The preparation method of a kind of metal-organic framework materials MIL-100 (Fe)
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).