CN103242374A - Preparation method of metal organic framework material MIL-100 (Fe) - Google Patents
Preparation method of metal organic framework material MIL-100 (Fe) Download PDFInfo
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- CN103242374A CN103242374A CN2013101993888A CN201310199388A CN103242374A CN 103242374 A CN103242374 A CN 103242374A CN 2013101993888 A CN2013101993888 A CN 2013101993888A CN 201310199388 A CN201310199388 A CN 201310199388A CN 103242374 A CN103242374 A CN 103242374A
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- 239000013291 MIL-100 Substances 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000013144 Fe-MIL-100 Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 244000124209 Crocus sativus Species 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000012423 maintenance Methods 0.000 description 7
- 229910000608 Fe(NO3)3.9H2O Inorganic materials 0.000 description 4
- 239000013292 MIL-100(Cr) Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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Abstract
The invention relates to a preparation method of a metal organic framework material MIL-100 (Fe), which comprises the following steps: proportionally adding an organic ligand and an iron source into a certain amount of deionized water, and mixing for 30 minutes; mixing the mixture obtained in the step (1) at 80-95 DEG C under atmospheric pressure to react for 5-20 hours; and filtering the solid obtained in the step (2), washing with anhydrous ethanol at 60-80 DEG C for 10-20 hours, treating with a 30-60 mmol/L ammonium fluoride solution at 60-80 DEG C for 10-20 hours, sufficiently washing with deionized water, and finally, drying at 100-200 DEG C for 5-10 hours to obtain the pure MIL-100 (Fe). The method has the advantages of mild synthesis conditions, high product yield and high product quality.
Description
Technical field
The invention belongs to the preparation method of metal-organic framework materials, particularly a kind of metal-organic framework materials MIL-100(Fe) the preparation method.
Background technology
(Metal-Organic Frameworks, MOFs) material is the Multifunction porous material with periodic network structure that organic ligand and transition metal ion form by self-assembly to metallic organic framework.It is big that this class material has specific surface area, the voidage height, and pore size distribution is even, characteristics such as structure plasticity-, and have bigger application potential in fields such as light, electricity, magnetic, catalysis, molecular recognition, absorption, ion-exchange, gas storage.
Metal-organic framework materials MIL-100(Cr) (MIL:Materials of Institut Lavoisier) took the lead in synthetic and report by French F é rey seminar in 2004, be a kind of with Cr metal tripolymer and organic ligand trimesic acid (1,3, the super tetrahedron that 5-BTC) is connected to form extends the final 3-dimensional metal-organic coordination compound with MTN topological framework that forms as secondary structure unit by the further self-assembly of super tetrahedron to the space.MIL-100(Cr) two kinds of mesoporous cages are arranged, the aperture is respectively 2.5nm and 2.9nm, and opening size is respectively 0.55nm and 0.86nm.This material have bigger specific surface area (the Langmuir specific surface area〉2800m
2/ g) and pore volume (380nm
3), thermal stability reaches 270 ℃, also has a large amount of unsatuated metal Lewis acidic sites.These character demonstrate MIL-100(Cr) be with a wide range of applications in fields such as gas adsorption separation and catalysis.
With respect to MIL-100(Cr), MIL-100(Fe) have nontoxic, environmentally safe, cost of material is cheap, and has plurality of advantages such as redox property, makes this material receive more and more investigators' concern.At present about MIL-100(Fe) bibliographical information of the research static hydrothermal synthesis method that adopts Horcajada etc. (P.Horcajada etc., Chem.Commun., 2007,2820 – 2822) to propose, i.e. 1.0Fe proportionally more
0: 0.661,3,5-BTC:2.0HF:1.2HNO
3: 280H
2O is under high temperature (150 ℃) high pressure, and static crystallization 6d obtains.The obvious deficiency of this method is not only under High Temperature High Pressure and is carried out, and synthesis cycle is long.Afterwards, Seo etc. (Y.K.Seo etc., Micropor.Mesopor.Mate., 2012,157,137 – 145) have optimized this method, proportionally with 1.0Fe (NO
3)
3.9H
2O:0.671,3,5-BTC:x H
2O (x=55 – 280) is under high temperature (160 ℃) high pressure, and static crystallization 12h can obtain MIL-100(Fe).Because this method still needs to prepare under high-temperature and high-pressure conditions, condition is still harsh relatively, and target product yield is totally still not high.In addition, (A.Dhakshinamoorthy etc. such as Dhakshinamoorthy, Dalton Trans., 2011,40,10719 – 10724) synthesized MIL-100(Fe by microwave method), though microwave method has shortened generated time, but the difficult control of this method condition, and very difficult industrial amplification production.
Summary of the invention
The objective of the invention is at existing preparation MIL-100(Fe) existing above-mentioned synthesis condition harshness in the process, product yield is not high and be difficult to the weak point of suitability for industrialized production, and a kind of synthesis condition gentleness, product yield height, the colory method of product are provided.
