CN110951089B - Method for promoting synthesis of ZIF-8 in aprotic polar solvent - Google Patents

Method for promoting synthesis of ZIF-8 in aprotic polar solvent Download PDF

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CN110951089B
CN110951089B CN201911337493.7A CN201911337493A CN110951089B CN 110951089 B CN110951089 B CN 110951089B CN 201911337493 A CN201911337493 A CN 201911337493A CN 110951089 B CN110951089 B CN 110951089B
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贺高红
杨旭茂
阮雪华
王佳铭
郑文姬
代岩
焉晓明
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Abstract

The invention provides a method for promoting synthesis of ZIF-8 in an aprotic polar solvent, belonging to the technical field of nano material preparation. The ZIF-8 pore cage structure is ordered and high in porosity, and can be used for preparing a high-performance gas separation membrane, but the brittleness is high, the defects are easy to occur, and the industrialization is difficult. The problems can be solved by doping ZIF-8 particles in a polymer to form a mixed matrix membrane, but the ZIF-8 is synthesized in water or methanol, and the membrane preparation process relates to a complex process of particle synthesis, centrifugation, drying and redispersion and is difficult to mix uniformly; the direct synthesis in a polar solvent has the problems of slow growth rate, harsh reaction conditions and the like. The invention dissolves the functional polymer in the aprotic polar solvent to form a microphase interface, forms a nucleation site relatively enriched with zinc ions through the adsorption effect of functional groups on the microphase interface, and promotes the growth of ZIF-8 through heterogeneous nucleation, thereby synthesizing the ZIF-8 nano-particles more quickly under mild conditions.

Description

Method for promoting synthesis of ZIF-8 in aprotic polar solvent
Technical Field
The invention relates to a method for promoting synthesis of ZIF-8 by adding a functional polymer into an aprotic polar solvent, belonging to the technical field of nano material preparation. The method comprises the steps of dissolving a functional polymer in an aprotic polar solvent to form a microphase interface, forming a nucleation site relatively enriched with zinc ions through the adsorption effect of a functional group on the microphase interface, and promoting the nucleation growth of ZIF-8 through a heterogeneous nucleation effect, so that the ZIF-8 nanoparticles are synthesized more quickly under mild reaction conditions.
Background
Zeolitic imidazole-like framework materials (ZIFs) are a class of metal-organic framework materials with a Zeolitic topology, usually formed by self-assembly of transition metal ions with imidazole or imidazole derivatives. ZIF-8 is a zeolite-like imidazole framework material formed by self-assembly of zinc ions and 2-methylimidazole, and has high thermal stability and chemical stability. In addition, ZIF-8 has a highly ordered and highly porous pore cage structure with a cage diameter of 1.16nm and a pore window diameter of 0.34nm, and is widely used for developing gas separation membranes with high selectivity and high permeability.
TABLE 1 kinetic diameters of common gas molecules
Figure BDA0002331339390000011
According to the kinetic diameters of common gas molecules in the table 1, the H can be screened by the gas separation membrane with ZIF-8 as a separation functional layer2/N2、H2/CH4、CO2/N2、CO2/CH4、H2/C2H4And H2/C3H6And the like. However, the ZIF-8 material has high brittleness and rigidity, the separation functional layer constructed by pure ZIF-8 is easy to have defects in the preparation process, and the continuous compact structure of the material is also easy to be damaged by deformation stress in the use process. In response to the bottleneck problem described above, many research institutes and researchers have proposed dispersing ZIF-8 particles in a polymer continuous phase to form a mixed matrix membrane, utilizing ZIF-8 high capacity and highly ordered poresThe cage structure features that high-selectivity and high-permeability mass transfer channels are constructed, and the good flexibility and deformability of the polymer matrix can ensure the large-scale preparation of the continuous compact defect-free separation function layer in the gas separation membrane.
