CN113042104B - MOF (metal organic framework) massive porous material as well as preparation method and application thereof - Google Patents
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Abstract
The invention provides an MOF (metal organic framework) bulk porous material as well as a preparation method and application thereof, belonging to the technical field of porous material preparation. According to the invention, an aqueous solution containing dimethylimidazole, zinc nitrate hexahydrate monomers and pre-prepared ZIF-8 nanoparticles is used as an aqueous phase, cyclohexane is used as an oil phase, the MOF bulk porous material is prepared by an emulsion template method, during the shearing emulsification process, the pre-prepared ZIF-8 nanoparticles are used as Pickering particles to stabilize the emulsion, and the ZIF-8 newly coordinated with dimethylimidazole and zinc nitrate hexahydrate in the aqueous phase is used as a support material of a porous material frame, no additional polymerizable monomer and surfactant are required to be added, only ZIF-8 exists in the prepared MOF bulk porous material, and the influence of a support or an adhesive (polymer) used in the existing preparation method on the MOF performance is effectively avoided.
Description
Technical Field
The invention relates to the technical field of porous material preparation, in particular to an MOF (metal organic framework) bulk porous material and a preparation method and application thereof.
Background
Metal Organic Frameworks (MOFs) are crystalline materials composed of metal ions or clusters linked by organic ligands. As the MOFs can be composed of different metal ions/clusters and different organic association structures, a specific MOF compound can be formed through reasonable molecular design, so that the MOFs has the characteristics of high surface area, large pore volume and the like. Accordingly, MOFs have received much attention in the fields of adsorption, separation, catalysis, and sensors. At present, the preparation methods of MOFs include traditional solution methods, hydrothermal methods, liquid diffusion methods, solid methods and the like. A wide variety of MOF particles have been designed and synthesized for target applications, but processing MOF particles into different ordered shapes and special morphologies for commercial applications remains a challenge.
Among them, monolithic MOF materials having three-dimensional structures are one of the important approaches for realizing practical MOF applications. The Pickering high internal phase emulsion template technology has been widely reported as an effective method for constructing three-dimensional monomers, and has been proven to have the performances of catalytic support, ion recovery, water/oil separation and the like. Emulsion templating techniques are typically high internal phase emulsions (dispersed phase volume ≧ 74.05% by volume based on the total volume of the emulsion) prepared by polymerizing a continuous phase containing the monomer. The Pickering high internal phase emulsion is a surfactant-free emulsion, is stabilized by amphiphilic nanoparticles, and is gradually applied to the preparation of porous materials, which can fix a nanoparticle stabilizer on the surface of pores, so that the porous materials are endowed with the properties of the nanoparticles. Recently, various organic and inorganic nanoparticles including MOFs have been used to stabilize high internal phase emulsions and to obtain a porous material prepared by Pickering high internal phase emulsion template by polymerizing monomers in a continuous phase (polymer obtained by polymerizing monomers as a support frame for the porous material). However, in practical applications, the presence of the polymer formed by the polymerization of the monomer may hinder the contact of the MOFs with the reaction substrate, thereby greatly reducing the catalytic efficiency thereof. Even in some cases, MOFs are only used as nanoparticles to stabilize emulsions or as fillers in porous polymers, severely limiting the value of MOF materials in applications.
Disclosure of Invention
The invention aims to provide an MOF (metal organic framework) bulk porous material, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an MOF (metal organic framework) bulk porous material, which comprises the following steps:
mixing 2-methylimidazole, zinc nitrate hexahydrate, ZIF-8 nanoparticles and water to obtain a water phase;
taking straight-chain alkane as an oil phase, dropwise adding the oil phase into a stirred water phase, and shearing and emulsifying the obtained mixture to form a high internal phase emulsion;
and freeze-drying the high internal phase emulsion to obtain the MOF bulk porous material.
Preferably, the preparation method of the ZIF-8 nanoparticles comprises the following steps: mixing 2-methylimidazole, nitric acid hexahydrate and water, and carrying out coordination polymerization to obtain the ZIF-8 nano particles.
Preferably, when the ZIF-8 nanoparticles are prepared, the molar ratio of the zinc nitrate hexahydrate to the 2-methylimidazole is 1 (50-70).
Preferably, the coordination polymerization is carried out under the condition of stirring, the rotating speed of the stirring is 500-900 rmp, and the reaction time is 12-24 h.
