CN115445448A - Preparation method of MOFs-based lithium ion imprinted PVDF (polyvinylidene fluoride) film - Google Patents
Preparation method of MOFs-based lithium ion imprinted PVDF (polyvinylidene fluoride) film Download PDFInfo
- Publication number
- CN115445448A CN115445448A CN202211190325.1A CN202211190325A CN115445448A CN 115445448 A CN115445448 A CN 115445448A CN 202211190325 A CN202211190325 A CN 202211190325A CN 115445448 A CN115445448 A CN 115445448A
- Authority
- CN
- China
- Prior art keywords
- mofs
- pvdf membrane
- lithium ion
- pvdf
- imprinted
- 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.)
- Granted
Links
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 49
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 80
- 239000012528 membrane Substances 0.000 claims abstract description 71
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000013207 UiO-66 Substances 0.000 claims abstract description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 27
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 229920001690 polydopamine Polymers 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000007853 buffer solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 29
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A preparation method of a lithium ion imprinted PVDF membrane based on MOFs relates to a preparation method of a lithium ion imprinted membrane. The invention aims to solve the problem that the existing ion imprinted molecule cannot have high adsorption capacity and high selectivity at the same time. The method comprises the following steps: 1. preparation of NH 2 -UIO-66 zirconium based organometallic framework; 2. preparing MOFs-LiIIPs imprinted polymer; 3. preparing an SP-PDA @ PVDF film; 4. introduction of SiO 2 A nano-interlayer; 5. preparing MOFs-Li II Ps @ PVDF film. The MOFs-based lithium ion imprinted PVDF membrane prepared by the method disclosed by the invention has the advantages that the loading rate of MOFs ion imprinted polymers is increased by 11.6%, and the adsorption capacity is correspondingly and remarkably increased; siO 2 2 The specific surface area and the anti-pollution performance of the membrane are improved by modification, so that the adsorption balance time is shorter, the anti-pollution performance is improved, and the membrane is continuously eluted for 10 timesIts performance is only reduced by 5.6%.
Description
Technical Field
The invention relates to a preparation method of a lithium ion imprinted membrane.
Background
The ion imprinting technology is evolved from a molecular imprinting process, and has the principle that ions are used as a template, a polymerized double-bond compound is used as a functional monomer, the monomer and target ions form a prepolymer through covalent and non-covalent interactions, a rigid polymer is prepared through crosslinking or polymerization, and after the template ions are eluted, corresponding three-dimensional pore channels are generated in the rigid polymer for specific identification of the target ions. The combination of the ion imprinting technology and other polymer preparation technologies not only improves the preparation method of the imprinting material, but also effectively expands the application range of the imprinting material. Generally, as the adsorption capacity increases, the selectivity of the ion imprinted polymer decreases because the specific adsorption sites formed during the ion imprinting process are not fixed, but rather increase the number of channels through which other ions can be adsorbed. Therefore, it is highly desirable to find a method to fix more imprinted channels, which can improve the adsorption capacity while retaining high selectivity of ion imprinting.
Disclosure of Invention
The invention aims to solve the problem that the existing ion imprinted molecules cannot have high adsorption capacity and high selectivity at the same time, and provides a preparation method of a lithium ion imprinted PVDF membrane based on MOFs.
Aiming at the problems in the prior art, the invention creatively provides a method for removing lithium ions by combining MOFs with an ion imprinting technology, and prepares an MOFs-LiIIPs @ PVDF film to realize high-selectivity removal of target pollutants in a complex system.
