CN113087918B - Zirconium-based metal organic framework material and preparation method and application thereof - Google Patents

Zirconium-based metal organic framework material and preparation method and application thereof Download PDF

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CN113087918B
CN113087918B CN202110253165.XA CN202110253165A CN113087918B CN 113087918 B CN113087918 B CN 113087918B CN 202110253165 A CN202110253165 A CN 202110253165A CN 113087918 B CN113087918 B CN 113087918B
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刘浩
周陈
周俊杰
陈亮
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a zirconium-based metal organic framework material, the molecular formula of which is Zr 6 O 4 (OH) 4 (C 4 H 4 O 4 ) 6 Solvent, zr 6 O 4 (OH) 4 (C 4 H 4 O 4 ) 6 In a solvent, zr 6 O 4 (OH) 4 The connection mode is 12 connection, the zirconium-based metal organic framework material is crystallized in Pn-3 space group, the invention also provides a preparation method and application of the zirconium-based metal organic framework material, the preparation method mainly comprises a microwave-assisted synthesis method, and the zirconium-based metal organic framework material prepared by the invention has better application effect on gas adsorption separation, especially on CO 2 The preparation method has the advantages of high synthesis efficiency, high utilization efficiency of raw materials and high popularization and use values.

Description

Zirconium-based metal organic framework material and preparation method and application thereof
Technical Field
The invention relates to the technical field of metal organic framework materials, in particular to a zirconium-based metal organic framework material and a preparation method thereof.
Background
With the great development of industrial production, fossil fuel consumption is rapidly increasing, and the greenhouse gases generated therewith are emitted in large quantities into the nature. Although CO is a relative to other greenhouse gases 2 Has a weak greenhouse effect, but has the highest content in the atmosphere. Thus, CO 2 Have received great attention from international society. Conventional CO 2 The separation techniques include cryogenic distillation, adsorption and membrane separation, in which an alcohol amine solution is used to absorb CO 2 The technology of (2) is most widely used, but has the disadvantages of high cost and large energy consumption. In contrast, porous solid adsorptive separations have the potential to be energy consuming and economicalAnd (4) the advantages are achieved. Conventional porous solids include zeolites, activated carbon and porous alumina, but these materials have not been widely used due to their simple structure and poor adjustability. In addition, in 2016, olefin and alkane separation has been listed as one of seven chemical separation processes affecting the world in the 2016, and ethylene ethane and propylene propane are the most representative, and due to the extremely similar physicochemical properties and the high separation difficulty, the traditional low-temperature distillation method has high energy consumption and high separation difficulty, so that a new separation technology is required to reduce the cost and solve the problem. In recent years, metal organic framework Materials (MOFs) have been considered as a promising adsorbing material due to their adsorption characteristics and ultra-high specific surface area.
MOF is a coordination polymer with three-dimensional pore structure, which has been rapidly developed in the last decade, generally uses metal ions as connection points, and supports organic ligands to form spatial 3D extension, and is another important new type of porous material besides zeolite and carbon nanotubes. In addition, the MOF structure is diverse and tunable, allowing the introduction of different metal ions and organic ligands to participate in the assembly of coordination polymers. For example, by introducing longer organic ligands, the pore size and specific surface area of MOFs can be altered; the functional group is used for modifying the MOF, so that the adsorption performance of the MOF can be improved; different metal ions can form different coordination structures due to different numbers of electrons outside the core and different ionic radii. Based on these characteristics, MOFs are widely used in various fields such as energy storage, gas adsorption and separation, heterogeneous catalysis, drug delivery, and chemical sensing.
Zr-based MOFs are of great interest due to their excellent thermodynamic and chemical stability and diverse structures. Among them, uiO-66 synthesized by solvothermal synthesis has a stable structure and a high specific surface area, and UiO-66 is reported to have a reference on CO 2 The adsorption capacity of (A) can reach 1.7mmol/g. More recently, zr-fum-fcu-MOF materials with a topology similar to UiO-66 were synthesized by solvothermal methods using fumaric acid as an organic ligand. The material is used for storing water and CO 2 The effects of trapping and olefin-alkane separation are remarkable, and defect formation of crystals can be controlled by adding formic acid as a regulator, so that the method further improvesThe performance of Zr-fum-fcu-MOF is improved. In general, zr-based MOFs are considered candidates for gas separation by their excellent properties.
