CN115960368A - MOF-based porous liquid and preparation method thereof - Google Patents
MOF-based porous liquid and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 14
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 45
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- KAVKNHPXAMTURG-UHFFFAOYSA-N n-(4-bromonaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C(Br)C2=C1 KAVKNHPXAMTURG-UHFFFAOYSA-N 0.000 description 1
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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Abstract
An MOF-based porous liquid and a preparation method thereof, wherein the MOF-based porous liquid mainly comprises 50-90% of ionic liquid and 50-10% of UIO-66-NH by mass percent 2 Preparing nano particles; the specific process is as follows: the UIO-66-NH is prepared by dissolving zirconium tetrachloride, 2-amino terephthalic acid and acetic acid in N, N-dimethylformamide, adding water to react under heating, centrifugally washing and purifying, and drying in vacuum 2 Nanoparticles using UIO-66-NH 2 Preparation of UIO-66-NH nanoparticles 2 Acetone solution; using UIO-66-NH 2 Acetone solution and ionic liquid [ HEMM][DCA]Preparing an acetone solution of UIO-66-PL, and preparing MOF-based porous liquid by using the acetone solution of UIO-66-PL; the invention is realized by mixing porous material UIO-66-NH 2 The particles being solid phase, ionic liquid [ HEMIM][DCA]As a mobile phase, the flow is maintained by maintaining the mobile phase at a similar hydrophilicity to the solidThe surface charges of the dynamic phase and the solid phase are different, so that good interface compatibility can be realized, and a stable core-shell structure can be constructed, therefore, the method has the characteristics of high stability, good dispersibility, strong universality and simple and convenient operation.
Description
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to an MOF-based porous liquid and a preparation method thereof.
Background
Porous liquids refer to a class of liquids with permanent porosity that combines the porosity of a porous solid material with the fluidity of the liquid. Such porous liquid itself is in a fluid state at normal temperature, and the unit molecules inside have a stable, permanent, shape-fixed cavity structure. At present, the types of porous liquids are mainly divided into three types, wherein type I porous liquid is a liquid with fluidity composed of single pore molecules, type II porous liquid is composed of organic pores with molecular scale dissolved in steric hindrance solvent, and type III porous liquid is composed of microporous materials dispersed in steric hindrance solvent, such as MOF, COF, etc.
The research of porous liquid is at the beginning stage at present, and the preparation and application of the porous liquid are at the early exploration stage at present. However, the existing abundant porous materials, including Covalent Organic Frameworks (COFs), zeolites, metal Organic Frameworks (MOFs), metal Organic Polyhedra (MOP), etc., in addition to various steric hindrance solvents (such as various types of ionic liquids), provide more possibilities for designing new porous liquids.
At present, the preparation process of the porous liquid mainly focuses on realizing fluidity by grafting organic molecular chains on the surface of a porous solid material, for example, firstly grafting a silane coupling agent KH560 in the middle layer on the surface of UIO-66-OH, then connecting oligomer M2070 through epoxy ring opening to obtain the porous liquid of UIO-66-liquid-M2070, or endowing MOF special functional groups through a certain method to provide binding sites for polymer chains to realize fluidity, for example, ZIF-8 is endowed with amino ligands through a physical stirring method, and then the amino ligands are grafted on the surface of ZIF-8 through ring opening reaction with epoxy-terminated PDMS, and the preparation method has the problems of complex operation process, low porous ratio, unsuitability for large-scale synthetic production and the like.
The name is 'a hyperbranched polyethylene-based porous liquid and a preparation method thereof', and the publication number is
The invention patent application of 'CN 113462051A' discloses hyperbranched polyvinyl porous liquid and a preparation method thereof, the hyperbranched polyvinyl porous liquid is prepared from hyperbranched polyethylene and a metal organic framework material, specifically, the hyperbranched polyethylene which is prepared by taking ethylene as a polymerization monomer, using an alpha-diimine nickel catalyst and a sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate NaBARF cocatalyst and using a coordination polymerization method to obtain low molecular weight, high branching degree and good fluidity is used as a steric hindrance solvent, a two-dimensional lamellar metal organic framework material prepared by mixing zirconium tetrachloride, ferrocene dicarboxylic acid and organic acid is used as a cavity carrier, and the porous liquid material is prepared by fully mixing tetrahydrofuran solvent.
