CN106278869B - A method of with the Fast back-projection algorithm MOFs materials of molecular sieve recycling design - Google Patents
A method of with the Fast back-projection algorithm MOFs materials of molecular sieve recycling design Download PDFInfo
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Abstract
The present invention relates to the preparation field of MOFs materials, the method for specifically a kind of Fast back-projection algorithm MOFs materials with molecular sieve recycling design.The present invention is in the synthesis process, introduce molecular sieve solvent recovery mechanism, reactant concentration can be kept in solution in higher level constantly, as solvent is volatized into molecular sieve, reactant crystallizes rapidly precipitation, accelerate the progress of reaction, and be evaporated completely completely in solvent and can be obtained more dry products, eliminates and be filtered, washed step.In addition, inventor is by way of introducing molecular sieve and being stored in solvent, solvent of the solvent after volatilizing and having reacted in molecular sieve 100% is recovered in molecular sieve when reaction can be completely secured, and avoid reacted solvent in temperature-fall period condense in reactant and caused by processing procedure, more dry products are obtained, eliminates and is filtered, washed step.
Description
Technical field
The present invention relates to the preparation field of MOFs materials, specifically a kind of Fast back-projection algorithm MOFs with molecular sieve recycling design
The method of material.
Background technology
In recent years, MOFs materials due to big specific surface area, uniform aperture, it is various can modulation structure etc. it is excellent
Performance and paid high attention to by researcher, and its catalysis, gas storage with detach, molecular recognition, ion exchange,
There is potential application in the fields such as photoelectromagnetic.As most well-known one of MOFs, Cu3(BTC)2Cu in structure+Ion and four carboxylic acids
Oxygen atom ligand forms secondary structure unit, which is interconnected to form with face centered cube space lattice class
The 3 D stereo duct structure of type.The main pore size size of the structure isSlightly smaller tetrahedron side pocket size
ForAnd it is by sizeTri-angle-holed window be connected with main aperture road.Cu3(BTC)2Preferable duct window, and
Specific surface area with nearly 2000m2/g, the excellent properties such as 300 DEG C thermal stability, makes it gradually penetrate into answering for various aspects
With.
The method that Ian D.Williams professors used solvent heat in 1999, with copper nitrate, trimesic acid, water/second
Alcohol 1:1 mixed solvent reacts 12 hours at 180 DEG C and has synthesized Cu3(BTC)2.The solvent heat under various environment is developed later
Synthesize Cu3(BTC)2Method be required for providing the coordination that preferable solvent environment promotes metal and ligand, or even to provide as N,
N`- dimethylformamides (DMF), the more expensive and environmentally harmful solvent such as dimethyl sulfoxide (DMSO) (DMOS).And solvent-thermal method is not
100% ground of energy remains the metal salt for not reacting and being dissolved in solvent and ligand will also result in the wave of raw material to solvent recovery
Take.For the MOFs for being intended to industrial applications, one of several MOFs materials of best performance (such as Cu has been found3
(BTC)2), how to reduce synthesis cost to the greatest extent is that we need the target captured.
Invention content
The present invention is intended to provide a kind of MOFs material synthesis technologies reducing synthesis cost and efficient quick, specifically a kind of
In the method for the Fast back-projection algorithm MOFs materials of molecular sieve recycling design.
The present invention is achieved by the following technical solutions：A kind of Fast back-projection algorithm MOFs materials with molecular sieve recycling design
Method, step is：The synthesis material of MOFs materials is uniformly mixed in reaction vessel with solvent, and reaction vessel, which is placed in, to be carried
In the closed environment of molecular sieve, and it is connected between the ambient enviroment of synthesis material and molecular sieve；Heat reaction vessel (heating temperature
Degree is reaction temperature), solvent is adsorbed in molecular sieve pore passage completely after the completion of reaction, and dry MOFs is obtained in reaction vessel
Material (implicit that solvent boiling range is required to be less than reaction temperature).