The present invention develops highly selective Li with enhanced hydrophilicity and stability + Blotting membrane (MOFs-Li II Ps @ PVDF membrane). In particular with Li + The imprinted polymer is used as an imprinted layer, 12 crown 4 is used as an adsorption unit, a selective Li + recognition site is formed, and the imprinted polymer is loaded on a membrane by an in-situ growth method, and the imprinted polymer is specifically completed by the following steps:
a preparation method of a MOFs-based lithium ion imprinted PVDF membrane is completed according to the following steps:
1. preparation of NH 2 UIO-66 zirconium-based organometallic framework:
first, zrCl was dissolved in DMF 4 And 2-amino terephthalic acid, stirring at room temperature to obtain a mixed solution(ii) a Pouring the mixed solution into a hydrothermal kettle made of polytetrafluoroethylene, and performing hydrothermal reaction to obtain a suspension; cooling and centrifuging to obtain solid matter, washing the solid matter, stoving and grinding to obtain yellow powder and obtain NH 2 -UIO-66 zirconium based organometallic framework;
2. preparing MOFs-LiIIPs imprinted polymer:
(1) mixing LiCl, 12-crown-4 and anhydrous methanol, then placing the mixture into a constant-temperature heating magnetic stirrer for prepolymerization, and then adding NH 2 -UIO-66 shaking of a zirconium-based organic metal framework, then adding alpha-methacrylic acid and azobisisobutyronitrile, and shaking under the conditions of nitrogen atmosphere, water bath at 70-80 ℃ and condensation reflux to obtain a solid substance;
(2) grinding and sieving the generated solid matter, repeatedly washing the obtained powder by using absolute ethyl alcohol and deionized water to remove redundant organic matters, and extracting Li on the imprinted polymer by using hydrochloric acid + Finally, repeatedly washing with deionized water, filtering, vacuum drying the obtained solid at 343K, grinding and sieving to obtain the MOFs-LiIIPs imprinted polymer;
3. preparation of SP-PDA @ PVDF film:
dissolving polydopamine into NaAC buffer solution, adding sodium periodate solution, and uniformly stirring to obtain SP-PDA solution; coating the SP-PDA solution on the PVDF membrane, and drying to obtain an SP-PDA @ PVDF membrane;
4. introduction of SiO 2 Nano intermediate layer:
(1) mixing ethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water to obtain a mixed solution;
(2) immersing the SP-PDA @ PVDF film into the mixed solution, taking out and then cleaning to obtain the introduced SiO 2 PVDF membrane behind the nanometer intermediate layer;
5. preparing MOFs-Li II Ps @ PVDF film:
dissolving the MOFs-LiIIPs imprinted polymer into absolute ethyl alcohol to obtain a MOFs-LiIIPs imprinted polymer solution; will introduce SiO 2 The PVDF membrane after the nanometer middle layer is immersed into MOFs-LiIIPs for imprinting polymerizationAnd stirring the solution for reaction, taking out and drying to obtain the MOFs-LiIIPs @ PVDF membrane, namely the MOFs-based lithium ion imprinted PVDF membrane.
The principle of the invention is as follows:
the metal organic framework is an organic-inorganic hybrid porous material which is self-assembled by taking metal ions as nodes and organic ligands as connectors through coordination bonds. The materials not only have the activity of metal ions, but also have the flexibility of organic ligands, the selectivity of functional groups and a specific space structure formed by coordination, thereby providing good basic conditions for the application of the materials in the fields of adsorption and catalysis. In the invention, the three-dimensional space structure of the MOFs material is creatively utilized, the MOFs material is combined with ion imprinting, and a large number of ion imprinting holes are loaded in the cavity of the MOFs, thereby solving the problems. According to the invention, an in-situ growth method is adopted to load the MOFs ion imprinted polymer on a polyvinylidene fluoride (PVDF) membrane modified by silicon dioxide particles by taking polydopamine (DA) as an interface adhesion layer, so as to prepare the MOFs-Li II Ps @ PVDF membrane. According to the invention, MOFs materials are introduced into the field of ion imprinting, and the interaction between template molecules and metal ions and organic ligands is utilized to prepare the MOFs ion imprinting membrane with specific recognition capability. The three-dimensional structure of the MOFs material increases the number of ion imprinting specific adsorption sites, and realizes high-selectivity removal of target pollutants in a complex system. The invention has the advantages of high adsorption capacity and high selectivity on lithium ions, green and environment-friendly preparation process, reduction in the use of dangerous organic solvents such as DMF, acetone and the like, excellent antifouling performance and hydrophilicity of the MOFs-Li II Ps @ PVDF membrane, short adsorption balance time and suitability for practical application.
The invention has the beneficial effects that:
1. in the field of combining the existing ion imprinting technology with other materials or technologies, one of the defects is that the adsorption capacity is low compared with the traditional adsorption material, the invention utilizes the abundant three-dimensional structure of MOFs materials, obviously improves the adsorption capacity of the ion imprinting, and simultaneously can retain the excellent selectivity of the ion imprinting technology:
2. NH 2 UIO-66 zirconium-based organometallic framesThe rack can show higher permselectivity to water molecules in the desalting process, has good hydrophilicity, acid resistance and stability, and has higher durability and reusability in a complex system;
3. polydopamine is used as an interface adhesion layer, the silica-modified SP-PDA @ PVDF membrane has good hydrophilicity and anti-pollution performance, the MOFs ion imprinted polymer is loaded on the modified PVDF membrane to form the MOFs-Li II Ps @ PVDF membrane which has good hydrophilicity and anti-pollution performance, and the performance is only reduced by 5.6% after more than 10 times of adsorption and desorption processes.
