CN104086594A - Method for quickly synthesizing metal organic framework material MIL-101 - Google Patents
Method for quickly synthesizing metal organic framework material MIL-101 Download PDFInfo
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- CN104086594A CN104086594A CN201410306140.1A CN201410306140A CN104086594A CN 104086594 A CN104086594 A CN 104086594A CN 201410306140 A CN201410306140 A CN 201410306140A CN 104086594 A CN104086594 A CN 104086594A
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Abstract
The invention discloses a method for quickly synthesizing a metal organic framework material MIL-101. The method comprises the following steps: adding chromic nitrate, hydrofluoric acid, terephthalic acid, de-ionized water and carbon nanotubes or carbon fibers into an airtight reaction kettle according to a certain ratio, and reacting at 220 DEG C for 0.5-2 hours; after the reaction is finished, slowly cooling to room temperature, then performing centrifugal separation to obtain upper-layer solid, flushing the upper-layer solid by adopting dimethylformamide and absolute ethanol, drying in vacuum and activating to obtain the metal organic framework material MIL-101. According to the method, the metal organic framework material MIL-101 is quickly synthesized under the induction effect of the carbon nanomaterial, the shortcoming of long preparation time of a conventional method is overcome, and quick controllable preparation of the metal organic framework material MIL-101 is realized. The method has the characteristics of low investment and low operating cost, has wide application prospect, and can create remarkable economic benefits.
Description
Technical field:
The invention belongs to polymeric material field, particularly containing the preparation method of chromium metallo organic material, be specifically related to the method for fast synthetic metal-organic framework materials MIL-101 a kind of.
Technical background:
Metal-organic framework (MOFs) material is the organic and inorganic supramolecular materials of a class heterozygosis, and it has very high specific surface area, large pore volume, adjustable hole dimension and multifarious skeleton structure.MOFs possesses high-crystallinity simultaneously and has the interaction of strong metal-ligand, and the existence of strong coordinate bond has strengthened its chemical stability and thermostability.These characteristics make MOFs become the novel multifunctional material of a class.MOFs and traditional porous material are as not identical in the pore structure of molecular sieve, in MOFs, there is no wall structure, and the delimitation of their internal spaces obtains by linker, constructs internal space just as support.This construction method makes different skeletons will produce different pore structures, makes the shape in hole have diversity.Thereby MOFs compares with carbon material and can realize application more widely with traditional zeolitic material, comprises storage, the absorption of gas and separates, catalysis and medicament slow release and fuel desulfuration etc.The synthetic MOFs material system of solvent-thermal method also has advantages of that crystal structure degree is high.Crystal form MOFs synthesis mechanism can be thought the process of a gathering that has comprised nucleation, oligomeric, crystal grain and growth, last crystallization.At organic ligand and concentration of metal ions, when higher, first three step is relatively very fast, has comprised the further polymerization of a lot of responseless point at grain surface, impels crystal grain merge fast and grow.As time goes on, the density loss of part and metal ion, the speed of nucleation reduces, and the growth velocity of crystal grain becomes the main ratedeterming step of crystallisation process.The essence of the synthetic MOFs material of solvent-thermal method is the reaction of Lewis acid-alkali in fact, and the part of deprotonation reacts as Lewis alkali with as the metal ion of Lewis acid.If the reaction times is too short or too fast, just have loose Precipitation, can not get monocrystalline.The deprotonation speed of the condition of reacting by adjusting and part matches, and being formed coordinate bond is the key of nucleation and crystallization.The crystal that can obtain high-ratio surface by adjusting reaction time, if but exceeding the optimum reaction times also can cause the damage of crystal.