Glassy polymers, such as aromatic polyimide, polysulfone, etc., are the main materials for the scale preparation of gas separation membranes with size sieving function at present. Glassy polymers generally have a backbone with high rigidity, and angstrom-scale free volume cavities formed by molecular chain packing are key to gas sieving. However, factors affecting the microstructure, such as the sequence of segments, the degree of distortion, the state of packing, and the distribution of crosslinking sites of the glassy polymer, are difficult to control precisely, and the size distribution of free volume cavities has a wide range. To overcome this constraint and to ensure a high selectivity of the glassy polymer gas separation membrane, there is a certain lower limit to the thickness of the separating functional layer, which is generally considered to be not less than 100 nm. Subject to this limitation, glassy polymer gas separation membranes have relatively low permeation rates, such as commercial polyimide membranes, CO2The permeation rate generally does not exceed 100 GPU. According to the characteristics and the limitation of the glassy polymer gas separation membrane, the ZIF-8 nano filler with high porosity and accurate pore structure is introduced into the separation functional layer, so that the defect that a polymer mass transfer channel is difficult to regulate and control is overcome, and the method is an important direction for the development of a mixed matrix membrane.
Solvents commonly used to formulate ZIF-8 synthetic solutions are N, N-Dimethylformamide (DMF), water, and methanol. According to the report of the document Angew.chem.int.Ed.2006,45,1557, Huang et al synthesize ZIF-8 for the first time, and the used synthesis solution is prepared by methanol; according to the literature PNAS,2006,103,10186, Park et al reported that ZIF-8 was synthesized for the first time based on amide solvents (such as DMF and DEF); pan et al, reported, for the first time, the synthesis of ZIF-8 material in aqueous solution according to the document chem. From the viewpoint of economy and environmental protection, the most suitable solvents for preparing the ZIF-8 synthetic solution are water and methanol. However, water and methanol are not good solvents for glassy polymers, ZIF-8 particles synthesized in a methanol solution or an aqueous solution can be transferred into a casting solution of the glassy polymer through the processes of centrifugation, drying, redispersion and the like, and particle agglomeration caused by the transfer process can increase the defects of a mixed matrix membrane and seriously affect the osmotic selectivity of the membrane. Amide aprotic polar solvents such as DMF (dimethyl formamide) and the like are good solvents of glassy polymer membrane materials such as polyimide, polysulfone and the like, can be used for synthesizing ZIF-8, and can also be used for dissolving the glassy polymer membrane materials and preparing membrane casting solutions, so that defect-free mixed matrix membranes can be prepared by better utilizing the glassy polymers.
According to literature reports, problems of high synthesis difficulty, low reaction rate and the like generally exist when ZIF-8 materials are synthesized based on amide aprotic polar solvents such as DMF and the like, and under mild reaction conditions (relatively low temperature), reaction usually needs tens of hours to obtain a sufficiently high yield of ZIF-8. To solve this problem, there are two main approaches: 1) the reaction temperature is increased in a closed reaction vessel, and is usually controlled to be about 140 ℃, so that on one hand, the energy consumption is high, and on the other hand, the batch synthesis is difficult to perform due to the limitation of the closed reaction vessel; 2) the enhancement of the synthesis of ZIF-8 by auxiliary means such as microwave or ultrasound is also limited by the difficulty of mass synthesis. In conclusion, the large-scale preparation of defect-free mixed matrix membranes of ZIF-8 and glassy polymers needs to solve the problem of low-cost batch synthesis of ZIF-8 in amide aprotic polar solvents such as DMF.
Disclosure of Invention
The invention aims to provide a method for promoting synthesis of ZIF-8 in an aprotic polar solvent. The method comprises the steps of dissolving a functional polymer in an aprotic polar solvent to form a microphase interface, forming a nucleation site relatively enriched with zinc ions through the adsorption effect of a functional group on the microphase interface, and promoting the nucleation growth of ZIF-8 through a heterogeneous nucleation effect, so that ZIF-8 nanoparticles are synthesized more quickly under mild reaction conditions, and the method is more favorable for batch synthesis of the ZIF-8 nanoparticles.