Preferably, when the aqueous phase is prepared, the concentration of the ZIF-8 nanoparticles in the aqueous phase is 0.01-0.25 g/mL, and the concentration of the 2-methylimidazole in the aqueous phase is 0.1-1.0 g/mL; the concentration of the zinc nitrate hexahydrate in the water phase is 0.027-0.074 g/mL.
Preferably, the straight-chain alkane comprises cyclohexane, n-hexane, n-heptane, decane or tetradecane; the volume ratio of the water phase to the oil phase is 1: 3-3: 20.
Preferably, the rotating speed of the stirred water phase is 600-1000 rmp.
Preferably, the rotating speed of the shearing emulsification is 12000-16000 mp, and the time of the shearing emulsification is 30-90 s.
The invention provides the MOF bulk porous material prepared by the preparation method in the technical scheme.
The invention provides an application of the MOF bulk porous material in the technical scheme in an oil absorption material.
The invention provides a preparation method of an MOF (metal organic framework) bulk porous material, which comprises the following steps: mixing 2-methylimidazole, zinc nitrate hexahydrate, ZIF-8 nanoparticles and water to obtain a water phase; taking straight-chain alkane as an oil phase, dropwise adding the oil phase into a stirred water phase, and shearing and emulsifying the obtained mixture to form a high internal phase emulsion; and freeze-drying the high internal phase emulsion to obtain the MOF bulk porous material. According to the invention, an aqueous solution containing dimethylimidazole, zinc nitrate hexahydrate monomers and pre-prepared ZIF-8 nanoparticles is used as an aqueous phase, cyclohexane is used as an oil phase, the MOF bulk porous material is prepared by an emulsion template method, during the shearing emulsification process, the pre-prepared ZIF-8 nanoparticles are used as Pickering particles to stabilize the emulsion, and the ZIF-8 newly coordinated with dimethylimidazole and zinc nitrate hexahydrate in the aqueous phase is used as a support material of a porous material frame, no additional polymerizable monomer and surfactant are required to be added, only ZIF-8 exists in the prepared MOF bulk porous material, and the influence of a support or an adhesive (polymer) used in the existing preparation method on the MOF performance is effectively avoided.
The preparation method is simple in preparation process and environment-friendly, and the prepared MOF bulk porous material is a three-dimensional bulk material and can fully exert the application value of the MOF material.
The MOF bulk porous material prepared by the invention only contains ZIF-8 and has an open pore structure, and due to the hydrophobicity and lipophilicity of the ZIF-8 and the highly intercommunicated pore structure of the porous material, the MOF bulk porous material has excellent oil absorption and catalytic properties. The results of the examples show that the MOF bulk porous materials prepared by the present invention have high water oil separation efficiency and high catalytic efficiency.
Drawings
FIG. 1 is an SEM image of a MOF bulk porous material prepared in example 1;
FIG. 2 is an SEM image of a MOF bulk porous material prepared in example 2;
FIG. 3 is an SEM image of a MOF bulk porous material prepared in example 3;
FIG. 4 is a chromatogram of the product of the MOF bulk porous material prepared in example 2 after catalyzing benzaldehyde reaction.
Detailed Description
The invention provides a preparation method of an MOF (metal organic framework) bulk porous material, which comprises the following steps:
mixing 2-methylimidazole, zinc nitrate hexahydrate, ZIF-8 nanoparticles and water to obtain a water phase;
taking straight-chain alkane as an oil phase, dropwise adding the oil phase into a stirred water phase, and shearing and emulsifying the obtained mixture to form a high internal phase emulsion;
and freeze-drying the high internal phase emulsion to obtain the MOF bulk porous material.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
According to the invention, 2-methylimidazole, zinc nitrate hexahydrate, ZIF-8 nanoparticles and water are mixed to obtain a water phase. In the present invention, the preparation method of the ZIF-8 nanoparticles preferably includes the steps of: mixing 2-methylimidazole, nitric acid hexahydrate and water, and carrying out coordination polymerization to obtain the ZIF-8 nano particles.
In the invention, when the ZIF-8 nanoparticles are prepared, the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole is preferably 1 (50-70), and more preferably 1 (55-65). In the invention, the total mass concentration of the zinc nitrate hexahydrate and the 2-methylimidazole in water is preferably 0.1-0.3 g/mL, more preferably 0.13-0.25 g/mL, and even more preferably 0.15-0.2 g/mL.