4. Compared with the prior patents, the MOFs-based lithium ion imprinted PVDF membrane prepared by the invention has the advantages that the loading rate of MOFs ion imprinted polymers is increased by 11.6%, and the adsorption capacity is correspondingly and remarkably increased; siO 2 2 The specific surface area and the anti-pollution performance of the membrane are improved through modification, so that the adsorption balance time is shorter, the anti-pollution performance is improved, the performance is reduced by only 5.6% after 10 times of continuous elution, and the performance is improved by 6.1% compared with the prior art.
Drawings
FIG. 1 shows NH changes in examples 1 to 5 2 -UIO-66 usage of zirconium based organometallic framework to prepare a map of the adsorption capacity of MOFs based lithium ion imprinted PVDF membranes for lithium ion adsorption;
fig. 2 is a graph showing the adsorption amount of lithium ions to the MOFs-based lithium ion imprinted PVDF film prepared by changing the stirring reaction time in the fifth step in example 1 and examples 6 to 9;
FIG. 3 is a graph showing the relationship between the regeneration frequency and the adsorption amount in the simulated water sample of example 1, wherein A is K + B is Na + C is Li + D is Ca 2+ E is Mg 2+ 。
Detailed Description
The present invention is described in further detail below, and the specific embodiments described herein are merely illustrative and are not intended to limit the present invention.
The first embodiment is as follows: the embodiment of the invention relates to a preparation method of a lithium ion imprinted PVDF membrane based on MOFs, which is completed according to the following steps:
1. preparation of NH 2 UIO-66 zirconium-based organometallic framework:
first, zrCl was dissolved in DMF 4 And 2-amino terephthalic acid, stirring at room temperature to obtain a mixed solution; pouring the mixed solution into a hydrothermal kettle made of polytetrafluoroethylene, and performing hydrothermal reaction to obtain a suspension; cooling and centrifuging to obtain solid matter, washing the solid matter, stoving and grinding to obtain yellow powder and obtain NH 2 -UIO-66 zirconium based organometallic framework;
2. preparing MOFs-LiIIPs imprinted polymer:
(1) mixing LiCl, 12-crown-4 and anhydrous methanol, then placing the mixture into a constant-temperature heating magnetic stirrer for prepolymerization, and then adding NH 2 -UIO-66 shaking of a zirconium-based organic metal framework, then adding alpha-methacrylic acid and azobisisobutyronitrile, and shaking under the conditions of nitrogen atmosphere, water bath at 70-80 ℃ and condensation reflux to obtain a solid substance;
(2) grinding and sieving the generated solid substance, repeatedly washing the obtained powder by using absolute ethyl alcohol and deionized water to remove redundant organic matters, and extracting Li on the imprinted polymer by using hydrochloric acid + Finally, repeatedly washing with deionized water, filtering, carrying out vacuum drying on the obtained solid at the temperature of 343K, grinding and sieving to obtain the MOFs-LiIIPs imprinted polymer;
3. preparation of SP-PDA @ PVDF film:
dissolving polydopamine into NaAC buffer solution, adding sodium periodate solution, and uniformly stirring to obtain SP-PDA solution; coating the SP-PDA solution on the PVDF membrane, and drying to obtain an SP-PDA @ PVDF membrane;
4. introduction of SiO 2 Nano intermediate layer:
(1) mixing ethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water to obtain a mixed solution;
(2) immersing the SP-PDA @ PVDF film into the mixed solution, taking out and then cleaning to obtain the introduced SiO 2 PVDF membrane behind the nanometer intermediate layer;
5. preparing MOFs-Li II Ps @ PVDF film:
dissolving the MOFs-LiIIPs imprinted polymer into absolute ethyl alcohol to obtain a MOFs-LiIIPs imprinted polymer solution; will introduce into SiO 2 And immersing the PVDF membrane behind the nano intermediate layer into MOFs-LiIIPs imprinted polymer solution, stirring for reaction, taking out and drying to obtain the MOFs-LiIIPs @ PVDF membrane, namely the MOFs-based lithium ion imprinted PVDF membrane.