However, the currently reported Zr-fum-fcu-MOF materials are synthesized directly by a solvothermal method, but the method has long synthesis time and low product synthesis rate, which causes a great amount of energy waste, and currently, the method generally adopts the solvothermal method to prepare the Zr-fum-fcu-MOF, namely, a mixed solution containing a zirconium source and an organic ligand is put into a reaction kettle to react for a certain time at a certain temperature to obtain a reaction product, and then the reaction product is washed, filtered and dried to obtain the Zr-fum-fcu-MOF. However, the solvothermal method requires a long reaction time, generally 24 hours or more, and thus consumes a lot of energy, and the formation rate of a Zr-fum-fcu-MOF powder having a good morphology is low.
Disclosure of Invention
One of the objects of the present invention is to provide a zirconium-based metal organic framework material having a high adsorption performance, which can adsorb a gas and has a high adsorption performance.
In order to solve the above problems, the present invention provides a zirconium-based metal organic framework material having a molecular formula of Zr 6 O 4 (OH) 4 (C 4 H 4 O 4 ) 6 Solvent, zr 6 O 4 (OH) 4 (C 4 H 4 O 4 ) 6 In solvent, zr 6 O 4 (OH) 4 The connection mode of (1) is 12 connection and is crystallized in the Pn-3 space group.
Preferably, the particle size of the zirconium-based metal organic framework material is 0.06-5 μm, the zirconium-based metal organic framework material has a regular octahedral microstructure, and the specific surface area of the zirconium-based metal organic framework material is 600-1300m 2 /g。
The second objective of the present invention is to provide a method for preparing a zirconium-based metal organic framework material, so as to solve the problems that the conventional method for synthesizing a zirconium-based metal organic framework material has a long synthesis time and a low product synthesis rate, which results in a large amount of energy waste.
In order to solve the above problems, the present invention provides a method for preparing the above zirconium-based metal organic framework material, comprising preparing the zirconium-based metal organic framework material by a microwave-assisted synthesis method.
Compared with the prior art, the preparation method of the zirconium-based metal organic framework material has the following advantages: the preparation method has higher yield and reaction efficiency.
Preferably, the microwave-assisted synthesis method comprises the following steps:
1) Reacting ZrOCl 2 ·8H 2 Dissolving O in N, N-Dimethylformamide (DMF), adding fumaric acid (fum), and stirring to obtain a solution A;
2) Adding Formic Acid (FA) into the solution A obtained in the step (1) to prepare a mixed solution, and stirring;
3) Placing the mixed solution obtained in the step (2) in a microwave reactor, and carrying out microwave reaction to obtain a reaction product; and then washing, filtering and drying the reaction product to obtain the Zr-fum-fcu-MOF powder.
Preferably, in the step (1), zrOCl is contained in the solution A 2 ·8H 2 The concentration of O is 0.01-0.60 mol.L -1 (ii) a The concentration of fumaric acid in the solution A is 0.01-0.60 mol.L -1 By reasonably controlling the concentration of the raw materials, the reaction efficiency can be improved and the utilization rate of the raw materials can be ensured.
Preferably, in the step (2), before adding the formic acid, the step of uniformly stirring the solution A in a water bath at 25 ℃ is further included, so that the solution A is fully reacted before adding the formic acid, and the efficiency of the subsequent reaction is further ensured.
Preferably, in the step (2), zrOCl is contained in the mixed solution 2 ·8H 2 The mass ratio of O to formic acid was 1 2 ·8H 2 The proportion of O and formic acid ensures the reaction and improves the utilization rate of raw materials.
Preferably, in the step (3), the reaction temperature is 60-140 ℃, the reaction time is 0.1-6h, and the reaction efficiency can be greatly improved by controlling the temperature and the reaction time.
The preferred scheme of the invention controls the conditions to obtain the high-quality and high-yield zirconium-based metal organic framework material powder by mainly controlling the molar concentration of the synthetic solution, the reaction time and the like, and improves the reaction efficiency and yield by controlling the reaction time and the mass ratio.
The third purpose of the invention is to provide the application of the zirconium-based metal organic framework material: the zirconium-based metal organic framework material is applied to the adsorption separation of treatment gas, especially CO 2 And the application of the adsorption separation of propylene and ethylene gases.
The inventors of the present invention conducted research and study on a method for producing a zirconium-based metal organic framework material (Zr-fum-fcu-MOF), and found that: the reaction time can be greatly shortened by placing the mixed solution containing the zirconium source and the organic ligand in a microwave reactor for reaction, the reaction product can be generated in the shortest 10 minutes, and the prepared Zr-fum-fcu-MOF powder has good regular octahedron shape, so that the synthesis efficiency of the Zr-fum-fcu-MOF is effectively improved, and the energy consumption is reduced. The method adopted in the invention is a microwave-assisted synthesis method.
