CN105854647B - The metal organic framework thin film and its application of kayexalate modification - Google Patents
The metal organic framework thin film and its application of kayexalate modification Download PDFInfo
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- CN105854647B CN105854647B CN201610228832.8A CN201610228832A CN105854647B CN 105854647 B CN105854647 B CN 105854647B CN 201610228832 A CN201610228832 A CN 201610228832A CN 105854647 B CN105854647 B CN 105854647B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/12—Composite membranes; Ultra-thin membranes
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Abstract
The invention discloses the metal organic framework thin films and its application of a kind of modification of kayexalate, steps are as follows: 1) preparing hydroxide nano line solution, the hydroxide nano line solution of preparation is mixed with kayexalate solution again, it stirs evenly, vacuum filtration obtains the composite membrane of hydroxide nano line and kayexalate；2) organic ligand is dissolved in the mixed solution of second alcohol and water, obtain organic ligand solution, the composite membrane of hydroxide nano line and kayexalate is placed in organic ligand solution, room temperature reaction obtains the metal organic framework thin film of kayexalate modification after 2~4 hours.The present invention, which is realized, is mixed kayexalate with nano wire by physical agitation, Electrostatic Absorption, kayexalate is introduced inside metal organic framework thin film in situ, modification is carried out to it, avoid the organic decoration process of Metal-organic frame ligand, it consumes energy low, it is pollution-free, rapidly and efficiently.
Description
Technical field
The present invention relates to the preparation methods of metal organic framework thin film, and in particular to a kind of kayexalate modification
Metal organic framework thin film and its application.
Background technique
Metal organic framework thin film is that a kind of thickness is thin in nanometer to micron range, the porous function being attached in matrix
Film, ideally, metal organic framework thin film surface is smooth, isotropic, has high porosity and good chemistry
Stability can be applied to the numerous areas such as separation, absorption, catalysis, slow releasing carrier of medication, hydrogen storage.
Fine and close continuous metal organic framework thin film can be used for ion isolation field.If to Metal-organic frame
The micropore inwall of film carries out the compatibility that modification can change inner wall to ion, by introducing different functional groups, to micropore
Inner wall is modified, it is more likely that it is made to have different selectivity can be to mixing under the driving of voltage different ions
Different kinds of ions in solion carries out selectivity and transports, and then realizes ion isolation.
The Chinese patent literature of Patent No. ZL201210383466.5 discloses a kind of hydroxide nano line and organic
The method that ligand quickly prepares metal organic framework thin film at normal temperature, steps are as follows: 1) under magnetic stirring, by ethanol amine
Aqueous solution is added in same volume copper nitrate, zinc nitrate or cadmium nitrate aqueous solution, slows down mixing speed, obtains corresponding hydroxide
Nanowire solution is directly filtered and forms one layer on multiaperture pellumina by copper, zinc hydroxide or cadmium hydroxide nanowires solution
Nano wire layer；2) nano wire layer is added in the organic ligand solution that solvent is ethyl alcohol, octanol or DMF, is reacted at normal temperature
30min obtains metal organic framework thin film.
It is upper specific to be frequently in grafting on organic ligand for the method for modifying of metal organic framework thin film micropore inwall at present
Functional group.This process is often complicated organic synthesis, cumbersome, and energy consumption is high, there is pollution, the limitation of these drawbacks
Its development and application.
Summary of the invention
The present invention provides a kind of preparation methods of the metal organic framework thin film of kayexalate modification, pass through
Physical agitation, Electrostatic Absorption keep kayexalate and metal hydroxides nano wire compound, realize in low temperature, low energy
Kayexalate is simply and easily introduced to the internal void of metal organic framework thin film under the conditions of consuming, being free of contamination,
Modification is modified to its inner wall, makes it have the function of ion isolation.
Using metal hydroxides nanostructure as the method for source metal synthesis metal organic framework thin film, operation letter
It is single, it consumes energy low, it is pollution-free.Metal hydroxides nanostructured surface often has positive charge simultaneously, can adsorb with anisotropic electricity
The molecule or nanostructure of lotus.It therefore, can be by metal hydroxide in the synthesis process of metal organic framework thin film
Object nanostructured surface adsorbs specific molecular or nanostructure, and specific molecular or nanostructure can be made to be combined to metal in situ
In the hole of organic framework, particular functional group is introduced into Metal-organic frame to realize, reaches and its inner wall is carried out
The effect of modifying and decorating, to realize that ion selectivity transports the separation with alkali metal ion.
