CN115960368B - MOF-based porous liquid and preparation method thereof - Google Patents
MOF-based porous liquid and preparation method thereof Download PDFInfo
- Publication number
- CN115960368B CN115960368B CN202211717974.2A CN202211717974A CN115960368B CN 115960368 B CN115960368 B CN 115960368B CN 202211717974 A CN202211717974 A CN 202211717974A CN 115960368 B CN115960368 B CN 115960368B
- Authority
- CN
- China
- Prior art keywords
- uio
- nano particles
- mof
- ionic liquid
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000002105 nanoparticle Substances 0.000 claims abstract description 92
- 239000002608 ionic liquid Substances 0.000 claims abstract description 69
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 15
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 15
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004220 aggregation Methods 0.000 claims description 11
- 230000002776 aggregation Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 230000005526 G1 to G0 transition Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000007790 solid phase Substances 0.000 abstract description 6
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 239000012621 metal-organic framework Substances 0.000 description 36
- 238000010586 diagram Methods 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011344 liquid material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007614 solvation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000013310 covalent-organic framework Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005102 attenuated total reflection Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000013213 metal-organic polyhedra Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- BKAFBBWDHTZFSB-UHFFFAOYSA-N 2-(3-methyl-2h-imidazol-1-yl)ethanol Chemical compound CN1CN(CCO)C=C1 BKAFBBWDHTZFSB-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000000302 molecular modelling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The MOF-based porous liquid is mainly prepared from 50-90% of ionic liquid and 50-10% of UIO-66-NH 2 nano particles by mass percent; the specific process is as follows: 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 then vacuum drying to prepare UIO-66-NH 2 nano particles, and preparing a UIO-66-NH 2 acetone solution by using the UIO-66-NH 2 nano particles; preparing an acetone solution of UIO-66-PL by using an acetone solution of UIO-66-NH 2 and an ionic liquid [ HEMIM ] [ DCA ], and preparing an MOF-based porous liquid by using the acetone solution of UIO-66-PL; according to the invention, the porous material UIO-66-NH 2 particles are used as a solid phase, the ionic liquid [ HEMIM ] [ DCA ] is used as a mobile phase, and the similar hydrophilia of the mobile phase and the solid phase is kept, so that different surface charges of the mobile phase and the solid phase are kept, good interface compatibility can be realized, and a stable core-shell structure is constructed, so that the porous material UIO-66-NH 2 has the characteristics of high stability, good dispersibility, strong universality and simplicity and convenience in operation.
Description
Technical Field
The invention belongs to the technical field of porous materials, and particularly relates to a MOF-based porous liquid and a preparation method thereof.
Background
Porous liquids refer to a class of liquids having a permanent porosity that combines the porosity of a porous solid material with the flowability of the liquid. Such porous liquids are themselves fluid at normal temperature, with the internal unit molecules having a stable, permanent, shape-fixed cavity structure. Currently, the types of porous liquids are mainly classified into three types, wherein type I porous liquid is a liquid having fluidity composed of a single pore molecule, type II porous liquid is composed of a molecular-sized organic pore dissolved in a sterically hindered solvent, and type III porous liquid is composed of a microporous material dispersed in a sterically hindered solvent, such as MOF, COF, etc.
The research of the porous liquid is currently in a starting stage, and the preparation and the application of the porous liquid are all in a previous exploratory period. However, existing abundant porous materials, including Covalent Organic Frameworks (COFs), zeolites, metal Organic Frameworks (MOFs), metal Organic Polyhedra (MOP), etc., plus various sterically hindered solvents (e.g., various types of ionic liquids) offer more possibilities for designing new porous liquids.
