CN111215032B - Rapid preparation method of MOF material - Google Patents
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- CN111215032B CN111215032B CN201811418810.3A CN201811418810A CN111215032B CN 111215032 B CN111215032 B CN 111215032B CN 201811418810 A CN201811418810 A CN 201811418810A CN 111215032 B CN111215032 B CN 111215032B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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Abstract
The invention provides a rapid preparation method of a MOF material, which comprises the following steps: dropping the organic ligand solution into the metal acetate aqueous solution at the temperature of 25-35 ℃ to obtain the MOF material; according to the method, the MOF material can be obtained by simply dripping the organic ligand solution into the metal acetate aqueous solution at room temperature, the technical prejudice that the MOF material needs to be subjected to long-time solvothermal reaction at high temperature in the preparation of the MOF material in the field is overcome, the MOF material with complete crystal growth and controllable particle size can be rapidly prepared within 1min, the preparation reaction can be continuously carried out, and the product is easy to separate, so that the method has high potential industrial application value.
Description
Technical Field
The invention relates to the field of organic-inorganic composite materials, in particular to a rapid preparation method of MOF materials.
Background
The Metal-organic framework compound (MOF for short) is a porous crystal material formed by self-assembling transition Metal ions and organic ligands through coordination bonds, has the advantages of more unsaturated Metal active sites, higher specific surface area, higher thermal stability and the like, and can be used for preparing various fields of gas separation, gas storage, chemical catalysis, chemical sensing or drug release.
MOF materials are typically prepared by solvothermal or hydrothermal methods, which typically require an extended period of hours or days to obtain a scale of MOF material. In addition, the crystal structure of the product obtained by the synthesis method is not unique, and as the combination modes of the organic ligand and the metal precursor are various, various factors such as solvent selection, temperature interval change, fine change of raw material proportion and the like can influence the reaction selectivity to a certain extent, and how to realize perfect growth of MOF crystals under certain conditions is more difficult.
At present, some new methods for synthesizing MOF materials have been proposed in the prior art, which can overcome the defects of simple solvothermal preparation methods, such as using non-traditional heat sources such as microwaves, ultrasonic waves, etc., to increase the crystallization rate of the MOF materials, etc., and even control the growth morphology of the product in some cases, to form MOF nanocrystal materials, etc., however, the methods for synthesizing MOF materials disclosed in the prior art still have long time. For example, miquel Gimeno-Fabra et al (GIMENO-FABRA, miquel, et al, instant MOFs: continuous synthesis of metal-organic frameworks by rapid solvent) for chemical Communications,2012, 48.86:10642-10644.) propose a first synthesis apparatus for the commercial production of MOF materials, which employs a counter-current mixing reactor consisting of a concentric arrangement of pipes, in which preheated water (downflow) is introduced, meeting the precursor solution (upflow, room temperature injection) at the mixing point, allowing continuous solvothermal reaction, expanding its applications in energy and environment, the design being advantageous for the mixing of the reaction mass to be carried out sufficiently in a short time, the suspension particles of the final MOF material being pumped and collected at the top of the reactor, the first MOF material synthesized by this method being Cu-BTC MOF, the commercial production of MOF materials being achieved for 3-12 hours. Lorenzo Maserati et al (MASERATI, lorenzo, et al, mine-MOFs: ultrafast Synthesis of M2 (dobpdc) Metal-Organic Frameworks from Divalent Metal Oxide Colloidal nanocrystallization of Materials,2016, 28.5:1581-1588.) reported a method for synthesizing high quality M2 (dobpdc) MOFs (dobpdc is 2, 5-dihydroxyterephthalic acid) using a divalent Metal oxide colloid instead of a conventional divalent Metal salt to synthesize MOF Materials of the M-MOF-74 series, which was the first method for rapid synthesis of M2 (dobpdc) from any starting material.
Although the above prior art techniques all achieve mass production of MOF materials, they still have the following problems: (1) The organic solvent is large in dosage, and particularly when the reaction reaches the industrial level, the characteristics of high cost, high toxicity, easy combustion and the like of the organic solvent seriously limit the industrialized application of the organic solvent; (2) The precursor contains anions such as nitrate radical or chloride ion, when the reaction scale is enlarged, the metal nitrate is a great potential safety hazard, and the metal chloride has stronger corrosiveness; (3) The limitations on the types of ligands are large, and many MOF materials require the customization of specific organic ligands, and industrial processes for producing these ligands are under development; (4) Particle size control is difficult to achieve, as MOF materials require control over their particle size range in applications such as nano-scale MOF particles when applied in the thin film field, and larger MOF particles are typically required when used in the gas storage field; (5) The MOF material needs to remove the non-volatile solvent and unreacted raw materials in the pores, which is a main problem for limiting the scale-up production of the MOF material; (6) The MOF material powder obtained by the prior art is difficult to form and also limits the application of the MOF material powder.
