CN115838481A - Preparation method and application of Zr-based metal organic framework UiO-66 - Google Patents
Preparation method and application of Zr-based metal organic framework UiO-66 Download PDFInfo
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- 239000013207 UiO-66 Substances 0.000 title claims abstract description 26
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 11
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 9
- 231100000719 pollutant Toxicity 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000017334 Alcea rosea Nutrition 0.000 claims abstract description 4
- 235000017303 Althaea rosea Nutrition 0.000 claims abstract description 4
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 240000000530 Alcea rosea Species 0.000 claims abstract 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 239000012621 metal-organic framework Substances 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000005611 electricity Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000002860 competitive effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 241000921356 Alcea Species 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010006895 Cachexia Diseases 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
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- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007665 chronic toxicity Effects 0.000 description 1
- 231100000160 chronic toxicity Toxicity 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention relates to the technical field of metal-organic framework materials, in particular to a preparation method and application of a Zr-based metal-organic framework material UiO-66, wherein the Zr-based metal-organic framework material UiO-66 comprises the following raw materials, zirconium tetrachloride, terephthalic acid and a multidimensional regulator, the molar ratio is 1/x/35, and the preparation method comprises the following steps: s1, adding zirconium tetrachloride, terephthalic acid (BDC), N-dimethylformamide and multidimensional regulators with different amounts into a 100 mL hollyhock bottle, uniformly mixing, and performing ultrasonic treatment until the solid is completely dissolved; s2, reacting 48 h in a 120 ℃ oven, and centrifuging and collecting precipitates; s3, cleaning with nitrogen-nitrogen dimethylformamide for three times, replacing with methanol for three times, dissolving unreacted raw materials, and replacing with a low-boiling-point solvent; s4, heating and activating 12 h at 250 ℃ under vacuum. According to the invention, by utilizing the exposed metal active sites and the pore diameter expanded to the mesoporous region, high-efficiency specific adsorption can be effectively realized on the negative electricity low-concentration high-risk emerging pollutants in the water body, and the method has the advantages of good cyclicity, easiness in regeneration and strong stability.
Description
Technical Field
The invention relates to the technical field of metal organic framework materials, in particular to a preparation method and application of a Zr-based metal organic framework UiO-66.
Background
PPCPs are a large and large number of new pollutants in the environment, including drugs, cosmetics, veterinary drugs, bactericides, disinfectants, pesticides, and the like. With the development of detection technology, 1980s first detected the presence of PPCPs in the environment due to its low concentration in the environment. Many studies have shown that PPCPs are widely present in rivers and lakes, and the presence of PPCPs has been detected in many famous rivers in the world. PPCPs have been reported to have potential risks, chronic toxicity, and bioaccumulation, and long-term accumulation of PPCPs can cause considerable cachexia. The traditional removal method cannot effectively remove the PPCPs, so that a suitable material is found, and the realization of the specific adsorption and degradation of the environmental low-concentration high-risk PPCPs is a hot point of research in recent years. Research shows that the excellent adsorption material has the characteristics of high specific surface area, rich active sites and the like, and the MOFs has the advantages.
The Metal Organic Frameworks (MOFs) are a crystalline porous material and have wide application prospects. The pore size and shape of MOFs can be modulated by varying inorganic units or organic ligands, and this controllable modulation has led to widespread interest in MOFs. MOFs have important applications in the fields of gas and vapor adsorption, separation and storage, and in recent years, many studies have been made to remove pollutants such as heavy metal ions, benzene, dyes, etc. from water bodies by MOF.
Zr-MOF is a group of MOFs with excellent stability, has high specific surface area and porosity, exposed active sites, a definite and convenient structure for modification and photocatalytic potential, and therefore has a huge application prospect in the aspect of removing emerging pollutants in water bodies.
