CN106866741A - A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr) - Google Patents
A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr) Download PDFInfo
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- CN106866741A CN106866741A CN201710124023.7A CN201710124023A CN106866741A CN 106866741 A CN106866741 A CN 106866741A CN 201710124023 A CN201710124023 A CN 201710124023A CN 106866741 A CN106866741 A CN 106866741A
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic System compounds without a metal-carbon linkage
Abstract
A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr).Method the present invention relates to synthesize metal-organic framework materials MIL 100 (Cr).The invention solves the problems that existing method time-consuming, reactor utilization rate is low and must using toxic hydrofluoric acid problem.Method：By CrCl3·6H2O is well mixed with trimesic acid, then grinds at room temperature, obtains mixture, and mixture is placed in carries out crystallization in the stainless steel cauldron of liner Teflon, cools down stainless steel cauldron, takes out product, obtains solid product；Solid product is washed, the solid product after being washed, finally dried the solid product after washing, you can obtain MIL 100 (Cr).The present invention is used for a kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr).
Description
Technical field
Method the present invention relates to synthesize metal-organic framework materials MIL-100 (Cr).
Background technology
Secondary structure unit and organic ligand that metal-organic framework materials (MOFs) are made up of inorganic metal ion, lead to
The material of the tridimensional network that too strong chemical bond links together and formed.At be found from MOFs materials more than 20 years
Between in, it presents good performance with separating, the numerous areas such as be catalyzed in the storage of gas.With to MOFs materials synthesis
Further investigation, the potential application scope of MOFs materials is also constantly expanding, and medicament slow release and sensor system are had been directed at present
The aspects such as work.Wherein MIL-100 (Cr) materials while with above advantage, also stronger stability, therefore have more
Big application potential.
MIL-100 (Cr), i.e. [Cr3F(H2O)3O(BTC)3·nH2O (n ≈ 28)] material be 2004 by France
The design synthesis of Ferey research groups, is connected with each other with part BTC by three core chromium clusters and formed.It has two kinds of different size micropores
Cage, less cage size is aboutIt is about with diameterRegular pentagon window；Larger cage size is aboutTool
There is diameter to be aboutRegular pentagon window.The BET specific surface area of MIL-100 (Cr) can reach 1500m2/ g~
2200m2/ g, total pore volume is close to 1.7cm3/ g, can adsorb substantial amounts of molecule.
Current MIL-100 (Cr) is synthesized using hydro-thermal method, with crome metal or CrO3As chromium source, with hydrofluoric acid
The aqueous solution is hybridly prepared into, the heating crystallization in a kettle. after mixing with trimesic acid.The method takes extremely long, reactor
Utilization rate it is low, it is necessary to use poisonous, dangerous hydrofluoric acid.Need the faster more environmentally friendly synthesis path of exploitation badly.
The content of the invention
The present invention is to solve existing method, time-consuming, reactor utilization rate is low and must use toxic hydrofluoric acid
Problem, and provide a kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr).
A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr), specifically according to following
What step was carried out：
First, by CrCl3·6H2O is well mixed with trimesic acid, and 10min~40min is then ground at room temperature, is obtained
Mixture, mixture is placed in carries out crystallization in the stainless steel cauldron of liner Teflon, crystallization temperature be 180 DEG C~
250 DEG C, the crystallization time is 4h~48h, cools down stainless steel cauldron, takes out product, obtains solid product；
Described CrCl3·6H2O is (0.33~3) with the mol ratio of trimesic acid:1；
2nd, under conditions of being 30 DEG C~90 DEG C in temperature, solid product is washed 2 times~4 times, each wash time is 2h
~20h, the solid product after being washed, under conditions of being finally 70 DEG C~180 DEG C in temperature by the solid product after washing
Drying, that is, obtain MIL-100 (Cr).
The beneficial effects of the invention are as follows：1st, generated time is foreshortened into 4h~48h, crystallization time is greatly shortened.
2nd, without any solvent is used, improve the utilization rate of reactor.
3rd, toxic hydrofluoric acid is not used.
4th, MIL-100 (Cr) specific surface area can reach 1848m2/ g is suitable with hydrothermal synthesis method.
The present invention is used for a kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr).