Invention further provides another in the method for the Fast back-projection algorithm MOFs materials of molecular sieve recycling design,
Step is：The synthesis material of MOFs materials is uniformly mixed in reaction vessel, and reaction vessel is placed in the closed environment with molecular sieve
It is interior, and be connected between the ambient enviroment of synthesis material and molecular sieve, the solvent needed for reaction is contained in molecular sieve pore passage；Heating
Reaction vessel (heating temperature, that is, reaction temperature), solvent is gradually desorbed out of molecular sieve pore passage and comes out, into the week of synthesis material
Collarette border, solvent is adsorbed in molecular sieve pore passage completely again after the completion of reaction, and dry MOFs materials are obtained in reaction vessel
Material (implicit that solvent boiling range is required to be less than reaction temperature)；Abovementioned steps are iteratively repeated, realize that the steam phase of solvent repeats to recycle.
The present invention also provides a kind of method of the Fast back-projection algorithm MOFs materials with molecular sieve recycling design, step is：
(1) solvent is evaporated recycling
The synthesis material of MOFs materials is uniformly mixed in reaction vessel with solvent, and reaction vessel is placed in molecular sieve
In closed environment, and it is connected between the ambient enviroment of synthesis material and molecular sieve；Heating reaction vessel, (heating temperature is reacted
Temperature), solvent is adsorbed in molecular sieve pore passage completely after the completion of reaction, and it is (hidden that dry MOFs materials are obtained in reaction vessel
It is less than reaction temperature containing solvent boiling range is required)；
(2) steam phase of solvent repeats to recycle
The synthesis material of same MOFs materials is uniformly mixed in reaction vessel again, reaction vessel is placed in step
(1) in the closed environment of molecular sieve, and it is connected between the ambient enviroment of synthesis material and molecular sieve；Heating reaction vessel (adds
Hot temperature, that is, reaction temperature), solvent (solvent in step (1)), which is gradually desorbed out of molecular sieve pore passage, to be come out, former into synthesis
The ambient enviroment of material, solvent is adsorbed in molecular sieve pore passage completely again after the completion of reaction, and drying is obtained in reaction vessel
MOFs materials；Step (2) abovementioned steps are iteratively repeated, realize that the steam phase of solvent repeats to recycle.
According to the coordination theory of metal and ligand, metal center, also referred to as node, the d tracks of electronics fill part,
Therefore either in atom or ionic condition, there can be a different hybridized orbitals and to form different coordinations several because environment is different
What is constructed.And ligand (atom or atomic group) can provide lone pair electrons to metal cation and be formed via a kind of Louis
The coordination polymer of acid/base relationship.Metal is frequently necessary to solvent during with ligands and is formed uniformly to dissolve reactant
Reaction system, and there may be dissociation, pass and can and influence reaction rate the effects that mass transfer, dielectric effect, or even change anti-
It answers process and mechanism and then obtains product.In the synthesis process, molecular sieve solvent recovery mechanism is introduced, solution can be kept constantly
Middle reactant concentration is in higher level, and as solvent is volatized into molecular sieve, reactant crystallizes rapidly precipitation, accelerate reaction into
Row, and be evaporated completely completely in solvent and can be obtained more dry products, it eliminates and is filtered, washed step.In addition, the synthesis of MOFs
Also the synthesis mode for gradually having invented solid phase, can during the synthesis ZIF-8 and ZIF-67 that Jinxiang professors Dong have found
To provide reaction environment using solvent vapo(u)r to promote the coordination of metal and ligand.But inventor is deposited by introducing molecular sieve
Enter the mode of solvent, solvent of the solvent after volatilizing and having reacted in molecular sieve 100% is recovered to when reaction can be completely secured
In molecular sieve, and avoid reacted solvent in temperature-fall period condense in reactant and caused by processing procedure, obtain compared with
For dry products, eliminates and be filtered, washed step.Therefore the MOFs synthesis carried out using such solvent-recovery process is had
100% solvent recovery and the advantage of 100% raw material reaction.