For solving this technical problem a kind of metal-organic framework materials MIL-100(Fe of the present invention) the preparation method, concrete steps are:
(1) organic ligand and source of iron are added in a certain amount of deionized water by proportioning, mix and stir 30min;
(2) mixture that step (1) is obtained is at normal pressure, 80～95 ℃ of following stirring reaction 5～20h;
(3) solid that step (2) is obtained after filtration, wash 10～20h with dehydrated alcohol down at 60～80 ℃, handle 10～20h down for 60～80 ℃ with the ammonium fluoride solution of 30～60mmol/L then, fully wash with deionized water subsequently, at 100～200 ℃ of down dry 5～10h, namely obtain pure MIL-100(Fe at last).
At described a kind of metal-organic framework materials MIL-100(Fe) the preparation method in, the organic ligand described in the step (1) is 1,3,5-benzene tricarboxylic acid or 1,3,5-benzene tricarboxylic acid trimethyl.
At described a kind of metal-organic framework materials MIL-100(Fe) the preparation method in, the source of iron described in the step (1) is iron nitrate or iron(ic) chloride.
At described a kind of metal-organic framework materials MIL-100(Fe) the preparation method in, in the step (1), the molar ratio of organic ligand and source of iron and deionized water is (0.5～2): 1:(50～300).
At described a kind of metal-organic framework materials MIL-100(Fe) the preparation method in, the selected reactor of step (2) is that there-necked flask adds the backflow prolong.
The present invention and existing metal-organic framework materials MIL-100(Fe) the preparation method compare, shorten generated time, reduced temperature of reaction and pressure, thereby reduced synthetic energy consumption, preparation process is to carry out under (stirring) dynamic condition simultaneously, overcome the low shortcoming of traditional static crystallization method productive rate, obtained colory metal-organic framework materials MIL-100(Fe).
Description of drawings
Fig. 1 is the XRD figure of the MIL-100 (Fe) of match.
Fig. 2 is the new synthetic XRD figure of placing MIL-100 (Fe) after month that reaches among the embodiment 1.
Fig. 3 is the XRD figure of embodiment 2 samples.
Embodiment
Further specify the present invention below by embodiment, but the present invention is not limited to this.
Embodiment 1
Successively with 2.02g Fe (NO
3)
3.9H
2O, 0.70g1,3,5-benzene tricarboxylic acid add and to fill in the there-necked flask of 5mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, be warming up to 95 ℃ after constant temperature maintenance 12h, selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 10h with dehydrated alcohol down at 70 ℃, the ammonium fluoride solution of 30mmol/L is handled 10h down for 80 ℃ then, fully washs with deionized water at last.150 ℃ of drying temperatures, time of drying, 10h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent (referring to Fig. 1, Fig. 2), illustrates that the crystal that obtains is pure MIL-100 (Fe).
Embodiment 2
Successively with 0.81g FeCl
3.6H
2O, 0.51g1,3,5-benzene tricarboxylic acid trimethyl add and to fill in the there-necked flask of 15mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, be warming up to 95 ℃ after constant temperature maintenance 12h, selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 15h with dehydrated alcohol down at 60 ℃, the ammonium fluoride solution of 40mmol/L is handled 15h down for 70 ℃ then, fully washs with deionized water at last.100 ℃ of drying temperatures, time of drying, 10h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent (referring to Fig. 1, Fig. 3), illustrates that the crystal that obtains is pure MIL-100 (Fe).
Embodiment 3
Successively with 2.02g Fe (NO
3)
3.9H
2O, 0.63g1,3,5-benzene tricarboxylic acid trimethyl add and to fill in the there-necked flask of 5mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, be warming up to 80 ℃ after constant temperature maintenance 20h, selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 20h with dehydrated alcohol down at 80 ℃, the ammonium fluoride solution of 50mmol/L is handled 10h down for 60 ℃ then, fully washs with deionized water at last.150 ℃ of drying temperatures, time of drying, 5h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent, and illustrates that the crystal that obtains is pure MIL-100 (Fe).
Embodiment 4
Successively with 0.81g FeCl
3.6H
2O, 0.42g1,3,5-benzene tricarboxylic acid add and to fill in the there-necked flask of 15mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, be warming up to 80 ℃ after constant temperature maintenance 20h, selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 10h with dehydrated alcohol down at 70 ℃, the ammonium fluoride solution of 30mmol/L is handled 20h down for 80 ℃ then, fully washs with deionized water at last.150 ℃ of drying temperatures, time of drying, 10h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent, and illustrates that the crystal that obtains is pure MIL-100 (Fe).