The technical scheme of the invention is as follows:
a method for promoting synthesis of ZIF-8 in an aprotic polar solvent comprises the following steps:
step one, preparing a functionalized polymer solution: fully dissolving a functional polymer in an aprotic polar solvent, wherein the mass ratio of the polymer to the aprotic polar solvent is not more than 5: 100;
secondly, the polymer pre-adsorbs zinc ions to form nucleation sites: fully dissolving a zinc source in the functional polymer solution prepared in the first step, wherein the molar ratio of zinc ions to the aprotic polar solvent is 1: 300-2: 100;
thirdly, preparing a ZIF-8 synthetic solution: fully dissolving 2-methylimidazole in the solution formed in the second step, wherein the molar ratio of 2-methylimidazole to zinc ions is 2: 1-8: 1;
fourthly, heterogeneous nucleation and ZIF-8 synthesis: transferring the ZIF-8 synthetic solution formed in the third step into a reaction kettle, wherein the reaction temperature ranges from 20 ℃ to 140 ℃, and the reaction time ranges from 6 hours to 24 hours;
fifthly, utilizing or separating and purifying ZIF-8 particles: and preparing a casting solution based on the synthetic solution after the reaction is finished, or carrying out liquid-solid separation, and cleaning the solid by adopting an aprotic polar solvent to obtain the powdered ZIF-8 material.
The functionalized polymer is a polymer with a main chain and/or a side chain containing polar groups and/or strong polar groups, and is imidazolium polysulfone, polyethyleneimine, polyvinyl alcohol, polyacrylonitrile or polyethylene glycol, but is not limited to the polymer.
The aprotic polar solvent is N, N-dimethylformamide, N-diethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylsulfoxide, acetonitrile or 1, 3-dimethyl-2-imidazolidinone, but is not limited thereto.
The zinc source is one or more of zinc-containing salts, oxides and hydroxides.
The invention has the beneficial effects that: adding a polymer containing polar groups and/or strong polar groups into an aprotic polar solvent system to form a solid/liquid microphase interface, forming nucleation sites relatively enriched with zinc ions through the adsorption effect of functional groups on the microphase interface, and promoting ZIF-8 nucleation growth through a heterogeneous nucleation effect, thereby synthesizing ZIF-8 nanoparticles more quickly under mild reaction conditions. Through the promotion effect of the functionalized polymer, the closed high-temperature reaction condition or the auxiliary means with limited action space such as microwave, ultrasound and the like are avoided, the ZIF-8 nano-particles can be synthesized in batch in the aprotic polar solvent, and the large-scale preparation of the defect-free mixed matrix membrane blended by the ZIF-8 and the glassy state polymer membrane material is facilitated.
Drawings
Fig. 1 is an XRD spectrum of four solid samples synthesized in example 1.
FIG. 2 is a scanning electron micrograph of four solid samples synthesized in example 1, wherein a) DMF at 25 ℃ is pure DMF, b) DMF at 55 ℃ is pure DMF, c) DMF at 85 ℃ is pure DMF, and d) DMF at 115 ℃.
FIG. 3 is a scanning electron micrograph of four solid samples synthesized in example 2, wherein a) DMF +0.5 wt% Mim-PSF at 25 ℃, b) DMF +0.5 wt% Mim-PSF at 55 ℃, c) DMF +0.5 wt% Mim-PSF at 85 ℃, d) DMF +0.5 wt% Mim-PSF at 115 ℃.
FIG. 4 is a scanning electron micrograph of four solid samples synthesized in example 3, wherein a) DMF +2.0 wt% Mim-PSF at 25 ℃, b) DMF +2.0 wt% Mim-PSF at 55 ℃, c) DMF +2.0 wt% Mim-PSF at 85 ℃, d) DMF +2.0 wt% Mim-PSF at 115 ℃.
FIG. 5 is a scanning electron micrograph of four solid samples synthesized in example 4, wherein a) DMF +2.0 wt% PEI at 25 ℃, b) DMF +2.0 wt% PEI at 55 ℃, c) DMF +2.0 wt% PEI at 85 ℃, d) DMF +2.0 wt% PEI at 115 ℃.
