CN112029105A - Method for continuously and rapidly purifying MOFs - Google Patents
Method for continuously and rapidly purifying MOFs Download PDFInfo
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- CN112029105A CN112029105A CN202010754521.1A CN202010754521A CN112029105A CN 112029105 A CN112029105 A CN 112029105A CN 202010754521 A CN202010754521 A CN 202010754521A CN 112029105 A CN112029105 A CN 112029105A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000746 purification Methods 0.000 claims abstract description 88
- 239000012043 crude product Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 20
- 230000002572 peristaltic effect Effects 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000006228 supernatant Substances 0.000 claims abstract description 15
- 239000012264 purified product Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005119 centrifugation Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 230000003321 amplification Effects 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000013207 UiO-66 Substances 0.000 description 35
- 239000011259 mixed solution Substances 0.000 description 12
- 239000013148 Cu-BTC MOF Substances 0.000 description 5
- 239000013177 MIL-101 Substances 0.000 description 5
- 239000013206 MIL-53 Substances 0.000 description 5
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 5
- 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013132 MOF-5 Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013260 porous coordination network Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
The invention discloses a method for continuously and rapidly purifying MOFs, which comprises the following specific steps: respectively mixing the purified solvent and the MOFs crude product by a T-shaped mixer for a peristaltic pump, and then, introducing the mixture into a coil reactor arranged in an ultrasonic water bath for purification; carrying out centrifugal separation on the purified product; selecting a solvent and repeating the purification and centrifugation steps; and (4) pouring out the supernatant liquid, and drying the solid sample to obtain the high-purity MOFs product. The method can quickly purify MOFs crude products by a continuous flow ultrasonic method, can solve the problems of large usage amount of MOFs solvent, long purification time, low purification efficiency and the like, can replace the current solvent exchange method, and provides a method for MOFs amplification preparation and purification.
Description
Technical Field
The invention relates to a method for continuously and rapidly purifying MOFs, belonging to the field of research of materials and chemical processes.
Background
The MOFs, metal organic framework materials, have been the focus of both academia and commerce due to their good structure with a large number of potential applications. The MOFs is widely applied to the fields of separation, storage, sensing, drug delivery and the like, and with the large-scale production of the MOFs, the production of the MOFs with high purity and low cost becomes a key, so that the development of an economic, environment-friendly and continuously-operated MOFs purification method has huge market prospects.
The common purification method of MOFs is solvent exchange method, but the method has long purification time and is difficult to be applied on large scale. The KyVo et al (CrystalGrowth)&Design,2019) the synthesized MOFs slurry was centrifuged, soaked with DMF at 70 ℃ for 6h (2 times) and ethanol at 70 ℃ for 6h (2 times) and dried at 70 ℃ for 24h, the specific surface area of the purified MOFs was 1320m2Per g, pore volume 1.50cm3The yield was 90% per g.
Florence et al (Inorganic chemistry,2014) synthesized MOFs in a 5L glass reactor equipped with a reflux condenser and a polytetrafluoroethylene mechanical stirrer, and the slurry was filtered to recover 510g of the MOFs crude product; the MOFs crude product was redispersed in 7LDMF at 333K, stirred for 6h, then the solid product was recovered by filtration, repeating the same procedure twice. The MOFs were then purified again in the same procedure using methanol instead of DMF, the specific surface area of the MOFs after conversion being 1375m2Per g, pore volume 1.27cm3The yield was 67%. The purification method has intermittent operation, long purification time and high operation cost.
In summary, the current methods for purifying MOFs have the following problems:
(1) the purification time is long, and the purification efficiency is low;
(2) the purification is an intermittent process, MOFs cannot be purified continuously in large batch, the operation cost is high, and certain potential safety hazards can be brought.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for continuously and rapidly purifying MOFs materials. The purification process of the MOFs is simple and has high purification efficiency.