The existing preparation process of the porous liquid mainly focuses on realizing fluidity by grafting an organic molecular chain on the surface of a porous solid material, for example, the intermediate layer silane coupling agent KH560 is firstly grafted on the surface of UIO-66-OH, then the porous liquid of UIO-66-liquid-M2070 obtained by connecting an oligomer M2070 through epoxy ring opening, or a special MOF functional group is endowed by a certain method to provide a binding site for a polymer chain to realize fluidity, for example, ZIF-8 is provided with an amino ligand by a physical stirring method, and then the amino ligand is grafted on the surface of ZIF-8 through ring opening reaction of epoxy group end-capped PDMS, and the preparation process has the problems of complex operation flow, low porous proportion, inapplicability to mass synthesis 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 CN113462051A discloses hyperbranched polyethylene-based porous liquid and a preparation method thereof, wherein the hyperbranched polyethylene-based porous liquid is prepared from hyperbranched polyethylene and a metal organic framework material, specifically ethylene is used as a polymerization monomer, alpha-diimine nickel catalyst and sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate NaBArF cocatalyst are used for preparing the hyperbranched polyethylene with low molecular weight, high branching degree and good fluidity by a coordination polymerization method, the hyperbranched polyethylene with high branching degree is used as a steric hindrance solvent, the 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 with a two-dimensional nano lamellar structure, which is prepared by regulating and controlling alkyl acids (acetic acid, caproic acid and capric acid) with different chain lengths, is dispersed in hyperbranched polyethylene with low molecular weight to prepare a novel third type porous liquid material, the gas adsorption and desorption or storage performance of the novel third type porous liquid material serving as porous liquid is verified through the adsorption and desorption process of gases such as nitrogen, methane and carbon dioxide, and the novel third type porous liquid material is used for preparing a mixed matrix film to explore the potential application of the novel third type porous liquid material in the field of gas separation, so the novel third type porous liquid material has the defects of poor stability, poor dispersibility, small application range and complex operation.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the MOF-based porous liquid and the preparation method thereof, which take UIO-66-NH 2 nano particles as a solid phase and ionic liquid [ HEMIM ] [ DCA ] as a mobile phase of a steric hindrance solvent, and maintain the similar hydrophilicity of the mobile phase and the solid phase, and maintain the different surface charges of the mobile phase and the solid phase, so that good interface compatibility can be realized, a stable core-shell structure can be constructed, and the MOF-based porous liquid has the characteristics of high stability, good dispersibility, strong universality and simplicity and convenience in operation.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the MOF-based porous liquid comprises, by mass, 50% -90% of an ionic liquid serving as a mobile phase and 50% -10% of UIO-66-NH 2 nano particles serving as a stationary phase.
The charges on the surfaces of the UIO-66-NH 2 nano particles are negative, the charges on the surfaces of the ionic liquid are positive, and the selected molecules of the ionic liquid are organic ions.
The UIO-66-NH 2 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 in the mobile phase is an oxygen-containing group which can improve the formation of hydrogen bonds with water molecules and the anion is one of hydrophilic ionic liquids.
The ionic liquid of the mobile phase is super-hydrophilic [ HEMIM ] [ DCA ], and the stationary phase is hydrophilic UIO-66-NH 2 nano particles.
A method for preparing a MOF-based porous liquid comprising the steps of:
Step one: according to mass percent, 0.8% -1.2 of zirconium tetrachloride, 0.7% -0.9% of 2-amino terephthalic acid and 27.8% -30.9% of acetic acid are dissolved in 62.4% -66.6% of N, N-dimethylformamide, then 4.7% -5.2% of water is added, stirring is carried out at 120-150 ℃ for 15-30min in an oil bath, cooling is carried out to room temperature, thus obtaining a precursor pale yellow solution of UIO-66-NH 2, respectively, ethanol and acetone are used for centrifugation for 5-15min at the rotating speed of 8000-12000rpm, after repeated centrifugation and washing, the lower precipitate is taken out, and vacuum drying is carried out at 40-60 ℃ for 12-48h, thus obtaining activated pale yellow UIO-66-NH 2 nano particles;
step two: dispersing the faint yellow UIO-66-NH 2 nano particles obtained in the first step in an acetone solution, wherein the mass ratio of the UIO-66-NH 2 nano particles to the acetone is 1:20-40, and carrying out ultrasonic treatment for 5-30min until no particles are aggregated at the bottom of a container, so as to obtain an acetone solution with uniformly dispersed UIO-66-NH 2 nano particles;
Step three: dropwise adding ionic liquid [ HEMIM ] [ DCA ] into the acetone solution of the UIO-66-NH 2 nano particles obtained in the second step, wherein the mass ratio of the UIO-66-NH 2 nano particles to the ionic liquid [ HEMIM ] [ DCA ] is 1:1-10, and magnetically mixing and stirring for 5-12h at 20-35 ℃ to obtain the acetone solution of the UIO-66-PL;
step four: stirring and drying the acetone solution of the UIO-66-PL obtained in the step three 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 drying in vacuum at the temperature of 30-60 ℃ for 12-48 hours to obtain the MOF-based porous liquid.
The particle size of the UIO-66-NH 2 nano particles obtained in the step one is 40-100nm, preferably 50-70nm.
Compared with the prior art, the invention has the beneficial effects that:
1. As the ionic liquid [ HEMIM ] [ DCA ] selected in the invention has super-hydrophilicity, after the ionic liquid is mixed and stirred with hydrophilic UIO-66-NH 2 nano particles, the interfacial compatibility and stable dispersion between the UIO-66-NH 2 nano particles and the ionic liquid can be ensured.
The UIO-66-NH 2 nano particles and the surface of the ionic liquid are oppositely charged, and the interaction force between the UIO-66-NH 2 nano particles and the ionic liquid can enhance the solvation effect, so that the stability of the MOF-based porous liquid system is enhanced.
3. As the unsaturated metal sites on the surfaces of UIO-66-NH 2 nano particles are coordinated with anions and cations of ionic liquid [ HEMIM ] [ DCA ], the solvation effect is enhanced, and therefore, the MOF-based porous liquid with high stability can be obtained.
