2000-3000); zn (CH) 3 COO) 2 ·2H 2 Dissolving O and an organic ligand 4-methyl-5-imidazole formaldehyde in deionized water;
s02, fully stirring the solution in the step S01 for 5-10 min at a stirring speed of 500-1000 r/min to enable Zn (CH) 3 COO) 2 ·2H 2 O and the organic ligand 4-methyl-5-imidazole formaldehyde are fully dissolved and evenly dispersed into deionized water;
s03, adding an inorganic proton removing agent NaOH into the mixed solution in the step S02, and adding Zn (CH 3 COO) 2 ·2H 2 The mol ratio of O to NaOH is (0.25-1): (1-2), stirring for 1-60 min, wherein the stirring speed is 1000-1500 r/min;
s04, centrifuging the product obtained in the step S03 for 10-15 min at a centrifugation speed of 10000rpm to obtain solid powder;
s05, continuously centrifugally washing the solid powder obtained in the step S04 for 2-3 times by using the same centrifugal program in the step S04, wherein the detergent is anhydrous methanol;
s06, placing the solid powder washed in the step S05 into a vacuum drying oven, and vacuum drying for 6-12 h at the temperature of 25-30 ℃ to obtain the ZIF-93 material with nanoscale hierarchical pores.
2. The nanoscale hierarchical porous ZIF-93 material obtained by the method for rapidly synthesizing nanoscale hierarchical porous ZIF-93 material in room temperature aqueous phase according to claim 1.
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