The Zr-Fc MOF-2/6/10 metal organic framework material which is prepared by regulating and controlling alkyl acids (acetic acid, caproic acid and capric acid) with different chain lengths and has a two-dimensional nano lamellar structure is dispersed in hyperbranched polyethylene with low molecular weight to prepare a novel third type of porous liquid material, the gas adsorption and desorption or storage performance of the porous liquid material is verified by the adsorption and desorption process of gases such as nitrogen, methane, carbon dioxide and the like, and the mixed matrix membrane is prepared by utilizing the porous liquid material to explore the potential application of the porous liquid material in the field of gas separation, so that the Zr-Fc MOF-2/6/10 metal organic framework material has the defects of poor stability, poor dispersibility, small application range and complex operation.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide an MOF-based porous liquid and a preparation method thereof, and UIO-66-NH is prepared 2 Nanoparticles as solid phase, ionic liquids [ HEMIs][DCA]As the mobile phase of the steric hindrance solvent, the good interface compatibility can be realized and a stable core-shell structure can be constructed by keeping the similar hydrophilicity of the mobile phase and the solid phase and keeping the different surface charges of the mobile phase and the solid phase, and the steric hindrance solvent has the characteristics of high stability, good dispersibility, strong universality and simple and convenient operation.
In order to achieve the purpose, the invention adopts the technical scheme that:
the MOF-based porous liquid comprises, by mass, 50-90% of an ionic liquid as a mobile phase and 50-10% of UIO-66-NH as a stationary phase 2 And (3) nanoparticles.
The UIO-66-NH 2 The surface of the nano particles is negatively charged, the surface of the ionic liquid is positively charged, and the selected ionic liquid molecules are organicIons.
The UIO-66-NH 2 The nano-particles comprise, by mass, 0.8% -1.2% of zirconium tetrachloride, 0.7% -0.9% of 2-amino terephthalic acid, 27.8% -30.9% of acetic acid, 62.4% -66.6% of N, N-dimethylformamide and 4.7% -5.2% of water.
The cation of the ionic liquid of the mobile phase is an oxygen-containing group which contains a side chain group and can improve the hydrogen bond with water molecules, and the anion of the ionic liquid is one of hydrophilic ionic liquids.
The ionic liquid of the mobile phase is super hydrophilic [ HEMIM][DCA]The stationary phase is hydrophilic UIO-66-NH 2 And (3) nanoparticles.
A method of making a MOF-based porous liquid comprising the steps of:
the method comprises the following steps: according to the mass percentage, 0.8 to 1.2 percent of zirconium tetrachloride, 0.7 to 0.9 percent of 2-amino terephthalic acid and 27.8 to 30.9 percent of acetic acid are dissolved in 62.4 to 66.6 percent of N, N-dimethylformamide, then 4.7 to 5.2 percent of water is added, the mixture is stirred and reacted for 15 to 30min at the temperature of 120 to 150 ℃ in an oil bath, and the mixture is cooled to the room temperature to obtain UIO-66-NH 2 Respectively centrifuging the precursor yellowish solution with ethanol and acetone at 8000-12000rpm for 5-15min, repeatedly centrifuging and washing, collecting the lower layer precipitate, and vacuum drying at 40-60 deg.C for 12-48h to obtain activated yellowish UIO-66-NH 2 A nanoparticle;
step two: subjecting the yellowish UIO-66-NH obtained in step one 2 Dispersing the nanoparticles in acetone solution, UIO-66-NH 2 The mass ratio of the nano particles to the acetone is 1 2 Acetone solution of nanoparticles;
step three: mixing ionic liquid [ HEMIM][DCA]Dropwise adding the UIO-66-NH obtained in the second step 2 In acetone solution of nanoparticles, UIO-66-NH 2 Nanoparticles and ionic liquids [ HEMI][DCA]The mass ratio of 1:1-10, and magnetically mixing and stirring for 5-12h at 20-35 ℃ to obtain an acetone solution of UIO-66-PL;
step four: and (3) stirring and drying the acetone solution of the UIO-66-PL obtained in the third step on a hot plate with the rotating speed of 100-400rpm at the temperature of 30-60 ℃ until the solvent acetone in the solution is completely volatilized, and performing vacuum drying at the temperature of 30-60 ℃ for 12-48h to obtain the MOF-based porous liquid.