In summary, in order to realize industrial production of the MOF material, those skilled in the art are urgent to develop a rapid large-scale preparation method of the MOF material with convenient operation and rapid reaction, so as to overcome the disadvantages of slow reaction process, incomplete crystal growth, uncontrollable particle size and the like in the conventional preparation method of the MOF material.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a rapid large-scale preparation method of MOF materials, which is convenient to operate and quick in reaction (less than 5 min), so as to overcome the defects of slow reaction process, incomplete crystal growth, uncontrollable particle size and the like in the traditional MOF material preparation method.
To achieve the object, one of the objects of the present invention is to provide a rapid preparation method of a MOF material, the preparation method comprising the steps of:
and (3) dripping the organic ligand solution into the metal acetate aqueous solution at 25-35 ℃ (such as 26 ℃, 27 ℃,28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃ or 34 ℃), and the like, thereby obtaining the MOF material.
Preferably, the dropping means dropping dropwise.
According to the invention, the organic ligand solution is simply dripped into the metal acetate at the normal temperature of 25-35 ℃, so that the organic ligand is in a state of larger local concentration in the reaction solution, the MOF material can be formed at an extremely fast speed, and the obtained MOF material has uniform particle size and a dimension of a micron level, and is suitable for the fields of gas adsorption, catalysis, detection and the like.
Preferably, the dripping time is controlled within 1min, for example, 2s, 4s, 6s, 8s, 12s, 16s, 20s, 24s, 28s, 32s, 36s, 40s, 44s, 48s, 52s, 56s or 58s, etc., and the dripping time is too long, which may rather cause the generated MOF material to be partially dissolved or agglomerated, reducing the yield and particle size uniformity of the obtained MOF material.
Preferably, the time of the dropping is controlled to be 20 to 30 seconds.
Preferably, the organic ligand solution is miscible with the aqueous metal acetate solution in any ratio.
Preferably, the solvent of the organic ligand solution is N, N-dimethylformamide.
Preferably, the metal acetate is any one or a mixture of at least two of copper acetate, zinc acetate, cadmium acetate, silver acetate or manganese acetate.
Preferably, the solute of the organic ligand solution is any one organic ligand of 4,4' -diphenyl ether dicarboxylic acid, terephthalic acid, trimesic acid or 2, 5-dihydroxyterephthalic acid.
Preferably, the organic ligand solution is an N, N-dimethylformamide solution of 4,4 '-diphenyl ether dicarboxylic acid, the metal acetate in the metal acetate aqueous solution is any one of copper acetate, zinc acetate, cadmium acetate, silver acetate or manganese acetate, the ratio of the amount of the 4,4' -diphenyl ether dicarboxylic acid in the organic ligand solution to the amount of the substance of the metal acetate in the metal acetate aqueous solution is 2 to 5:1, for example, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1 or 4.8:1, and the like, and more preferably 2 to 2.5:1.
Preferably, the organic ligand solution is an N, N-dimethylformamide solution of trimesic acid, the metal acetate in the metal acetate aqueous solution is copper acetate or zinc acetate, and the ratio of the amount of trimesic acid in the organic ligand solution to the amount of the metal acetate in the metal acetate aqueous solution is 1.5-3:1, for example, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, or 2.8:1, etc., and more preferably 1.6-2:1.
Preferably, the organic ligand solution is an N, N-dimethylformamide solution of 2, 5-dihydroxyterephthalic acid, the metal acetate in the metal acetate aqueous solution is copper acetate, and the ratio of the amount of the 2, 5-dihydroxyterephthalic acid in the organic ligand solution to the amount of the metal acetate in the metal acetate aqueous solution is 1:1.
Preferably, the preparation method comprises the following steps:
step (1), preparing an aqueous solution of metal acetate and an N, N-dimethylformamide solution of an organic ligand respectively;
step (2), dropwise adding the N, N-dimethylformamide solution of the organic ligand obtained in the step (1) into an aqueous solution of metal acetate at the temperature of 25-35 ℃ for 1min to obtain a MOF material crude product;
and (3) carrying out post-treatment on the crude product of the MOF material obtained in the step (2) to obtain the MOF material.
Preferably, the post-treatment comprises centrifugal precipitation, washing and drying.
Preferably, the washing is washing the precipitate obtained by centrifugation with N, N-dimethylformamide or ethanol.