The second embodiment is as follows: the first difference between the present embodiment and the present embodiment is: in step one, 1mmol of ZrCl is firstly dissolved in 50mL of DMF 4 And 1mmol of 2-amino terephthalic acid, stirring for 0.5h at room temperature to obtain a mixed solution; carrying out hydrothermal reaction at 120 ℃ for 24 hours to obtain a suspension; cooling and centrifuging to obtain a solid substance, washing the solid substance with absolute ethyl alcohol and deionized water respectively, and finally drying and grinding to obtain yellow powder and obtain NH 2 -UIO-66 zirconium based organometallic framework. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the volume ratio of the LiCl to the absolute methanol in the step two (1) is 0.3g; the volume ratio of the 12-crown-4 to the anhydrous methanol in the step two (1) is 0.3; NH described in step two (1) 2 The volume ratio of the mass of the UIO-66 zirconium-based organic metal framework to the volume of the anhydrous methanol is (3 g-6 g) 100mL; the volume ratio of the alpha-methacrylic acid to the anhydrous methanol in the step two (1) is 0.3; the volume ratio of the mass of the azobisisobutyronitrile to the anhydrous methanol in the step two (1) is 0.03g. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode is as follows: the difference between this embodiment and one of the first to third embodiments is as follows: mixing LiCl, 12-crown-4 and absolute methanol, and then placing the mixture into a constant-temperature heating magnetic stirrer for prepolymerization for 10 to 13min, wherein the temperature of the constant-temperature heating magnetic stirrer is 70 to 80 ℃, and the stirring speed is 80 to 100r/min; adding NH into the step two (1) 2 Oscillating the-UIO-66 zirconium-based organic metal framework for 1min to 2min, and then adding alpha-methacrylic acid and azoOscillating for 22-24 h under the conditions of nitrogen atmosphere, water bath at 70-80 ℃ and condensation reflux to obtain solid matter; the concentration of the hydrochloric acid in the second step (2) is 1mol/L; and (3) drying the solid obtained in the step one (2) for 10-12 h under vacuum at the temperature of 343K. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the ratio of the mass of the polydopamine to the volume of the NaAC buffer in the third step is as follows: (0.2 g-0.25 g): 245 mL-255 mL; the concentration of the NaAC buffer solution in the third step is 50 mmol-60mmol, and the pH value is 5.0; the concentration of the sodium periodate solution in the step three is 20 mmol-25 mmol; the volume ratio of the NaAC buffer solution to the sodium periodate solution in the third step is (245-255) to (5.0-15). The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the thickness of the PVDF film in the step three is 15-22 μm; the thickness of the SP-PDA film on the SP-PDA @ PVDF film in the step three is 10 nm-20 nm. The other steps are the same as those in the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and one of the first to sixth embodiments is: the volume ratio of the ethyl orthosilicate, the deionized water, the absolute ethyl alcohol and the ammonia water in the step four (1) is 1; the mass fraction of the ammonia water in the step four (1) is 28%. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: in the step four (2), the SP-PDA @ PVDF membrane is immersed in the mixed solution for 6 to 8 hours, and is taken out and then washed for 1 to 3 times by using absolute ethyl alcohol and then washed for 1 to 3 times by using deionized water to obtain the introduced SiO 2 PVDF membrane behind the nanometer intermediate layer. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the volume ratio of the mass of the MOFs-LiIIPs imprinted polymer in the fifth step to the absolute ethyl alcohol is (3.5 g-5.0 g): 245 mL-250 mL. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: and the stirring reaction time in the fifth step is 5-7 h. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a MOFs-based lithium ion imprinted PVDF membrane is specifically completed according to the following steps:
1. preparation of NH 2 UIO-66 zirconium-based organometallic framework:
first, 1mmol of ZrCl was dissolved in 50mL of DMF 4 And 1mmol of 2-amino terephthalic acid, stirring for 0.5h at room temperature to obtain a mixed solution; pouring the mixed solution into a polytetrafluoroethylene hydrothermal kettle, carrying out hydrothermal reaction at 120 ℃ for 24h, cooling and centrifuging the obtained suspension to obtain a solid matter, washing the solid matter for 3 times by using absolute ethyl alcohol and deionized water respectively, and finally drying and grinding to obtain yellow powder, namely NH 2 -UIO-66 zirconium based organometallic framework;
2. preparing MOFs-LiIIPs imprinted polymer:
(1) mixing 0.3g LiCl, 0.3 mL12-crown-4 and 100mL of anhydrous methanol, then placing the mixture into a constant-temperature heating magnetic stirrer for prepolymerization, and then adding 3.0g of NH 2 -UIO-66 shaking the zirconium-based organic metal framework for 2min, then adding 0.3mL of alpha-methacrylic acid and 0.03g of azodiisobutyronitrile, introducing nitrogen for 10min, and shaking for 22h under the conditions of nitrogen atmosphere, water bath at 75 ℃ and condensation reflux to obtain a solid substance;