FIG. 6 is a scanning electron micrograph of four solid samples synthesized in example 5, wherein a) DMF at 55 ℃ is pure DMF, b) DMF +0.5 wt% Mim-PSF at 55 ℃, c) DMF +1.0 wt% Mim-PSF at 55 ℃, d) DMF +2.0 wt% Mim-PSF at 55 ℃.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
The molar ratio of the ZIF-8 synthetic precursor is as follows: hmim is 1: 8.
Pure DMF is taken as a solvent, and a polymer containing polar groups and/or strong polar groups is not added.
Preparing a ZIF-8 synthesis system: 0.4452 g of zinc nitrate hexahydrate is added into 30 ml of DMF solvent, after the solid is fully dissolved, 0.9830 g of 2-methylimidazole is added, and the mixture is stirred and mixed for 3 minutes at high speed. Preparing 4 parts of synthetic solution in parallel according to the requirements of a synthetic system, and standing and reacting for 24 hours in reaction environments with the temperatures of 25 ℃, 55 ℃, 85 ℃ and 115 ℃ respectively. After the reaction, solid-liquid separation was performed by a high-speed centrifuge at 500rpm, and the obtained solid was washed twice with DMF and methanol alternately. And drying the obtained solid, preparing a sample, and characterizing by an X-ray diffractometer and a field emission scanning electron microscope.
The XRD spectrum obtained by X-ray diffractometer is shown in figure 1. From the height ratios of characteristic peaks at different positions in the figure, a sample with typical ZIF-8 spectrogram characteristics cannot be obtained after a ZIF-8 synthetic solution prepared by taking pure DMF as a solvent is reacted at 25 ℃, 55 ℃ and 85 ℃ for 24 hours, and only a solid sample obtained after the reaction is carried out at 115 ℃ for 24 hours is relatively close to the typical XRD spectrogram characteristics of ZIF-8.
The morphology of the solid sample obtained by the field emission scanning electron microscope is shown in figure 2. According to the microscopic morphology of the solid sample in the figure, a sample with the typical ZIF-8 crystal morphology cannot be obtained after a reaction is carried out for 24 hours at 25 ℃ and 55 ℃ by using pure DMF as a solvent to prepare a synthetic solution, the sample obtained after the reaction is carried out for 24 hours at 85 ℃ initially has the ZIF-8 crystal morphology, and the relatively obvious ZIF-8 crystal face and edge structure can be observed in the solid sample obtained after the reaction is carried out for 24 hours at 115 ℃.
Example 2
The molar ratio of the ZIF-8 synthetic precursor is as follows: hmim is 1: 8.
An appropriate amount of imidazolium-containing polymer, namely, imidazolium-containing polysulfone Mim-PSF, was added to DMF as a solvent, and the content of the polymer in the solvent was 0.5 wt%.
Preparing a ZIF-8 synthesis system: 0.4452 g of zinc nitrate hexahydrate is added into 30 ml of DMF solvent with 0.5 wt% of imidazolium polysulfone content, after the solid is fully dissolved, 0.9830 g of 2-methylimidazole is added, and the mixture is stirred and mixed at high speed for 3 minutes. Preparing 4 parts of synthetic solution in parallel according to the requirements of a synthetic system, and standing and reacting for 24 hours in reaction environments with the temperatures of 25 ℃, 55 ℃, 85 ℃ and 115 ℃ respectively. After the reaction, solid-liquid separation was performed by a high-speed centrifuge at 500rpm, and the obtained solid was washed twice with DMF and methanol alternately. And drying the obtained solid, preparing a sample, and characterizing by a field emission scanning electron microscope.
The morphology of the solid sample obtained by the field emission scanning electron microscope is shown in figure 3. According to the microscopic morphology of the solid sample in the figure, a synthetic solution is prepared by taking a DMF (dimethyl formamide) solution with 0.5 wt% of imidazolium polysulfone as a solvent system, a sample with a ZIF-8 crystal morphology is obtained after the reaction is carried out at 25 ℃ for 24 hours, and relatively obvious ZIF-8 crystal face and corner structure can be observed in the solid sample obtained after the reaction is carried out at 55 ℃, 85 ℃ and 115 ℃ for 24 hours. With the increase of the temperature, the ZIF-8 crystal is more regular in morphology, the edge angle and the crystal face structure of the ZIF-8 crystal are clearer, and the size of the ZIF-8 particles is gradually increased.