4. Through a coordination chemistry method, the selected cations and anions have ionic liquid with large coordination site sizes, and through coordination with reaction sites on the surfaces of UIO-66-NH 2 nano particles, the solvation effect is enhanced, so that porous UIO-66-NH 2 nano particles are stably dispersed in the ionic liquid [ HEMIM ] [ DCA ], and the fluidity of the UIO-66-NH 2 nano particles is ensured.
5. As the surface of the UIO-66-NH 2 nano-particles is wrapped with the hydrophilic ionic liquid [ HEMIM ] [ DCA ], the MOF-based porous liquid can be stably dispersed in water.
Drawings
FIG. 1 is a schematic diagram of a method for preparing a MOF-based porous liquid according to the present invention;
FIG. 2 is a schematic diagram of the structure of UIO-66-NH 2 nanoparticles used in the present invention;
FIG. 3 is a schematic diagram of the structure of an ionic liquid [ HEMIM ] [ DCA ] used in the present invention;
FIG. 4 is a schematic diagram of a MOF-based porous liquid according to the present invention;
FIG. 5 is an XRD contrast pattern of ionic liquid [ HEMIM ] [ DCA ], UIO-66-NH 2 nanoparticles and UIO-66-PL in the present invention;
FIG. 6 is SEM image (left a) and TEM image (left c) of UIO-66-NH 2 nano-particles and SEM image (right b) and TEM image (right d) of UIO-66-PL according to the present invention;
FIG. 7 is a BET plot of UIO-66-NH 2 nanoparticles in accordance with the present invention;
FIG. 8 is a graph showing pore size distribution and molecular modeling of UIO-66-NH 2 nanoparticles according to the present invention;
FIG. 9 is a chart showing the comparison of Fourier infrared spectra of ionic liquid [ HEMIM ] [ DCA ], UIO-66-NH 2 nanoparticles and UIO-66-PL in the present invention;
FIG. 10 is a DSC comparison of [ HEMIM ] [ DCA ] with UIO-66-PL in the present invention;
FIG. 11 is a TGA comparison of [ HEMIM ] [ DCA ] and UIO-66-PL according to the present invention;
FIG. 12 is a graph comparing water contact angles of [ HEMIM ] [ DCA ], UIO-66-NH 2 nanoparticles and UIO-66-PL in the present invention;
FIG. 13 is a graph showing the comparison of the dispersion of UIO-66-NH 2 nanoparticles and UIO-66-PL in water before and after 24 hours of standing in accordance with the present invention;
FIG. 14 is a graph showing the comparison of UIO-66-NH 2 nanoparticles and UIO-66-PL dispersed in acetone before and after 5min of standing in accordance with the present invention;
FIG. 15 is a diagram showing the UIO-66-PL according to the present invention;
FIG. 16 is a ZETA potential map of [ HEMIM ] [ DCA ], UIO-66-NH 2 nanoparticles, and UIO-66-PL in the present invention;
FIG. 17 is a graph of CO 2 adsorption data for [ HEMIM ] [ DCA ], UIO-66-NH 2 nanoparticles, and UIO-66-PL according to the present invention;
FIG. 18 is a graph of N 2 adsorption data for [ HEMIM ] [ DCA ], UIO-66-NH 2 nanoparticles, and UIO-66-PL according to the present invention.
Detailed Description
The working principle of the invention is described in detail below with reference to the accompanying drawings.
Example 1
Referring to fig. 1, a MOF-based porous liquid comprises, by mass, 84.21% of an ionic liquid as a mobile phase and 15.79% of UIO-66-NH 2 nanoparticles as a stationary phase.
A method for preparing a MOF-based porous liquid comprising the steps of:
Step one: dissolving 12.8g of zirconium tetrachloride, 10.0g of 2-amino terephthalic 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, cooling to room temperature to obtain a light yellow solution containing a precursor of UIO-66-NH 2, centrifuging for 5min with ethanol and acetone at the rotating speed of 10000rpm, repeatedly centrifuging, washing and purifying for three times, removing unreacted zirconium tetrachloride, 2-amino terephthalic acid, acetic acid and N, N-dimethylformamide to obtain a light yellow UIO-66-NH 2 acetone solution, vacuum drying the light yellow UIO-66-NH 2 acetone solution at 50 ℃ for 12h, and completely volatilizing acetone to obtain light yellow UIO-66-NH 2 nano particles, wherein the structure of the UIO-66-NH 2 nano particles is shown in figure 2;
Step two: dispersing 0.3g of UIO-66-NH 2 nano particles obtained in the first step in 10mL of acetone solution, carrying out ultrasonic treatment for 10min, and obtaining the UIO-66-NH 2 acetone solution with uniform dispersion when no obvious particle aggregation exists at the bottom of a container bottle, which indicates that no aggregation exists in the UIO-66-NH 2 acetone solution;
Step three: 1.6g of a specific super-hydrophilic ionic liquid [ HEMIM ] [ DCA ] (IL, 1- (2-2-hydroxyethyl) -3-methylimidazole dicyandiamide) is dropwise added into the acetone solution containing 0.3g of UIO-66-NH 2 nano particles obtained in the step two, and the mixture is magnetically mixed and stirred for 5 hours at 25 ℃ to obtain an acetone solution of UIO-66-PL; the structural schematic diagram of the ionic liquid [ HEMIM ] [ DCA ] is shown in FIG. 3;
Step four: stirring and drying the acetone solution of the UIO-66-PL obtained in the step three on a hot plate at 35 ℃ at a rotating speed of 150rpm, volatilizing most of the acetone solvent, and vacuum drying the stirred and dried substance at 35 ℃ for 12 hours to obtain MOF-based porous liquid; the schematic of the structure of the MOF-based porous liquid is shown in fig. 4.