MIL-101 (Cr) is the one in MOFs material, utilizes hydrothermal method preparation, is Cr (N0
3)
39H
20, HF, terephthalic acid and deionized water according to a certain percentage, react 8h in closed reactor at 220 DEG C.After reaction finishes, centrifugation, rinses, and vacuum-drying activation obtains.MIL-101 is to N
2adsorption isothermal line be I and IV type, in crystalline structure, there are micropore and mesoporous two kinds of pore structures: a kind of micropore is pentagon, and aperture is
another kind is hexagon, and aperture is
mesoporous aperture is respectively
and
its pore volume approaches 2.0cm
3/ g.Another character of MIL-101 is to have high thermostability and chemical stability, is exposed in air and processes and can not affect its structure with many different organic solvents, and still can holding structure 220 DEG C time complete, thermal stable temperature approaches 300 DEG C.MIL-101 hole surface comprises hydrophobic surface and water-wetted surface character simultaneously in addition.MIL-101 has air, and chemical stability is good, and in reaction, structure keeps stable feature, thereby MIL-101 is also applied to the reaction such as hydrogenation, oxidation as carrier, and in the preparation of fine chemicals.Realize the widespread use of MIL-101, synthetic MIL-101, just can have attracting prospect fast.Carbon nanotube it be the graphene sheet layer that formed by carbon atom be rolled into seamless, the body of hollow, can play inducing action to MIL-101 nucleation and crystallization, promotes fast synthetic MIL-101.Other carbon nanomaterial that contains graphite-structure, all reflects and can promote MIL-101 synthetic characteristic fast.Therefore taking carbon nanomaterial as nucleation and crystallization promotor, can realize the quick controlled preparation of MIL-101 crystal.
Summary of the invention:
The object of the invention is to overcome metal-organic framework materials MIL-101 long shortcoming of tradition preparation method's time, the method for fast synthetic metal-organic framework materials MIL-101 a kind of is provided.The present invention, by the inducing action synthetic MIL-101 fast of carbon nanomaterial, has realized the quick controlled preparation of MIL-101 crystalline material.The present invention has less investment, and the feature that running cost is low, is with a wide range of applications, and can produce significant economic benefit.
The quick building-up process of metal-organic framework materials MIL-101 of the present invention is as follows:
By chromium nitrate, hydrofluoric acid, terephthalic acid, deionized water, within 1: 1: 0.5～1: 266, mix according to material molar weight ratio, then add closed reactor, finally add the carbon nanomaterial of certain mass, at 220 DEG C, react certain hour.After reaction finishes, slow cooling is to room temperature, then centrifugation, and solid that upper strata obtains adopts dimethyl formamide and dehydrated alcohol to rinse, and vacuum-drying activates and obtains metal-organic framework materials MIL-101.The carbon nanomaterial adding in building-up reactions is carbon nanotube or carbon fiber, and the mass ratio of carbon nanomaterial add-on and chromium nitrate is 0.005: 1～0.2: 1, and the reaction times is to be 0.5～2 hour.
Advantage of the present invention:
The present invention impels metallo organic material MIL-101 nucleation and crystallization process to accelerate by the inducing action of carbon nanomaterial, has realized the quick controlled preparation of MIL-101 crystalline material, has shortened generated time, has solved the problem that traditional preparation method's generated time is grown.Metallo organic material MIL-101 has tool application prospect widely, and the present invention has less investment, and the feature that running cost is low can produce significant economic benefit.
Brief description of the drawings:
Fig. 1 is the N containing chromium metal-organic framework materials MIL-101 of the embodiment of the present invention 1 and 2 preparations
2adsorption isothermal line.
Fig. 2 is the X ray diffracting spectrum containing chromium metal-organic framework materials MIL-101 of the embodiment of the present invention 1 and 2 preparations.
Fig. 3 is the scanning electron microscope (SEM) photograph containing chromium metal-organic framework materials MIL-101 prepared by the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscope (SEM) photograph containing chromium metal-organic framework materials MIL-101 prepared by the embodiment of the present invention 2.