In order to enable the purity higher of MOFs materials, the boiling range for choosing by-product after the completion of synthesis material preferably reacts is less than
The reaction temperature of synthesis material.
When it is implemented, the MOFs materials are Cu3(BTC)2, synthesis material is copper acetate and trimesic acid, Huo Zhewei
Kocide SD and trimesic acid.Certainly the method for the present invention is not limited to Cu3(BTC)2The synthesis of this MOFs material, it is conventional
The zeolite and MOFs that vapor phase transport process can synthesize are also suitable the method, and those skilled in the art can be according to preparation method of the present invention
The synthesis of other MOFs materials is obtained by the experiment of limited number of time, such as inventor has found that synthesis material is Cu through overtesting
(NO3)2·3H2O and HINA (isonicotinic acid) synthesis Cu (INA)2During, it is also applied for preparation method of the present invention.
Experiment：Cu3(BTC)2Study on the synthesis experiment
First Cu is synthesized with the solvent of 5A molecular sieves recycling original solution evaporation in turn3(BTC)2, secondly to be adsorbed on molecular sieve
In solvent be steam phase source repeat Cu3(BTC)2Synthesis.Its step is：
(1) solvent is evaporated recycling
Weigh a water copper acetate (Cu (OAC)2·H2O), 0.043g ± 0.001g, trimesic acid (H3BTC)0.03g±
0.001g measures deionized water and ethyl alcohol 1 in 5mL small beakers:1 mixed solution 5mL ± 0.001mL, is placed in beaker, stirs
Mix mixing 5min.
The Na types 5A molecular sieves 50g of a diameter of 0.5cm is taken in the polytetrafluoroethylkettle kettle lining of 100mL, then above
The small beaker for installing reaction drug is inserted into molecular sieve, keeps balance.The good steel kettle of finally sealed, is put into 120 DEG C of baking ovens and reacts
12h。
After having reacted, solvent disappears from small beaker completely, is inhaled into molecular sieve pore passage；Metal in solution and ligand
Also coordination has grown up to Cu3(BTC)2, obtained product is dry, does not have to filtration washing.
(2) steam phase of solvent repeats to recycle
Weigh single water copper acetate 0.043g ± 0.001g, trimesic acid (H3BTC) 0.03g ± 0.001g is in 5mL small beakers
In, and be uniformly mixed.
Polytetrafluoroethylkettle kettle in-core after above-mentioned reaction is directly placed into the small beaker for preparing reactant, and steel kettle is sealed,
It is put into 120 DEG C of baking ovens and reacts 12h.
After having reacted, directly become Cu from solid mixture in small beaker3(BTC)2Crystal does not have to filtration washing.
The present invention relates to two different crystallization process, first step solvent is evaporated in recycling reaction, reacts original state
Or conventional solvent thermal response state, using water and ethyl alcohol 1:1 mixed solvent contributes to the dissolving of reactant.And in reactant
Cu：The molar ratio of BTC is exactly the proportioning 3 of material simplest formula:2, the material grown in this way 100% is Cu3(BTC)2.With when
Between passage, when crystal is grown into, and with the continuous volatilization of solvent, can promote the concentration of reactant in solution maintain to compared with
High level, also, rapid reaction can be promoted to complete in this way.As seen from Figure 1, steam seasoning solvent-recovery process is in 8h
Grow up to the Cu with preferable XRD3(BTC)2, the peaks XRD of 12h illustrates to react after 8h and tend to complete also without too big enhancing,
Crystallinity is also without too big change.The electron microscope of differential responses time is shown in Fig. 2, over time, the Cu synthesized3
(BTC)2Particle can constantly become larger, therefore can pass through the granular size of time modulation product.
