CN110128668A - A method of MOFs is combined to based on immobilized solvent combination solvent heat and steam - Google Patents
A method of MOFs is combined to based on immobilized solvent combination solvent heat and steam Download PDFInfo
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- CN110128668A CN110128668A CN201910387435.9A CN201910387435A CN110128668A CN 110128668 A CN110128668 A CN 110128668A CN 201910387435 A CN201910387435 A CN 201910387435A CN 110128668 A CN110128668 A CN 110128668A
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Abstract
The present invention relates to the synthesis field of MOFs material, the method that specifically a kind of combination solvent heat and steam phase substep synthesize MOFs, synthesis process is using adsorbent come immobilized solvent.The reactant being placed in liquid solvent and the adsorbent containing liquid solvent are placed in closed reactor, control heating, solvent thermal reaction occurs for the phase before the reaction, generates intermediate state product；When liquid solvent be adsorbed agent it is all immobilized after, subsequent generation steam phase reaction, intermediate state product is gradually transformed into target MOFs product.The present invention is in quantity of solvent, and under solvent state and temperature control, solvent constantly volatilizees immobilized in adsorbent, and reaction process is changed into steam phase reaction from solvent thermal reaction, finally can rapid synthesis obtain the MOFs product of gram-grade or more.This preparation method carries out the regulation of solvent state using adsorbent, and the substep for controlling reaction carries out, sufficiently combine solvent heat reactant distribution is uniform and the swift feature of vapor phase transport process, be a kind of by immobilized solvent, the method for efficiently quickly preparing MOFs.
Description
Technical field
The present invention relates to the synthesis field of MOFs material, specifically a kind of combination solvent heat and steam phase substep synthesis MOFs
Method, synthesis process is using adsorbent come immobilized solvent.
Background technique
New material is quickly grown in recent years, and irreplaceable advantage makes new material have very big development latent
Power.MOFs material as typical new material, due to huge specific surface area, uniform aperture, multiplicity structure,
Highest attention of the features such as can modifying by researcher, and catalysis, gas absorption separation, molecular recognition, ion exchange,
The multiple fields such as photoelectromagnetic have potential application.Typical Representative of the Cu-BTC and ZIF-8 as MOFs, their special structures and property
Matter promotes it constantly to stride forward to industrialization.Meanwhile the various synthetic technologys of Cu-BTC and ZIF-8 are also constantly explored, this paper's
Synthetic method precisely in order to MOFs industrial applications, carry out new trial.
Cu-BTC (HKUST-1 or Cu3(BTC)2) earliest by Hong Kong University of Science and Thchnology Williams professor seminar in 2002
Report, the three-dimensional porous MOFs material as made of divalent metal copper and trimesic acid coordination.ZIF-8(Zn(mIm)2) earliest by
Chen little Ming teaches seminar and Yaghi seminar and reported in 2006, is coordinated and is formed by divalent metal zinc and 2 methylimidazoles
MOFs material with class skeleton structure of zeolite.Both MOFs have 1400m2The BET specific surface area of/g or more, in gas
Adsorbing separation field shows excellent performance.To show the more preparation methods of both materials, the present invention uses solvent heat
The method substep combined with steam phase synthesizes.
Summary of the invention
The present invention, come immobilized solvent, is the side of a kind of combination solvent heat and steam phase substep synthesis MOFs using adsorbent
Method.
In the synthetic reaction of traditional molecular sieve and MOFs, solvent thermal reaction, that is, liquid phase reactor are generallyd use.Dong
Professor Jin Xiang is the synthesis in solid state mode for probing into molecular sieve, innovatively proposes steam phase synthesi.Then, Shi Qi etc. is this
Method is applied in the synthesis of MOFs material, successfully prepares ZIF-8, explores new approach for the synthesis mode of MOFs.Solvent
Thermal response facilitates the dissolution of reactant and is uniformly distributed, and steam phase reaction has the reaction of solid phase reaction fast, and quantity of solvent makes
With few advantage.To have feature in conjunction with both synthetic methods, set forth herein immobilized solvent methods, in conjunction with solvent heat and steam phase
The synthesis that method carries out two kinds of MOFs of Cu-BTC and ZIF-8 is explored.This method solvent-recovery process traditional for before has further
Method and theoretic improvement, by quantity of solvent between bringing forward in the reaction, the regulation of immobilized adsorbent and temperature, control
Synthetic reaction substep processed carries out, and realizes the combination of solvent thermal reaction and steam phase reaction, gives full play to the advantage of two methods.?
Early period is reacted, reactant coexists with liquid solvent, and solvent thermal reaction occurs for this stage, and reactant is dissolution or ionic state in solution
In come into full contact with, be uniformly mixed；As solvent is gradually immobilized by the molecular sieve absorption in reactor, reaction process is gradually converted into
Steam phase reaction (solid phase reaction), this stage liquid solvent all become gaseous state or immobilized in molecular sieve, and solid phase reaction increases
Reactant concentration and the progress for accelerating reaction.So the present invention uses immobilized solvent method, solvent heat and steam phase can be combined
The advantages that method substep synthesis MOFs, is uniformly mixed with reactant, and solvent realizes recycling, and the reaction time is fast.