A kind of preparation method of the metal organic framework thin film of kayexalate modification, includes the following steps:
1) hydroxide nano line solution is prepared, then by the hydroxide nano line solution and kayexalate of preparation
Solution mixing, stirs evenly, and vacuum filtration obtains the composite membrane of hydroxide nano line and kayexalate；
2) organic ligand is dissolved in the mixed solution of second alcohol and water, obtains organic ligand solution, by hydroxide nano line
It is placed in organic ligand solution with the composite membrane of kayexalate, room temperature reaction obtained polystyrene sulphur after 2~24 hours
The metal organic framework thin film of sour sodium modification.
Preferably, the hydroxide nano line solution manufacturing method are as follows: copper nitrate is added in aqueous ethanolamine
In aqueous solution, stirring, and reaction vessel is sealed, after 12~48 hours, obtain Kocide SD nanowire solution.
Further, the concentration of the aqueous ethanolamine is 1.4mM；The copper nitrate aqueous solution concentration is 4mM；
The kayexalate solution takes water as a solvent, and the concentration of the kayexalate solution is 0.0003~
0.03wt%；The volume ratio of the nanowire solution and kayexalate solution is 30:1；The organic ligand is
Trimesic acid, concentration are 5~15mM, and the volume ratio for the ethyl alcohol and water that dissolve organic ligand is 1:1.
As another preferred embodiment, the hydroxide nano line solution manufacturing method are as follows: by ethanol amine be added ethyl alcohol and
In the mixed liquor of water, ethanolamine solutions are obtained；Zinc nitrate is added in the mixed liquor of second alcohol and water, obtains zinc nitrate solution；Again
Ethanolamine solutions are mixed with zinc nitrate solution, are stirred, and reaction vessel is sealed, after 0.5~1.5 hour, obtain hydrogen-oxygen
Change zinc nanowire solution.
Further, the concentration of the ethanolamine solutions is 1.6mM；The zinc nitrate solution concentration is 4mM；It is described
Kayexalate solution take water as a solvent, the concentration of the kayexalate solution is 0.0003~
0.03wt%；The volume ratio of the nanowire solution and kayexalate solution is 30:1；The organic ligand is
Methylimidazole, concentration 25mM, the volume ratio for the ethyl alcohol and water that dissolve organic ligand are 1:4；For dissolving ethanol amine
Or the ethyl alcohol of zinc nitrate and the volume ratio of water are 1:1.5.
The kayexalate modification for the method preparation that another object of the present invention is to provide a kind of according to
Metal organic framework thin film, the Metal-organic frame are HKUST-1, molecular formula Cu3(BTC)2·3H2O, polyphenyl
Vinyl sulfonic acid sodium is uniformly distributed in Metal-organic frame hole, the continuous free from flaw of metal organic framework thin film.
Another object of the present invention is to provide the kayexalate modifications that another kind is prepared according to the method
Metal organic framework thin film, the Metal-organic frame be ZIF-8, molecular formula C8H12N4Zn, polystyrene sulphur
Sour sodium is uniformly distributed in Metal-organic frame hole, the continuous free from flaw of metal organic framework thin film.
Another object of the present invention is to provide a kind of Metal-organic frames such as kayexalate modification
Application of the film in alkali metal ion separation.
Compared with prior art, the present invention has the advantage that
For the present invention by the way that kayexalate and metal hydroxides nanowire solution to be mixed, Electrostatic Absorption is multiple
It closes, and then in situ introduces kayexalate in metal organic framework thin film hole, realize that sulfonate radical has metal
The modification of machine frame object film hole inner wall changes its affine performance to ion, realizes and transmits to the selectivity of different ions,
Ion isolation is realized under voltage driving.It is easy to operate the invention avoids ligand modified complicated organic synthesis step, energy consumption
It is low, it is pollution-free, rapidly and efficiently.