Example two
Referring to fig. 1, a MOF-based porous liquid comprises, in mass%, 83.33% of an ionic liquid as a mobile phase and 16.67% of UIO-66-NH 2 nanoparticles as a stationary phase.
A method for preparing a MOF-based porous liquid comprising the steps of:
Step one: dissolving 15.0g of zirconium tetrachloride, 11.7g of 2-amino terephthalic acid and 440mL of acetic acid in a three-necked flask containing 1000mL of N, N-dimethylformamide, adding 75mL of water, stirring the obtained uniform solution in an oil bath kettle at 120 ℃ for reaction for 20min, cooling to room temperature to obtain a light yellow solution containing a precursor of UIO-66-NH 2, centrifuging for 10min with ethanol and acetone at the rotating speed of 8000rpm, repeatedly centrifuging, washing and purifying for three times, and removing unreacted zirconium tetrachloride, 2-amino terephthalic acid, acetic acid and N, N-dimethylformamide to obtain a light yellow UIO-66-NH 2 acetone solution, and vacuum drying the light yellow UIO-66-NH 2 acetone solution at 40 ℃ for 40h to obtain light yellow UIO-66-NH 2 nano particles; the UIO-66-NH 2 nanoparticle structure is shown in figure 2;
Step two: dispersing 0.4g of UIO-66-NH 2 nano particles obtained in the first step in 15mL of acetone solution, carrying out ultrasonic treatment for 8min, and obtaining the UIO-66-NH 2 acetone solution with uniform dispersion when no obvious particle aggregation exists at the bottom of a container bottle, which indicates that no aggregation exists in the UIO-66-NH 2 acetone solution;
Step three: 2.0g of a specific super-hydrophilic ionic liquid [ HEMIM ] [ DCA ] (IL, 1- (2-2-hydroxyethyl) -3-methylimidazole dicyandiamide) is dropwise added into the acetone solution containing 0.4g of UIO-66-NH 2 nano particles obtained in the step two, and the mixture is magnetically mixed and stirred for 12 hours at 20 ℃ to obtain an acetone solution of UIO-66-PL; the structural schematic diagram of the ionic liquid [ HEMIM ] [ DCA ] is shown in FIG. 3;
Step four: stirring and drying the acetone solution of the UIO-66-PL obtained in the step three on a hot plate at 30 ℃ at a rotating speed of 200rpm, volatilizing most of the acetone solvent, and vacuum drying the stirred and dried substance at 40 ℃ for 20 hours to obtain MOF-based porous liquid; the schematic of the structure of the MOF-based porous liquid is shown in fig. 4.
Example III
Referring to fig. 1, a MOF-based porous liquid comprises, in mass%, 80.85% of an ionic liquid as a mobile phase and 19.15% of UIO-66-NH 2 nanoparticles as a stationary phase.