UIO-66-NH obtained in the first step 2 The nanoparticles have a particle size of 40-100nm, preferably 50-70nm.
Compared with the prior art, the invention has the beneficial effects that:
1. because of the ionic liquid [ HEMIM ] selected in the invention][DCA]Having super-hydrophilicity, in contact with hydrophilic UIO-66-NH 2 After the nano particles are mixed and stirred, the UIO-66-NH can be ensured 2 The interface compatibility between the nano particles and the ionic liquid and stable dispersion.
2.UIO-66-NH 2 The nanoparticles and the ionic liquid surface are charged oppositely, and the interaction force between the nanoparticles and the ionic liquid surface can enhance the solvation effect, so that the stability of the MOF-based porous liquid system is enhanced.
3. Due to the use of UIO-66-NH 2 Unsaturated metal sites on nanoparticle surfaces with ionic liquids [ HEMIM][DCA]The coordination of the anions and cations is realized, and the solvation effect is enhanced, so that the MOF-based porous liquid with high stability can be obtained.
4. By means of coordination chemistry, selected ionic liquids with cations and anions having large coordination site size are reacted with UIO-66-NH 2 The coordination of the reaction sites on the surface of the nano-particles enhances the solvation effect, so that the porous UIO-66-NH 2 The nanoparticles are stably dispersed in the ionic liquid [ HEMIM][DCA]In ensuring UIO-66-NH 2 The fluidity of the nano particles is endowed on the basis of the porosity of the nano particles.
5. Due to UIO-66-NH 2 The surface of the nano-particles is coated with hydrophilic ionic liquid [ HEMIM][DCA]Thus, MOF-based porous liquids can be stably dispersed in water.
Drawings
FIG. 1 is a schematic illustration of a MOF-based porous liquid preparation process of the present invention;
FIG. 2 is a diagram of UIO-66-NH used in the present invention 2 A schematic of the structure of the nanoparticle;
FIG. 3 is a schematic diagram of the structure of the ionic liquid [ HEMI ] [ DCA ] used in the present invention;
FIG. 4 is a schematic diagram of the structure of an MOF-based porous liquid of the present invention;
FIG. 5 shows an ionic liquid [ HEMIM ] according to the present invention][DCA],UIO-66-NH 2 XRD contrast of nanoparticles to UIO-66-PL;
FIG. 6 shows the UIO-66-NH of the present invention 2 SEM (left a) and TEM (left c) of nanoparticles and SEM (right b) and TEM (right d) of UIO-66-PL;
FIG. 7 shows UIO-66-NH of the present invention 2 BET plot of nanoparticles;
FIG. 8 shows UIO-66-NH of the present invention 2 The pore size distribution diagram and the molecular simulation diagram of the nano particles;
FIG. 9 shows an ionic liquid [ HEMI ] of the present invention][DCA],UIO-66-NH 2 Fourier comparison of the IR spectra of the nanoparticles with UIO-66-PL;
FIG. 10 is a DSC of [ HEMIM ] [ DCA ] versus UIO-66-PL in accordance with the present invention;
FIG. 11 is a TGA comparison of [ HEMIM ] [ DCA ] with UIO-66-PL of the present invention;
FIG. 12 is [ HEMIM ] of the present invention][DCA]、UIO-66-NH 2 Water contact angle contrast plots of nanoparticles and UIO-66-PL;
FIG. 13 is a diagram of UIO-66-NH in the present invention 2 A comparison graph of the nanoparticles and UIO-66-PL before and after being dispersed in water and left standing for 24 h;
FIG. 14 shows UIO-66-NH in the present invention 2 A comparison graph of the nanoparticles and UIO-66-PL before and after being dispersed in acetone and standing for 5 min;
FIG. 15 is a pictorial view of UIO-66-PL of the present invention;
FIG. 16 shows [ HEMI ] of the present invention][DCA]、UIO-66-NH 2 ZETA potential map of nanoparticles and UIO-66-PL;
FIG. 17 shows [ HEMI ] of the present invention][DCA]、UIO-66-NH 2 CO of nanoparticles and UIO-66-PL 2 An adsorption data graph;
FIG. 18 shows [ HEMIM ] of the present invention][DCA]、UIO-66-NH 2 Nanoparticles and UIO-66-PLN of (2) 2 Adsorption data graph.