The steam phase of second step solvent repeats in recycling, and is primarily related to solid phase reaction mechanism, or chooses original
Reaction raw materials proportioning, it is desirable that solid reaction composition granule mill it is relatively thin, and both are anti-single water copper acetate and trimesic acid
It answers object to be uniformly mixed, step reaction is in addition used to be adsorbed on the solvent in molecular sieve pores.In reaction process, with temperature by
Step increases, and water and ethyl alcohol are gradually desorbed out of molecular sieve pores and come out, into the ambient enviroment of solid-phase reactant, due to water and ethyl alcohol
The effect of gaseous molecular, metal start to be coordinated with ligand, gradually form big Cu3(BTC)2Crystal.Fig. 3 is shown, with the time
Passage, the peaks XRD of product are gradually to Cu3(BTC)2Crystal form passage, when 12h can grow up to the preferable Cu of crystallinity3
(BTC)2.Fig. 4 is the shape appearance figure of different time product, it can be seen that over time, product caking is bigger, and crystal form
Gradually long perfection.
The Cu that both the above solvent recovery mode synthesizes3(BTC)2With preferable duct, 20% solvent has been adsorbed, and
And material can be stabilized to 300 DEG C (referring to Fig. 5), and compared to for conventional solvent thermal synthesis method, the ratio table with bigger
Area, BET specific surface area reach 1300cm2/ g or more, Langmuir specific surface area reach 1900cm2/ g or more (referring to Fig. 6).
In addition, inventor studies the solvent recovery synthesis of different copper sources, can exploration use more cheap reaction
Raw material carries out Cu3(BTC)2Synthesis.Solvent is carried out respectively according to each parameter in table 1 and is evaporated recycling synthesis, and composite result is shown in
Figure.
Table 1
Note：It is complete to refer to partial reaction raw material unreacted for mixed phase in table；It is not to refer to that unreacted forms target product.
It is relatively easily-synthesized compared to copper acetate, other copper sources are in synthesis Cu3(BTC)2On have certain difficulty.For different copper sources
Carry out Cu3(BTC)2The XRD diagram of composite result show (referring to Fig. 7), more green reactant Cu (OH)2Addition, also can one
Determine the Cu of generating portion in degree3(BTC)2Crystal.As a result, with Cu (OH)2For copper source, by the adjusting of subtleer condition, into one
Step obtains the higher Cu of purity3(BTC)2Product, response parameter such as table 2.
Table 2
Note：Pure phase refers to reaction raw materials reaction completely and forms target product in table；It is complete that mixed phase refers to partial reaction raw material unreacted
Entirely；It is not to refer to that unreacted forms target product.
With Cu (OH)2XRD results for copper source, the adjusting of the subtleer condition of use are shown (referring to Fig. 8).Matched by raw material
Than, quantity of solvent, the adjusting of reaction temperature and time, it will be seen that Cu (OH)2With H3The amount of BTC substances is 3:2 proportioning is appropriate high
Quantity of solvent and temperature, the reaction time be 12h can preferably synthesize Cu3(BTC)2Crystal.
The present invention has the advantages that compared with existing synthetic technology：With Cu3(BTC)2For synthesis, the present invention is
With 1:1 water is mixed solvent with ethyl alcohol, can ensure that solvent all recycles by the method for 5A molecular sieve lyosoptions, not have
Loss and waste；Copper acetate or Kocide SD are copper source, and trimesic acid is ligand, manufactured Cu3(BTC)2Product is complete, without original
Material loss；The product drying and free from admixture of synthesis, are not required to subsequent processing.In short, this preparation method solvent all recycles, reaction
Object Atom economy is good, and the reaction time is short, and informative data is accurate.
Description of the drawings
Fig. 1 is that X-ray diffraction instrument is evaporated absorption method using prepared by the differential responses time to present invention solvent
Cu3(BTC)2Carry out the XRD spectrum of crystal material phase analysis.Show that product constantly crystallizes over time in figure, the peaks XRD by
It is cumulative strong and complete to crystallization after 12h.
Fig. 2 is the Cu of solvent being evaporated prepared by the absorption method differential responses time3(BTC)2It is scanned Electronic Speculum characterization.Figure
In over time, crystal grain becomes larger, and crystalline particle eventually becomes the polyhedron knot that size is about 8 μm
Structure.