Brief description of the drawings
Fig. 1 is the XRD of MIL-100 (Cr)；1 is MIL-100 (Cr) prepared by conventional hydrothermal method, and 2 make for embodiment two
Standby MIL-100 (Cr), 3 is MIL-100 (Cr) prepared by embodiment one, and 4 is MIL-100 (Cr) prepared by embodiment three, and 5 are
MIL-100 (Cr) prepared by example IV；
Fig. 2 is the nitrogen Adsorption and desorption isotherms of MIL-100 (Cr) prepared by embodiment one；
Fig. 3 is MIL-100 (Cr) prepared by example IV and the nitrogen adsorption desorption of the MIL-100 (Cr) of the preparation of embodiment two
Thermoisopleth, 1 is MIL-100 (Cr) prepared by example IV, and 2 is MIL-100 (Cr) prepared by embodiment two；
Fig. 4 is the nitrogen Adsorption and desorption isotherms of MIL-100 (Cr) prepared by embodiment three；
Fig. 5 be the reaction time be 15h when, CrCl3·6H2The MIL-100 that O is prepared with trimesic acid different mol ratio
(Cr) nitrogen Adsorption and desorption isotherms, 1 is MIL-100 (Cr) prepared by embodiment six, and 2 is MIL-100 prepared by embodiment five
(Cr), 3 is MIL-100 (Cr) prepared by embodiment one.
Specific embodiment
Technical solution of the present invention is not limited to the specific embodiment of act set forth below, also including each specific embodiment it
Between any combination.
Specific embodiment one：A kind of solventless method Fast back-projection algorithm metal-organic framework materials described in present embodiment
The method of MIL-100 (Cr), specifically follows the steps below：
First, by CrCl3·6H2O is well mixed with trimesic acid, and 10min~40min is then ground at room temperature, is obtained
Mixture, mixture is placed in carries out crystallization in the stainless steel cauldron of liner Teflon, crystallization temperature be 180 DEG C~
250 DEG C, the crystallization time is 4h~48h, cools down stainless steel cauldron, takes out product, obtains solid product；
Described CrCl3·6H2O is (0.33~3) with the mol ratio of trimesic acid:1；
2nd, under conditions of being 30 DEG C~90 DEG C in temperature, solid product is washed 2 times~4 times, each wash time is 2h
~20h, the solid product after being washed, under conditions of being finally 70 DEG C~180 DEG C in temperature by the solid product after washing
Drying, that is, obtain MIL-100 (Cr).
The beneficial effect of this specific embodiment is：1st, generated time is foreshortened into 4h~48h, when crystallization is greatly shortened
Between.
2nd, without any solvent is used, improve the utilization rate of reactor.
3rd, toxic hydrofluoric acid is not used.
4th, MIL-100 (Cr) specific surface area can reach 1848m2/ g is suitable with hydrothermal synthesis method.
Specific embodiment two：Present embodiment from unlike specific embodiment one：In step one during crystallization
Between be 15h.Other are identical with specific embodiment one.
Specific embodiment three：Unlike one of present embodiment and specific embodiment one or two：It is brilliant in step one
The change reaction time is 12h.Other are identical with specific embodiment one or two.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：It is brilliant in step one
The change reaction time is 18h.Other are identical with specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：It is brilliant in step one
The change reaction time is 24h.Other are identical with specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Institute in step one
The CrCl for stating3·6H2O is 2 with the mol ratio of trimesic acid:1.Other are identical with specific embodiment one to five.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Institute in step one
The CrCl for stating3·6H2O is 1.5 with the mol ratio of trimesic acid:1.Other are identical with specific embodiment one to six.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Institute in step one
The CrCl for stating3·6H2O is 1 with the mol ratio of trimesic acid:1.Other are identical with specific embodiment one to seven.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：It is brilliant in step one
It is 180 DEG C~200 DEG C to change temperature.Other are identical with specific embodiment one to eight.