(2) grinding and sieving the generated solid substance, repeatedly washing the obtained powder by using absolute ethyl alcohol and deionized water to remove redundant organic matters, and extracting Li on the imprinted polymer by using 1mol/L hydrochloric acid + Finally, repeatedly washing with deionized water, filtering, vacuum drying the obtained solid at 343K for 10h, grinding and sieving to obtain the MOFs-LiIIPs imprinted polymer;
3. preparation of SP-PDA @ PVDF film:
dissolving 0.2g of polydopamine into 240mL of NaAC buffer solution, adding 10mL of sodium periodate solution, and uniformly stirring to obtain SP-PDA solution; coating the SP-PDA solution on the PVDF membrane, and drying to obtain an SP-PDA @ PVDF membrane;
the concentration of the NaAC buffer solution in the third step is 50mmol, and the pH value is 5.0;
the concentration of the sodium periodate solution in the third step is 20mmol;
the thickness of the SP-PDA film on the SP-PDA @ PVDF film in the third step is 20nm;
4. introduction of SiO 2 Nano intermediate layer:
(1) mixing 1.0mL of ethyl orthosilicate, 5.0mL of deionized water, 30mL of absolute ethyl alcohol and 0.5mL of ammonia water to obtain a mixed solution;
the mass fraction of the ammonia water in the step four (1) is 28%;
(2) soaking the SP-PDA @ PVDF membrane into the mixed solution for 6h, taking out, washing with anhydrous ethanol for 2 times, and washing with deionized water for 2 times to obtain introduced SiO 2 PVDF membrane behind the nanometer intermediate layer;
5. preparing MOFs-Li II Ps @ PVDF film:
dissolving the MOFs-LiIIPs imprinted polymer into absolute ethyl alcohol to obtain a MOFs-LiIIPs imprinted polymer solution; will introduce SiO 2 Immersing the PVDF membrane behind the nano intermediate layer into MOFs-LiIIPs imprinted polymer solution, stirring for reaction for 6 hours, taking out and drying to obtain the MOFs-LiIIPs @ PVDF membrane, namely the MOFs-based lithium ion imprinted PVDF membrane;
and the volume ratio of the mass of the MOFs-Li II Ps imprinted polymer in the step five to the volume of the absolute ethyl alcohol is 3.5g.
Example 2: the difference between this example and example 1 is: in the second step (1), 3.5g of NH was added 2 UIO-66 shaking the zirconium-based organometallic framework for 2min. The other steps and parameters were the same as in example 1.
Example 3: the difference between this example and example 1 is: in the second step (1), 4.0g of NH was added 2 UIO-66 shaking of the zirconium-based organometallic framework for 2min. The other steps and parameters were the same as in example 1.
Example 4: the difference between this example and example 1 is: in the second step (1), 4.5g of NH was added 2 UIO-66 shaking of the zirconium-based organometallic framework for 2min. The other steps and parameters were the same as in example 1.
Example 5: the difference between this example and example 1 is: in the second step (1), 5.0g of NH was added 2 UIO-66 shaking of the zirconium-based organometallic framework for 2min. The other steps and parameters were the same as in example 1.
Example 6: the difference between this example and example 1 is: in step five, siO is introduced 2 And immersing the PVDF membrane behind the nano intermediate layer into MOFs-LiIIPs imprinted polymer solution, and stirring for reaction for 5 hours. The other steps and parameters were the same as in example 1.
Example 7: the difference between this example and example 1 is: in step five, siO is introduced 2 And immersing the PVDF membrane behind the nano intermediate layer into MOFs-LiIIPs imprinted polymer solution, and stirring for reaction for 5.5 hours. The other steps and parameters were the same as in example 1.
Example 8: the difference between this example and example 1 is: in step five, siO is introduced 2 And immersing the PVDF film behind the nano middle layer into MOFs-LiIIPs imprinted polymer solution, and stirring for reacting for 6.5 hours. The other steps and parameters were the same as in example 1.
Example 9: the difference between this example and example 1 is: in step five, siO is introduced 2 And immersing the PVDF membrane behind the nano middle layer into MOFs-LiIIPs imprinted polymer solution, and stirring for reaction for 7 hours. The other steps and parameters were the same as in example 1.
FIG. 1 shows NH changes in examples 1 to 5 2 -UIO-66 usage of zirconium based organometallic framework to prepare a map of the adsorption capacity of MOFs based lithium ion imprinted PVDF membranes for lithium ion adsorption;
as can be seen from FIG. 1, NH 2 The optimal usage amount of UIO-66 zirconium-based organic metal frame is 5.5g, the adsorption amount of the experiment is tested by taking an ion imprinted membrane with the size of 0.5cm multiplied by 0.5cm, and the ion imprinted membrane absorbs the ion imprinted membrane under the condition that the membrane size is enoughThe adhesion rate can reach 99.9%.
Fig. 2 is a graph showing the adsorption amount of lithium ions to the MOFs-based lithium ion imprinted PVDF membrane prepared by changing the stirring reaction time in the fifth step in example 1, example 6 to example 9;
as can be seen from FIG. 2, the optimum stirring time in the fifth step was 6 hours.