The MOF in the mesoporous region is more matched with the molecular size of PPCPs, so that the mesoporous region is easy to synthesize, high in stability and clear in structure, and the UiO-66 with high specific surface area and porosity is the Zr-MOF in the mesoporous region, so that the UiO-66 has a great promoted space on the effect of adsorbing and removing the PPCPs.
Disclosure of Invention
In order to solve at least one technical problem, the invention provides a preparation method and application of a Zr-based metal organic framework UiO-66. According to the invention, by utilizing the exposed metal active sites and the pore diameter extending to the mesoporous region, high-efficiency specific adsorption can be effectively realized on the negative electricity low-concentration high-risk emerging pollutants in the water body, and the method has the advantages of good cyclicity, easiness in regeneration and strong stability.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a Zr-based metal-organic framework UiO-66, comprising the following raw materials: zirconium tetrachloride, terephthalic acid and a multidimensional regulator, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the multidimensional regulator is 1/x/35, wherein x =0.3,0.5,0.8,1.0, and the preparation method comprises the following steps: the method comprises the following steps:
s1, adding zirconium tetrachloride, terephthalic acid (BDC), N-dimethylformamide and multidimensional regulators with different amounts into a 100 mL hollyhock bottle, uniformly mixing, and performing ultrasonic treatment until the solid is completely dissolved;
s2, reacting 48 h in an oven at 120 ℃, and centrifuging and collecting precipitates;
s3, cleaning with nitrogen-nitrogen dimethylformamide for three times, replacing with methanol for three times, dissolving unreacted raw materials, and replacing with a low-boiling-point solvent;
s4, heating and activating 12 h at 250 ℃ under vacuum.
Preferably, the coordination number of the zirconium tetrachloride and the terephthalic acid in S1 is unsaturated.
Preferably, x =0.3.
Preferably, the multi-dimensional regulator is a single-sided carboxylic acid.
Preferably, the unilateral carboxylic acid is one of acetic acid, n-valeric acid, n-caprylic acid, n-dodecanoic acid, n-tetradecanoic acid and n-heptadecanoic acid.
The second aspect of the invention provides application of the Zr-based metal organic framework UiO-66 in removing emerging pollutants in a water body.
Compared with the prior art, the invention has the following beneficial effects:
the metal organic framework material with the continuously adjustable defect structure is obtained by adding the multidimensional regulator into a precursor synthesized by the metal organic framework material, uniformly mixing the multidimensional regulator in a nitrogen-nitrogen dimethyl formamide solution and adopting a solvothermal method. According to the invention, by utilizing the exposed metal active sites and the pore diameter extending to the mesoporous region, high-efficiency specific adsorption can be effectively realized on the negative electricity low-concentration high-risk emerging pollutants in the water body, and the method has the advantages of good cyclicity, easiness in regeneration and strong stability.
Unilateral carboxylic acid regulators with different sizes are introduced, three competitive coordination environments, namely weak, medium and strong, of the regulators and BDC are designed in the process of re-synthesis, and the unilateral carboxylic acid regulators react in a drying oven capable of being heated and cooled by a program for 48 hours, so that the continuous regulation and control of properties such as the aperture range, the specific surface area and the like of the Zr-MOF are realized, and the adsorption effect of the Zr-MOF on PPCPs is optimized.
With the increase of the size of the regulator, the pore size distribution of the material shows an increasing trend, and the adsorption rate of the material to ibuprofen drug molecules is obviously improved, which shows that the adsorption effect of Zr-MOF on new pollutants is really improved by the strategy.
Drawings
FIGS. 1-4 are X-ray powder diffraction patterns of UiO-66 materials synthesized with different modifiers of example 1 of the present invention.
FIGS. 5-10 are graphs showing nitrogen adsorption desorption test curves and pore size distribution of UiO-66 material synthesized with different regulators in example 1 of the present invention.
FIGS. 11 to 12 are scanning electron microscope images in example 1 of the present invention.
FIG. 13 is a thermogravimetric plot of the UiO-66 material synthesized with different modulators in example 1 of the present invention.