In the present invention, the mixing of 2-methylimidazole, nitric acid hexahydrate and water is preferably performed by dissolving 2-methylimidazole in water to obtain a 2-methylimidazole solution, dissolving zinc nitrate hexahydrate in water to obtain a zinc nitrate aqueous solution, and adding the zinc nitrate aqueous solution dropwise to the 2-methylimidazole solution to perform coordination polymerization. The dropping rate is not particularly limited in the present invention, and the dropping may be carried out according to a procedure well known in the art.
In the invention, the coordination polymerization is preferably carried out under the condition of stirring at room temperature, the rotation speed of the stirring is preferably 500-900 rmp, more preferably 600-800 rpm, and the reaction time is preferably 12-24 h, more preferably 15-20 h.
After the coordination polymerization is completed, the invention preferably carries out centrifugation, washing and filtration on the obtained mixed material in sequence to obtain the ZIF-8 nano particles. In the invention, the rotation speed of the centrifugation is preferably 10000rmp, and the time is preferably 5 min; the washing reagent is preferably deionized water, and the number of washing is preferably three. The filtration process is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The process for mixing the 2-methylimidazole, the zinc nitrate hexahydrate, the ZIF-8 nanoparticles and the water is not particularly limited, and the materials can be uniformly mixed according to the process well known in the art.
In the invention, the concentration of the ZIF-8 nanoparticles in an aqueous phase is preferably 0.01-0.25 g/mL, more preferably 0.03-0.2 g/mL, and further preferably 0.1-0.15 g/mL; the concentration of the 2-methylimidazole in the water phase is preferably 0.1-1.0 g/mL, and more preferably 0.615 g/mL; the concentration of the zinc nitrate hexahydrate in the water phase is preferably 0.027-0.074 g/mL, more preferably 0.03-0.07 g/mL, and even more preferably 0.065 g/mL.
After the water phase is obtained, the invention takes the straight-chain alkane as the oil phase, the oil phase is dripped into the stirred water phase, and the obtained mixture is sheared and emulsified to form the high internal phase emulsion. In the present invention, the linear alkane preferably includes cyclohexane, n-hexane, n-heptane, decane or tetradecane; the volume ratio of the water phase to the oil phase is preferably 1: 3-3: 20, and more preferably 0.2: 1. The dropping rate is not particularly limited in the present invention, and may be carried out according to a procedure well known in the art.
In the invention, the rotation speed of the stirred water phase is preferably 600 to 1000rmp, and more preferably 700 to 900 rmp.
In the invention, the rotation speed of the shearing emulsification is preferably 12000-16000 mp, more preferably 13000-15000 mp, and the time of the shearing emulsification is preferably 30-90 s, more preferably 50-80 s. In the present invention, the shear emulsification is preferably carried out on an Ultra Turrax T18 shear emulsifier.
In the shearing emulsification process, the ZIF-8 nano particles are used for stabilizing the high internal phase emulsion, meanwhile, the ZIF-8 nano particles are used as a template polymer material for a water phase (namely an external phase or a continuous phase) of the high internal phase emulsion, and the ZIF-8 nano particles with the porous structure are prepared in situ in the continuous phase without introducing other substances.
After the high internal phase emulsion is formed, the high internal phase emulsion is freeze-dried to obtain the MOF bulk porous material. The particular process of freeze-drying is not particularly limited in the present invention, and the resulting high internal phase emulsion is freeze-dried to remove the internal phase (i.e., oil phase) according to procedures well known in the art. According to the invention, a porous structure ZIF formed in the high internal phase emulsion is fixed by freeze drying.
The invention adopts an emulsion template method, takes ZIF-8 nano particles, monomer 2-methylimidazole and zinc nitrate hexahydrate aqueous solution as aqueous phases together, utilizes the ZIF-8 nano particles to stabilize high internal phase emulsion, prepares the ZIF-8 nano particles in situ in a continuous phase, utilizes hydrogen bonding force existing between the synthesized ZIF-8 nano particles to play a role of 'bonding' the ZIF-8 particles so as to form a framework material supporting integral structure, thereby leading the ZIF-8 nano particles to be used as the continuous phase and synthesizing stable high internal phase emulsion under the condition of not adding any surfactant and polymerizable monomer, and fixing the ZIF-8 nano particles on an oil-water interface of the emulsion, and effectively avoiding the influence of a bracket or an adhesive (such as a polymer) on MOFs performance.