The numerical ranges recited herein include not only the above-listed point values, but also any point values between the above-listed numerical ranges that are not listed, and are limited in space and for the sake of brevity, the present invention is not intended to be exhaustive of the specific point values that the stated ranges include.
Compared with the prior art, the invention has the beneficial effects that:
according to the method, the MOF material can be obtained by simply dripping the organic ligand solution into the metal acetate aqueous solution at room temperature, the technical prejudice that the MOF material needs to be subjected to long-time solvothermal reaction at high temperature in the preparation of the MOF material in the field is overcome, the MOF material with complete crystal growth and controllable particle size can be rapidly prepared within 1min, the preparation reaction can be continuously carried out, and the product is easy to separate, so that the method has high potential industrial application value.
Drawings
FIG. 1 shows the MOF material Cu (H) obtained in example 1 and example 2 in the embodiment of the present invention 2 oba) and Zn (H) 2 oba) photographs of the preparation process.
FIG. 2 shows the MOF material Cu (H) obtained in example 1 of the present invention 2 XRD spectrum of oba).
FIG. 3 shows the MOF material Zn (H) obtained in example 2 of the embodiment of the present invention 2 XRD spectrum of oba).
FIG. 4 is an SEM photograph of a Cu-BTCMOF MOF material obtained in example 6 of the present invention.
FIG. 5 is an SEM photograph of a Zn-BTCMOF MOF material obtained in example 7 of the present invention.
FIG. 6 is an SEM photograph of MOF-74Cu of the MOF material obtained in example 8 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
The MOF material Cu (H) was prepared by the following steps 2 oba)：
Step (1), 100mg of copper acetate is dissolved in 2mL of water to obtain a copper acetate aqueous solution, 258mg of 4,4' -diphenyl ether dicarboxylic acid is dissolved in 1.5mL of N, N-Dimethylformamide (DMF), and a DMF solution of an organic ligand is obtained;
step (2), dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a copper acetate aqueous solution at the temperature of 30 ℃, and controlling the dropwise adding time to be about 50s to obtain a suspension of a crude product of the MOF material;
step (3), centrifugally separating the suspension of the crude MOF material obtained in the step (2), and cleaning the precipitate obtained by centrifugal separation with DMF and methanol respectively to obtain the MOF material Cu (H) 2 oba)。
Example 2
The MOF material Zn (H) was prepared by the following steps 2 oba)：
Step (1), 87.6mg of zinc acetate is dissolved in 2mL of water to obtain zinc acetate aqueous solution, 258mg of 4,4' -diphenyl ether dicarboxylic acid is dissolved in 1.5mL of N, N-Dimethylformamide (DMF) to obtain DMF solution of an organic ligand;
step (2), dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a zinc acetate aqueous solution at 30 ℃, and controlling the dropwise adding time to be 20-30 s to obtain a suspension of a crude product of the MOF material;
step (3), centrifugally separating the suspension of the crude MOF material obtained in the step (2), and cleaning the precipitate obtained by centrifugal separation with DMF and methanol respectively to obtain the MOF material Zn (H) 2 oba)。
Example 3
MOF material Cd (H) was prepared by the following steps 2 oba)：
Step (1), 133mg of cadmium acetate is dissolved in 1mL of water to obtain a cadmium acetate aqueous solution, 258mg of 4,4' -diphenyl ether dicarboxylic acid is dissolved in 1.5mL of N, N-Dimethylformamide (DMF), and a DMF solution of an organic ligand is obtained;
dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a cadmium acetate aqueous solution at 35 ℃, and controlling the adding time to be 20-30 s to obtain a suspension of a MOF material crude product;
step (3), centrifugally separating the suspension of the crude MOF material obtained in the step (2), and cleaning the precipitate obtained by centrifugal separation with DMF and methanol respectively to obtain the MOF material Cd (H) 2 oba)。
Example 4
The MOF material Ag (H) is prepared by the following steps 2 oba)：
Step (1), 83mg of silver acetate is dissolved in 2mL of water to obtain a silver acetate aqueous solution, 258mg of 4,4' -diphenyl ether dicarboxylic acid is dissolved in 1.5mL of N, N-Dimethylformamide (DMF), and a DMF solution of an organic ligand is obtained;
step (2), dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a silver acetate aqueous solution at 25 ℃, and controlling the dropwise adding time to be 20s to obtain a suspension of a crude product of the MOF material;
step (3), centrifugally separating the suspension of the crude MOF material obtained in the step (2), and cleaning the precipitate obtained by centrifugal separation with DMF and methanol respectively to obtain the MOF material Ag (H) 2 oba)。