Example 3
The molar ratio of the ZIF-8 synthetic precursor is as follows: hmim is 1: 6.
An appropriate amount of imidazolium-containing polymer, namely, imidazolium-containing polysulfone Mim-PSF, was added to DMF as a solvent, and the content of the polymer in the solvent was 2.0 wt%.
Preparing a ZIF-8 synthesis system: 0.4452 g of zinc nitrate hexahydrate is added into 30 ml of DMF solvent with the imidazolium polysulfone content of 2.0 wt%, after the solid is fully dissolved, 0.7373 g of 2-methylimidazole is added, and the mixture is stirred and mixed at high speed for 3 minutes. Preparing 4 parts of synthetic solution in parallel according to the requirements of a synthetic system, and standing and reacting for 24 hours in reaction environments with the temperatures of 25 ℃, 55 ℃, 85 ℃ and 115 ℃ respectively. After the reaction, solid-liquid separation was performed by a high-speed centrifuge at 500rpm, and the obtained solid was washed twice with DMF and methanol alternately. And drying the obtained solid, preparing a sample, and characterizing by a field emission scanning electron microscope.
The morphology of the solid sample obtained by the field emission scanning electron microscope is shown in figure 4. As can be seen from the microscopic morphology of the solid sample in the figure, the obvious ZIF-8 crystal face and corner structure can be observed in the solid sample obtained by reacting the solid sample at 25 ℃, 55 ℃, 85 ℃ and 115 ℃ for 24 hours by using DMF solution with the imidazolium polysulfone content of 2.0 wt% as a solvent system to prepare a synthetic solution. Along with the increase of the temperature, the ZIF-8 crystal is more regular in morphology, clearer in edge angle and crystal face structure, and gradually increased in particle size of the ZIF-8.
Example 4
The molar ratio of the ZIF-8 synthetic precursor is as follows: hmim is 1: 6.
A proper amount of polymers containing polar groups, including polyetherimide PEI, polysulfone PSF, polyethersulfone PES and imidazolium polysulfone Mim-PSF, are added into a solvent DMF, and the content of the polymers in the solvent is 2.0 wt%.
Preparing a ZIF-8 synthesis system: 0.4452 g of zinc nitrate hexahydrate is added into 30 ml of DMF solvent with the polymer content of 2.0 wt%, after the solid is fully dissolved, 0.7373 g of 2-methylimidazole is added, and the mixture is stirred and mixed at high speed for 3 minutes. According to the requirements of a synthesis system, synthesis solutions containing Polyetherimide (PEI), Polysulfone (PSF), polyether sulfone (PES) and imidazolium polysulfone (Mim-PSF) are prepared in parallel, and are respectively kept stand and reacted for 24 hours in a reaction environment at the temperature of 85 ℃. After the reaction, solid-liquid separation was performed by a high-speed centrifuge at 500rpm, and the obtained solid was washed twice with DMF and methanol alternately. And drying the obtained solid, preparing a sample, and characterizing by a field emission scanning electron microscope.
The morphology of the solid sample obtained by the field emission scanning electron microscope is shown in figure 5. According to the microscopic morphology of the solid sample, the formation of ZIF-8 particles can be remarkably promoted by adding 2.0 wt% of polyetherimide PEI, polysulfone PSF, polyether sulfone PES or imidazolium polysulfone Mim-PSF into DMF solvent. Compared with solid samples obtained under the conditions of pure DMF solvent and the temperature of 85 ℃, particularly as shown in figure 2, the solid samples obtained by adding the polar polymer can observe obvious ZIF-8 crystal face and edge structure. In addition, because the imidazolium polysulfone belongs to a polymer containing a strong polar group, the accelerating effect of the imidazolium polysulfone is obviously stronger than that of other three polymers containing a weak polar group, the ZIF-8 crystal morphology is more regular, the edge angle and the crystal face structure are clearer, and the ZIF-8 particle size is larger.