Detailed Description
The operation of the present invention will be described in detail with reference to the accompanying drawings.
Example one
Referring to FIG. 1, an MOF-based porous liquid is prepared from 84.21% by mass of an ionic liquid as a mobile phase and 15.79% by mass of UIO-66-NH as a stationary phase 2 And (3) nanoparticles.
A method of making a MOF-based porous liquid, comprising the steps of:
the method comprises the following steps: dissolving 12.8g of zirconium tetrachloride, 10.0g of 2-aminoterephthalic acid and 420mL of acetic acid in a three-necked flask containing 950mL of N, N-dimethylformamide, adding 70mL of water, stirring the obtained uniform solution in an oil bath at 120 ℃ for reaction for 15min, and cooling to room temperature to obtain a solution containing UIO-66-NH 2 Centrifuging the precursor yellowish solution with ethanol and acetone at 10000rpm for 5min, repeatedly centrifuging, washing and purifying for three times to remove unreacted zirconium tetrachloride, 2-amino terephthalic acid, acetic acid and N, N-dimethylformamide to obtain yellowish UIO-66-NH 2 Acetone solution, light yellow UIO-66-NH 2 Vacuum drying the acetone solution at 50 deg.C for 12h, and completely volatilizing acetone to obtain pale yellow UIO-66-NH 2 Nanoparticles, UIO-66-NH 2 Nanoparticle structure see figure 2;
step two: obtaining 0.3g of UIO-66-NH from the first step 2 Dispersing the nano particles in 10mL of acetone solution, performing ultrasonic treatment for 10min, and when no particles are obviously aggregated at the bottom of the container, indicating that the UIO-66-NH is 2 No agglomeration in the acetone solution to obtain uniformly dispersed UIO-66-NH 2 Acetone solution;
step three: 1.6g of a specific super-hydrophilic ionic liquid [ HEMIM ]][DCA](IL, 1- (2-hydroxyethyl) -3-methylimidazolidinedicyanamide) was added dropwise to the solution obtained in step two containing 0.3g of UIO-66-NH 2 Magnetically mixing and stirring the nano-particles in an acetone solution at 25 ℃ for 5 hours to obtain an acetone solution of UIO-66-PL; ionic liquids [ HEMI][DCA]See fig. 3 for a schematic structural view;
step four: stirring and drying the UIO-66-PL acetone solution obtained in the third step on a hot plate at the temperature of 35 ℃ at the rotating speed of 150rpm, volatilizing most of acetone solvent, and drying the stirred and dried substance at the temperature of 35 ℃ for 12 hours in vacuum to obtain MOF-based porous liquid; a schematic of the MOF-based porous liquid structure is shown in fig. 4.
Example two
Referring to FIG. 1, an MOF-based porous liquid is prepared from 83.33% by mass of an ionic liquid as a mobile phase and 16.67% by mass of UIO-66-NH as a stationary phase 2 And (3) nanoparticles.
A method of making a MOF-based porous liquid, comprising the steps of:
the method comprises the following steps: dissolving 15.0g of zirconium tetrachloride, 11.7g of 2-aminoterephthalic acid and 440mL of acetic acid in 1000mL of N, N-dimethylformamide-containing three-necked flask, adding 75mL of water, stirring the obtained uniform solution in an oil bath kettle at 120 ℃ for reacting for 20min, and cooling to room temperature to obtain a solution containing UIO-66-NH 2 Centrifuging the precursor light yellow solution with ethanol and acetone at 8000rpm for 10min, repeatedly centrifuging, washing and purifying for three times to remove unreacted zirconium tetrachloride, 2-amino terephthalic acid, acetic acid and N, N-dimethylformamide to obtain light yellow UIO-66-NH 2 Acetone solution, light yellow UIO-66-NH 2 Vacuum drying the acetone solution at 40 deg.C for 40h, and volatilizing acetone completely to obtain pale yellow UIO-66-NH 2 A nanoparticle; UIO-66-NH 2 Nanoparticle structure see figure 2;
step two: obtaining 0.4g of UIO-66-NH from the step one 2 Dispersing the nano particles in 15mL of acetone solution, performing ultrasonic treatment for 8min, and when no particles are obviously aggregated at the bottom of the container, indicating that the UIO-66-NH is 2 No agglomeration in the acetone solution to obtain uniformly dispersed UIO-66-NH 2 Acetone solution;
step three: 2.0g of a specific super-hydrophilic ionic liquid [ HEMIM ]][DCA](IL, 1- (2-hydroxyethyl) -3-methylimidazolidinedicyanamide) was added dropwise to the solution obtained in step two containing 0.4g of UIO-66-NH 2 Magnetically mixing and stirring the nano-particles in acetone solution at 20 ℃ for 12h to obtain the product UIO-66-PLA ketone solution; ionic liquids [ HEMI][DCA]See fig. 3 for a schematic structural view;
step four: stirring and drying the UIO-66-PL acetone solution obtained in the third step on a hot plate at the temperature of 30 ℃ at the rotating speed of 200rpm, volatilizing most of acetone solvent, and drying the stirred and dried substance at the temperature of 40 ℃ for 20 hours in vacuum to obtain MOF-based porous liquid; a schematic of the MOF based porous liquid structure is shown in fig. 4.
