CN116063689A - Preparation method of zirconium-based metal organic framework material hierarchical pore UiO-66 - Google Patents
Preparation method of zirconium-based metal organic framework material hierarchical pore UiO-66 Download PDFInfo
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- 239000013207 UiO-66 Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 23
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002149 hierarchical pore Substances 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 6
- 239000010935 stainless steel Substances 0.000 claims abstract description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 150000003754 zirconium Chemical class 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract 3
- 238000001291 vacuum drying Methods 0.000 claims abstract 2
- 239000007787 solid Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004689 octahydrates Chemical class 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical group Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 16
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 239000000446 fuel Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 31
- 238000002474 experimental method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910006251 ZrOCl2.8H2O Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010457 zeolite Substances 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of preparation of new energy materials, and particularly relates to a preparation method of a zirconium-based metal organic framework material porous grade UiO-66. The preparation method of the porous grade UiO-66 of the zirconium-based metal-organic framework material comprises the following steps: firstly, mixing and grinding inorganic zirconium salt and phthalic acid according to a certain proportion at room temperature, adding a certain proportion of metal chloride after grinding for a certain time, then transferring the obtained object into a stainless steel reaction kettle with a polytetrafluoroethylene lining for crystallization reaction, cooling after a certain time and a certain temperature of reaction, and finally washing with ethanol, carrying out ultrasonic treatment and vacuum drying to obtain the porous grade UiO-66. The preparation method of the zirconium-based metal organic framework material porous grade UiO-66 provided by the invention adopts a template-free and solvent-free method, is simple and feasible, has mild reaction conditions and high production efficiency, and the produced porous grade UiO-66 has higher thermal stability and chemical stability, regular pore channels and larger specific surface area, and has larger application potential in the aspects of fuel storage, carbon dioxide adsorption, catalysis and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of new energy materials, and particularly relates to a preparation method of a zirconium-based metal organic framework material hierarchical pore UiO-66.
Background
Metal organic framework materials (metal organic framework, MOFs for short) are a class of porous crystalline materials formed by the connection of metal clusters to multi-site organic ligands. Compared with the traditional pore materials such as zeolite molecular sieve and hierarchical pore active carbon, the porous material has the characteristics of large specific surface area, low skeleton density, large pore volume, changeable composition and the like, and has great application potential in the aspects of fuel storage (hydrogen and methane), carbon dioxide adsorption, catalysis and the like. The zirconium-based MOFs represented by UiO-66 have the characteristics of higher thermal stability, higher chemical stability, regular pore channels, larger specific surface area, larger pore volume and the like, and have wide application prospects in various fields. But the micropore structure (the pore diameter is less than 2 nm) prevents large-size molecules from entering, so that the application of the polymer is limited in the fields of catalysis, chemical conversion of medicine molecules, medicine transmission and the like. Therefore, it is necessary to prepare hierarchical pore UiO-66 for the purpose of eliminating or slowing down the above-mentioned obstruction.
The most commonly used preparation of hierarchical pore UiO-66 to date is the solvothermal synthesis of Zr metal salts and their corresponding organic ligands in solution in N, N-dimethylformamide. On the basis, the pore diameter is increased by prolonging the length of the organic ligand, however, the method reduces the stability of MOFs materials and connectivity of pore structures, and therefore, the method has certain use limitations; in the method, the complexing agent is connected with metal or metal clusters, and the other end of the complexing agent is connected with the template agent to play a role of an intermediate medium, so that the hierarchical pore material is prepared. However, the disadvantages of the template agent such as removal, limitation of the use condition, low reaction rate and the like limit the industrialized development of the template agent.
Therefore, the development of a simple and efficient method for preparing hierarchical pore UiO-66 is the development direction of future research.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art and solve the technical bottleneck problem of preparing MOFs materials of the porous UiO-66, the invention provides a method for rapidly preparing the porous UiO-66 without a template agent and a solvent, which can rapidly improve the preparation production efficiency of the UiO-66 and accelerate the industrialized development.
The invention provides a preparation method of zirconium-based metal organic framework material porous grade UIO-66, which adopts no template agent and no solvent and comprises the following steps:
1. inorganic zirconium salt and phthalic acid were mixed in a molar ratio of 1:1 and ground for 10 minutes at room temperature to give solid powder A. The inorganic zirconium salt is zirconium oxychloride octahydrate, and the purity is analytically pure;
2. and adding a certain proportion of metal chloride into the solid powder A, and grinding at room temperature to obtain solid powder B. The grinding time is 10min; the metal chloride is FeCl3.6H2O, and the purity is analytically pure; the molar ratio of FeCl3.6H2O to ZrOCl2.8H2O is 3:1;
3. transferring the solid powder B into a stainless steel reaction kettle with a polytetrafluoroethylene lining for crystallization reaction to obtain white solid powder C; the method comprises the steps of carrying out a first treatment on the surface of the The crystallization reaction temperature is 100 ℃ and the time is 12 hours;
4. after the reaction kettle is cooled, taking out the solid C, washing with ethanol at 60 ℃ and carrying out ultrasonic treatment, then drying in vacuum at 80 ℃ for 12 hours,
a hierarchical pore UiO-66 was obtained.