The technical scheme of the invention is as follows: a method for continuously and rapidly purifying MOFs comprises the following specific steps: respectively mixing a purified solvent and a MOFs crude product by a T-shaped mixer for a peristaltic pump, and then, introducing the mixture into a coil reactor (with the general volume of 20-200 mL) placed in an ultrasonic water bath for purification; wherein the feeding flow rate is 1-10 mL/min; the purification temperature is 30-70 ℃; the purification time is 2-20 min; ultrasonic frequency is 30-130 KHz; carrying out centrifugal separation on the purified product; selecting a solvent and repeating the purification and centrifugation steps; and (4) pouring out the supernatant liquid, and drying the solid sample to obtain the high-purity MOFs product.
Preferably, the purification solvent is one or two of water, N-Dimethylformamide (DMF), ethanol or methanol.
Preferably, the liquid-solid ratio of the purified solvent to the MOFs crude product is 10-70 g/g; more preferably, the purified liquid-solid ratio is 10 to 30 g/g.
Preferably, the centrifugal rotation speed of centrifugal separation is 6000-12000 r/min, and the centrifugal time is 8-15 min; more preferably, the centrifugal rotating speed is 8000-10000 r/min; more preferably, the centrifugation time is 10-12 min.
Preferably, the solvent selected for repeating the above purification and centrifugation steps is water, ethanol or methanol; the number of times of repeating the purification and centrifugation steps is preferably 1 to 3 times, and more preferably 2 to 3 times.
Preferably, the coil reactor is any one of fusible Polytetrafluoroethylene (PFA), Polytetrafluoroethylene (PTFE), or stainless steel.
Preferably, after the supernatant liquid is poured out, the drying temperature of the solid sample is 60-100 ℃, and the drying time is 6-24 hours; more preferably, the drying temperature is 70-100 ℃; more preferably, the drying time is 8-12 h.
The high-purity MOFs product obtained by the method has a clear crystal morphology, and the purity is 90-99.9%.
The purification method can be applied to MOFs materials such as IRMOF, ZIF, MIL, PCN, UiO and the like.
Preferably, the volume of the coil reactor is 4-16 mL; preferably, the feeding flow rate of MOFs crude products is 2-4 mL/min; the preferred ultrasonic frequency is 40-80 KHz; preferably, the purification temperature is 30-50 ℃; preferably, the purification time is 2-4 min.
Has the advantages that:
1. the invention can purify a large amount of MOFs crude products in a short time, and has high purification efficiency;
2. the invention has lower purification temperature and obviously reduces energy consumption;
3. the purity of MOFs purified by the method is 90-99.9%, and the structure of the MOFs is not affected;
4. the invention provides a method for continuously purifying MOFs, reduces the operation cost and provides a method for large-scale production of MOFs.
Drawings
FIG. 1 is a schematic diagram of a device for continuous purification of MOFs; wherein, 1-MOFs crude product solution; 2-a solvent; 3-a peristaltic pump; 4-PFA tubing; a 5-T type mixer; 6-a coil pipe; 7-ultrasonic water bath; 8-a collector.
FIG. 2 is an XRD pattern of UiO-66 before and after purification of example 1; wherein (1) -before purification (2) -after purification.
FIG. 3 is a TG-DTA plot of UiO-66 before and after purification of example 1; wherein (1) -before purification (2) -after purification.
FIG. 4 is a nitrogen adsorption/desorption isotherm at 77K of purified UiO-66 of example 1.
FIG. 5 is an SEM image of purified UiO-66 of example 1.
Detailed Description
The purity described in the examples below was calculated by means of a combination of TG-DTA model WCT-1 with a thermobalance analysis. The specific surface area is measured by an ASAP2020 type specific surface pore size tester, and the specific surface area is measured at 77K after a sample is degassed at 200 ℃ for 12 h. The SEM image was measured by a Hitachi (Hitachi) Seiki model S4800 field emission Scanning Electron Microscope (SEM).
Example 1
The device for continuously purifying MOFs is shown in FIG. 1, and the purification process comprises: the crude product solution (1) of UiO-66 and the DMF solution (2) respectively enter a T-shaped mixer (5) through a peristaltic pump (3), the mixed solution enters a PFA coil reactor (6), the mixed solution is fully purified in an ultrasonic water bath kettle (7), and a collector (8) is adopted to collect the purified solution.