FIG. 3 is a graph showing the relationship between the regeneration frequency and the adsorption amount in the simulated water sample of example 1, wherein A is K + B is Na + C is Li + D is Ca 2+ E is Mg 2+ ；
As can be seen from FIG. 3, the adsorption amount of lithium ions in the blotting membrane was significantly higher than that of Na + 、K + 、Mg 2+ 、Ca 2+ Isocommon competitive ions, li under optimal preparation conditions + /Na + 、Li + /K + 、Li + /Mg 2+ 、Li + /Ca 2+ The selection coefficients of (A) are 6.72, 7.4, 8.2 and 8.7 respectively, and it can be seen that the selectivity is remarkably improved while high adsorption capacity is ensured.
Claims (10)
1. A preparation method of a lithium ion imprinted PVDF membrane based on MOFs is characterized by comprising the following steps:
1. preparation of NH 2 UIO-66 zirconium-based organometallic framework:
first, zrCl was dissolved in DMF 4 And 2-amino terephthalic acid, stirring at room temperature to obtain a mixed solution; pouring the mixed solution into a hydrothermal kettle made of polytetrafluoroethylene, and performing hydrothermal reaction to obtain a suspension; cooling and centrifuging to obtain solid matter, washing the solid matter, stoving and grinding to obtain yellow powder and obtain NH 2 -UIO-66 zirconium based organometallic framework;
2. preparing MOFs-LiIIPs imprinted polymer:
(1) mixing LiCl, 12-crown-4 and anhydrous methanol, then placing the mixture into a constant-temperature heating magnetic stirrer for prepolymerization, and then adding NH 2 Shaking of the UIO-66 zirconium-based organometallic framework followed by the addition of the alpha-methylpropaneOlefine acid and azodiisobutyronitrile are shaken under the conditions of nitrogen atmosphere, water bath at 70-80 ℃ and condensation reflux to obtain solid substances;
(2) grinding and sieving the generated solid substance, repeatedly washing the obtained powder by using absolute ethyl alcohol and deionized water to remove redundant organic matters, and extracting Li on the imprinted polymer by using hydrochloric acid + Finally, repeatedly washing with deionized water, filtering, vacuum drying the obtained solid at 343K, grinding and sieving to obtain the MOFs-LiIIPs imprinted polymer;
3. preparation of SP-PDA @ PVDF film:
dissolving polydopamine in NaAC buffer solution, adding sodium periodate solution, and stirring uniformly to obtain SP-PDA solution; coating the SP-PDA solution on the PVDF membrane, and drying to obtain an SP-PDA @ PVDF membrane;
4. introduction of SiO 2 Nano intermediate layer:
(1) mixing ethyl orthosilicate, deionized water, absolute ethyl alcohol and ammonia water to obtain a mixed solution;
(2) immersing the SP-PDA @ PVDF film into the mixed solution, taking out the mixed solution and then cleaning the mixed solution to obtain the introduced SiO 2 PVDF membrane behind the nanometer intermediate layer;
5. preparing MOFs-Li II Ps @ PVDF film:
dissolving the MOFs-LiIIPs imprinted polymer into absolute ethyl alcohol to obtain a MOFs-LiIIPs imprinted polymer solution; will introduce SiO 2 And immersing the PVDF membrane behind the nano intermediate layer into MOFs-LiIIPs imprinted polymer solution, stirring for reaction, taking out and drying to obtain the MOFs-LiIIPs @ PVDF membrane, namely the MOFs-based lithium ion imprinted PVDF membrane.
2. The method for preparing a MOFs-based lithium ion imprinted PVDF membrane according to claim 1, wherein in step one, 1mmol ZrCl is first dissolved in 50mL DMF 4 And 1mmol of 2-amino terephthalic acid, stirring for 0.5h at room temperature to obtain a mixed solution; carrying out hydrothermal reaction at 120 ℃ for 24 hours to obtain a suspension; cooling, centrifuging to obtain solid substance, and adding anhydrous ethanol and deionized water to the solid substanceWashing the substance, drying, grinding to obtain yellow powder, and obtaining NH 2 UIO-66 zirconium-based organometallic framework.
3. The method for preparing a MOFs-based lithium ion imprinted PVDF membrane according to claim 1, wherein the ratio of the mass of LiCl to the volume of absolute methanol in step (1) is 0.3 g; the volume ratio of the 12-crown-4 to the anhydrous methanol in the step two (1) is 0.3; NH described in step two (1) 2 The volume ratio of the mass of the UIO-66 zirconium-based organometallic framework to the volume of the anhydrous methanol is (3 g-6 g) 100mL; the volume ratio of the alpha-methacrylic acid to the anhydrous methanol in the step two (1) is 0.3; the volume ratio of the mass of the azobisisobutyronitrile to the anhydrous methanol in the step two (1) is 0.03g.