EXAMPLE III
Referring to FIG. 1, an MOF-based porous liquid is prepared from 80.85% by mass of an ionic liquid as a mobile phase and 19.15% by mass of UIO-66-NH as a stationary phase 2 And (3) nanoparticles.
A method of making a MOF-based porous liquid, comprising the steps of:
the method comprises the following steps: dissolving 16.0g of zirconium tetrachloride, 12.5g of 2-aminoterephthalic acid and 450mL of acetic acid in a 1100mL of N, N-dimethylformamide-containing three-neck flask, then adding 80mL of water, stirring and reacting the obtained uniform solution in an oil bath kettle at 140 ℃ for 25min, and cooling to room temperature to obtain a solution containing UIO-66-NH 2 Centrifuging the precursor light yellow solution with ethanol and acetone at 11000rpm for 15min, repeatedly centrifuging, washing and purifying for three times to remove unreacted zirconium tetrachloride, 2-amino terephthalic acid, acetic acid and N, N-dimethylformamide to obtain light yellow UIO-66-NH 2 Acetone solution, light yellow UIO-66-NH 2 Vacuum drying the acetone solution at 50 deg.C for 35 hr, and completely volatilizing acetone to obtain yellowish UIO-66-NH 2 A nanoparticle; UIO-66-NH 2 Nanoparticle structure see figure 2;
step two: obtaining 0.45g of UIO-66-NH from the first step 2 Dispersing the nano particles in 20mL of acetone solution, performing ultrasonic treatment for 20min, and when no particles are obviously aggregated at the bottom of the container, indicating that the UIO-66-NH is 2 No agglomeration in the acetone solution to obtain uniformly dispersed UIO-66-NH 2 Acetone solution;
step three: 1.9g of a specific super-hydrophilic ionic liquid [ HEMIM ]][DCA](IL, 1- (2-hydroxyethyl) -3-methylimidazolidinedicyanamide) was added dropwise to the solution obtained in step two containing 0.45g of UIO-66-NH 2 Magnetically mixing and stirring the nano particles in acetone solution at 30 ℃ for 8 hours to obtain the acetone solution of UIO-66-PL; ionic liquids [ HEMI][DCA]See fig. 3 for a schematic structural view;
step four: stirring and drying the UIO-66-PL acetone solution obtained in the third step on a hot plate at the temperature of 30 ℃ at the rotating speed of 250rpm, volatilizing most of acetone solvent, and drying the stirred and dried substance at the temperature of 40 ℃ for 20 hours in vacuum to obtain MOF-based porous liquid; a schematic of the MOF-based porous liquid structure is shown in fig. 4.
Example four
Referring to FIG. 1, an MOF-based porous liquid is prepared from 76.19% by mass of an ionic liquid as a mobile phase and 23.81% by mass of UIO-66-NH as a stationary phase 2 And (3) nanoparticles.