UiO: the liquid-solid ratio of the DMF and the crude product of UiO-66 is 30g/g, the crude product of UiO-66 and the DMF respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PFA coil reactor (volume is 8mL) in an ultrasonic bath, the ultrasonic frequency is 120KHz, the feeding flow rate is 2mL/min, the purification temperature is 40 ℃, and the purification time is 4 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 8000r/min, and the centrifugal time is 12 min; selecting methanol solvent, and repeating the above purification steps for 2 times; after pouring out the supernatant, the solid sample was dried at 80 ℃ for 12 hours to obtain pureThe purity of the purified UiO-66 product is 99.9% (the purity of the UiO-66 product before purification is 67.5%). The XRD patterns of UiO-66 before and after purification are shown in FIG. 2. As shown in FIG. 2, UiO-66 after purification had better crystallinity than before purification and had fewer peaks. The TG-DTA pattern of UiO-66 before and after purification is shown in FIG. 3. As can be seen from FIG. 3, the weight loss of purified UiO-66 before 350 ℃ is lower than that before purification, indicating that purified UiO-66 contains significantly lower impurities than before purification. The adsorption/desorption isotherm diagram of purified UiO-66 on nitrogen is shown in FIG. 4, and the BET specific surface area of purified UiO-66 is 1242m2(ii) in terms of/g. An SEM image of the purified UiO-66 is shown in figure 5, and the purified UiO-66 is in an octahedron shape, crystal particles are between 100 and 150nm, and the shape is clear.
Example 2
IRMOF: the liquid-solid ratio of the DMF and the IRMOF-1 crude product is 10g/g, the UiO-66 crude product and the DMF respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PFA coil reactor (the volume is 80mL) in an ultrasonic bath, the ultrasonic frequency is 130KHz, the feeding flow rate is 10mL/min, the purification temperature is 30 ℃, and the purification time is 8 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 8000r/min, and the centrifugal time is 15 min; selecting ethanol solvent, and repeating the above purification steps for 3 times; and (3) after the supernatant liquid is poured out, drying the solid sample at 60 ℃ for 24h to obtain a purified IRMOF-1 product, wherein the purity of the IRMOF-1 product is 96.5% (the purity of the IRMOF-1 before purification is 63.1%).
Example 3
ZIF: the liquid-solid ratio of methanol and the crude ZIF-8 product is 30g/g, the crude ZIF-8 product and the methanol are respectively fed into a T-shaped mixer through a peristaltic pump, the mixed solution is fed into a PTFE coil reactor (with the volume of 16mL) in an ultrasonic bath, the ultrasonic frequency is 40KHz, the feeding flow rate is 4mL/min, the purification temperature is 50 ℃, and the purification time is 4 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 12000r/min, and the centrifugal time is 10 min; selecting methanol solvent, and repeating the above purification step for 1 time; and (3) after the supernatant liquid is poured out, drying the solid sample at 70 ℃ for 8 hours to obtain a purified ZIF-8 product, wherein the purity of the ZIF-8 product is 97.6% (the purity of the ZIF-8 before purification is 53.1%).
Example 4
And (3) MIL: the liquid-solid ratio of water to the MIL-101 crude product is 30g/g, the MIL-101 crude product and water respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PTFE coil reactor (the volume is 8mL) in an ultrasonic bath, the ultrasonic frequency is 80KHz, the feeding flow rate is 2mL/min, the purification temperature is 30 ℃, and the purification time is 4 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 10000r/min, and the centrifugal time is 12 min; selecting water solvent and repeating the above purification step for 2 times; after the supernatant was decanted, the solid sample was dried at 100 ℃ for 12h to give a purified MIL-101 product with a MIL-101 purity of 96.7%. (MIL-101 before purification was 70.1% pure).