Fig. 3 is that X-ray diffraction instrument is anti-using difference to present invention vapor phase transport process (steam phase of solvent repeats to recycle)
Prepared Cu between seasonable3(BTC)2Carry out the XRD spectrum of crystal material phase analysis.Show that over time, product is not in figure
Disconnected crystallization, the peaks XRD gradually increase, and complete to crystallization after 12h.
Fig. 4 is the Cu prepared by vapor phase transport process (steam phase of solvent repeats to recycle) the differential responses time3(BTC)2It carries out
Scanning electron microscope characterizes.In figure over time, gradually crystallization becomes larger crystal grain, and it is complete to eventually become crystalline particle
Big crystal.
Fig. 5 is the Cu that two kinds of preparation methods of the invention obtain3(BTC)2TGA schematic diagrames.
Fig. 6 is the prepared Cu obtained of the present invention3(BTC)2Nitrogen absorption under low temperature characterize schematic diagram.It is shown in figure, two kinds molten
Cu prepared by agent absorption method3(BTC)2Method hotter than conventional solvent has higher specific surface area.
Fig. 7 is that being recycled with evaporation of the solvent for different copper sources synthesizes Cu3(BTC)2XRD spectrum.Number 1 corresponds in table 1 in figure
Serial number 1, and so on.
Fig. 8 is with Cu (OH)2For copper source Cu is synthesized to carry out the solvent recovery of test parameters setting3(BTC)2XRD diagram
Spectrum.Number 1 corresponds to the serial number 1 in table 2 in figure, and so on.
Specific implementation mode
In order to which the present invention is explained in detail, come to synthetic method of the present invention with reference to specific experiment process
It illustrates.
Chemical substance material：5A molecular sieves, copper acetate, Kocide SD, trimesic acid, deionized water, ethyl alcohol, a combination thereof are accurate
Reserve level is as follows：It is measurement unit with gram, milliliter
Embodiment 1
For one kind using copper acetate or Kocide SD as copper source, trimesic acid is ligand, utilizes 5A molecular sieve adsorption recovery solvents
To Fast back-projection algorithm Cu3(BTC)2Method, step is：
(1) solvent is evaporated recycling
Solvent, which is evaporated recycling, to be carried out in reaction kettle closed 100mL, and heat tracing, solvent volatilization, molecular sieve are inhaled
It receives, crystal growing process：
1. molecular sieve detergent activates
5A molecular sieves 50g is weighed in 100mL polytetrafluoroethylcontainer containers, is washed with distilled water and puts 180 DEG C of baking ovens afterwards for several times
Middle activation 5h.
2. reactant is prepared
A water copper acetate 0.043g or Kocide SD 0.0214g is weighed, trimesic acid 0.03g is measured in 5mL small beakers
Deionized water and ethyl alcohol 1:1 mixed solution 5mL, is placed in beaker, is stirred 5min.
3. the beaker for preparing reactant is positioned over in the reaction kettle for having activated molecular sieve, it is subsequently placed in 120 DEG C
In baking oven, heating time 12h, mixed reaction solution carries out crystallization.
4. after the completion of reaction, stopping heating, steam is reduced with temperature in gradually sucking molecular sieve pores in kettle, until dropping to room
Temperature.
5. any subsequent processing need not be done by obtaining product, it is dry, does not have the pure phase of impurity.
(2) steam phase of solvent repeats to recycle
The steam phase of solvent, which repeats to recycle, to be carried out in reaction kettle closed 100mL, and heat tracing, solvent are released
It puts, crystal growth, solvent absorption process：
1. reactant is prepared
A water copper acetate 0.043g or Kocide SD 0.0214g is weighed, trimesic acid 0.03g is in 5mL small beakers, fully
It is uniformly mixed.