4. The preparation method of the MOFs-based lithium ion imprinted PVDF membrane according to claim 1, wherein in the step two (1), liCl, 12-crown-4 and absolute methanol are mixed, and then the mixture is placed into a constant temperature heating magnetic stirrer for prepolymerization for 10min to 13min, wherein the temperature of the constant temperature heating magnetic stirrer is 70 ℃ to 80 ℃, and the stirring speed is 80r/min to 100r/min; adding NH into the second step (1) 2 Oscillating a UIO-66 zirconium-based organic metal framework for 1 min-2 min, then adding alpha-methacrylic acid and azodiisobutyronitrile, and oscillating for 22 h-24 h under the conditions of nitrogen atmosphere, water bath at 70-80 ℃ and condensation reflux to obtain a solid substance; the concentration of the hydrochloric acid in the step two (2) is 1mol/L; and (3) drying the solid obtained in the step one (2) for 10-12 h under vacuum at the temperature of 343K.
5. The method for preparing a MOFs-based lithium ion imprinted PVDF membrane according to claim 1, wherein the ratio of the mass of polydopamine to the volume of NaAC buffer in step three is: (0.2 g-0.25 g): 245 mL-255 mL; the concentration of the NaAC buffer solution in the third step is 50 mmol-60mmol, and the pH value is 5.0; the concentration of the sodium periodate solution in the third step is 20 mmol-25 mmol; the volume ratio of the NaAC buffer solution to the sodium periodate solution in the third step is (245-255) to (5.0-15).
6. The preparation method of the MOFs-based lithium ion imprinted PVDF film according to claim 1, wherein the thickness of the PVDF film in step three is 15 μm-22 μm; the thickness of the SP-PDA film on the SP-PDA @ PVDF film in the third step is 10 nm-20 nm.
7. The preparation method of the MOFs-based lithium ion imprinted PVDF membrane according to claim 1, wherein the volume ratio of the ethyl orthosilicate, the deionized water, the anhydrous ethanol and the ammonia water in the step four (1) is 1; the mass fraction of the ammonia water in the step four (1) is 28%.
8. The MOFs-based preparation method of lithium ion imprinted PVDF membrane according to claim 1, wherein in the step four (2), the SP-PDA @ PVDF membrane is immersed in the mixed solution for 6-8 h, taken out, washed with absolute ethyl alcohol for 1-3 times, and then washed with deionized water for 1-3 times to obtain the introduced SiO 2 PVDF membrane behind the nanometer intermediate layer.
9. The method as claimed in claim 1, wherein the volume ratio of the mass of the MOFs-LiIIPs imprinted polymer to the absolute ethyl alcohol in the step five is (3.5 g-5.0 g): 245 mL-250 mL).
10. The method for preparing a MOFs-based lithium ion imprinted PVDF membrane according to claim 1, wherein the stirring reaction time in the fifth step is 5-7 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190325.1A CN115445448B (en) | 2022-09-28 | 2022-09-28 | Preparation method of MOFs-based lithium ion imprinting PVDF membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211190325.1A CN115445448B (en) | 2022-09-28 | 2022-09-28 | Preparation method of MOFs-based lithium ion imprinting PVDF membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115445448A true CN115445448A (en) | 2022-12-09 |
| CN115445448B CN115445448B (en) | 2024-10-11 |
Family
ID=84307791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211190325.1A Active CN115445448B (en) | 2022-09-28 | 2022-09-28 | Preparation method of MOFs-based lithium ion imprinting PVDF membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115445448B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344095A (en) * | 2017-08-29 | 2017-11-14 | 江苏大学 | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage |
| CN108144559A (en) * | 2018-02-24 | 2018-06-12 | 清华大学 | A kind of catalytic film reactor based on nuclear track membrane and preparation method thereof |
| CN113351180A (en) * | 2021-06-08 | 2021-09-07 | 东北电力大学 | Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane |
| CN113509913A (en) * | 2021-04-21 | 2021-10-19 | 东北电力大学 | Preparation method and application of lithium ion imprinting nano composite membrane with high magnetism, high adsorption amount and high selectivity |
| EP3991831A1 (en) * | 2020-10-30 | 2022-05-04 | Zhou, Xiang-Qian | Method for fabricating nanoporous thin film, nanoporous thin film and its applications |
| CN114797799A (en) * | 2022-04-15 | 2022-07-29 | 东北电力大学 | Preparation method of MOFs-based lithium ion imprinting composite nanofiber membrane |
-
2022
- 2022-09-28 CN CN202211190325.1A patent/CN115445448B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107344095A (en) * | 2017-08-29 | 2017-11-14 | 江苏大学 | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage |
| CN108144559A (en) * | 2018-02-24 | 2018-06-12 | 清华大学 | A kind of catalytic film reactor based on nuclear track membrane and preparation method thereof |
| EP3991831A1 (en) * | 2020-10-30 | 2022-05-04 | Zhou, Xiang-Qian | Method for fabricating nanoporous thin film, nanoporous thin film and its applications |
| CN113509913A (en) * | 2021-04-21 | 2021-10-19 | 东北电力大学 | Preparation method and application of lithium ion imprinting nano composite membrane with high magnetism, high adsorption amount and high selectivity |
| CN113351180A (en) * | 2021-06-08 | 2021-09-07 | 东北电力大学 | Preparation method and application of temperature response type bionic lithium ion imprinting composite membrane |
| CN114797799A (en) * | 2022-04-15 | 2022-07-29 | 东北电力大学 | Preparation method of MOFs-based lithium ion imprinting composite nanofiber membrane |
Non-Patent Citations (3)
| Title |
|---|
| SUN, DS等: "Fabrication of highly selective ion imprinted macroporous membranes with crown ether for targeted separation of lithium ion", SEPARATION AND PURIFICATION TECHNOLOGY, vol. 175, 24 March 2017 (2017-03-24), pages 19 - 26, XP029853783, DOI: 10.1016/j.seppur.2016.11.029 * |
| 张宇锋: "仿生离子印迹纳米复合膜的制备及其对锂离子吸附性能的研究", 中国优秀硕士学位论文全文数据库 (工程科技Ⅰ辑), no. 03, 15 March 2019 (2019-03-15), pages 016 - 1 * |
| 汪润田;柳春丽;陈振斌;: "印迹复合膜", 化学进展, no. 07 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115445448B (en) | 2024-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106902654B (en) | Preparation method and application of lithium ion imprinted polyether sulfone composite membrane | |
| CN110479109B (en) | Preparation method of polyvinylidene fluoride mixed matrix membrane with high flux and strong pollution resistance | |
| CN114797799B (en) | Preparation method of MOFs-based lithium ion imprinting composite nanofiber membrane | |
| CN110292912B (en) | MOF-derived clustered cerium-based phosphorus removal adsorbent and preparation method thereof | |
| CN112646095A (en) | Dopamine-modified diatomite-adsorbed heavy metal hydrogel and preparation method and application thereof | |
| CN109364769A (en) | The preparation method of pollution-resistant Enoxacin molecularly imprinted composite membrane material | |
| CN113117651B (en) | Method for preparing glass fiber-metal organic framework composite film | |
| CN111939878A (en) | Ternary composite aerogel and preparation method and application thereof | |
| CN114984927A (en) | Hydrophobic MOF-based porous liquid carbon trapping absorbent and preparation method thereof | |
| CN113522061B (en) | Preparation method of high-adsorption-capacity lithium ion imprinting nano composite membrane | |
| CN114700050A (en) | Polyethyleneimine functionalized magnetic graphene oxide adsorbent and preparation method and application thereof | |
| CN113398776B (en) | Preparation method and application of bionic MOFs (metal organic frameworks) -based double-layer molecular imprinting nano composite membrane based on dual continuous imprinting system | |
| CN108889285B (en) | Limited-feeding chromatographic packing, preparation method thereof, stationary phase containing limited-feeding chromatographic packing and application of stationary phase | |
| CN115445448B (en) | Preparation method of MOFs-based lithium ion imprinting PVDF membrane | |
| CN108079798B (en) | Preparation method of super-hydrophilic organic membrane based on nano hydrotalcite-like compound | |
| CN115212856B (en) | Preparation and application of surface polymer functionalized spherical metal organic framework material | |
| CN113368708B (en) | Preparation method and application of suction filtration type double-layer molecular imprinting nano composite membrane based on multiple nano composite imprinting system | |
| CN113368707B (en) | Preparation method and application of three-dimensional porous MOFs/poly dopamine-based polycarbonate track etching imprinted membrane | |
| CN111363185B (en) | Preparation method and application of molecularly imprinted composite membrane initiated by surface functional monomer prepolymerization system | |
| CN114588882A (en) | Sodium alginate/molybdenum disulfide sponge-like adsorbent and preparation method and application thereof | |
| CN111841341B (en) | Composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and preparation method thereof | |
| CN114367271A (en) | Load type MnOXPreparation method of @ NiCo-MOF composite material | |
| CN113522057A (en) | Thin-layer nano composite film loaded with hydrophilic/charged metal organic framework | |
| CN115337914B (en) | Nano cyclodextrin crystal adsorption material with broad-spectrum adsorptivity and preparation method thereof | |
| CN116078190B (en) | Separation membrane 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 |