Example 5
PCN: the liquid-solid ratio of the ethanol and the crude product of HKUST-1 is 10g/g, the crude product of HKUST-1 and the ethanol respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a stainless steel coil reactor (with the volume of 4mL) in an ultrasonic bath, the ultrasonic frequency is 80KHz, the feeding flow rate is 4mL/min, the purification temperature is 40 ℃, and the purification time is 2 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 9000r/min, and the centrifugal time is 11 min; selecting ethanol solvent, and repeating the above purification steps for 1 time; after the supernatant was decanted, the solid sample was dried at 90 ℃ for 10h to obtain a purified HKUST-1 product, HKUST-1 having a purity of 94.8% (HKUST-1 having a purity of 62.1% before purification).
Example 6
And (3) MIL: the liquid-solid ratio of the DMF and the MIL-53 crude product is 30g/g, the MIL-53 crude product and the DMF respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PTFE coil reactor (the volume is 12mL) in an ultrasonic bath, the ultrasonic frequency is 100KHz, the feeding flow rate is 4mL/min, the purification temperature is 50 ℃, and the purification time is 3 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 8000r/min, and the centrifugal time is 10 min; selecting ethanol solvent, and repeating the above purification steps for 2 times; after decanting the supernatant, the solid sample was dried at 80 ℃ for 16h to yield purified MIL-53 product having a MIL-53 purity of 98.8% (MIL-53 before purification was 68.3%).
Example 7
UiO: the liquid-solid ratio of the DMF and the crude product of UiO-66 is 70g/g, the crude product of UiO-66 and the DMF respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PFA coil reactor (volume is 2mL) in an ultrasonic bath, the ultrasonic frequency is 30KHz, the feeding flow rate is 1mL/min, the purification temperature is 70 ℃, and the purification time is 2 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 6000r/min, and the centrifugal time is 8 min; selecting methanol solvent, and repeating the above purification step for 1 time; after the supernatant was decanted, the solid sample was dried at 100 ℃ for 6h to give a purified UiO-66 product with a purity of 95.5% UiO-66 (purity of 67.5% of UiO-66 before purification).
Example 8
UiO: the liquid-solid ratio of the DMF and the crude product of UiO-66 is 20g/g, the crude product of UiO-66 and the DMF respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PFA coil reactor (with the volume of 200mL) in an ultrasonic bath, the ultrasonic frequency is 80KHz, the feeding flow rate is 10mL/min, the purification temperature is 30 ℃, and the purification time is 20 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 9000r/min, and the centrifugal time is 12 min; selecting methanol solvent, and repeating the above purification steps for 3 times; after the supernatant was decanted, the solid sample was dried at 80 ℃ for 12h to give a purified UiO-66 product having a purity of 98.1% for UiO-66 (67.5% for UiO-66 before purification).
Example 9
UiO: DMF and UiO-66-NH2The liquid-solid ratio of the crude product is 20g/g, the crude product UiO-66 and DMF respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PFA coil reactor (the volume is 16mL) in an ultrasonic bath, the ultrasonic frequency is 80KHz, the feeding flow rate is 4mL/min, the purification temperature is 30 ℃, and the purification time is 4 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 8000r/min, and the centrifugal time is 8 min; selecting methanol solvent, and repeating the above purification steps for 3 times; after the supernatant was decanted, the solid sample was dried at 70 ℃ for 12h to obtain purified UiO-66-NH2Product, UiO-66-NH2The purity was 96.1% (UiO-66-NH before purification)2Purity 65.8%).
Example 10
UiO: the liquid-solid ratio of the DMF and the crude product of UiO-66 is 10g/g, the crude product of UiO-66 and the DMF respectively enter a T-shaped mixer through a peristaltic pump, the mixed solution enters a PFA coil reactor (the volume is 15mL) in an ultrasonic bath, the ultrasonic frequency is 30KHz, the feeding flow rate is 3mL/min, the purification temperature is 50 ℃, and the purification time is 3 min; carrying out centrifugal separation on the purified product, wherein the centrifugal rotation speed is 8000r/min, and the centrifugal time is 12 min; selecting methanol solvent, and repeating the above purification step for 1 time; after the supernatant was decanted, the solid sample was dried at 80 ℃ for 12h to give a purified UiO-66 product with a purity of 94.7% UiO-66 (67.5% UiO-66 before purification).