Detailed description of the invention
Fig. 1 is the preparation flow figure of the metal organic framework thin film of kayexalate modification in embodiment 1；
Fig. 2 is the SEM photograph on the surface of the HKUST-1 film of the kayexalate modification prepared in embodiment 1；
Fig. 3 is the SEM photograph on the surface of the HKUST-1 film of the kayexalate modification prepared in embodiment 2；
Fig. 4 is the SEM photograph on the surface of the HKUST-1 film of the kayexalate modification prepared in embodiment 3；
Fig. 5 is the SEM photograph on the surface of the ZIF-8 film of the kayexalate modification prepared in embodiment 1；
Fig. 6 is the SEM photograph on the surface of the ZIF-8 film of the kayexalate modification prepared in embodiment 2；
Fig. 7 is the SEM photograph on the surface of the ZIF-8 film of the kayexalate modification prepared in embodiment 3；
Fig. 8 is the photograph of the HKUST-1 film of the kayexalate modification of dimethyl silicone polymer encapsulation in application examples 1
Piece；
Fig. 9 is the I- of the HKUST-1 film of the kayexalate modification of dimethyl silicone polymer encapsulation in application examples 1
V curve and conductivity；
Figure 10 be application examples 2 in dimethyl silicone polymer encapsulation kayexalate modification HKUST-1 film from
Sub- separating resulting.
Specific embodiment
The present invention is further elaborated and is illustrated with reference to the accompanying drawings and examples.Each embodiment in the present invention
Technical characteristic can carry out the corresponding combination under the premise of not conflicting with each other.
In the present invention Kocide SD nanowire solution the preparation method comprises the following steps:
Aqueous ethanolamine is added in copper nitrate aqueous solution, stirring and seals reaction vessel, 12~48 hours it
Afterwards, Kocide SD nanowire solution is obtained.The concentration of the aqueous ethanolamine is 1.4mM；The copper nitrate aqueous solution
Concentration is 4mM.
In the present invention zinc hydroxide nano-wire solution the preparation method comprises the following steps:
Ethanol amine is added in the mixed liquor of second alcohol and water, obtains ethanolamine solutions；Second alcohol and water is added in zinc nitrate
In mixed liquor, zinc nitrate solution is obtained；Ethanolamine solutions are mixed with zinc nitrate solution again, are stirred, and reaction vessel is sealed,
After 0.5~1.5 hour, zinc hydroxide nano-wire solution is obtained.The concentration of the ethanolamine solutions is 1.6mM；Described
Zinc nitrate solution concentration is 4mM；Volume ratio for the ethyl alcohol and water that dissolve ethanol amine or zinc nitrate is 1:1.5.
Embodiment 1
1) 30ml Kocide SD nanowire solution is mixed with 1ml 0.0003wt% kayexalate solution, magnetic force
5min is stirred, directly vacuum filtration forms the composite membrane of one layer of nano wire and kayexalate on polyethersulfone porous membrane,
The diameter of polyethersulfone porous membrane is 2.5cm, aperture 200nm, porosity 25~50%.；
2) nano wire kayexalate film is put into 10ml, in 10mM trimesic acid solution (ethyl alcohol and water
Volume is 1:1), it reacts at room temperature 2 hours.It is washed 3 times after reaction with the mixed solvent of same ratio, obtains kayexalate
The HKUST-1 film of modification, is shown in Fig. 2.The HKUST-1 film of kayexalate modification shown in Fig. 2 is polycrystal film, brilliant
Grain intergrowth is good, the continuous free from flaw of film.
Embodiment 2
1) 30ml Kocide SD nanowire solution is mixed with 1ml 0.003wt% kayexalate solution, magnetic force
5min is stirred, directly vacuum filtration forms the composite membrane of one layer of nano wire and kayexalate on polyethersulfone porous membrane,
The diameter of polyethersulfone porous membrane is 2.5cm, aperture 200nm, porosity 25~50%.；
2) nano wire kayexalate film is put into 10ml, in 10mM trimesic acid solution (ethyl alcohol and water
Volume is 1:1), it reacts at room temperature 2 hours.It is washed 3 times after reaction with the mixed solvent of same ratio, obtains kayexalate
The HKUST-1 film of modification, is shown in Fig. 3.The HKUST-1 film of kayexalate modification shown in Fig. 3 is polycrystal film, brilliant
Grain intergrowth is good, the continuous free from flaw of film.