Example 5
The molar ratio of the ZIF-8 synthetic precursor is as follows: hmim is 1: 8.
An appropriate amount of imidazolium-containing polymer, namely, imidazolium-containing polysulfone Mim-PSF, is added into a solvent DMF, and the content of the polymer in the solvent is respectively 0.0 wt%, 0.5 wt%, 1.0 wt% and 2.0 wt%.
Preparing a ZIF-8 synthesis system: 0.4452 g of zinc nitrate hexahydrate is added into 30 ml of Mim-PSF DMF solution, after the solid is fully dissolved, 0.9830 g of 2-methylimidazole is added, and the mixture is stirred and mixed for 3 minutes at a high speed. Four parts of synthetic solution are prepared in parallel according to the system requirements, the Mim-PSF content in DMF is respectively 0.0 wt%, 0.5 wt%, 1.0 wt% and 2.0 wt%, and the four parts are respectively kept stand and react for 24 hours in a reaction environment with the temperature of 55 ℃. After the reaction, solid-liquid separation was performed by a high-speed centrifuge at 500rpm, and the obtained solid was washed twice with DMF and methanol alternately. And drying the obtained solid, preparing a sample, and characterizing by a field emission scanning electron microscope.
The morphology of the solid sample obtained by the field emission scanning electron microscope is shown in figure 6. According to the microscopic morphology of the solid sample, no imidazolium polysulfone Mim-PSF is added into the synthetic solution, and a sample with the typical ZIF-8 spectrogram characteristic cannot be obtained after the reaction is carried out for 24 hours at 55 ℃; the formation of ZIF-8 particles was significantly promoted by the addition of 0.5 wt%, 1.0 wt% and 2.0 wt% imidazolium polysulfone Mim-PSF in DMF solvent. In addition, in the range of research conditions, the accelerating effect on the synthesis effect of ZIF-8 is gradually strengthened along with the increase of the addition amount of Mim-PSF in DMF solvent. When the addition amount of Mim-PSF is 1.0 wt% and 2.0 wt%, the synthesized ZIF-8 crystal has good morphology, and the edge angle and crystal face structure are very clear.

Claims (3)

1. A method for promoting synthesis of ZIF-8 in an aprotic polar solvent is characterized by comprising the following steps:
step one, preparing a functionalized polymer solution: fully dissolving a functional polymer in an aprotic polar solvent, wherein the mass ratio of the polymer to the aprotic polar solvent is not more than 5: 100;
secondly, the polymer pre-adsorbs zinc ions to form nucleation sites: fully dissolving a zinc source in the functional polymer solution prepared in the first step, wherein the molar ratio of zinc ions to the aprotic polar solvent is 1: 300-2: 100;
thirdly, preparing a ZIF-8 synthetic solution: fully dissolving 2-methylimidazole in the solution formed in the second step, wherein the molar ratio of 2-methylimidazole to zinc ions is 2: 1-8: 1;
fourthly, heterogeneous nucleation and ZIF-8 synthesis: transferring the ZIF-8 synthetic solution formed in the third step into a reaction kettle, wherein the reaction temperature is 20-140 ℃, and the reaction time is 6-24 hours;
fifthly, utilizing or separating and purifying ZIF-8 particles: preparing a membrane casting solution based on the synthetic solution after the reaction is finished, or carrying out liquid-solid separation, and cleaning the solid by adopting an aprotic polar solvent to obtain a powdered ZIF-8 material;
the functional polymer is imidazolium polysulfone, polyethyleneimine, polyvinyl alcohol, polyacrylonitrile or polyethylene glycol.
2. The method of promoting ZIF-8 synthesis in aprotic polar solvent of claim 1, wherein the aprotic polar solvent is N, N-dimethylformamide, N-diethylformamide, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylsulfoxide, acetonitrile or 1, 3-dimethyl-2-imidazolidinone.
3. The method for promoting synthesis of ZIF-8 in an aprotic polar solvent as claimed in claim 1 or 2, wherein the zinc source is one or a mixture of two or more of zinc-containing salts, oxides and hydroxides.
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