The UiO-66BET specific surface area obtained by the steps is 1161.9m2/g, the mesoporous volume is 1.21cm3g-1, the mesoporous pore diameter range is 10-30nm, and the total pore volume is 1.51mL/g.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention overcomes the problems that the prior art needs to adopt a template agent and a solvent, adopts a template-free and solvent-free method, has simple and feasible preparation method, does not need complicated steps and raw materials, has mild reaction conditions and high production efficiency.
2. The porous grade UiO-66 produced by the invention has higher thermal stability and chemical stability, more regular pore channels and larger specific surface area, and has larger application potential in the aspects of fuel storage, carbon dioxide adsorption, catalysis and the like.
Drawings
FIG. 1 (a) shows the PXRD of UIO-66-solvent, UIO-66-solvent free, and MES-UIO-66.
FIG. 1 (b) is an N2 adsorption/desorption isotherm plot of UIO-66-solvent, UIO-66-solvent free, MES-UIO-66.
FIG. 1 (c) shows mesoporous pore diameter distribution diagrams of UIO-66-solvent, UIO-66-solvent free and MES-UIO-66.
FIG. 1 (d) shows the TG thermogravimetric analysis of UIO-66-solvent, UIO-66-solvent free and MES-UIO-66.
Detailed Description
According to the preparation method of the zirconium-based metal organic framework material porous grade UiO-66, the porous grade UiO-66 is rapidly prepared through the following experiments, and the beneficial results of the invention are verified through the following experiments.
The experimental instrument and the experimental reagent mainly used in the invention are as follows:
experimental instrument: stainless steel reaction kettle and vacuum dryer.
Experimental reagent: zirconium oxychloride zrocl2.8h2o octahydrate, terephthalic acid and ethanol.
Experiment 1, preparation method of porous grade UiO-66 of zirconium-based metal-organic framework material of the invention
1. ZrOC is to 12 8H 2 O (0.605 g,1.8 mmol) was mixed with terephthalic acid (0.311 g,1.8 mmol) and ground at room temperature for 10min to give solid powder A.
2. And adding a certain proportion of metal chloride into the solid powder A, and grinding for 10min at room temperature to obtain solid powder B. FeC (FeC) 13 ·6H 2 O and ZrOC 12 ·8H 2 The mol ratio of O is 3:1;
3. transferring the solid powder B into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and carrying out crystallization reaction for 12 hours at 100 ℃ to obtain white solid powder C;
4. after the reaction vessel was cooled, the solid C was taken out, washed with ethanol at 60℃and sonicated, and then dried under vacuum at 80℃for 12 hours to give porous grade UiO-66.
1. ZrOC is to 12 8H 2 O (0.605 g,1.8 mmol) was mixed with terephthalic acid (0.311 g,1.8 mmol) and ground at room temperature for 10min to give solid powder A.
2. Transferring the solid powder A into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing at 120 ℃ for 24 hours to obtain white solid powder D;
3. after the reaction kettle is cooled, the solid D is taken out, washed by ethanol at 60 ℃ and treated by ultrasonic, and then dried in vacuum at 80 ℃ for 12 hours, thus obtaining the zirconium-based metal organic framework material porous grade UiO-66. The synthesized sample was labeled UIO-66-solvent free (solid powder D)
Experiment 3, the solvent was added to synthesize the conventional UIO-66 (Zr)
1. ZrC is to 14 (0.159 g,0.68 mmol) and 1, 4-terephthalic acid (H) 2 BDC) (0.113 g,0.68 mmol) was dissolved in DMF (30 mL) at room temperature. Solution a was obtained.
2. The solution A is sealed in a 50mL reaction kettle and crystallized at 120 ℃ for 24h.
3. After cooling to room temperature, precipitate E was recovered by centrifugation and washed with DMF. The solid was then soaked and washed with ethanol several times and then dried in a vacuum oven to give a zirconium-based metal organic framework material porous grade UiO-66. The synthesized samples were labeled UIO-66-solvent (solid powder E), respectively.
Experimental results and beneficial effects
For comparison, a conventional UIO-66 (Zr) was synthesized by adding a solvent according to the reported method (experiment 3) and UIO-66 without adding a solvent (experiment 2). The synthesized samples were labeled UIO-66-solvent free (solid powder E) and UIO-66-solvent free (solid powder D), respectively.