The present invention is achieved by the following technical solutions: one kind is combined to based on immobilized solvent combination solvent heat and steam
The method of MOFs, comprising the following steps: the reactant being placed in liquid solvent and the adsorbent containing liquid solvent are placed in close
It closes in reactor, process control heating, solvent thermal reaction occurs for the phase before the reaction, generates intermediate state product；When liquid solvent quilt
After adsorbent is all immobilized, subsequent generation steam phase reaction, intermediate state product is gradually transformed into target MOFs product.
The present invention passes through the regulation of quantity of solvent, immobilized adsorbent and temperature, and control synthetic reaction substep carries out, and passes through solvent
It is volatilized into gaseous state from liquid, it is last immobilized into molecular sieve, by the regulation of solvent state, in conjunction with the excellent of solvent heat and steam phase
Point, the substep for controlling reaction carry out.
As the further improvement of technical solution of the present invention, the MOFs is Cu-BTC, ZIF-8, ZSA-1, UiO series
Or MIL series.
As the further improvement of technical solution of the present invention, the time of controllable solvent thermal reaction is 6 hours, and steam is opposite
The time answered is 6 hours.
In the present invention, it is preferred to solvent boiling point should not too high (no more than 180 DEG C), solvent molecule should not be too big.It is excellent
The corresponding solvent of the sorbent used aperture Suitable adsorptive of immobilized solvent of choosing, and it is easier to activating and regenerating.As the technology of the present invention side
The further improvement of case, the liquid solvent are at least one of water, ethyl alcohol, methanol, DMF, and the adsorbent is according to immobilized
The different of liquid solvent choose molecular sieves, active carbon or silica gel.
Invention further provides the preparation method of two kinds of MOFs materials, specifically: in Cu-BTC preparation, mixing is abundant
Cu (OAc)2·H2O and trimesic acid (H3BTC) powder is placed in the mixed solvent small beaker containing a small amount of second alcohol and water,
By small beaker and inhaling has the Na-4A molecular sieve of appropriate above-mentioned mixed solvent to be put in closed reaction kettle together.It is risen by control
Temperature, solvent thermal reaction occurs for the phase before the reaction, generates intermediate state product, subsequent to steam when solvent is all recycled by molecular sieve
Vapour-phase reaction process, intermediate state product gradate as target product Cu-BTC.In ZIF-8 preparation, sufficient Zn (OH) is mixed2
It is placed in the small beaker containing a small amount of distilled water with 2-methylimidazole (mIm) powder, then there is the Na-4A molecule of suitable quantity of water with suction
Sieve is put in closed reaction kettle together through control heating, and solvent thermal reaction occurs for the phase before the reaction, generates intermediate state product,
When solvent is all recycled by molecular sieve, subsequent generation steam phase reaction process, intermediate state product is gradated as target product
ZIF-8。
The present invention is in quantity of solvent, and under solvent state and temperature control, solvent constantly volatilizees immobilized in adsorbent, reacts
Journey is changed into steam phase reaction from solvent thermal reaction, finally can rapid synthesis obtain the MOFs product of gram-grade or more.This preparation side
Method carries out the regulation of solvent state using adsorbent, and the substep for controlling reaction carries out, and sufficiently combines the reactant point of solvent heat
Cloth is uniform and the swift feature of vapor phase transport process, is a kind of by immobilized solvent, the method for efficiently quickly preparing MOFs.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the schematic diagram that MOFs is synthesized in conjunction with solvent heat and steam phase substep.
Fig. 2 is reaction controlling during solvent heat, the PXRD figure of the intermediates product generated in 6 hours.Cu-
The pre-synthesis phase transition state of BTC is Cu (HBTC) (H that solvent-thermal process obtains2O)3The Cu (OAc) of reaction is not participated in2·
H2O；The pre-synthesis phase transition state of ZIF-8 is the dia (Zn) and the Zn (OH) for not participating in reaction that solvent-thermal process obtains2。
Fig. 3 is Cu-BTC and ZIF-8 in amplification synthesis and repeats the PXRD synthesized figure.The peak of figure is all corresponding consistent, says
Product all can be obtained in bright amplification synthesis and repetition synthesis.
Fig. 4 is the shape appearance figure that Cu-BTC sintetics changes over time, and product ultimately becomes crystalline state from unformed state.
Fig. 5 is the shape appearance figure that ZIF-8 sintetics changes over time, and product ultimately becomes crystalline state from unformed state.
Fig. 6 is the nitrogen absorption under low temperature figure of different time product, and the product correspondence of fully reacting has larger adsorbance.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Technical solution of the present invention is described in detail with reference to the accompanying drawing.
Chemical substance material: copper acetate monohydrate, zinc hydroxide, trimesic acid, 2-methylimidazole, Na-4A molecular sieve, nothing
Water-ethanol, distilled water.
Embodiment one
Using the method for immobilized solvent, the advantage being combined to using solvent heat and steam is closed in conjunction with both modes substep
At the method for Cu-BTC, the steps include:
1. being sufficiently mixed the copper acetate monohydrate and 0.9g of 1.284g (6.45mmol) using grinding blender
The trimesic acid powder of (4.29mmol).