Compared with the prior art, the invention discovers that the Zr-fum-fcu-MOF powder is to CO 2 Has high selective adsorption performance and can be used for CO 2 In addition, the Zr-fum-fcu-MOF powder synthesized by the invention has higher adsorption selectivity performance on propylene and can also be used for adsorption separation of propylene. In addition, the invention preferably adopts a microwave method to prepare the Zr-fum-fcu-MOF powder, can greatly shorten the reaction time, reduce the energy consumption and save the cost, and prepares the Zr-fum-fcu-MOF powder with good appearance, high repeatability and excellent performance.
Drawings
Fig. 1 is an SEM photograph of octahedral zirconium-based metal organic framework material powders prepared by a microwave method and a solvothermal method according to an embodiment of the present invention.
FIG. 2 is an XRD diagram of powders of zirconium-based metal organic framework materials prepared by microwave method and hydrothermal method according to an embodiment of the present invention.
FIG. 3 is a diagram of gas adsorption performance of zirconium-based metal organic framework powder synthesized by microwave method at 0 deg.C under different pressure conditions in the embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of a zirconium-based metal organic framework material (namely, zr-fum-fcu-MOF powder, the same below), which specifically comprises the following steps:
(1) 0.92g of ZrOCl 2 ·8H 2 Dispersing O in 72ml of DMF (N, N-dimethylformamide), and stirring and configuring to obtain a solution A; then 0.324g of fum (fumaric acid) was added;
(2) And (3) placing the solution A in a water bath at 25 ℃ and stirring uniformly, continuously adding 15.9ml of FA (formic acid), and stirring until the solution is clear to obtain a mixed solution.
(3) And transferring the mixed solution into a microwave reaction kettle, carrying out microwave reaction for 1h at 100 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven at 120 ℃ for 24h to obtain Zr-fum-fcu-MOF powder.
The white powder of Zr-fum-fcu-MOF prepared by the embodiment 1 has SEM pictures as shown in (a) in figure 1, and shows that the powder has uniform particle size which is about 1.0 mu m and regular octahedral appearance, and the Zr powder has the following characteristics 6 O 4 (OH) 4 (C 4 H 4 O 4 ) 6 In solvent, zr 6 O 4 (OH) 4 The connection mode of (1) is 12 connection and is crystallized in the Pn-3 space group.
The XRD pattern of the Zr-fum-fcu-MOF powder prepared in the way is shown as a curve marked by a microwave method in figure 2, and the Zr-fum-fcu-MOF powder is highly crystallized.
Example 2:
(1) 0.92g of ZrOCl 2 ·8H 2 Dispersing O in 72ml DMF to obtain solution A; then 0.324g of fum is added, and the solution A is placed in a water bath condition at 25 ℃ and is stirred evenly;
(2) Placing the solution A in a water bath at 25 ℃, uniformly stirring, continuously adding 10.6ml of FA, and stirring until the solution is clear to obtain a mixed solution;
(3) Same as in step (3) in example 1.
Example 3:
(1) 0.92g of ZrOCl 2 ·8H 2 Dispersing O in 36ml DMF to obtain solution A; then 0.324g of fum is added, and the solution A is placed in a water bath condition at 25 ℃ and is stirred evenly;
(2) Uniformly stirring the solution A in a water bath at 25 ℃, continuously adding 18.6ml of FA, and stirring until the solution is clear to obtain a mixed solution;
(3) Same as in step (3) in example 1.
Example 4:
(1) Same as in step (1) in example 1;
(2) Same as step (2) in example 1;
(3) And transferring the mixed solution into a microwave reaction kettle, carrying out microwave reaction for 1.0h at 120 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven for 24h at 120 ℃ to obtain Zr-fum-fcu-MOF powder.
Example 5:
(1) Same as in step (1) in example 1;
(2) Same as step (2) in example 1;
(3) And transferring the mixed solution into a microwave reaction kettle, carrying out microwave reaction for 2.0h at 140 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven at 120 ℃ for 24h to obtain Zr-fum-fcu-MOF powder.
The Zr-fum-fcu-MOF powder prepared by the embodiment 5 is white, has the grain diameter of about 2.0 mu m, and has a regular octahedral shape.
Example 6:
(1) Same as in step (1) in example 1;
(2) Same as step (2) in example 1;
(3) And transferring the mixed solution into a microwave reaction kettle, carrying out microwave reaction for 0.5h at 100 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven for 24h at 120 ℃ to obtain Zr-fum-fcu-MOF powder.