A method of making a MOF-based porous liquid, comprising the steps of:
the method comprises the following steps: dissolving 16.5g of zirconium tetrachloride, 12.9g of 2-aminoterephthalic acid and 460mL of acetic acid in a three-necked flask containing 1200mL of N, N-dimethylformamide, then adding 82mL of water, stirring and reacting the obtained uniform solution in an oil bath kettle at 150 ℃ for 18min, and cooling to room temperature to obtain a solution containing UIO-66-NH 2 Centrifuging the precursor yellowish solution with ethanol and acetone at 12000rpm for 8min, repeatedly centrifuging, washing and purifying for three times to remove unreacted zirconium tetrachloride, 2-aminoterephthalic acid, acetic acid and N, N-dimethylformamide to obtain yellowish UIO-66-NH 2 Acetone solution, light yellow UIO-66-NH 2 Vacuum drying the acetone solution at 60 deg.C for 15h, and completely volatilizing acetone to obtain pale yellow UIO-66-NH 2 A nanoparticle; UIO-66-NH 2 Nanoparticle structure see figure 2;
step two: obtaining 0.5g of UIO-66-NH from the first step 2 Dispersing the nano particles in 23mL of acetone solution, performing ultrasonic treatment for 30min, and when no obvious particles are aggregated at the bottom of a container, indicating that UIO-66-NH is formed 2 No agglomeration in the acetone solution to obtain uniformly dispersed UIO-66-NH 2 Acetone solution;
step three: 1.6g of a specific super-hydrophilic ionic liquid[HEMIM][DCA](IL, 1- (2-hydroxyethyl) -3-methylimidazolidinedicyanamide) the solution obtained in step two containing 0.5g of UIO-66-NH was added dropwise 2 Magnetically mixing and stirring the nano-particles in acetone solution at 35 ℃ for 6 hours to obtain the acetone solution of UIO-66-PL; ionic liquids [ HEMI][DCA]See fig. 3 for a schematic structural view;
step four: stirring and drying the UIO-66-PL obtained in the third step on a hot plate at the temperature of 30 ℃ at the rotating speed of 300rpm, volatilizing most of acetone solvent, and drying the stirred and dried substance at the temperature of 60 ℃ in vacuum for 12 hours to obtain MOF-based porous liquid; a schematic of the MOF-based porous liquid structure is shown in fig. 4.
See FIG. 5,X ray diffraction diagram for UIO-66-PL and ionic liquid [ HEMI][DCA]All show amorphous peak at 23 deg., in the wide-angle XRD mode of UIO-66-PL, amorphous ionic liquid [ HEMIM ] can be clearly observed][DCA]Peak sum UIO-66-NH 2 Characteristic peak of (A), indicating UIO-66-NH 2 The crystal structure of (A) was well preserved in UIO-66-PL and confirmed that the ionic liquid [ HEMIM][DCA]UIO-66-NH after surface coating 2 The crystal structure of (a) is complete.
Referring to FIG. 6, in SEM picture, UIO-66-NH 2 The nanoparticles (left a) have obvious particle agglomeration and protrusion, and in UIO-66-PL (right b), UIO-66-NH 2 The nanoparticles are uniformly distributed, and the surface of the particles is coated with ionic liquid [ HEMIM][DCA]The agglomeration and the protrusion disappear, indicating that UIO-66-NH 2 Nanoparticles and ionic liquids [ HEMI][DCA]Has better interface compatibility; in comparison in a TEM image, UIO-66-NH 2 The nanoparticles (left c) were sharp and smooth in profile, while in UIO-66-PL (right d), the particle edges were blurred, indicating UIO-66-NH 2 The surface of the nano-particles is coated with ionic liquid, and the ionic liquid is filled in UIO-66-NH 2 Ionic liquids [ HEMI ] between nanoparticles][DCA]Provides good flow behavior at room temperature for UIO-66-PL.
Referring to FIG. 7, the UIO-66-NH prepared is illustrated 2 The specific surface area of the particles was 905m 2 In the normal range of 650-1100 m/g 2 Within/g, meets the requirement of synthesizing the filler in the porous liquid.
Refer to FIG. 8 for a description of the present inventionPrepared UIO-66-NH 2 The pore size is less than 1.6nm and within the normal range of 0.7-1.8nm, and the method meets the requirement of synthesizing the filler in the porous liquid.
Referring to FIG. 9, ionic liquids [ HEMI ] are shown separately][DCA]、UIO-66-NH 2 Attenuated total reflectance infrared (ATR-IR) spectra of nanoparticles and UIO-66-PL, and ionic liquid [ HEMI ] can be observed][DCA]Almost the same attenuated total reflectance infrared (ATR-IR) spectrum as that of the ATR-IR of UIO-66-PL, and UIO-66-NH 2 The functional group vibrational stretching peak of the nanoparticle was not substantially observed in the ATR-IR spectrum of UIO-66-PL, demonstrating that the ionic liquid [ HEMI][DCA]Indeed as a shell covering the UIO-66-NH 2 The external surface of the nanoparticles, indicating that the ionic liquid did not destroy UIO-66-NH 2 Integrity of the nanoparticle structure.