Claims (8)
1. A method for continuously and rapidly purifying MOFs comprises the following specific steps: respectively mixing the purified solvent and the MOFs crude product by a T-shaped mixer for a peristaltic pump, and then, introducing the mixture into a coil reactor arranged in an ultrasonic water bath for purification; wherein the feeding flow rate is 1-10 mL/min; the purification temperature is 30-70 ℃; the purification time is 2-20 min; ultrasonic frequency is 30-130 KHz; carrying out centrifugal separation on the purified product; selecting a solvent and repeating the purification and centrifugation steps; and (4) pouring out the supernatant liquid, and drying the solid sample to obtain the high-purity MOFs product.
2. The method of claim 1, wherein the purification solvent is one or two of water, N-Dimethylformamide (DMF), ethanol, or methanol.
3. The method according to claim 1, characterized in that the liquid-solid ratio of the purification solvent to the MOFs crude product is 10-70 g/g.
4. The method according to claim 1, wherein the centrifugation is performed at a rotation speed of 6000 to 12000r/min for 8 to 15 min.
5. The method of claim 1, wherein the solvent selected for repeating the purifying and centrifuging steps is water, ethanol or methanol; the number of times of repeating the purification and centrifugation steps is 1-3 times.
6. The process of claim 1, wherein the coil reactor is any one of meltable Polytetrafluoroethylene (PFA), Polytetrafluoroethylene (PTFE), or stainless steel.
7. The method according to claim 1, wherein the temperature for drying the solid sample after pouring out the supernatant is 60 to 100 ℃ and the drying time is 6 to 24 hours.
8. The method according to claim 1, wherein the high purity MOFs product has a purity of 90-99.9%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601652A (en) * | 2014-10-28 | 2016-05-25 | 中国石油化工股份有限公司 | Method for preparing metal organic framework material |
| US20170361300A1 (en) * | 2016-06-17 | 2017-12-21 | Battelle Memorial Institute | System and process for continuous and controlled production of metal-organic frameworks and metal-organic framework composites |
| CN107614097A (en) * | 2015-05-27 | 2018-01-19 | 联邦科学与工业研究组织 | The production of metal organic frame |
| CN107614100A (en) * | 2015-05-27 | 2018-01-19 | 联邦科学与工业研究组织 | The separation of metal organic frame |
| CN107602874A (en) * | 2017-11-01 | 2018-01-19 | 中国药科大学 | A kind of method based on microflow control technique synthesis metal-organic framework materials |
-
2020
- 2020-07-31 CN CN202010754521.1A patent/CN112029105A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601652A (en) * | 2014-10-28 | 2016-05-25 | 中国石油化工股份有限公司 | Method for preparing metal organic framework material |
| CN107614097A (en) * | 2015-05-27 | 2018-01-19 | 联邦科学与工业研究组织 | The production of metal organic frame |
| CN107614100A (en) * | 2015-05-27 | 2018-01-19 | 联邦科学与工业研究组织 | The separation of metal organic frame |
| US20170361300A1 (en) * | 2016-06-17 | 2017-12-21 | Battelle Memorial Institute | System and process for continuous and controlled production of metal-organic frameworks and metal-organic framework composites |
| CN107602874A (en) * | 2017-11-01 | 2018-01-19 | 中国药科大学 | A kind of method based on microflow control technique synthesis metal-organic framework materials |
Non-Patent Citations (3)
| Title |
|---|
| YU XIN ET AL.: ""Continuous flow synthesis of porous materials"", 《CHINESE CHEMICAL LETTERS》 * |
| 彭金辉等编著: "《微流体溶剂萃取技术》", 30 June 2015, 北京：冶金工业出版社 * |
| 谢昆等著: "《纳米技术在水污染控制中的应用》", 30 June 2016, 武汉大学出版社 * |
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