Example 7:
(1) Same as in step (1) in example 1;
(2) Same as step (2) in example 1;
(3) And transferring the mixed solution into a microwave reaction kettle, carrying out microwave reaction for 2.5h at 100 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven for 24h at 120 ℃ to obtain Zr-fum-fcu-MOF powder.
Example 8:
(1) 9.20g of ZrOCl 2 ·8H 2 O is dispersed in 144ml DMF to obtain solution A; then 3.24g of fum was added;
(2) Adding 31.8ml of FA continuously, stirring until the solution is clear to obtain a mixed solution
(3) And transferring the mixed solution into a microwave reaction kettle, carrying out microwave reaction for 0.2h at 100 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven at 120 ℃ for 24h to obtain Zr-fum-fcu-MOF powder.
The Zr-fum-fcu-MOF powder prepared by the embodiment 8 is white, has the grain diameter of about 0.06 mu m, and has a regular octahedral shape.
Example 9:
(1) 0.92g of ZrOCl 2 ·8H 2 O is dispersed in 144ml DMF to obtain solution A; then 3.24g of fum was added;
(2) Adding 31.8ml of FA continuously, stirring until the solution is clear to obtain a mixed solution
(3) And transferring the mixed solution into a microwave reaction kettle, carrying out microwave reaction for 5h at 140 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven for 24h at 120 ℃ to obtain Zr-fum-fcu-MOF powder.
The Zr-fum-fcu-MOF powder prepared by the embodiment 9 is white, has a particle size of about 5.0 μm, and has a regular octahedral shape.
Experimental example 10:
(1) Same as in step (1) in example 1;
(2) Same as step (2) in example 1;
(3) And transferring the mixed solution into a hydrothermal reaction kettle, carrying out solvothermal reaction for 24h at 100 ℃, taking out a reaction product after the reaction is finished, washing the reaction product for multiple times by using DMF (dimethyl formamide), and drying the washed powder in a drying oven for 24h at 120 ℃ to obtain the powder of Zr-fum-fcu-MOF.
The white powder of Zr-fum-fcu-MOF prepared in example 10, the SEM photograph of which is shown in (b) of FIG. 1, shows that the powder particles have uniform particle size, about 0.2 μm particle size and regular octahedral morphology.
The XRD pattern of the Zr-fum-fcu-MOF powder prepared in example 10 above is shown by the plot labeled "hydrothermal method" in FIG. 2, which shows that the Zr-fum-fcu-MOF powder is highly crystallized.
The embodiment equipment comprises: hitachi S-4800 field emission scanning electron microscope.
Example 11: EXAMPLES adsorption Performance testing of Zr-fum-fcu-MOF powders prepared
The gas adsorption performance test of the Zr-fum-fcu-MOF powder prepared in the examples 1 to 3 is carried out, and the test equipment comprises the following steps: a physical adsorption analyzer model ASAP 2020 available from Micrometrics corporation.
The Zr-fum-fcu-MOF prepared in the embodiments 1 to 3 all show good CO under the conditions of 0 ℃ and different pressures 2 The adsorption performance and the test result are shown in fig. 3, and are specifically as follows:
as shown in FIG. 3, the pair of CO of Zr-fum-fcu-MOF prepared by the microwave method in example 1 2 、CH 4 、N 2 The maximum adsorption amount of (a) is 3.15 mmol/g -1 、0.85mmol·g -1 、0.21mmol·g -1 。
Example 2 preparation of Zr-fum-fcu-MOF by microwave vs. CO 2 、CH 4 、N 2 The maximum adsorption amount of (2) is 3.20 mmol/g -1 、0.86mmol·g -1 、0.18mmol·g -1 。
Zr-fum-fcu-MOF prepared by microwave method in example 3 for CO 2 、CH 4 、N 2 The maximum adsorption amount of (b) is 3.46 mmol/g -1 、0.89mmol·g -1 、0.23mmol·g -1 。
Thus, the Zr-fum-fcu-MOF prepared in examples 1 to 3 can be used for CO 2 Adsorption and separation.