Referring to FIG. 10, the melting temperature (T) of UIO-66-PL was found from DSC plot analysis m ) Well below 25 ℃ at room temperature, indicating that UIO-66-PL has a liquid-like behavior at room temperature.
Referring to FIG. 11, there was no significant mass loss of UIO-66-PL at 200 ℃ by Thermogravimetric (TGA) analysis of the porous liquid, indicating that there was no residual solvent (e.g., acetone, water), i.e., UIO-66-PL has zero vapor pressure characteristics, is hardly volatilized, and has good fluidity.
See FIG. 12 for comparison of Ionic liquids [ HEMI][DCA]、UIO-66-NH 2 The contact angle of the nanoparticles and UIO-66-PL was known as UIO-66-NH 2 The water contact angle of the nano-particles is 44.37 degrees and 44.83 degrees, the water contact angle of UIO-66-PL is 7.53 degrees and 7.98 degrees, the water contact angle of UIO-66-PL can be obviously reduced, and the ionic liquid [ HEMIM ] is shown][DCA]Effectively enhance UIO-66-NH 2 Hydrophilic character of the nanoparticles.
Referring to FIG. 13, UIO-66-NH 2 The bottom of the water solution of the nano-particles (left) is obviously precipitated after standing for 24 hours, while the UIO-66-PL (right) is dispersed in the water, and the UIO-66-PL has no obvious precipitate after standing for 24 hours, thus showing that the UIO-66-PL has better dissolution stability.
Referring to FIG. 14, agglomeration and sedimentation occurred soon after the UIO-66-PL (right) was left standing in acetone solution for 5min, indicating that the ionic liquid [ HEMIM][DCA]With UIO-66-NH 2 (left) of the particlesStrong interaction force exists between UIO-66-PL and UIO-66-PL, so that UIO-66-PL is settled by gravity after being rapidly gathered in acetone solution.
Referring to FIG. 15, the UIO-66-PL after standing for half a year still maintained good fluidity, and when the glass bottle containing the UIO-66-PL was inverted, the UIO-66-PL flowed down along the inner wall of the bottle, indicating that the UIO-66-PL prepared in the present invention exhibited good stability and liquid flow ability.
Referring to FIG. 16, UIO-66-NH by ZETA potential map analysis 2 Nanoparticle surface charge is negative, ionic liquid [ HEMI][DCA]The positive surface charge indicates that strong positive and negative charge attraction exists between the UIO-66-PL and the solvation effect can be enhanced by the interaction force between the UIO-66-NH and the positive surface charge, so that the stability of the UIO-66-PL system is enhanced 2 Ionic liquids for nanoparticles [ HEMI][DCA]After the coating, UIO-66-PL is obtained, and the ZETA potential is obviously changed, which shows that the ionic liquid [ HEMI][DCA]Successful coverage was at UIO-66-NH 2 The surface of the nanoparticles.
Referring to FIG. 17, ionic liquids [ HEMI][DCA]、UIO-66-NH 2 The nanoparticles and UIO-66-PL have different CO 2 Adsorption behavior, contrast to ionic liquids [ HEMI][DCA]The UIO-66-PL adsorption capacity of the gas of (1) is obviously increased, indicating the existence of a porous structure in the gas.
Referring to FIGS. 17 and 18, ionic liquids [ HEMI][DCA]、UIO-66-NH 2 And N of UIO-66-PL 2 The adsorption capacity is lower than that of CO 2 The prepared UIO-66-PL is shown to have excellent gas adsorption selectivity.
In conclusion, the MOF-based porous liquid obtained by the simple universal preparation method provided by the invention has porosity and good fluidity at room temperature, is expected to be applied to fluid carrier transportation and the like, and has application prospects in aspects of gas adsorption, organic catalysis and the like.
In the above examples, zirconium tetrachloride (ZrCl) 4 98%), 2-aminoterephthalic acid (C) 8 H 7 NO 4 98%, acetic acid (CH) 3 COOH, 99.5%), N, N-dimethylformamide (C) 3 H 7 NO, 99.8%), 1- (2-hydroxyethyl) -3-methylimidazoleAzole dicyanamide ([ HEMI)][DCA]97%) acetone (CH) from McClin Biochemical technology, inc 3 COCH 3 99.5% or more) was purchased from Fouchun chemical agents, inc.