Specific embodiment ten：Unlike one of present embodiment and specific embodiment one to nine：It is brilliant in step one
It is 200 DEG C~250 DEG C to change temperature.Other are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：
A kind of method of the solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) described in the present embodiment,
Specifically follow the steps below：
First, by CrCl3·6H2O is well mixed with trimesic acid, and 30min is then ground at room temperature, obtains mixture,
Mixture is placed in carries out crystallization in the stainless steel cauldron of liner Teflon, crystallization temperature is 220 DEG C, during crystallization
Between be 15h, cool down stainless steel cauldron, take out product, obtain solid product；
Described CrCl3·6H2O is 2 with the mol ratio of trimesic acid:1；
2nd, under conditions of being 70 DEG C in temperature, solid product is washed 2 times, each wash time is 3h, after being washed
Solid product, finally by the solid product after washing temperature be 150 DEG C under conditions of dry, that is, obtain MIL-100 (Cr).
Embodiment two：The present embodiment from unlike embodiment one：The crystallization time is 12h in step one.Other with
Embodiment one is identical.
Embodiment three：The present embodiment from unlike embodiment one：The crystallization time is 18h in step one.Other with
Embodiment one is identical.
Example IV：The present embodiment from unlike embodiment one：The crystallization time is 24h in step one.Other with
Embodiment one is identical.
Fig. 1 is the XRD of MIL-100 (Cr)；1 is MIL-100 (Cr) prepared by conventional hydrothermal method, and 2 make for embodiment two
Standby MIL-100 (Cr), 3 is MIL-100 (Cr) prepared by embodiment one, and 4 is MIL-100 (Cr) prepared by embodiment three, and 5 are
MIL-100 (Cr) prepared by example IV；As seen from the figure, the material of the generation of embodiment one to four is really for MIL-100 (Cr) is tied
Structure.
Fig. 2 is the nitrogen Adsorption and desorption isotherms of MIL-100 (Cr) prepared by embodiment one；Fig. 3 is prepared by example IV
The nitrogen Adsorption and desorption isotherms of MIL-100 (Cr) prepared by MIL-100 (Cr) and embodiment two, 1 is prepared by example IV
MIL-100 (Cr), 2 is MIL-100 (Cr) prepared by embodiment two；Fig. 4 is the nitrogen of MIL-100 (Cr) prepared by embodiment three
Adsorption and desorption isotherms；As seen from the figure, the isothermal feature of all of sample adsorption meets the report on MIL-100 (Cr) crystal
Road.
Table 1
Table 1 is CrCl3·6H2O is 2 with the mol ratio of trimesic acid:When 1, MIL-100 prepared by different generated times
(Cr) BET specific surface area and pore volume.When being 15h between when reacted, the specific surface area of material is maximum, reaches 1848m2/g。
Embodiment five：The present embodiment from unlike embodiment one：CrCl described in step one3·6H2O and equal benzene three
The mol ratio of formic acid is 1.5:1.Other are identical with embodiment one.
Embodiment six：The present embodiment from unlike embodiment one：CrCl described in step one3·6H2O and equal benzene three
The mol ratio of formic acid is 1:1.Other are identical with embodiment one.
Table 2
Table 2 be the reaction time be 15h when, CrCl3·6H2The MIL-100 that O is prepared with trimesic acid different mol ratio
(Cr) BET specific surface area and pore volume, work as CrCl3·6H2The ratio of O and trimesic acid is 2:When 1, the specific surface of material
Product is maximum, reaches 1848m2/g。
Fig. 5 be the reaction time be 15h when, CrCl3·6H2The MIL-100 that O is prepared with trimesic acid different mol ratio
(Cr) nitrogen Adsorption and desorption isotherms, 1 is MIL-100 (Cr) prepared by embodiment six, and 2 is MIL-100 prepared by embodiment five
(Cr), 3 is MIL-100 (Cr) prepared by embodiment one.As seen from the figure, the isothermal feature of all of sample adsorption meet on
The report of MIL-100 (Cr) crystal.
Claims (10)
1. a kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr), it is characterised in that Yi Zhongwu
The method of solvent method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) is followed the steps below：
First, by CrCl3·6H2O is well mixed with trimesic acid, and 10min~40min is then ground at room temperature, is mixed
Thing, mixture is placed in carries out crystallization in the stainless steel cauldron of liner Teflon, crystallization temperature is 180 DEG C~250 DEG C,
The crystallization time is 4h~48h, cools down stainless steel cauldron, takes out product, obtains solid product；
Described CrCl3·6H2O is (0.33~3) with the mol ratio of trimesic acid:1；
2nd, temperature be 30 DEG C~90 DEG C under conditions of, by solid product wash 2 times~4 times, each wash time be 2h~
20h, the solid product after being washed finally dries the solid product after washing under conditions of temperature is for 70 DEG C~180 DEG C
It is dry, that is, obtain MIL-100 (Cr).
2. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that the crystallization time is 15h in step one.
3. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that the crystallization time is 12h in step one.
4. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that the crystallization time is 18h in step one.
5. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that the crystallization time is 24h in step one.
6. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that the CrCl described in step one3·6H2O is 2 with the mol ratio of trimesic acid:1.
7. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that the CrCl described in step one3·6H2O is 1.5 with the mol ratio of trimesic acid:1.
8. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that the CrCl described in step one3·6H2O is 1 with the mol ratio of trimesic acid:1.
9. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that crystallization temperature is 180 DEG C~200 DEG C in step one.
10. the side of a kind of solventless method Fast back-projection algorithm metal-organic framework materials MIL-100 (Cr) according to claim 1
Method, it is characterised in that crystallization temperature is 200 DEG C~250 DEG C in step one.
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Cited By (7)
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| CN107445820A (en) * | 2017-08-10 | 2017-12-08 | 哈尔滨工业大学 | Floride-free, the solvent-free and Fast back-projection algorithm high yield metal-organic framework materials MIL 100 of one kind（Fe）Method |
| CN107875863A (en) * | 2017-10-31 | 2018-04-06 | 华南理工大学 | A kind of solvent-free inverting method for preparing metal organic framework film |
| CN109261204A (en) * | 2018-10-18 | 2019-01-25 | 哈尔滨工业大学 | A kind of green scale is combined to the method and application of functionalization UiO-66 (Zr) |
| CN109762176A (en) * | 2019-01-24 | 2019-05-17 | 太原理工大学 | A method of rapid synthesis MIL-100 (Cr) is assisted with steam phase |
| CN111892713A (en) * | 2020-07-30 | 2020-11-06 | 太原理工大学 | Method for synthesizing MIL-100Cr integral material by sol-gel method |
| CN114380869A (en) * | 2022-01-12 | 2022-04-22 | 太原科技大学 | Metal-organic framework material and preparation method and application thereof |
| CN114957694A (en) * | 2022-05-30 | 2022-08-30 | 天津大学 | Solvent-free coordination rare earth MOF material and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107445820A (en) * | 2017-08-10 | 2017-12-08 | 哈尔滨工业大学 | Floride-free, the solvent-free and Fast back-projection algorithm high yield metal-organic framework materials MIL 100 of one kind（Fe）Method |
| CN107445820B (en) * | 2017-08-10 | 2020-08-25 | 哈尔滨工业大学 | Method for rapidly synthesizing high-yield metal organic framework material MIL-100(Fe) without fluorine and solvent |
| CN107875863A (en) * | 2017-10-31 | 2018-04-06 | 华南理工大学 | A kind of solvent-free inverting method for preparing metal organic framework film |
| CN109261204A (en) * | 2018-10-18 | 2019-01-25 | 哈尔滨工业大学 | A kind of green scale is combined to the method and application of functionalization UiO-66 (Zr) |
| CN109762176A (en) * | 2019-01-24 | 2019-05-17 | 太原理工大学 | A method of rapid synthesis MIL-100 (Cr) is assisted with steam phase |
| CN109762176B (en) * | 2019-01-24 | 2022-02-01 | 太原理工大学 | Method for rapidly synthesizing MIL-100(Cr) by steam phase assistance |
| CN111892713A (en) * | 2020-07-30 | 2020-11-06 | 太原理工大学 | Method for synthesizing MIL-100Cr integral material by sol-gel method |
| CN111892713B (en) * | 2020-07-30 | 2022-02-18 | 太原理工大学 | Method for synthesizing MIL-100Cr integral material by sol-gel method |
| CN114380869A (en) * | 2022-01-12 | 2022-04-22 | 太原科技大学 | Metal-organic framework material and preparation method and application thereof |
| CN114380869B (en) * | 2022-01-12 | 2023-12-22 | 太原科技大学 | Metal-organic framework material and preparation method and application thereof |
| CN114957694A (en) * | 2022-05-30 | 2022-08-30 | 天津大学 | Solvent-free coordination rare earth MOF material and preparation method and application thereof |
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