A method for preparing a MOF-based porous liquid comprising the steps of:
Step one: dissolving 16.0g zirconium tetrachloride, 12.5g 2-amino terephthalic acid and 450mL acetic acid in a three-necked flask containing 1100mL of N, N-dimethylformamide, adding 80mL of water, stirring the obtained uniform solution in an oil bath at 140 ℃ for reaction for 25min, cooling to room temperature to obtain a light yellow solution containing a precursor of UIO-66-NH 2, centrifuging for 15min under the condition that the rotation speed is 11000rpm by using ethanol and acetone, repeatedly centrifuging, washing and purifying for three times, and removing unreacted zirconium tetrachloride, 2-amino terephthalic acid, acetic acid and N, N-dimethylformamide to obtain a light yellow UIO-66-NH 2 acetone solution, and vacuum drying the light yellow UIO-66-NH 2 acetone solution at 50 ℃ for 35h to obtain light yellow UIO-66-NH 2 nano particles; the UIO-66-NH 2 nanoparticle structure is shown in figure 2;
Step two: dispersing 0.45g of UIO-66-NH 2 nano particles obtained in the first step in 20mL of acetone solution, carrying out ultrasonic treatment for 20min, and obtaining the UIO-66-NH 2 acetone solution with uniform dispersion when no obvious particle aggregation exists at the bottom of a container bottle, which indicates that no aggregation exists in the UIO-66-NH 2 acetone solution;
step three: 1.9g of a specific super-hydrophilic ionic liquid [ HEMIM ] [ DCA ] (IL, 1- (2-2-hydroxyethyl) -3-methylimidazole dicyandiamide) is dropwise added into the acetone solution containing 0.45g of UIO-66-NH 2 nano particles obtained in the step two, and the mixture is magnetically mixed and stirred for 8 hours at 30 ℃ to obtain an acetone solution of UIO-66-PL; the structural schematic diagram of the ionic liquid [ HEMIM ] [ DCA ] is shown in FIG. 3;
Step four: stirring and drying the acetone solution of the UIO-66-PL obtained in the step three on a hot plate at the temperature of 30 ℃ at the rotating speed of 250rpm, volatilizing most of the acetone solvent, and vacuum drying the stirred and dried substance at the temperature of 40 ℃ for 20 hours to obtain MOF-based porous liquid; the schematic of the structure of the MOF-based porous liquid is shown in fig. 4.
Example IV
Referring to fig. 1, a MOF-based porous liquid comprises 76.19% by mass of an ionic liquid as a mobile phase and 23.81% by mass of UIO-66-NH 2 nanoparticles as a stationary phase.
A method for preparing a MOF-based porous liquid comprising the steps of:
step one: dissolving 16.5g of zirconium tetrachloride, 12.9g of 2-amino terephthalic acid and 460mL of acetic acid in a three-necked flask containing 1200mL of N, N-dimethylformamide, adding 82mL of water, stirring the obtained uniform solution in an oil bath at 150 ℃ for reaction for 18min, cooling to room temperature to obtain a light yellow solution containing a precursor of UIO-66-NH 2, centrifuging for 8min with ethanol and acetone at the rotating speed of 12000rpm, repeatedly centrifuging, washing and purifying for three times, and removing unreacted zirconium tetrachloride, 2-amino terephthalic acid, acetic acid and N, N-dimethylformamide to obtain a light yellow UIO-66-NH 2 acetone solution, and vacuum drying the light yellow UIO-66-NH 2 acetone solution at 60 ℃ for 15h to obtain light yellow UIO-66-NH 2 nano particles; the UIO-66-NH 2 nanoparticle structure is shown in figure 2;
Step two: dispersing 0.5g of UIO-66-NH 2 nano particles obtained in the first step in 23mL of acetone solution, carrying out ultrasonic treatment for 30min, and obtaining the UIO-66-NH 2 acetone solution with uniform dispersion when no obvious particle aggregation exists at the bottom of a container bottle, which indicates that no aggregation exists in the UIO-66-NH 2 acetone solution;
Step three: 1.6g of a specific super-hydrophilic ionic liquid [ HEMIM ] [ DCA ] (IL, 1- (2-2-hydroxyethyl) -3-methylimidazole dicyandiamide) is dropwise added into the acetone solution containing 0.5g of UIO-66-NH 2 nano particles obtained in the step two, and the mixture is magnetically mixed and stirred for 6 hours at 35 ℃ to obtain an acetone solution of UIO-66-PL; the structural schematic diagram of the ionic liquid [ HEMIM ] [ DCA ] is shown in FIG. 3;
Step four: stirring and drying the acetone solution of the UIO-66-PL obtained in the step three on a hot plate at the temperature of 30 ℃ at the rotating speed of 300rpm, volatilizing most of the acetone solvent, and vacuum drying the stirred and dried substance at the temperature of 60 ℃ for 12 hours to obtain MOF-based porous liquid; the schematic of the structure of the MOF-based porous liquid is shown in fig. 4.
Referring to FIG. 5, in the X-ray diffraction diagram, an amorphous peak appears at 23 degrees in both UIO-66-PL and ionic liquid [ HEMIM ] [ DCA ], and in the wide-angle XRD mode of UIO-66-PL, the peak of amorphous ionic liquid [ HEMIM ] [ DCA ] and the characteristic peak of UIO-66-NH 2 can be clearly observed, which shows that the crystal structure of UIO-66-NH 2 is well preserved in UIO-66-PL, and the crystal structure of UIO-66-NH 2 after the surface of ionic liquid [ HEMIM ] [ DCA ] is covered is confirmed to be complete.