In conclusion, the invention effectively reduces the complexity and complexity of the current preparation of porous liquid.
Claims (7)
1. An MOF-based porous liquid is characterized in that the raw materials comprise 50-90% of ionic liquid serving as a mobile phase and 50-10% of UIO-66-NH serving as a stationary phase according to mass percentage 2 And (3) nanoparticles.
2. An MOF-based porous liquid according to claim 1, wherein said UIO-66-NH 2 The surface of the nano particles is charged negatively, the surface of the ionic liquid is charged positively, and the molecules of the selected ionic liquid are organic ions.
3. A MOF-based porous liquid according to claim 1 or 2, characterized in that said UIO-66-NH 2 The nano-particles comprise, by mass, 0.8% -1.2% of zirconium tetrachloride, 0.7% -0.9% of 2-amino terephthalic acid, 27.8% -30.9% of acetic acid, 62.4% -66.6% of N, N-dimethylformamide and 4.7% -5.2% of water.
4. A MOF-based porous liquid according to claim 1, wherein the ionic liquid of the mobile phase has a cation containing oxygen-containing group in its side chain group which enhances hydrogen bonding with water molecules and an anion which is one of hydrophilic ionic liquids.
5. A MOF-based porous liquid according to claim 1 or 4, characterized in that said mobile phase ionic liquid is super-hydrophilic [ HEMIM ™ HEMIM][DCA]The stationary phase is hydrophilic UIO-66-NH 2 And (3) nanoparticles.
6. A method of making a MOF-based porous liquid, comprising the steps of:
the method comprises the following steps: according to the mass percentage, 0.8 to 1.2 percent of zirconium tetrachloride, 0.7 to 0.9 percent of 2-amino terephthalic acid and 27.8 to 30.9 percent of acetic acid are dissolved in 62.4 to 66.6 percent of N, N-dimethylformamide, then 4.7 to 5.2 percent of water is added, the mixture is stirred and reacted for 15 to 30min at the temperature of 120 to 150 ℃ in an oil bath, and the mixture is cooled to room temperature to obtain UIO-66-NH 2 Respectively centrifuging the precursor yellowish solution with ethanol and acetone at 8000-12000rpm for 5-15min, repeatedly centrifuging and washing, collecting the lower layer precipitate, and vacuum drying at 40-60 deg.C for 12-48h to obtain activated yellowish UIO-66-NH 2 A nanoparticle;
step two: the pale yellow UIO-66-NH obtained in step one 2 Dispersing nanoparticles in acetone solution, UIO-66-NH 2 The mass ratio of the nano particles to the acetone is 1 2 Acetone solution of nanoparticles;
step three: mixing ionic liquid [ HEMIM][DCA]Dropwise adding the UIO-66-NH obtained in the second step 2 In acetone solution of nanoparticles, UIO-66-NH 2 Nanoparticles and ionic liquids [ HEMI][DCA]The mass ratio of 1:1-10, and magnetically mixing and stirring for 5-12h at 20-35 ℃ to obtain an acetone solution of UIO-66-PL;
step four: and (3) stirring and drying the acetone solution of the UIO-66-PL obtained in the third step on a hot plate with the rotating speed of 100-400rpm at the temperature of 30-60 ℃ until the solvent acetone in the solution is completely volatilized, and performing vacuum drying at the temperature of 30-60 ℃ for 12-48h to obtain the MOF-based porous liquid.
7. The method of claim 6, wherein the UIO-66-NH obtained in step one 2 The nanoparticles have a particle size of 40-100nm, preferably 50-70nm.
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| CN112670565A (en) * | 2020-09-07 | 2021-04-16 | 华中科技大学 | Amino-containing MOF-based composite gel solid electrolyte with high specific surface area, and preparation method and application thereof |
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| CN113694894A (en) * | 2020-05-21 | 2021-11-26 | 湖南大学 | Porous fluid and preparation method and application thereof |
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| CN113913020A (en) * | 2021-09-26 | 2022-01-11 | 西北工业大学 | Low-viscosity I-type porous liquid, preparation method and use method thereof |
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