2. the beaker for mixing reactant is transferred to the polytetrafluoroethylcontainer container equipped with molecular sieve (absorption previous step solvent)
It in (100mL), places it in stainless steel cauldron, then reaction kettle is placed in 120 DEG C of baking ovens.
3. as temperature increases, solvent molecule can be discharged into environment out of molecular sieve pores, then promote reactant to carry out brilliant
Change and react, the reaction was complete after 12h.
4. after having reacted, stopping heating, as environment temperature is down to room temperature, the solvent in environment is recovered to molecular sieve again
In hole, in case next time uses.
(3) product is handled
The by-product of above-mentioned reaction can be in solvent recovery to molecular sieve, and the product after having reacted is dry pure
Phase, therefore product does not have to washing, directly seals up for safekeeping spare.
Embodiment 2
For one kind using copper acetate or Kocide SD as copper source, trimesic acid is ligand, utilizes 5A molecular sieve adsorption recovery solvents
To Fast back-projection algorithm Cu3(BTC)2Method, reaction is carried out in reaction kettle closed 100mL, and heat tracing, solvent are waved
Hair, molecular sieve absorption, crystal growing process：
1. molecular sieve detergent activates
5A molecular sieves 50g is weighed in 100mL polytetrafluoroethylcontainer containers, is washed with distilled water and puts 180 DEG C of baking ovens afterwards for several times
Middle activation 5h.
2. reactant is prepared
A water copper acetate 0.043g or Kocide SD 0.0214g is weighed, trimesic acid 0.03g is measured in 5mL small beakers
Deionized water and ethyl alcohol 1:1 mixed solution 5mL, is placed in beaker, is stirred 5min.
3. the beaker for preparing reactant is positioned over in the reaction kettle for having activated molecular sieve, it is subsequently placed in 120 DEG C
In baking oven, heating time 12h, mixed reaction solution carries out crystallization.
4. after the completion of reaction, stopping heating, steam is reduced with temperature in gradually sucking molecular sieve pores in kettle, until dropping to room
Temperature.
5. any subsequent processing need not be done by obtaining product, it is dry, does not have the pure phase of impurity.
Embodiment 3
For one kind using copper acetate or Kocide SD as copper source, trimesic acid is ligand, utilizes 5A molecular sieve adsorption recovery solvents
To Fast back-projection algorithm Cu3(BTC)2Method, reaction is carried out in reaction kettle closed 100mL, and heat tracing, solvent are waved
Hair, molecular sieve absorption, crystal growing process：
1. molecular sieve detergent activates
5A molecular sieves 50g is weighed in 100mL polytetrafluoroethylcontainer containers, is washed with distilled water and puts 180 DEG C of baking ovens afterwards for several times
Middle activation 5h.
2. reactant is prepared
A water copper acetate 0.043g or Kocide SD 0.0214g is weighed, trimesic acid 0.03g is in 5mL small beakers, fully
It is uniformly mixed.Measure deionized water and ethyl alcohol 1:1 mixed solution 5mL (solvent), heating by molecular sieve so that adsorbed completely.
3. the beaker for mixing reactant is transferred in the polytetrafluoroethylcontainer container equipped with molecular sieve (100mL), set
In stainless steel cauldron, then reaction kettle is placed in 120 DEG C of baking ovens.
4. as temperature increases, solvent molecule can be discharged into environment out of molecular sieve pores, then promote reactant to carry out brilliant
Change and react, the reaction was complete after 12h.
5. after having reacted, stopping heating, as environment temperature is down to room temperature, the solvent in environment is recovered to molecular sieve again
In hole, in case next time uses.
6. product is handled
The addition product of above-mentioned reaction can be in solvent recovery to molecular sieve, and the product after having reacted is dry pure
Phase, therefore product does not have to washing, directly seals up for safekeeping spare.