Example 5
MOF material Mn (H) was prepared by the following steps 2 oba)：
Step (1), 70mg of manganese acetate is dissolved in 1mL of water to obtain a manganese acetate aqueous solution, 258mg of 4,4' -diphenyl ether dicarboxylic acid is dissolved in 1.5mL of N, N-Dimethylformamide (DMF), and a DMF solution of an organic ligand is obtained;
step (2), dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a manganese acetate aqueous solution at 25 ℃, and controlling the dropwise adding time to be 20s to obtain a suspension of a MOF material crude product;
step (3), centrifugally separating the suspension of the crude MOF material obtained in the step (2), and cleaning the precipitate obtained by centrifugal separation with DMF and methanol respectively to obtain the MOF material Mn (H) 2 oba)。
Example 6
The MOF material Cu-BTCMOF was prepared by the following steps:
step (1), 100mg of copper acetate is dissolved in 1.5mL of water to obtain a copper acetate aqueous solution, and 210mg of trimesic acid is dissolved in 1.5mL of N, N-Dimethylformamide (DMF) to obtain a DMF solution of an organic ligand;
step (2), dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a copper acetate aqueous solution at 25 ℃, and controlling the dropwise adding time to be 20s to obtain a suspension of a crude product of the MOF material;
and (3) carrying out centrifugal separation on the suspension of the crude MOF material obtained in the step (2), cleaning a precipitate obtained by centrifugal separation by using DMF and methanol respectively, and drying at room temperature to obtain the Cu-BTCMOF MOF material.
Example 7
The MOF material Zn-BTCMOF was prepared by the following steps:
step (1), 110mg of zinc acetate is dissolved in 1.5mL of water to obtain zinc acetate aqueous solution, and 210mg of trimesic acid is dissolved in 1.5mL of N, N-Dimethylformamide (DMF) to obtain DMF solution of the organic ligand;
step (2), dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a zinc acetate aqueous solution at 25 ℃, and controlling the dropwise adding time to be 30s to obtain a suspension of a crude product of the MOF material;
and (3) carrying out centrifugal separation on the suspension of the crude MOF material obtained in the step (2), cleaning a precipitate obtained by centrifugal separation by using DMF and methanol respectively, and drying at room temperature to obtain the Zn-BTCMOF MOF material.
Example 8
The MOF material MOF-74Cu was prepared by the following steps:
step (1), dissolving 100mg of copper acetate in 1.5mL of water to obtain a copper acetate aqueous solution, and dissolving 99mg of 2, 5-dihydroxyterephthalic acid in 3mL of N, N-Dimethylformamide (DMF) to obtain a DMF solution of an organic ligand;
step (2), dropwise adding the DMF solution of the organic ligand obtained in the step (1) into a copper acetate aqueous solution at 25 ℃, and controlling the dropwise adding time to be 50s to obtain a suspension of a crude product of the MOF material;
and (3) carrying out centrifugal separation on the suspension of the MOF material crude product obtained in the step (2), cleaning a precipitate obtained by centrifugal separation by using DMF and methanol respectively, and drying at room temperature to obtain the MOF material MOF-74Cu.
The MOF materials obtained in the above examples were characterized by the following test methods:
(1) Crystal structure test
The MOF materials obtained in examples 1 to 8 were each tested for X-ray diffraction patterns using a Rigaku D/MAX-TTRIII (CBO) X-ray diffractometer (XRD), and the respective crystal structures and purities were analyzed with the test parameters: the scanning range is 3-80 degrees, and the scanning speed is 10 degrees/min.
(2) Topography testing
The morphology of the MOF materials obtained in examples 1 to 8 was tested by using a Scanning Electron Microscope (SEM) model S4800 manufactured by Hitachi, inc., respectively, and the test parameters were: the voltage is 6kv and the amplification factor is 30k times.
FIG. 1 shows the MOF material Cu (H) obtained in examples 1 and 2 of the present invention 2 oba) and Zn (H) 2 The photograph of the oba) preparation process, wherein the whole process of generating the MOF material by dripping the organic ligand solution into the aqueous solution of the metal acetate at room temperature can be obviously seen, so that the time for dripping the organic ligand solution is calculated, the generation of the suspension of the MOF material can be obviously seen at about 10s, the generation rate of the MOF material is maximum at 20-30 s, and the suspension of the MOF material is clear to a certain extent after 60s, which indicates that the conditions of partial MOF material dissolution and agglomeration precipitation exist.