As shown in FIG. 1 (a), the powder XRD patterns of UIO-66-solvent free (solid powder D), UIO-66-solvent free (solid powder C) showed well-resolved diffraction peaks, and distinct diffraction peaks were observed at 2 theta equal to 7.36 DEG and 8.5 DEG, which are characteristic peaks of the structure of UIO-66 (Zr), and no additional impurity peaks were observed, indicating that no impure crystal phase was formed, confirming successful synthesis of UIO-66. In contrast, the width of the diffraction peak of MES-UIO-66 is greater than that of UIO-66-solvent and UIO-66-solvent free, indicating that the crystal size of MES-UIO-66 may be smaller than that of UIO-66-solvent or UIO-66-solvent free.
As shown in the N2 adsorption and desorption isotherms of FIG. 1 (b), it is evident that the adsorption isotherms of UIO-66-solvent and UIO-66-solvent free all exhibit type I isotherms, which are typical features of microporous materials. Whereas mesoporous MES-UIO-66 is obviously an Iv-type adsorption isotherm with hysteresis, and the Iv-type adsorption isotherm is a typical characteristic of mesoporous materials and indicates the formation of mesopores. And the curve does not rise sharply in the range of the relative pressure P/P0 value of less than 0.02, indicating that the microporous structure is very small. And FIG. 1 (c) also demonstrates the presence of mesopores with a pore size in the range of 10nm to 30nm. MES-UIO-66 has larger specific surface area and pore volume, BET surface area can reach 1161.9m2g-1, mesoporous pore volume is 1.21cm3g-1, and is far larger than UIO-66-solvent and UIO-66-solvent free. BET tests have shown that mesopores were successfully introduced in UiO-66.
FIG. 1 (d) Thermogravimetric (TG) analysis shows that MES-UIO-66 has slightly poorer stability than UIO-66-solvent and UIO-66-solvent free, but can be kept stable at 400 ℃. These results indicate that MES-UIO-66 can be used as a host for binding macromolecules, and the structure and thermal stability of the MES-UIO-66 remain unchanged.
It will be appreciated by those skilled in the art that the above experimental methods are merely illustrative of the present invention and not intended to be limiting, and that variations of the above experimental methods will fall within the scope of the claims of the present invention as long as they are within the spirit of the present invention.
Claims (6)
1. The preparation method of the zirconium-based metal organic framework material porous grade UiO-66 is characterized by comprising the following steps of:
step one: mixing inorganic zirconium salt and phthalic acid, and grinding for 5-30 minutes at room temperature to obtain solid powder A;
step two: adding a certain proportion of metal chloride into the solid powder A, and grinding at room temperature to obtain solid powder B;
step three: transferring the solid powder B into a stainless steel reaction kettle with a polytetrafluoroethylene lining for crystallization reaction to obtain white solid powder C;
step four: after the reaction kettle is cooled, taking out the solid C, washing with ethanol at 40-60 ℃ and carrying out ultrasonic treatment, and then carrying out vacuum drying at 60-90 ℃ for 6-24 hours to obtain the hierarchical pore UiO-66.
2. The method for preparing zirconium-based metal organic framework material porous grade UiO-66 as claimed in claim 1, wherein: the inorganic zirconium salt is zirconium oxychloride ZrOCl octahydrate 2 ·8H 2 O, purity of analytically pure, zirconium oxychloride octahydrate ZrOCl 2 ·8H 2 The mixing proportion of O and phthalic acid is 1-5:1-5.
3. The method for preparing zirconium-based metal organic framework material porous grade UiO-66 as claimed in claim 1, wherein: the metal chloride is FeCl 3 ·6H 2 O, purity is analytically pure, feCl 3 ·6H 2 O and ZrOCl 2 ·8H 2 The mol ratio of O is 1-3:1-3.
4. The method for preparing zirconium-based metal organic framework material porous grade UiO-66 as claimed in claim 1, wherein: the grinding time is 5-30 minutes at room temperature.
5. The method for preparing zirconium-based metal organic framework material porous grade UiO-66 as claimed in claim 1, wherein: the crystallization reaction temperature is 100 ℃ and the time is 6-24 hours.
6. The method for preparing zirconium-based metal organic framework material porous grade UiO-66 as claimed in claim 1, wherein: and in the fourth step, the washing reagent is ethanol at 40-60 ℃, and the ultrasonic treatment method is adopted, so that the washing reagent is dried in vacuum at 60-90 ℃ for 6-24 hours.
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| WO2017210874A1 (en) * | 2016-06-08 | 2017-12-14 | Xia, Ling | Imperfect mofs (imofs) material, preparation and use in catalysis, sorption and separation |
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