FIG. 14 is an elemental analysis of the UiO-66 material synthesized with different modulators of example 1 of the present invention.
FIGS. 15-16 are graphs of the adsorption kinetics data for IBU-model compound molecules for the UiO-66 material with different modulators involved in the synthesis of example 1 of the present invention.
Detailed description of the preferred embodiments
In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments of the present invention.
Referring to fig. 1 to 16, some of the instrument information used in the embodiment of the present invention is as follows:
infrared spectrometer, model: bruker Foucus D8; manufacturer: bruker, germany;
x-ray powder diffractometer, type: miniFlex 600 diffractometer, manufacturer: rigaku corporation, japan;
scanning electron microscope, model: JEM-2010, manufacturer: hitachi, japan;
elemental analyzer, model: VARIO EL-III, manufacturer: elementar Analyzensystem GmbH, germany;
nitrogen adsorption and aperture analyzer, model: prodigy 7, manufacturer: leeman corporation;
the thermogravimetric-thermal difference comprehensive thermal analyzer has the model: TG-DTA 6200, manufacturer: hitachi Seiko;
high performance liquid chromatograph, model: LC-20, manufacturer: shimadzu.
Example 1
The embodiment provides a preparation method and application of Zr-based metal organic framework UiO-66,
specifically, the preparation method comprises the following steps of adding zirconium tetrachloride 0.16 g, terephthalic acid (BDC) 0.034 g, 0.057 g, 0.091 g, 0.114 g,40 mL of nitrogen-nitrogen dimethylformamide and different amounts of regulator into a 100 mL hollyhock bottle, and carrying out ultrasonic treatment for 20 min until all solids are dissolved. Reacting 48 h in a 120 ℃ oven, centrifuging, collecting the precipitate, washing three times with nitrogen-nitrogen dimethylformamide, replacing three times with methanol to dissolve unreacted raw materials, replacing low boiling point solvent, and heating and activating 12 h at 250 ℃ under vacuum.
The amount of regulator used is as shown in the table:
experimental example 1
FIGS. 1-4 show X-ray powder diffraction patterns of UiO-66 materials synthesized with different modulators according to example 1 of the present invention, which completely correspond to the simulated patterns, thus demonstrating the successful synthesis of UiO-66 materials.
FIGS. 5-10 are graphs of nitrogen adsorption and desorption test curves and pore size distribution of UiO-66 material synthesized by different regulators in example 1 of the present invention, and the specific surface area generally shows a rule of increasing first and then smoothing as the size of the regulator increases. The pore size distribution always shows an increasing trend.
FIGS. 11-12 are scanning electron micrographs of the material of example 1 of the invention, and it can be seen that the material size tends to decrease with increasing competitive coordination environment under the same conditioning agent. Under the strong competitive coordination environment, the size of the material is gradually reduced as the size of the regulator is increased.
FIG. 13 is a thermogravimetric plot of the UiO-66 material synthesized with different modulators according to example 1 of the present invention, showing that the thermal stability of the same modulator decreases with increasing competitive coordination environment, and the thermal stability of different modulators decreases with increasing size.
FIG. 14 is an elemental analysis of the UiO-66 material synthesized with different modifiers in example 1 of the present invention, showing a decrease in the gradient of the C element.
FIGS. 15-16 are graphs of adsorption kinetics data for molecules of IBU-model compounds of UiO-66 materials with different modulators involved in synthesis in example 1 of the present invention, and the adsorption performance of the present invention was evaluated. The acetic acid group, with the increase in the competitive environment of the regulator, tends to increase the adsorption rate. The valeric acid, caprylic acid, lauric acid group also exhibited the same regularity. The kinetic constant of lauric acid group is improved by 13.33-28.33 times compared with acetic acid group. Under the same competitive coordination environment, the adsorption rate is obviously improved along with the increase of the size of the regulator, and the rate constant of the lauric acid group is 22 times that of the acetic acid group.
While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the appended claims.