2. 1. mixture is dispersed to be packed into be sufficiently mixed solvent (H containing 8mL2O/EtOH in mini-reactor).
3. the Na-4A molecular sieve for taking 80g sufficiently to activate adsorbs the above-mentioned (H of 12mL as immobilized solvent adsorption agent2O/
EtOH) mixed solution.
By the reactor with reactant and solvent in 2. and 3. it is set together 4. the immobilized solvent molecule of adsorption solvent sieves in
In in autoclave.
5. being warming up to 120 DEG C by temperature programming control, 6 hours early periods of progress solvent thermal reaction is reacted；Subsequent 6 hours
Steam phase reaction is carried out, corresponding product can be obtained in last natural cooling.Cu-BTC:1.9g, 97.4%.
Embodiment two
By the way of immobilized solvent, the advantage being combined to using solvent heat and steam is closed in conjunction with both modes substep
At the method for ZIF-8, the steps include:
1. being sufficiently mixed the 2- of 0.544g (5.49mmol) zinc hydroxide and 0.9g (10.98mmol) using grinding blender
Methylimidazole powder.
2. 1. mixture is dispersed to be fitted into the mini-reactor containing 8mL distilled water.
3. the Na-4A molecular sieve for taking 80g sufficiently to activate adsorbs the distilled water of 12mL as immobilized solvent adsorption agent.
By the reactor with reactant and solvent in 2. and 3. it is set together 4. the immobilized solvent molecule of adsorption solvent sieves in
In in autoclave.
5. being warming up to 120 DEG C by temperature programming control, 6 hours early periods of progress solvent thermal reaction is reacted；Subsequent 6 hours
Steam phase reaction is carried out, corresponding product can be obtained in last natural cooling.ZIF-8:1.21g, 96.3%.
The specific surface area variation diagram of table 1 Cu-BTC and ZIF-8 in the synthesis process
As can be seen from Table 1, with the passage in reaction time, the specific surface area of synthetic product is all gradually increased, finally all
It has been more than 1300m2/g。
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (5)
1. a kind of method for being combined to MOFs based on immobilized solvent combination solvent heat and steam, which is characterized in that including following step
It is rapid: the reactant being placed in liquid solvent and the adsorbent containing liquid solvent to be placed in closed reactor, process control liter
Temperature, solvent thermal reaction occurs for the phase before the reaction, generates intermediate state product；When liquid solvent be adsorbed agent it is all immobilized after, it is subsequent
Steam phase reaction occurs, intermediate state product is gradually transformed into target MOFs product.
2. a kind of method that MOFs is combined to based on immobilized solvent combination solvent heat and steam according to claim 1,
It is characterized in that, the MOFs is Cu-BTC, ZIF-8, ZSA-1, UiO series or MIL series.
3. a kind of method that MOFs is combined to based on immobilized solvent combination solvent heat and steam according to claim 1 or 2,
It is characterized in that, the time of controllable solvent thermal reaction is 6 hours, the time of steam phase reaction is 6 hours.
4. a kind of method that MOFs is combined to based on immobilized solvent combination solvent heat and steam according to claim 1 or 2,
It is characterized in that, the liquid solvent is at least one of water, ethyl alcohol, methanol, DMF, the adsorbent is according to immobilized liquid
The different of state solvent choose molecular sieve, active carbon or silica gel.
5. a kind of method that MOFs is combined to based on immobilized solvent combination solvent heat and steam according to claim 3,
It is characterized in that, the liquid solvent is at least one of water, ethyl alcohol, methanol, DMF, and the adsorbent is according to immobilized liquid
The different of solvent choose molecular sieve, active carbon or silica gel.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113019133A (en) * | 2021-02-25 | 2021-06-25 | 大连理工大学 | Preparation method for in-hole film forming synthesis of ZIF-67 film |
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| JP2002060944A (en) * | 2000-04-20 | 2002-02-28 | Internatl Business Mach Corp <Ibm> | Precursory raw material mixture, film deposition method and formation of structure |
| CN106215866A (en) * | 2016-08-31 | 2016-12-14 | 太原理工大学 | The method that bimetallic MOFs material is prepared in steam assistant metal displacement |
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| JP2002060944A (en) * | 2000-04-20 | 2002-02-28 | Internatl Business Mach Corp <Ibm> | Precursory raw material mixture, film deposition method and formation of structure |
| CN106278869A (en) * | 2016-07-27 | 2017-01-04 | 太原理工大学 | A kind of method of the Fast back-projection algorithm MOFs material with molecular sieve recycling design |
| CN106215866A (en) * | 2016-08-31 | 2016-12-14 | 太原理工大学 | The method that bimetallic MOFs material is prepared in steam assistant metal displacement |
Non-Patent Citations (2)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113019133A (en) * | 2021-02-25 | 2021-06-25 | 大连理工大学 | Preparation method for in-hole film forming synthesis of ZIF-67 film |
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Application publication date: 20190816 |