Embodiment 3
1) 30ml Kocide SD nanowire solution is mixed with 1ml 0.03wt% kayexalate solution, magnetic force stirs
5min is mixed, directly vacuum filtration forms the composite membrane of one layer of nano wire and kayexalate on polyethersulfone porous membrane, gathers
The diameter of ether sulfone perforated membrane is 2.5cm, aperture 200nm, porosity 25~50%.；
2) nano wire kayexalate film is put into 10ml, in 10mM trimesic acid solution (ethyl alcohol and water
Volume is 1:1), it reacts at room temperature 2 hours.It is washed 3 times after reaction with the mixed solvent of same ratio, obtains kayexalate
The HKUST-1 film of modification, is shown in Fig. 4.The HKUST-1 film of kayexalate modification shown in Fig. 4 is polycrystal film, brilliant
Grain intergrowth is good, the continuous free from flaw of film.
Embodiment 4
1) 15ml zinc hydroxide nano-wire solution is mixed with 0.5ml 0.0003wt% kayexalate solution, magnetic
Power stirs 5min, is directly filtered by vacuum on polyethersulfone porous membrane, forms the compound of one layer of nano wire and kayexalate
Film, the diameter of polyethersulfone porous membrane are 2.5cm, aperture 200nm, porosity 25~50%.；
2) nano wire kayexalate film is put into the 2ml, (body of ethyl alcohol and water in 25mM methylimidazole solution
Product is 1:1.5), and micro sodium formate is added, it reacts at room temperature 24 hours.It is washed 3 times after reaction with the mixed solvent of same ratio,
The ZIF-8 film of kayexalate modification is obtained, sees Fig. 5.The ZIF-8 of kayexalate modification shown in fig. 5 is thin
Film is polycrystal film, and crystal grain intergrowth is good, the continuous free from flaw of film.
Embodiment 5
1) 15ml zinc hydroxide nano-wire solution is mixed with 0.5ml 0.003wt% kayexalate solution, magnetic
Power stirs 5min, is directly filtered by vacuum on polyethersulfone porous membrane, forms the compound of one layer of nano wire and kayexalate
Film, the diameter of polyethersulfone porous membrane are 2.5cm, aperture 200nm, porosity 25~50%.；
2) nano wire kayexalate film is put into the 2ml, (body of ethyl alcohol and water in 25mM methylimidazole solution
Product is 1:1.5), and micro sodium formate is added, it reacts at room temperature 24 hours.It is washed 3 times after reaction with the mixed solvent of same ratio,
The ZIF-8 film of kayexalate modification is obtained, sees Fig. 6.The ZIF-8 of kayexalate modification shown in fig. 6 is thin
Film is polycrystal film, and crystal grain intergrowth is good, the continuous free from flaw of film.
Embodiment 6
1) 15ml zinc hydroxide nano-wire solution is mixed with 0.5ml 0.03wt% kayexalate solution, magnetic force
5min is stirred, directly vacuum filtration forms the composite membrane of one layer of nano wire and kayexalate on polyethersulfone porous membrane,
The diameter of polyethersulfone porous membrane is 2.5cm, aperture 200nm, porosity 25~50%.
2) nano wire kayexalate film is put into the 2ml, (body of ethyl alcohol and water in 25mM methylimidazole solution
Product is 1:1.5), and micro sodium formate is added, it reacts at room temperature 24 hours.It is washed 3 times after reaction with the mixed solvent of same ratio,
The ZIF-8 film of kayexalate modification is obtained, sees Fig. 7.The ZIF-8 of kayexalate modification shown in Fig. 7 is thin
Film is polycrystal film, and crystal grain intergrowth is good, the continuous free from flaw of film.