Claims (3)
1. a kind of method of Fast back-projection algorithm MOFs materials with molecular sieve recycling design, which is characterized in that its step is：MOFs materials
The synthesis material of material is uniformly mixed in reaction vessel with solvent, and reaction vessel is placed in the closed environment with molecular sieve, and
It is connected between the ambient enviroment of synthesis material and molecular sieve；Reaction vessel is heated, solvent is adsorbed to completely after the completion of reaction
Dry MOFs materials are obtained in molecular sieve pore passage, in reaction vessel；The boiling range of by-product is less than synthesis material after the completion of reaction
Reaction temperature；The MOFs materials are Cu3(BTC)2, synthesis material be copper acetate and trimesic acid, or be Kocide SD
And trimesic acid；The Cu3(BTC)2It is 1 that solvent needed for being formed, which is volume ratio,:1 water and the mixed solution of ethyl alcohol；Cu3
(BTC)2Synthesis material reaction temperature be 120 DEG C.
2. a kind of method of Fast back-projection algorithm MOFs materials with molecular sieve recycling design, which is characterized in that its step is：MOFs materials
The synthesis material of material is uniformly mixed in reaction vessel, and reaction vessel is placed in the closed environment with molecular sieve, and synthesis material
Ambient enviroment and molecular sieve between be connected, the solvent needed for reaction is contained in molecular sieve pore passage；Heat reaction vessel, solvent
It is gradually desorbed and comes out out of molecular sieve pore passage, into the ambient enviroment of synthesis material, solvent is inhaled completely again after the completion of reaction
It is attached in molecular sieve pore passage, dry MOFs materials is obtained in reaction vessel；Abovementioned steps are iteratively repeated, realize the steam of solvent
It mutually repeats to recycle；The boiling range of by-product is less than the reaction temperature of synthesis material after the completion of reaction；The MOFs materials are Cu3
(BTC)2, synthesis material be copper acetate and trimesic acid, or be Kocide SD and trimesic acid；The Cu3(BTC)2It is formed
Required solvent is that volume ratio is 1:1 water and the mixed solution of ethyl alcohol；Cu3(BTC)2Synthesis material reaction temperature be 120
℃。
3. a kind of method of Fast back-projection algorithm MOFs materials with molecular sieve recycling design, which is characterized in that its step is：
（1）Solvent is evaporated recycling
The synthesis material of MOFs materials is uniformly mixed in reaction vessel with solvent, and reaction vessel is placed in the closed of molecular sieve
In environment, and it is connected between the ambient enviroment of synthesis material and molecular sieve；Reaction vessel is heated, solvent is complete after the completion of reaction
It is adsorbed in molecular sieve pore passage, dry MOFs materials is obtained in reaction vessel；
（2）The steam phase of solvent repeats to recycle
The synthesis material of same MOFs materials is uniformly mixed in reaction vessel again, reaction vessel is placed in step（1）Point
In the closed environment of son sieve, and it is connected between the ambient enviroment of synthesis material and molecular sieve；Reaction vessel is heated, solvent is gradual
It is desorbed and comes out out of molecular sieve pore passage, into the ambient enviroment of synthesis material, solvent is adsorbed to completely again after the completion of reaction
Dry MOFs materials are obtained in molecular sieve pore passage, in reaction vessel；It is iteratively repeated step（2）Abovementioned steps realize solvent
Steam phase repeats to recycle；The boiling range of by-product is less than the reaction temperature of synthesis material after the completion of reaction；The MOFs materials are
Cu3(BTC)2, synthesis material be copper acetate and trimesic acid, or be Kocide SD and trimesic acid；The Cu3(BTC)2
It is 1 that solvent needed for being formed, which is volume ratio,:1 water and the mixed solution of ethyl alcohol；Cu3(BTC)2Synthesis material reaction temperature
It is 120 DEG C.
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| CN105214442B (en) * | 2015-10-26 | 2018-01-12 | 马军 | A kind of efficient recovery system for organic solvent |
| CN105294741A (en) * | 2015-12-03 | 2016-02-03 | 大连大学 | Method for synthesizing Cu-BTC material by utilizing deep-eutectic solvent as solvent |
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