Embodiment
1. embodiment 1
By 4.00g chromium nitrate, the hydrofluoric acid of 0.45ml40% mass concentration, 1.66g terephthalic acid, adds in 48g water and is uniformly mixed, and then adds closed reactor, finally adds the carbon nanotube of 0.02g, at 220 DEG C, reacts 2h.After reaction finishes, slow cooling is to room temperature, then centrifugation, and solid that upper strata obtains adopts dimethyl formamide and dehydrated alcohol to rinse, and 150 DEG C of vacuum-dryings activate and obtain metal-organic framework materials MIL-101.
2. embodiment 2
By 4.00g chromium nitrate, the hydrofluoric acid of 0.23ml40% mass concentration, 1.66g terephthalic acid, adds in 48g water and is uniformly mixed, and then adds closed reactor, finally adds the carbon nano fiber of 0.8g, at 220 DEG C, reacts 0.5h.After reaction finishes, slow cooling is to room temperature, then centrifugation, and solid that upper strata obtains adopts dimethyl formamide and dehydrated alcohol to rinse, and 150 DEG C of vacuum-dryings activate and obtain metal-organic framework materials MIL-101.
Claims (4)
1. a method of fast synthetic metal-organic framework materials MIL-101, is characterized in that, process is as follows:
By chromium nitrate, hydrofluoric acid, terephthalic acid, deionized water, within 1: 1: 0.5～1: 266, mix and then add closed reactor according to material molar weight ratio, finally add the carbon nanomaterial of certain mass, at 220 DEG C, react certain hour.After reaction finishes, slow cooling is to room temperature, then centrifugation, and the solid that upper strata obtains adopts dimethyl formamide and dehydrated alcohol to rinse, and 150 DEG C of dry activation of vacuum obtain metal-organic framework materials MIL-101.
2. method according to claim 1, is characterized in that, described carbon nanomaterial is carbon nanotube or carbon fiber.
3. method according to claim 1, is characterized in that, described carbon nanomaterial add-on and the mass ratio of chromium nitrate are 0.005: 1～0.2: 1.
4. method according to claim 1, is characterized in that, the described reaction times is to be 0.5～2 hour.
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| CN201410306140.1A CN104086594A (en) | 2014-06-26 | 2014-06-26 | Method for quickly synthesizing metal organic framework material MIL-101 |
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| CN201410306140.1A CN104086594A (en) | 2014-06-26 | 2014-06-26 | Method for quickly synthesizing metal organic framework material MIL-101 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530109A (en) * | 2014-12-30 | 2015-04-22 | 南开大学 | Preparation method for metal organic framework compound Al-MIL-100 |
| CN105080490A (en) * | 2015-08-04 | 2015-11-25 | 华南理工大学 | Magnesite-chrome bimetallic MOFs adsorbent MIL-101 (Cr, Mg) and preparation method thereof |
| CN105524112A (en) * | 2015-08-28 | 2016-04-27 | 浙江理工大学 | Preparation method of DMF-modified MIL-101 |
| CN108126755A (en) * | 2018-01-31 | 2018-06-08 | 中国民航大学 | A kind of preparation method of fluorine/chlorine exchange catalysts based on modified MOF |
-
2014
- 2014-06-26 CN CN201410306140.1A patent/CN104086594A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104530109A (en) * | 2014-12-30 | 2015-04-22 | 南开大学 | Preparation method for metal organic framework compound Al-MIL-100 |
| CN105080490A (en) * | 2015-08-04 | 2015-11-25 | 华南理工大学 | Magnesite-chrome bimetallic MOFs adsorbent MIL-101 (Cr, Mg) and preparation method thereof |
| CN105524112A (en) * | 2015-08-28 | 2016-04-27 | 浙江理工大学 | Preparation method of DMF-modified MIL-101 |
| CN108126755A (en) * | 2018-01-31 | 2018-06-08 | 中国民航大学 | A kind of preparation method of fluorine/chlorine exchange catalysts based on modified MOF |
| CN108126755B (en) * | 2018-01-31 | 2020-09-15 | 中国民航大学 | Preparation method of fluorine/chlorine exchange catalyst based on modified MOF |
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