Application examples 1
The HKUST-1 film dimethyl silicone polymer for the kayexalate modification that embodiment 3 is prepared
(PDMS) it is packaged, carries out electrochemistry I-V test, electrolyte is respectively 0.5M KCl, the second of 0.5M NaCl, 0.5M LiCl
Alcohol-water solution (volume ratio of ethyl alcohol and water be 1:1), electrode are platinum electrode, sweep speed 0.05V/s, scanning range is-
As a result 0.4~0.4V is shown in Fig. 9.When Fig. 9 (a) shows 0.5M KCl, NaCl or LiCl solution as electrolyte, prepared by embodiment 3
The conductivity of the I-V curve of the HKUST-1 film of obtained kayexalate modification, slope of a curve and film to ion
It is directly proportional；When Fig. 9 (b) shows 0.5M KCl, NaCl or LiCl solution as electrolyte, polyphenyl second that embodiment 3 is prepared
The conductivity of the HKUST-1 film of alkene sodium sulfonate modification, the ratio of conductivity are the HKUST-1 of kayexalate modification
Desired separated ratio of the film to different ions.
Application examples 2
The HKUST-1 film dimethyl silicone polymer for the kayexalate modification that embodiment 3 is prepared
(PDMS) be packaged, original electrolyte be 0.5M KCl and LiCl mixed solution and 0.5M NaCl and LiCl mixed solution, it is molten
Agent is the ethanol-water mixed solvent that volume ratio is 1:1, and collecting terminal is that the alcohol-water mixing that isometric volume ratio is 1:1 is molten
Agent applies 0.4V voltage 12 hours, and separating resulting is shown in Figure 10.Figure 10 shows the mixed ion solutions of same concentrations through polystyrene
Ion ratio after the HKUST-1 thin film separation of sodium sulfonate modification, Figure 10 (a) indicate 0.5M KCl and LiCl mixed solution through poly-
After the HKUST-1 thin film separation of sodium styrene sulfonate modification, solute 96.97% is LiCl, 3.03% is in the solution that is collected into
KCl；Figure 10 (b) indicates the HKUST-1 thin film separation that 0.5M NaCl and LiCl mixed solution are modified through kayexalate
Afterwards, solute 94.92% is LiCl, 5.08% is NaCl in the solution being collected into.
Claims (4)
1. a kind of preparation method of the metal organic framework thin film of kayexalate modification, which is characterized in that including such as
Lower step:
1) aqueous ethanolamine is added in copper nitrate aqueous solution, stirring, and reaction vessel is sealed, after 12 ~ 48 hours, obtained
Obtain Kocide SD nanowire solution；The hydroxide nano line solution of preparation is mixed with kayexalate solution again, is stirred
It mixes uniformly, vacuum filtration obtains the composite membrane of hydroxide nano line and kayexalate；
2) organic ligand is dissolved in the mixed solution of second alcohol and water, obtains organic ligand solution, by hydroxide nano line and is gathered
The composite membrane of sodium styrene sulfonate is placed in organic ligand solution, and room temperature reaction obtains kayexalate after 2 ~ 4 hours and repairs
The metal organic framework thin film of decorations.
2. the preparation method of the metal organic framework thin film of kayexalate modification as described in claim 1, special
Sign is that the concentration of the aqueous ethanolamine is 1.4 mM；The copper nitrate aqueous solution concentration is 4 mM；Described is poly-
Styrene sulfonic acid sodium solution takes water as a solvent, and the concentration of the kayexalate solution is 0.0003 ~ 0.03 wt%；Institute
The volume ratio of the nanowire solution and kayexalate solution stated is 30:1；The organic ligand is trimesic acid,
Concentration is 5 ~ 15 mM, and the volume ratio for the ethyl alcohol and water that dissolve organic ligand is 1:1.
3. a kind of Metal-organic frame of the kayexalate modification of method according to claim 11 preparation is thin
Film, which is characterized in that the Metal-organic frame is HKUST-1, molecular formula Cu3(BTC)2•3H2O, polystyrene sulphur
Sour sodium is uniformly distributed in Metal-organic frame hole, the continuous free from flaw of metal organic framework thin film.
4. a kind of metal organic framework thin film of kayexalate modification as claimed in claim 3 is in alkali metal ion point
Application from.
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