The Zr-fum-fcu-MOFs prepared in examples 1 to 3 all showed good propylene adsorption performance at 25 ℃ under different pressure conditions, which are as follows:
the maximum adsorption amounts of the Zr-fum-fcu-MOF prepared by the microwave method in example 1 to propylene, propane, ethylene and ethane were 3.28mmol g in this order -1 、0.64mmol·g -1 、3.50mmol·g -1 、0.52mmol·g -1 。
In example 2, the maximum adsorption amounts of Zr-fum-fcu-MOF prepared by the microwave method to propylene, propane, ethylene and ethane were 3.21mmol g in this order -1 、0.59mmol·g -1 、3.31mmol·g -1 、0.54mmol·g -1 。
The maximum adsorption amounts of Zr-fum-fcu-MOF prepared by the microwave method in example 3 to propylene, propane, ethylene and ethane were 3.30mmol g in this order -1 、0.64mmol·g -1 、3.55mmol·g -1 、0.50mmol·g -1 。
Therefore, the Zr-fum-fcu-MOF prepared in the examples 1 to 3 can also be used for the adsorption and separation of gases such as propylene, ethylene and the like.
The above examples further demonstrate that the zirconium-based metal organic framework material prepared by the present invention has better adsorption performance on gas, especially on CO 2 Propylene and ethylene, and the preparation method has high synthesis efficiency and excellent energy consumption control.
Example 12: comparing the adsorption capacity of the Zr-fum-fcu-MOF powder to different gases:
the invention provides a calculation formula of an adsorption separation factor:
S ads ＝q 1 p 2 /q 2 p 1
the adsorptive separation factor is determined by the following formula:
wherein S ads To adsorb the separation factor, q 1 As the adsorption amount (mmol. G) of the component 1 -1 )，p 1 Partial pressure (bar), q of component i 2 As the adsorption amount (mmol. G) of the component 2 -1 )，p 2 Partial pressure (bar) of component 2;
through the experiments of the above examples, it follows that: at 1 atmosphere and 0 deg.C for CO 2 The adsorption capacity of the adsorbent can reach 3.46 mmol/g -1 (ii) a The adsorption capacity to propylene is more than 3.30 mmol-g under the conditions of 1 atmosphere and 25 DEG C -1 An adsorption capacity for ethylene of more than 3.55 mmol/g -1 (ii) a And with N 2 By contrast, CO 2 The adsorption separation factor of the gas reaches more than 20; compared with propane, the adsorption separation factor of the zirconium-based metal organic framework material to propylene is more than 5.1; compared with ethane, the adsorption separation factor of the zirconium-based metal organic framework material to ethylene reaches more than 7.1; thus, the Zr-fum-fcu-MOF material can be used for the adsorption separation application of gas, especially CO 2 The gas adsorption separation effect is particularly remarkable.
The technical solutions of the present invention have been described in detail with reference to the above embodiments, it should be understood that the above embodiments are only specific examples of the present invention and should not be construed as limiting the present invention, and any modifications, additions or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.

Claims (2)

1. A method for preparing a zirconium-based metal organic framework material, characterized in that: preparing the zirconium-based metal organic framework material by adopting a microwave-assisted synthesis method;
of said zirconium-based metal-organic framework materialMolecular formula of Zr6O 4 (OH) 4 (C 4 H 4 O 4 ) 6 Solvent, said Zr 6 O 4 (OH) 4 (C 4 H 4 O 4 ) 6 In a solvent, zr 6 O 4 (OH) 4 The connection mode of (2) is 12 connection, and the crystals are crystallized in a Pn-3 space group; the particle size of the zirconium-based metal organic framework material is 0.06-5 mu m, the zirconium-based metal organic framework material is in an octahedral microstructure, and the specific surface area is 600-1300m & lt 2 & gt/g;
the microwave-assisted synthesis method comprises the following steps:
1) ZrOCl 2 ·8H 2 Dissolving O in N, N-dimethylformamide, adding fumaric acid, and stirring to obtain a solution A;
2) Adding formic acid into the solution A obtained in the step (1), preparing a mixed solution, and stirring;
3) Placing the mixed solution obtained in the step 2) in a microwave reactor, and carrying out microwave reaction to obtain a reaction product; then washing, filtering and drying the reaction product to obtain zirconium-based metal organic framework material powder;
in the step 1), zrOCl in the solution A 2 ·8H 2 The concentration of O is 0.01-0.60 mol.L < -1 >; the concentration of fumaric acid in the solution A is 0.01-0.60 mol.L -1 ；
In the step 2), before adding formic acid, the method also comprises the step of uniformly stirring the solution A in a water bath at 25 ℃;
in the step 2), zrOCl is contained in the mixed solution 2 ·8H 2 The mass ratio of O to formic acid is 1;
in the step 3), the reaction temperature is 60-140 ℃ and the reaction time is 0.1-6h.
2. Use of a zirconium-based metal organic framework material prepared by the method of claim 1, wherein: comprising the application of the zirconium-based metal organic framework material in the adsorptive separation of process gases, including CO 2 And adsorption separation of propylene and ethylene gases.
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