FIGS. 2 and 3 show the MOF materials Cu (H) obtained in examples 1 and 2, respectively, of the present invention 2 oba) and Zn (H) 2 The XRD spectrum of oba) shows that the crystallization peak in the XRD spectrum of the MOF material prepared by the method is very clear, and the content of random matters is very small, so that the purity and the crystallization degree of the MOF material prepared by the method are higher.
FIG. 4 is a SEM photograph of the MOF material Cu-BTCMOF obtained in example 6 of the present invention, FIG. 5 is a SEM photograph of the MOF material Zn-BTCMOF obtained in example 7 of the present invention, and FIG. 6 is a SEM photograph of the MOF material MOF-74Cu obtained in example 8 of the present invention, as can be seen from the above-mentioned electron microscope photographs, the MOF material prepared by the method of the present invention has a uniform particle size, a dimension of 1 μm or more, and is suitable for use as a gas adsorption, catalytic and detection material.
In summary, the MOF material can be obtained by simply dripping the organic ligand solution into the metal acetate aqueous solution at room temperature, the method overcomes the technical prejudice that the MOF material needs to be subjected to long-time solvothermal reaction at high temperature in the field, can rapidly prepare the MOF material with complete crystal growth and controllable particle size within 1min, can continuously perform the preparation reaction, is easy to separate products, and has higher potential industrial application value.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (11)
1. A rapid preparation method of a MOF material, characterized in that the preparation method comprises the following steps:
dropping the organic ligand solution into the metal acetate aqueous solution at the temperature of 25-35 ℃ to obtain the MOF material;
the dripping time is controlled to be 20-50 s;
the solute of the organic ligand solution is any one organic ligand of 4,4' -diphenyl ether dicarboxylic acid, terephthalic acid, trimesic acid or 2, 5-dihydroxyterephthalic acid;
the metal acetate is any one or a mixture of at least two of copper acetate, zinc acetate, cadmium acetate, silver acetate or manganese acetate.
2. The method according to claim 1, wherein the time for dropping is controlled to be 20 to 30 seconds.
3. The method of claim 1, wherein the solvent of the organic ligand solution is N, N-dimethylformamide.
4. The method of claim 1, wherein the organic ligand solution is an N, N-dimethylformamide solution of 4,4' -diphenylether dicarboxylic acid;
the metal acetate in the metal acetate aqueous solution is any one of copper acetate, zinc acetate, cadmium acetate, silver acetate or manganese acetate;
the ratio of the amount of the 4,4' -diphenyl ether dicarboxylic acid in the organic ligand solution to the amount of the substance of the metal acetate in the metal acetate aqueous solution is 2-5:1.
5. The method according to claim 4, wherein the ratio of the amount of 4,4' -diphenylether dicarboxylic acid in the organic ligand solution to the amount of the substance of the metal acetate in the metal acetate aqueous solution is 2 to 2.5:1.
6. The method of claim 1, wherein the organic ligand solution is an N, N-dimethylformamide solution of trimesic acid;
the metal acetate in the metal acetate aqueous solution is copper acetate or zinc acetate;
the ratio of the trimesic acid in the organic ligand solution to the metal acetate in the metal acetate aqueous solution is 1.5-3:1.
7. The method according to claim 6, wherein the ratio of the amount of trimesic acid in the organic ligand solution to the amount of the metal acetate in the aqueous metal acetate solution is 1.6-2:1.
8. The method of claim 1, wherein the organic ligand solution is an N, N-dimethylformamide solution of 2, 5-dihydroxyterephthalic acid;
the metal acetate in the metal acetate aqueous solution is copper acetate;
the ratio of the amount of 2, 5-dihydroxyterephthalic acid in the organic ligand solution to the amount of metal acetate in the aqueous metal acetate solution is 1:1.
9. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
step (1), preparing an aqueous solution of metal acetate and an N, N-dimethylformamide solution of an organic ligand respectively;
step (2), dropwise adding the N, N-dimethylformamide solution of the organic ligand obtained in the step (1) into an aqueous solution of metal acetate at the temperature of 25-35 ℃ for 20-50 s to obtain a MOF material crude product;
step (3), performing post-treatment on the MOF material crude product obtained in the step (2) to obtain the MOF material;
the organic ligand is any one of 4,4' -diphenyl ether dicarboxylic acid, terephthalic acid, trimesic acid or 2, 5-dihydroxyterephthalic acid.
10. The method of claim 9, wherein the post-treatment comprises centrifugal precipitation, washing, and drying.
11. The method according to claim 10, wherein the washing is washing the centrifuged precipitate with N, N-dimethylformamide or ethanol.
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