Claims (6)
1. The preparation method of the Zr-based metal organic framework UiO-66 is characterized by comprising the following raw materials: zirconium tetrachloride, terephthalic acid and a multidimensional regulator, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the multidimensional regulator is 1/x/35, wherein x =0.3,0.5,0.8,1.0, and the preparation method comprises the following steps:
s1, adding zirconium tetrachloride, terephthalic acid (BDC), N-dimethylformamide and multidimensional regulators with different amounts into a 100 mL hollyhock bottle, uniformly mixing, and performing ultrasonic treatment until the solid is completely dissolved;
s2, reacting 48 h in an oven at 120 ℃, and centrifuging and collecting precipitates;
s3, cleaning with nitrogen-nitrogen dimethylformamide for three times, replacing with methanol for three times, dissolving unreacted raw materials, and replacing with a low-boiling-point solvent;
s4, heating and activating 12 h under vacuum at 250 ℃.
2. The method of claim 1, wherein the coordination number of zirconium tetrachloride and terephthalic acid in S1 is unsaturated.
3. The method of claim 2, wherein x =0.3, for preparing the Zr-based metal-organic framework UiO-66.
4. The method of claim 1, wherein the multi-dimensional adjusting agent is a mono-carboxylic acid.
5. The method for preparing the Zr-based metal organic framework UiO-66 according to claim 4, wherein said mono-side carboxylic acid is one of acetic acid, n-pentanoic acid, n-octanoic acid, n-dodecanoic acid, n-tetradecanoic acid, and n-heptadecanoic acid.
6. Use of the Zr-based metal organic framework UiO-66 prepared by the method of any one of claims 1 to 5 for removing emerging pollutants from a body of water.
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| CN108066773A (en) * | 2017-12-22 | 2018-05-25 | 华东理工大学 | The preparation method and thus obtained nano material of a kind of adjustable mesoporous metal organic backbone nano material of grain size |
| CN108084453A (en) * | 2018-01-10 | 2018-05-29 | 蚌埠学院 | The aperture expanding method of UiO-66 metal-organic framework materials and application |
| CN108114699A (en) * | 2017-12-22 | 2018-06-05 | 华东理工大学 | The preparation method and thus obtained nano material of a kind of adjustable multi-stage porous metal organic framework nano material in aperture and its application |
| CN109400890A (en) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A kind of preparation method of multi-stage porous metal-organic framework materials |
| CN110256683A (en) * | 2019-04-19 | 2019-09-20 | 武汉理工大学 | A kind of preparation method and applications of hierarchical porous structure metal-organic framework materials |
| CN112646192A (en) * | 2020-12-17 | 2021-04-13 | 东华大学 | Method for preparing hierarchical porous metal-organic framework compound by template method and application |
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- 2023-02-16 CN CN202310120083.7A patent/CN115838481A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400890A (en) * | 2017-08-18 | 2019-03-01 | 中国石化扬子石油化工有限公司 | A kind of preparation method of multi-stage porous metal-organic framework materials |
| CN108066773A (en) * | 2017-12-22 | 2018-05-25 | 华东理工大学 | The preparation method and thus obtained nano material of a kind of adjustable mesoporous metal organic backbone nano material of grain size |
| CN108114699A (en) * | 2017-12-22 | 2018-06-05 | 华东理工大学 | The preparation method and thus obtained nano material of a kind of adjustable multi-stage porous metal organic framework nano material in aperture and its application |
| CN108084453A (en) * | 2018-01-10 | 2018-05-29 | 蚌埠学院 | The aperture expanding method of UiO-66 metal-organic framework materials and application |
| CN110256683A (en) * | 2019-04-19 | 2019-09-20 | 武汉理工大学 | A kind of preparation method and applications of hierarchical porous structure metal-organic framework materials |
| CN112646192A (en) * | 2020-12-17 | 2021-04-13 | 东华大学 | Method for preparing hierarchical porous metal-organic framework compound by template method and application |
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