Referring to FIG. 6, in the SEM image, the UIO-66-NH 2 nano particles (left a) have obvious particle aggregation and protrusion, in the UIO-66-PL (right b), the UIO-66-NH 2 nano particles are uniformly distributed, the surfaces of the particles are wrapped with the ionic liquid [ HEMIM ] [ DCA ], the aggregation and protrusion disappear, and the good interface compatibility between the UIO-66-NH 2 nano particles and the ionic liquid [ HEMIM ] [ DCA ] is shown; in contrast to the TEM image, the UIO-66-NH 2 nanoparticles (left c) were sharp and smooth in contour, while in the UIO-66-PL (right d), the edges of the particles were blurred, indicating that the surfaces of the UIO-66-NH 2 nanoparticles were coated with ionic liquid, and that these ionic liquids [ HEMIM ] [ DCA ] filled between the UIO-66-NH 2 nanoparticles provided good flow behavior for the UIO-66-PL at room temperature.
Referring to FIG. 7, it is illustrated that the prepared UIO-66-NH 2 particles have a specific surface area of 905m 2/g and meet the requirements of filler in synthetic porous liquid within a normal range of 650-1100m 2/g.
Referring to FIG. 8, it is illustrated that the prepared UIO-66-NH 2 has a pore size smaller than 1.6nm and has a filler requirement in the synthetic porous liquid within a normal range of 0.7-1.8 nm.
Referring to FIG. 9, the attenuated total reflectance infrared (ATR-IR) spectra of the ionic liquid [ HEMIM ] [ DCA ], the UIO-66-NH 2 nanoparticle and the UIO-66-PL are shown, respectively, and the attenuated total reflectance infrared (ATR-IR) spectra of the ionic liquid [ HEMIM ] [ DCA ] and the UIO-66-PL can be seen to be almost the same, and the functional group vibration expansion peak of the UIO-66-NH 2 nanoparticle is not substantially present in the ATR-IR spectrum of the UIO-66-PL, so that the ionic liquid [ HEMIM ] [ DCA ] is proved to be truly covered on the outer surface of the UIO-66-NH 2 nanoparticle as a shell, and the ionic liquid is not proved to damage the structural integrity of the UIO-66-NH 2 nanoparticle.
Referring to FIG. 10, from DSC trace analysis, the melting temperature (T m) of UIO-66-PL was well below room temperature of 25℃indicating that UIO-66-PL had liquid-like behavior at room temperature.
Referring to FIG. 11, by Thermogravimetric (TGA) analysis of the porous liquid, UIO-66-PL had no significant mass loss at 200℃indicating no residual solvents (e.g., acetone, water), i.e., UIO-66-PL had zero vapor pressure characteristics, almost no volatilization, and good flowability.
Referring to FIG. 12, comparing the water contact angles of the ionic liquid [ HEMIM ] [ DCA ], the UIO-66-NH 2 nanoparticle and the UIO-66-PL, the water contact angles of the UIO-66-NH 2 nanoparticle are 44.37 degrees, 44.83 degrees and the water contact angles of the UIO-66-PL are 7.53 degrees, 7.98 degrees, and the obvious reduction of the water contact angle of the UIO-66-PL can be seen, which indicates that the hydrophilic characteristic of the UIO-66-NH 2 nanoparticle is effectively enhanced by the ionic liquid [ HEMIM ] [ DCA ].
Referring to FIG. 13, the aqueous solution of UIO-66-NH 2 nano particles (left) has obvious precipitation at the bottom after standing for 24 hours, while UIO-66-PL (right) is dispersed in water, and has no obvious precipitation after standing for 24 hours, thus showing that the UIO-66-PL has better dissolution stability.
Referring to FIG. 14, the UIO-66-PL (right) was allowed to stand in the acetone solution for 5min and then quickly agglomerated and settled, indicating that a strong interaction force exists between the ionic liquid [ HEMIM ] [ DCA ] and the UIO-66-NH 2 (left) particles, so that the UIO-66-PL was allowed to quickly agglomerate in the acetone solution and then to settle by gravity.
Referring to FIG. 15, the UIO-66-PL prepared in the invention has good stability and liquid flowability as shown by the fact that the UIO-66-PL can flow down along the inner wall of the bottle after the glass bottle containing the UIO-66-PL is inverted after the bottle is left for half a year.
Referring to FIG. 16, according to ZETA potential diagram analysis, the surface charge of the UIO-66-NH 2 nano-particles is negative, the surface charge of the ionic liquid [ HEMIM ] [ DCA ] is positive, which indicates that strong positive and negative charge attraction exists between the UIO-66-NH 2 nano-particles and the surface charge of the ionic liquid, the interaction force between the UIO-66-NH 2 nano-particles can enhance the solvation effect, so that the stability of a UIO-66-PL system is enhanced, the UIO-66-PL is obtained after the UIO-66-NH 2 nano-particles are wrapped by the ionic liquid [ HEMIM ] [ DCA ], and the ZETA potential is obviously changed, which indicates that the ionic liquid [ HEMIM ] [ DCA ] is successfully covered on the surfaces of the UIO-66-NH 2 nano-particles.