Embodiment 5
Successively with 2.02g Fe (NO
3)
3.9H
2O, 0.70g1,3,5-benzene tricarboxylic acid add and to fill in the there-necked flask of 5mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, be warming up to 95 ℃ after constant temperature maintenance 5h, selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 15h with dehydrated alcohol down at 60 ℃, the ammonium fluoride solution of 60mmol/L is handled 10h down for 80 ℃ then, fully washs with deionized water at last.180 ℃ of drying temperatures, time of drying, 6h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent, and illustrates that the crystal that obtains is pure MIL-100 (Fe).
Embodiment 6
Successively with 0.81g FeCl
3.6H
2O, 1.51g1,3,5-benzene tricarboxylic acid trimethyl add and to fill in the there-necked flask of 16mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, be warming up to 95 ℃ after constant temperature maintenance 5h, selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 10h with dehydrated alcohol down at 70 ℃, the ammonium fluoride solution of 30mmol/L is handled 10h down for 80 ℃ then, fully washs with deionized water at last.150 ℃ of drying temperatures, time of drying, 8h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent, and illustrates that the crystal that obtains is pure MIL-100 (Fe).
Embodiment 7
Successively with 2.02g Fe (NO
3)
3.9H
2O, 2.10g1,3,5-benzene tricarboxylic acid add and to fill in the there-necked flask of 27mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, be warming up to 90 ℃ after constant temperature maintenance 12h, selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 10h with dehydrated alcohol down at 60 ℃, the ammonium fluoride solution of 30mmol/L is handled 10h down for 80 ℃ then, fully washs with deionized water at last.200 ℃ of drying temperatures, time of drying, 5h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent, and illustrates that the crystal that obtains is pure MIL-100 (Fe).
Embodiment 8
Successively with 0.81g FeCl
3.6H
2O, 0.38g1,3, the adding of 5-benzene tricarboxylic acid trimethyl fills in the there-necked flask of 3mL deionized water, behind the about 30min of magnetic agitation, reflux condensation mode, constant temperature keeps 12h after being warming up to 90 ℃, and selected reactor is that there-necked flask adds the backflow prolong, and selected reactor is that there-necked flask adds the backflow prolong.After reaction finishes, with sample filtering, behind the capacity deionized water wash, put into loft drier freeze-day with constant temperature 5h.
Dried sample is further purified with ethanol and Neutral ammonium fluoride respectively.At first handle 10h with dehydrated alcohol down at 70 ℃, the ammonium fluoride solution of 30mmol/L is handled 10h down for 80 ℃ then, fully washs with deionized water at last.100 ℃ of drying temperatures, time of drying, 10h obtained light safran powder.Through XRD analysis, the MIL-100 of its characteristic peak and match (Fe) characteristic peak is consistent, and illustrates that the crystal that obtains is pure MIL-100 (Fe).
Claims (5)
1. preparation method metal-organic framework materials MIL-100(Fe) is characterized in that this preparation method's concrete steps are:
(1) organic ligand and source of iron are added in a certain amount of deionized water by proportioning, mix and stir 30min;
(2) mixture that step (1) is obtained is at normal pressure, 80～95 ℃ of following stirring reaction 5～20h;
(3) solid that step (2) is obtained after filtration, wash 10～20h with dehydrated alcohol down at 60～80 ℃, handle 10～20h down for 60～80 ℃ with the ammonium fluoride solution of 30～60mmol/L then, fully wash with deionized water subsequently, at 100～200 ℃ of down dry 5～10h, namely obtain pure MIL-100(Fe at last).
2. preparation method according to claim 1 is characterized in that, the organic ligand described in the step (1) is 1,3,5-benzene tricarboxylic acid or 1,3,5-benzene tricarboxylic acid trimethyl.
3. preparation method according to claim 1 is characterized in that, the source of iron described in the step (1) is iron nitrate or iron(ic) chloride.
4. preparation method according to claim 1 is characterized in that, in the step (1), the molar ratio of organic ligand and source of iron and deionized water is (0.5～2): 1:(50～300).
5. preparation method according to claim 1 is characterized in that, the selected reactor of step (2) is that there-necked flask adds the backflow prolong.
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| CN110563962B (en) * | 2019-09-25 | 2022-03-11 | 暨南大学 | Metal organic framework material and preparation method thereof |
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| CN112126072A (en) * | 2020-09-17 | 2020-12-25 | 福建工程学院 | Super-tetrahedral metal organic framework material, and preparation method and application thereof |
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| CN112521619B (en) * | 2020-11-13 | 2022-04-01 | 太原理工大学 | Anion post-displacement green synthesis MIL-101(Cr) -X-Method (2) |
| CN113013424A (en) * | 2021-04-12 | 2021-06-22 | 武汉氢能与燃料电池产业技术研究院有限公司 | High-efficiency composite catalyst applied to fuel cell and preparation method thereof |
| WO2022236879A1 (en) * | 2021-05-11 | 2022-11-17 | 西北工业大学 | Mn-mof-based cold-adapted nano-enzyme, preparation method therefor and use thereof |
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