The invention provides the MOF bulk porous material prepared by the preparation method in the technical scheme. The MOF bulk porous material prepared by the invention has a porous structure and a three-dimensional bulk structure, and the pore size and the density of the MOF bulk porous material can be regulated and controlled by adjusting the volume ratio of a dispersed phase (oil phase) to a continuous phase (water phase) and the concentration of ZIF particles in the continuous phase. In the invention, the aperture of the MOF bulk porous material is 30-100 μm.
The invention provides an application of the MOF bulk porous material in the technical scheme in an oil absorption material. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the 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
Dissolving 18.47g (0.22mol) of 2-methylimidazole in 135mL of deionized water to obtain a 2-methylimidazole solution, dissolving 1.116g (0.00375mol) of zinc nitrate hexahydrate in 15mL of deionized water to obtain a zinc nitrate solution, dripping the zinc nitrate solution into the 2-methylimidazole solution at room temperature, stirring for 24 hours at 600rmp, centrifuging the obtained mixed material for 5 minutes at 10,000rmp, filtering, and washing with deionized water for three times to obtain ZIF-8 nanoparticles;
adding 1.23g of 2-methylimidazole, 0.0744g of zinc nitrate hexahydrate and 0.132g of ZIF-8 nanoparticles into 2mL of deionized water to serve as a water phase; 12mL of cyclohexane was used as the oil phase; dropwise adding the oil phase into a 900rmp stirred water phase, uniformly mixing, and emulsifying the obtained mixed liquid for 60s at 12000rmp by using an Ultra Turrax T18 shearing emulsifying instrument to obtain a high internal phase emulsion; and freeze-drying the high internal phase emulsion to obtain the MOF bulk porous material.
Example 2
ZIF-8 nanoparticles prepared in example 1 were used;
adding 1.23g of 2-methylimidazole, 0.0744g of zinc nitrate hexahydrate and 0.264g of ZIF-8 nanoparticles into 2mL of deionized water to serve as a water phase; 12mL of cyclohexane was used as the oil phase; dropwise adding the oil phase into a 900rmp stirred water phase, uniformly mixing, and emulsifying the obtained mixed liquid for 60s at 12000rmp by using an Ultra Turrax T18 shearing emulsifying instrument to obtain a high internal phase emulsion; and freeze-drying the high internal phase emulsion to obtain the MOF bulk porous material.
Example 3
ZIF-8 nanoparticles prepared in example 1 were used;
1.23g of 2-methylimidazole, 0.0744g of zinc nitrate hexahydrate and 0.397g of ZIF-8 nanoparticles were added to 2mL of deionized water as an aqueous phase; 12mL of cyclohexane was used as the oil phase; dropwise adding the oil phase into a 900rmp stirred water phase, uniformly mixing, and emulsifying the obtained mixed liquid for 60s at 12000rmp by using an Ultra Turrax T18 shearing emulsifying instrument to obtain a high internal phase emulsion; and freeze-drying the high internal phase emulsion to obtain the MOF bulk porous material.
Performance testing and characterization
1) SEM tests of the MOF bulk porous materials prepared in the examples 1 to 3 are respectively shown in the figures 1 to 3, and the results of the SEM tests show that the pore diameter of the bulk porous material obtained in the example 1 is 50 to 100 micrometers; the aperture of the blocky porous material prepared in the embodiment 2 is 30-70 mu m; the pore diameter of the bulk porous material prepared in example 3 is 10 to 50 μm.
2) Hexadecane, n-heptane, n-hexane and toluene are used as oil to be adsorbed, the oil absorption capacity of the ZIF-8 blocky porous material prepared in the embodiment 1-3 is measured, 1g of the ZIF-8 blocky porous material is respectively placed in the oil to be adsorbed, and the mass of the ZIF-8 blocky porous material is weighed after adsorption saturation.
The relative absorption capacity (Q) of the ZIF-8 bulk porous material was calculated using equation (1)t)：
Wherein, WinitialAnd WwetRespectively the mass of the initial ZIF-8 bulk porous material and the mass of the oil-absorbed ZIF-8 bulk porous material.