Referring to FIG. 17, ionic liquids [ HEMIM ] [ DCA ], UIO-66-NH 2 nanoparticles and UIO-66-PL have different CO 2 adsorption conditions, and compared with the gas adsorption data of ionic liquid [ HEMIM ] [ DCA ], the adsorption amount of UIO-66-PL is obviously increased, which indicates the existence of a porous structure in the ionic liquid.
Referring to FIGS. 17 and 18, the adsorption amounts of N 2 of the ionic liquids [ HEMIM ] [ DCA ], UIO-66-NH 2 and UIO-66-PL are lower than that of CO 2, which shows that the prepared UIO-66-PL has excellent gas adsorption selectivity.
In a comprehensive view, the MOF-based porous liquid obtained by the simple universal preparation method has both porosity and good fluidity at room temperature, is expected to be applied to applications such as mobile carrier transportation, and has application prospects in the aspects of gas adsorption, organic catalysis and the like.
In the above examples, zirconium tetrachloride (ZrCl 4, 98%), 2-amino terephthalic acid (C 8H7NO4, 98%), acetic acid (CH 3 COOH, 99.5%), N, N-dimethylformamide (C 3H7 NO, 99.8%), 1- (2-hydroxyethyl) -3-methylimidazole dicyandiamide ([ HEMIM ] [ DCA ], 97%) were purchased from Michelin Biochemical Co., ltd, and acetone (CH 3COCH3,. Gtoreq.99.5%) was purchased from Fuchen (Tianjin) chemical Co., ltd.
In conclusion, the method effectively reduces the complexity and complexity of the current preparation of the porous liquid.
Claims (6)
1. The MOF-based porous liquid is characterized in that the raw materials of the MOF-based porous liquid consist of 50-90% of ionic liquid serving as a mobile phase and 50-10% of UIO-66-NH 2 nano particles serving as a stationary phase in percentage by mass;
The ionic liquid of the mobile phase is super-hydrophilic [ HEMIM ] [ DCA ];
The UIO-66-NH 2 nano particles are uniformly distributed, the ionic liquid is wrapped on the surfaces of the particles, the aggregation and the protrusion disappear, and the UIO-66-NH 2 nano particles and the ionic liquid have better interface compatibility; the UIO-66-NH 2 nano particles are clear and smooth in outline, the surfaces of the UIO-66-NH 2 nano particles are wrapped with ionic liquid, the ionic liquid among the UIO-66-NH 2 nano particles provides flow behavior for the UIO-66-PL at room temperature, and the UIO-66-PL is MOF-based porous liquid.
2. The MOF-based porous liquid of claim 1, wherein the charge on the surface of said UIO-66-NH 2 nanoparticles is negative, the charge on the surface of the ionic liquid is positive, and the molecules of the ionic liquid are organic ions.
3. A MOF-based porous liquid according to claim 1 or 2, wherein the UIO-66-NH 2 nano-particles comprise, by mass, 0.8% -1.2% zirconium tetrachloride, 0.7% -0.9% 2-amino terephthalic acid, 27.8% -30.9% acetic acid, 62.4% -66.6% N, N-dimethylformamide and 4.7% -5.2% water.
4. The MOF-based porous liquid of claim 1, wherein the stationary phase is hydrophilic UIO-66-NH 2 nanoparticles.
5. A method for preparing a MOF-based porous liquid according to any one of claims 1 to 4, comprising the steps of:
Step one: according to mass percent, 0.8% -1.2% of zirconium tetrachloride, 0.7% -0.9% of 2-amino terephthalic acid and 27.8% -30.9% of acetic acid are dissolved in 62.4% -66.6% of N, N-dimethylformamide, then 4.7% -5.2% of water is added, stirring is carried out for 15-30min at 120-150 ℃ of oil bath, cooling is carried out to room temperature, thus obtaining a precursor pale yellow solution of UIO-66-NH 2, respectively, ethanol and acetone are respectively used for centrifugation for 5-15min at 8000-12000rpm, after repeated centrifugation and washing, the lower precipitate is taken out, and vacuum drying is carried out for 12-48h at 40-60 ℃ to obtain activated pale yellow UIO-66-NH 2 nano particles;
step two: dispersing the faint yellow UIO-66-NH 2 nano particles obtained in the first step in an acetone solution, wherein the mass ratio of the UIO-66-NH 2 nano particles to the acetone is 1:20-40, and carrying out ultrasonic treatment for 5-30min until no particles are aggregated at the bottom of a container, so as to obtain an acetone solution with uniformly dispersed UIO-66-NH 2 nano particles;
Step three: dropwise adding ionic liquid [ HEMIM ] [ DCA ] into the acetone solution of the UIO-66-NH 2 nano particles obtained in the second step, wherein the mass ratio of the UIO-66-NH 2 nano particles to the ionic liquid [ HEMIM ] [ DCA ] is 1:1-10, and magnetically mixing and stirring for 5-12h at 20-35 ℃ to obtain the acetone solution of the UIO-66-PL;
step four: stirring and drying the acetone solution of the UIO-66-PL obtained in the step three 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 drying in vacuum at the temperature of 30-60 ℃ for 12-48 hours to obtain the MOF-based porous liquid.