TABLE 1 relative capacity of absorption of different oils by MOF bulk porous materials prepared in examples 1-3
| Case(s) | Hexadecane (g/g) | N-heptane (g/g) | N-hexane (g/g) | Toluene (g/g) |
| Example 1 | 10.84 | 10.08 | 8.43 | 7.66 |
| Example 2 | 8.85 | 8.35 | 7.10 | 7.00 |
| Example 3 | 8.34 | 7.68 | 6.48 | 6.81 |
As can be seen from Table 1, the MOF bulk porous materials prepared in examples 1 to 3 have excellent oil-absorbing effect,
3) the oil absorption rate of the ZIF-8 bulk material prepared in example 2 was measured using hexadecane as an example, the weight of the ZIF-8 bulk material was measured at intervals, and the relative absorption capacity was calculated until saturation was reached, and the specific time and results are shown in table 2.
TABLE 2 MOF bulk porous materials prepared in example 2 have hexadecane uptake capacity at various times
| Time(s) | 0 | 5 | 15 | 30 | 60 | 90 | 300 | 900 |
| Adsorption capacity (g/g) | 0 | 6.81 | 7.03 | 7.05 | 7.09 | 7.12 | 7.08 | 7.12 |
As can be seen from Table 2, the ZIF-8 has a very fast oil absorption rate, and can reach an absorption equilibrium value, i.e., a maximum saturated adsorption amount, within 5 seconds, and the absorption equilibrium time is significantly shorter than that of the conventional high oil absorption material (usually tens of seconds to hours).
3) Placing the ZIF-8 bulk porous material prepared in example 2 in a chromatography column having an inner diameter of 1.6 cm and a length of 15 cm to obtain a ZIF-8 chromatography column, dissolving a mixture of 0.2mL of benzaldehyde and 0.25g of malononitrile in 5mL of toluene, dropping the obtained mixed solution into the ZIF-8 chromatography column and allowing the mixed solution to flow through the ZIF-8 chromatography column within 130s under the drive of gravity, and detecting the concentration of benzaldehyde by gas chromatography-mass spectrometry (GC-MS, Agilent 7890A-5975C, americica) to obtain a product, wherein the result is shown in fig. 4; as can be seen from FIG. 4, the presence of benzaldehyde in the product cannot be detected, and the reaction is proved to be complete, which indicates that the ZIF-8 chromatographic column shows higher activity in the Knoevenagel reaction, and the MOF bulk porous material prepared by the method has high catalytic efficiency.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of MOF bulk porous material is characterized by comprising the following steps:
mixing 2-methylimidazole, zinc nitrate hexahydrate, ZIF-8 nanoparticles and water to obtain a water phase;
taking straight-chain alkane as an oil phase, dropwise adding the oil phase into a stirred water phase, and shearing and emulsifying the obtained mixture to form a high internal phase emulsion;
and freeze-drying the high internal phase emulsion to obtain the MOF bulk porous material.
2. The method of manufacturing of claim 1, wherein the ZIF-8 nanoparticles are manufactured by a method comprising the steps of: mixing 2-methylimidazole, zinc nitrate hexahydrate and water, and carrying out coordination polymerization to obtain the ZIF-8 nano particles.
3. The method according to claim 2, wherein the molar ratio of zinc nitrate hexahydrate to 2-methylimidazole in the preparation of the ZIF-8 nanoparticles is 1 (50-70).
4. The method according to claim 2, wherein the coordination polymerization is carried out under stirring conditions, wherein the stirring speed is 500 to 900rmp, and the reaction time is 12 to 24 hours.
5. The method according to claim 1, wherein the concentration of the ZIF-8 nanoparticles in the aqueous phase is 0.01 to 0.25g/mL, and the concentration of the 2-methylimidazole in the aqueous phase is 0.1 to 1.0 g/mL; the concentration of the zinc nitrate hexahydrate in the water phase is 0.027-0.074 g/mL.
6. The production method according to claim 1, wherein the linear alkane includes n-hexane, n-heptane, decane, or tetradecane; the volume ratio of the water phase to the oil phase is 1: 3-3: 20.
7. The method according to claim 1, wherein the rotation speed of the stirred aqueous phase is 600 to 1000 rmp.
8. The method according to claim 1, wherein the rotation speed of the shear emulsification is 12000-16000 mp, and the time of the shear emulsification is 30-90 s.
9. A MOF bulk porous material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the MOF bulk porous material of claim 9 in an oil absorbing material.
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