6. The method for preparing a MOF-based porous liquid according to claim 5, wherein the UIO-66-NH 2 nanoparticles obtained in the first step have a particle size of 40-100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211717974.2A CN115960368B (en) | 2022-12-29 | 2022-12-29 | MOF-based porous liquid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211717974.2A CN115960368B (en) | 2022-12-29 | 2022-12-29 | MOF-based porous liquid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115960368A CN115960368A (en) | 2023-04-14 |
| CN115960368B true CN115960368B (en) | 2024-06-11 |
Family
ID=87358409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211717974.2A Active CN115960368B (en) | 2022-12-29 | 2022-12-29 | MOF-based porous liquid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115960368B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113694894A (en) * | 2020-05-21 | 2021-11-26 | 湖南大学 | Porous fluid and preparation method and application thereof |
| 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 |
| CN114539550A (en) * | 2022-03-16 | 2022-05-27 | 江苏大学 | Third-class porous ionic liquid based on UiO-66 and preparation method and application thereof |
-
2022
- 2022-12-29 CN CN202211717974.2A patent/CN115960368B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694894A (en) * | 2020-05-21 | 2021-11-26 | 湖南大学 | Porous fluid and preparation method and application thereof |
| 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 |
| 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 |
| CN114539550A (en) * | 2022-03-16 | 2022-05-27 | 江苏大学 | Third-class porous ionic liquid based on UiO-66 and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Core-Shell Type Ionic Liquid/Metal Organic Framework Composite: An Exceptionally High CO2/CH4 Selectivity;Muhammad Zeeshan等;《J. Am. Chem. Soc.》;第140卷;第10113页第1-2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115960368A (en) | 2023-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mehdinia et al. | Cation exchange superparamagnetic Al-based metal organic framework (Fe3O4/MIL-96 (Al)) for high efficient removal of Pb (II) from aqueous solutions | |
| US20030152759A1 (en) | Method of fabricating nanostructured materials | |
| CN105289749B (en) | Amorphous Fe2O3@Cd MOF and magnetic Fe3O4@Cd MOF nano composite materials and preparation method thereof | |
| Meng et al. | Preparation of highly monodisperse hybrid silica nanospheres using a one-step emulsion reaction in aqueous solution | |
| Hu et al. | Magnetic nanoparticle sorbents | |
| CN111701599B (en) | montmorillonite/TiO2@MoS2Preparation method of composite catalyst, product obtained by preparation method and application of composite catalyst | |
| CN108793226B (en) | Method for preparing transparent zinc oxide liquid-phase dispersion by supergravity technology | |
| WO2014057976A1 (en) | Core-shell silica nanoparticles and production method thereof, hollow silica nanoparticle production method using same, and hollow silica nanoparticles obtained by said production method | |
| CN1427041A (en) | Preparation method of spherical composite nano silver/silicon dioxide functional material | |
| Li et al. | An electrostatic repulsion strategy construct ZIFs based liquids with permanent porosity for efficient CO2 capture | |
| Cho et al. | The rise of morphology-engineered microporous organic polymers (ME-MOPs): synthesis and benefits | |
| CN109731549A (en) | Adsorbed film is blended in MoS2-PAN | |
| WO2014058014A1 (en) | Organic-inorganic hybrid silica nanoparticle and production method thereof | |
| CN115960368B (en) | MOF-based porous liquid and preparation method thereof | |
| CN108405879A (en) | A kind of preparation method of nano zero valence iron@meso pore silicon oxide materials | |
| CN1325577C (en) | Process for synthesizing organic ligand coated titanium dioxide nano particles | |
| RU2402584C2 (en) | Modified carbon products and use thereof | |
| CN109181367B (en) | Method for preparing transparent zinc oxide liquid phase dispersion | |
| CN113559927A (en) | g-C3N4CuS quantum dot modified COFs composite material and preparation method thereof | |
| CN112898588B (en) | Nano zeolite imidazole ester framework material, preparation method thereof and application thereof in oil displacement | |
| CN114713202B (en) | MOF-801@MIL-101 metal organic framework super-particle with core-shell structure and preparation method and application thereof | |
| CN109384895A (en) | Aluminum hydroxide nanosheet/polymer composite material and preparation method thereof | |
| CN108654697B (en) | Preparation method of mesoporous polyion liquid- (metal) phthalocyanine nano material | |
| CN110117368B (en) | Bell-shaking type magnetic nanocomposite material with cavity structure and preparation method thereof | |
| CN113694894A (en) | Porous fluid and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |