CN105854647A - Sodium polystyrene sulfonate modified metal organic framework film and application thereof - Google Patents
Sodium polystyrene sulfonate modified metal organic framework film and application thereof Download PDFInfo
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- CN105854647A CN105854647A CN201610228832.8A CN201610228832A CN105854647A CN 105854647 A CN105854647 A CN 105854647A CN 201610228832 A CN201610228832 A CN 201610228832A CN 105854647 A CN105854647 A CN 105854647A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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Abstract
The invention discloses a sodium polystyrene sulfonate modified metal organic framework film and an application thereof. A production method of the sodium polystyrene sulfonate modified metal organic framework film comprises the following steps: 1, preparing a hydroxide nano-wire solution, mixing the prepared hydroxide nano-wire solution with a sodium polystyrene sulfonate solution, uniformly stirring, and carrying out vacuum pumping filtration to obtain a hydroxide nano-wire and sodium polystyrene sulfonate composite film; and 2, dissolving an organic ligand in an ethanol and water mixed solution to obtain an organic ligand solution, placing the hydroxide nano-wire and sodium polystyrene sulfonate composite film in the organic ligand solution, and carrying out a room temperature reaction for 2-4h to obtain the sodium polystyrene sulfonate modified metal organic framework film. Sodium polystyrene sulfonate and nano-wires are mixed through physical stirring and electrostatic adsorption, and sodium polystyrene sulfonate is introduced into the metal organic framework film in situ in order to carry out modification, so the method has the advantages of avoiding of the organic modification process of the metal organic framework ligand, low energy consumption, no pollution, fastness and high efficiency.
Description
Technical field
The present invention relates to the preparation method of metal organic framework thin film, be specifically related to a kind of polystyrene
The metal organic framework thin film of sodium sulfonate modification and application thereof.
Background technology
Metal organic framework thin film be a kind of thickness in nanometer to micrometer range, be attached in matrix
Porous function film, ideally, metal organic framework thin film smooth surface, isotropic,
There is high porosity and good chemical stability, can apply to separate, adsorb, be catalyzed, medicine
The numerous areas such as thing slow-released carrier, hydrogen storage.
Fine and close continuous print metal organic framework thin film may be used for ion isolation field.If to metal
The micropore inwall of organic framework film carries out modification can change the inwall compatibility to ion, passes through
Introduce different functional groups, micropore inwall is modified, it is more likely that make it that different ions to be had
Different selectivity, under the driving of voltage, can be carried out the different kinds of ions in mixed ion solutions
Selectivity transports, and then realizes ion isolation.
The Chinese patent literature of Patent No. ZL201210383466.5 discloses a kind of hydroxide and receives
Rice noodles and organic ligand the most quickly prepare the method for metal organic framework thin film, and step is such as
Under: 1) under magnetic stirring, aqueous ethanolamine is added same volume copper nitrate, zinc nitrate or nitre
In the acid cadmium aqueous solution, slow down mixing speed, it is thus achieved that corresponding Kocide SD, zinc hydroxide or hydroxide
Cadmium nanowire solution, directly filters one layer of nano wire of formation on multiaperture pellumina by nanowire solution
Layer；2) nano wire layer is joined in the organic ligand solution that solvent is ethanol, octanol or DMF,
Reaction 30min obtains metal organic framework thin film at normal temperatures.
The method of modifying of metal current organic framework film micropore inwall is frequently on organic ligand
Specific functional group in grafting.This process is often complicated organic synthesis, complex operation, consumption
Can be high, there is pollution, these drawbacks limit its development and application.
Summary of the invention
The invention provides the system of the metal organic framework thin film that a kind of kayexalate is modified
Preparation Method, makes kayexalate and metal hydroxides nanometer by physical agitation, Electrostatic Absorption
Line be combined, it is achieved that low temperature, low energy consumption, free of contamination under the conditions of simply and easily by polystyrene
Sodium sulfonate introduces the internal void of metal organic framework thin film, is modified its inwall modifying, makes
It has the function of ion isolation.
Utilize metal hydroxides nanostructured as source metal synthesis metal organic framework thin film
Method, simple to operate, consume energy low, pollution-free.Metal hydroxides nanostructured surface often carries simultaneously
There is positive charge, the molecule with the charges of different polarity or nanostructured can be adsorbed.Therefore, organic at metal
In the building-up process of framework thing film, can be by metal hydroxides nanostructured surface absorption spy
Determining molecule or nanostructured, specific molecular or nanostructured can be made to be compound to metal in situ machine frame
In the hole of frame thing, thus realize introducing particular functional group in Metal-organic frame, reach it
Inwall is modified the effect modified, and transports the separation with alkali metal ion realizing ion selectivity.
The preparation method of the metal organic framework thin film that a kind of kayexalate is modified, including such as
Lower step:
1) hydroxide nano line solution is prepared, then by the hydroxide nano line solution of preparation with poly-
Styrene sulfonic acid sodium solution mixes, and stirs, and vacuum filtration obtains hydroxide nano line and polyphenyl
The composite membrane of vinyl sulfonic acid sodium；
2) organic ligand is dissolved in the mixed solution of second alcohol and water, obtains organic ligand solution, by hydroxide
The composite membrane of thing nano wire and kayexalate is placed in organic ligand solution, room temperature reaction 2～24
The metal organic framework thin film that kayexalate is modified is obtained after hour.
As preferably, described hydroxide nano line solution manufacturing method is: by aqueous ethanolamine
Add in copper nitrate aqueous solution, stirring, and reaction vessel is sealed, after 12～48 hours, it is thus achieved that
Kocide SD nanowire solution.
Further, the concentration of described aqueous ethanolamine is 1.4mM；Described copper nitrate water
Solution concentration is 4mM；Described kayexalate solution with water as solvent, described polyphenyl
The concentration of vinyl sulfonic acid sodium solution is 0.0003～0.03wt%；Described nanowire solution and polyphenyl second
The volume ratio of alkene sodium sulfonate solution is 30:1；Described organic ligand is trimesic acid, and concentration is
5～15mM, the volume ratio of ethanol and water for dissolving organic ligand is 1:1.
Preferred as another kind, described hydroxide nano line solution manufacturing method is: by monoethanolamine
Add in the mixed liquor of second alcohol and water, obtain ethanolamine solutions；Zinc nitrate is added the mixed of second alcohol and water
Close in liquid, obtain zinc nitrate solution；Again ethanolamine solutions is mixed with zinc nitrate solution, stirring, and
Reaction vessel is sealed, after 0.5～1.5 hour, it is thus achieved that zinc hydroxide nano-wire solution.
Further, the concentration of described ethanolamine solutions is 1.6mM；Described zinc nitrate solution
Concentration is 4mM；Described kayexalate solution with water as solvent, described polystyrene
The concentration of sodium sulfonate solution is 0.0003～0.03wt%；Described nanowire solution and polystyrene sulphur
The volume ratio of acid sodium solution is 30:1；Described organic ligand is methylimidazole, and concentration is 25mM,
The volume ratio of ethanol Yu water for dissolving organic ligand is 1:4；For dissolving monoethanolamine or zinc nitrate
The volume ratio of ethanol and water be 1:1.5.
Another object of the present invention is to the polystyrene sulphur providing a kind of method described in basis to prepare
The metal organic framework thin film that acid sodium is modified, described Metal-organic frame is HKUST-1,
Molecular formula is Cu3(BTC)2·3H2O, kayexalate is uniformly distributed in Metal-organic frame
In hole, the continuous free from flaw of metal organic framework thin film.
Another object of the present invention is to provide the another kind of polystyrene prepared according to described method
The metal organic framework thin film that sodium sulfonate is modified, described Metal-organic frame is ZIF-8, point
Minor is C8H12N4Zn, kayexalate 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 modified such as described kayexalate
The application in alkali metal ion separates of the organic framework film.
Compared with prior art, present invention have the advantage that
The present invention by by kayexalate and metal hydroxides nanowire solution mix and blend,
Electrostatic Absorption is combined, and then kayexalate introduces metal organic framework thin film hole in situ
In gap, it is achieved the sulfonate radical modification to metal organic framework thin film hole inwall, change it to ion
Affine performance, it is achieved the selectivity of different ions is transmitted, under voltage drives, realizes ion isolation.
Present invention, avoiding ligand modified complicated organic synthesis step, simple to operate, consume energy low, pollution-free,
Rapidly and efficiently.
Accompanying drawing explanation
Fig. 1 is the preparation flow of the metal organic framework thin film that kayexalate is modified in embodiment 1
Figure；
Fig. 2 is the surface of the HKUST-1 film that the kayexalate of preparation is modified in embodiment 1
SEM photograph；
Fig. 3 is the surface of the HKUST-1 film that the kayexalate of preparation is modified in embodiment 2
SEM photograph；
Fig. 4 is the surface of the HKUST-1 film that the kayexalate of preparation is modified in embodiment 3
SEM photograph；
Fig. 5 is the SEM on the surface of the ZIF-8 film that the kayexalate of preparation is modified in embodiment 1
Photo；
Fig. 6 is the SEM on the surface of the ZIF-8 film that the kayexalate of preparation is modified in embodiment 2
Photo；
Fig. 7 is the SEM on the surface of the ZIF-8 film that the kayexalate of preparation is modified in embodiment 3
Photo；
Fig. 8 is the HKUST-1 that in application examples 1, the kayexalate of dimethyl silicone polymer encapsulation is modified
The photo of film；
Fig. 9 is the HKUST-1 that in application examples 1, the kayexalate of dimethyl silicone polymer encapsulation is modified
The I-V curve of film and electrical conductivity；
Figure 10 is that in application examples 2, the kayexalate of dimethyl silicone polymer encapsulation is modified
HKUST-1 membrane ion separating resulting.
Detailed description of the invention
With embodiment the present invention it is further elaborated below in conjunction with the accompanying drawings and illustrates.In the present invention each
The technical characteristic of embodiment, on the premise of not colliding with each other, all can carry out respective combination.
In the present invention, the preparation method of Kocide SD nanowire solution is:
Aqueous ethanolamine is added in copper nitrate aqueous solution, stirring, and reaction vessel is sealed,
After 12～48 hours, it is thus achieved that Kocide SD nanowire solution.The concentration of described aqueous ethanolamine
For 1.4mM；Described copper nitrate aqueous solution concentration is 4mM.
In the present invention, the preparation method of zinc hydroxide nano-wire solution is:
Monoethanolamine is added in the mixed liquor of second alcohol and water, obtain ethanolamine solutions；Zinc nitrate is added
In the mixed liquor of second alcohol and water, obtain zinc nitrate solution；Again ethanolamine solutions is mixed with zinc nitrate solution
Close, stirring, and reaction vessel is sealed, after 0.5～1.5 hour, it is thus achieved that zinc hydroxide nano-wire
Solution.The concentration of described ethanolamine solutions is 1.6mM；Described zinc nitrate solution concentration is 4
mM；The volume ratio of ethanol Yu water for dissolving monoethanolamine or zinc nitrate is 1:1.5.
Embodiment 1
1) by 30ml Kocide SD nanowire solution and 1ml 0.0003wt% kayexalate
Solution mixes, and magnetic agitation 5min, direct vacuum filtration, on polyethersulfone porous membrane, forms one layer
Nano wire and the composite membrane of kayexalate, a diameter of 2.5cm of polyethersulfone porous membrane, aperture
For 200nm, porosity 25～50%.；
2) nano wire kayexalate film is put into 10ml, 10mM trimesic acid molten
(ethanol is 1:1 with the volume of water), room temperature reaction 2 hours in liquid.Mixing by same ratio after reaction
Bonding solvent washs 3 times, obtains the HKUST-1 film that kayexalate is modified, sees Fig. 2.
The HKUST-1 film that kayexalate shown in Fig. 2 is modified is polycrystal film, crystal grain intergrowth
Well, the continuous free from flaw of film.
Embodiment 2
1) by 30ml Kocide SD nanowire solution and 1ml 0.003wt% kayexalate
Solution mixes, and magnetic agitation 5min, direct vacuum filtration, on polyethersulfone porous membrane, forms one layer
Nano wire and the composite membrane of kayexalate, a diameter of 2.5cm of polyethersulfone porous membrane, aperture
For 200nm, porosity 25～50%.；
2) nano wire kayexalate film is put into 10ml, 10mM trimesic acid molten
(ethanol is 1:1 with the volume of water), room temperature reaction 2 hours in liquid.Mixing by same ratio after reaction
Bonding solvent washs 3 times, obtains the HKUST-1 film that kayexalate is modified, sees Fig. 3.
The HKUST-1 film that kayexalate shown in Fig. 3 is modified is polycrystal film, crystal grain intergrowth
Well, the continuous free from flaw of film.
Embodiment 3
1) by molten with 1ml 0.03wt% kayexalate for 30ml Kocide SD nanowire solution
Liquid mixes, and magnetic agitation 5min, direct vacuum filtration, on polyethersulfone porous membrane, forms one layer and receives
Rice noodles and the composite membrane of kayexalate, a diameter of 2.5cm of polyethersulfone porous membrane, aperture is
200nm, porosity 25～50%.；
2) nano wire kayexalate film is put into 10ml, 10mM trimesic acid molten
(ethanol is 1:1 with the volume of water), room temperature reaction 2 hours in liquid.Mixing by same ratio after reaction
Bonding solvent washs 3 times, obtains the HKUST-1 film that kayexalate is modified, sees Fig. 4.
The HKUST-1 film that kayexalate shown in Fig. 4 is modified is polycrystal film, crystal grain intergrowth
Well, the continuous free from flaw of film.
Embodiment 4
1) by 15ml zinc hydroxide nano-wire solution and 0.5ml 0.0003wt% polystyrolsulfon acid
Sodium solution mixes, magnetic agitation 5min, and direct vacuum filtration, on polyethersulfone porous membrane, forms one
Layer nano wire and the composite membrane of kayexalate, a diameter of 2.5cm of polyethersulfone porous membrane, hole
Footpath is 200nm, porosity 25～50%.；
2) nano wire kayexalate film is put into 2ml, 25mM methylimidazole solution
In (volume of ethanol and water is 1:1.5), and add trace sodium formate, room temperature reaction 24 hours.Instead
The mixed solvent of the same ratio of Ying Houyong washs 3 times, obtains the ZIF-8 that kayexalate is modified
Film, is shown in Fig. 5.The ZIF-8 film that kayexalate shown in Fig. 5 is modified is polycrystal film,
Crystal grain intergrowth is good, the continuous free from flaw of film.
Embodiment 5
1) by 15ml zinc hydroxide nano-wire solution and 0.5ml 0.003wt% kayexalate
Solution mixes, and magnetic agitation 5min, direct vacuum filtration, on polyethersulfone porous membrane, forms one layer
Nano wire and the composite membrane of kayexalate, a diameter of 2.5cm of polyethersulfone porous membrane, aperture
For 200nm, porosity 25～50%.；
2) nano wire kayexalate film is put into 2ml, 25mM methylimidazole solution
In (volume of ethanol and water is 1:1.5), and add trace sodium formate, room temperature reaction 24 hours.Instead
The mixed solvent of the same ratio of Ying Houyong washs 3 times, obtains the ZIF-8 that kayexalate is modified
Film, is shown in Fig. 6.The ZIF-8 film that kayexalate shown in Fig. 6 is modified is polycrystal film,
Crystal grain intergrowth is good, the continuous free from flaw of film.
Embodiment 6
1) by 15ml zinc hydroxide nano-wire solution and 0.5ml 0.03wt% kayexalate
Solution mixes, and magnetic agitation 5min, direct vacuum filtration, on polyethersulfone porous membrane, forms one layer
Nano wire and the composite membrane of kayexalate, a diameter of 2.5cm of polyethersulfone porous membrane, aperture
For 200nm, porosity 25～50%.
2) nano wire kayexalate film is put into 2ml, 25mM methylimidazole solution
In (volume of ethanol and water is 1:1.5), and add trace sodium formate, room temperature reaction 24 hours.Instead
The mixed solvent of the same ratio of Ying Houyong washs 3 times, obtains the ZIF-8 that kayexalate is modified
Film, is shown in Fig. 7.The ZIF-8 film that kayexalate shown in Fig. 7 is modified is polycrystal film,
Crystal grain intergrowth is good, the continuous free from flaw of film.
Application examples 1
The HKUST-1 film that kayexalate embodiment 3 prepared is modified is with poly-two
Methylsiloxane (PDMS) is packaged, and carries out the test of electrochemistry I-V, and electrolyte is respectively 0.5
The ethanol-water solution (ethanol is 1:1 with the volume ratio of water) of M KCl, 0.5M NaCl, 0.5M LiCl,
Electrode is platinum electrode, and sweep speed is 0.05V/s, and sweep limits is-0.4～0.4V, and result is shown in Fig. 9.
When Fig. 9 (a) illustrates 0.5M KCl, NaCl or LiCl solution as electrolyte, embodiment 3 is prepared into
The I-V curve of the HKUST-1 film that the kayexalate arrived is modified, slope of a curve is with thin
The electrical conductivity of ion is directly proportional by film；Fig. 9 (b) illustrates that 0.5M KCl, NaCl or LiCl solution is made
During for electrolyte, the HKUST-1 film that the kayexalate that embodiment 3 prepares is modified
Electrical conductivity, the ratio of electrical conductivity be kayexalate modify HKUST-1 film to not
Homo-ion desired separated ratio.
Application examples 2
The HKUST-1 film that kayexalate embodiment 3 prepared is modified is with poly-two
Methylsiloxane (PDMS) is packaged, and original electrolyte is that 0.5M KCl and LiCl mixing is molten
Liquid and 0.5M NaCl and LiCl mixed solution, solvent be volume ratio be that the alcohol-water mixing of 1:1 is molten
Agent, collecting terminal be isopyknic volume ratio be the ethanol-water mixed solvent of 1:1, apply 0.4V voltage
12 hours, separating resulting was shown in Figure 10.Figure 10 illustrates that the mixed ion solutions of same concentrations is through polyphenyl second
Ion ratio after the HKUST-1 thin film separation that alkene sodium sulfonate is modified, Figure 10 (a) represents 0.5M KCl
With LiCl mixed solution after the HKUST-1 thin film separation that kayexalate is modified, collect
Solution in solute 96.97% be LiCl, 3.03% for KCl；Figure 10 (b) represent 0.5M NaCl and
LiCl mixed solution, after the HKUST-1 thin film separation that kayexalate is modified, is collected
In solution solute 94.92% be LiCl, 5.08% for NaCl.
Claims (8)
1. a preparation method for the metal organic framework thin film that kayexalate is modified, it is special
Levy and be, comprise the steps:
1) hydroxide nano line solution is prepared, then by the hydroxide nano line solution of preparation with poly-
Styrene sulfonic acid sodium solution mixes, and stirs, and vacuum filtration obtains hydroxide nano line and polyphenyl
The composite membrane of vinyl sulfonic acid sodium；
2) organic ligand is dissolved in the mixed solution of second alcohol and water, obtains organic ligand solution, by hydroxide
The composite membrane of thing nano wire and kayexalate is placed in organic ligand solution, room temperature reaction 2～4
The metal organic framework thin film that kayexalate is modified is obtained after hour.
2. the metal organic framework thin film that kayexalate as claimed in claim 1 is modified
Preparation method, it is characterised in that described hydroxide nano line solution manufacturing method is: by ethanol
Amine aqueous solution adds in copper nitrate aqueous solution, stirring, and is sealed by reaction vessel, 12～48 hours it
After, it is thus achieved that Kocide SD nanowire solution.
3. the metal organic framework thin film that kayexalate as claimed in claim 1 is modified
Preparation method, it is characterised in that described hydroxide nano line solution manufacturing method is: by ethanol
Amine adds in the mixed liquor of second alcohol and water, obtains ethanolamine solutions；Zinc nitrate is added second alcohol and water
In mixed liquor, obtain zinc nitrate solution；Again ethanolamine solutions is mixed with zinc nitrate solution, stirring,
And reaction vessel is sealed, after 0.5～1.5 hour, it is thus achieved that zinc hydroxide nano-wire solution.
4. the metal organic framework thin film that kayexalate as claimed in claim 2 is modified
Preparation method, it is characterised in that the concentration of described aqueous ethanolamine is 1.4mM；Described
Copper nitrate aqueous solution concentration be 4mM；Described kayexalate solution with water as solvent,
The concentration of described kayexalate solution is 0.0003～0.03wt%；Described nano wire is molten
The volume ratio of liquid and kayexalate solution is 30:1；Described organic ligand is equal benzene front three
Acid, concentration is 5～15mM, and the volume ratio of ethanol and water for dissolving organic ligand is 1:1.
5. the metal organic framework thin film that kayexalate as claimed in claim 3 is modified
Preparation method, it is characterised in that the concentration of described ethanolamine solutions is 1.6mM；Described
Zinc nitrate solution concentration is 4mM；Described kayexalate solution is with water as solvent, described
The concentration of kayexalate solution be 0.0003～0.03wt%；Described nanowire solution and
The volume ratio of kayexalate solution is 30:1；Described organic ligand is methylimidazole, dense
Degree is 25mM, and the volume ratio of ethanol and water for dissolving organic ligand is 1:4；For dissolving second
The ethanol of hydramine or zinc nitrate and the volume ratio of water are 1:1.5.
6. the metal that the kayexalate that prepared by a method according to claim 2 is modified
Organic framework film, it is characterised in that described Metal-organic frame is HKUST-1, point
Minor is Cu3(BTC)2·3H2O, kayexalate is uniformly distributed in Metal-organic frame hole
In gap, the continuous free from flaw of metal organic framework thin film.
7. the metal that the kayexalate that prepared by a method according to claim 3 is modified
Organic framework film, it is characterised in that described Metal-organic frame is ZIF-8, molecular formula
For C8H12N4Zn, kayexalate is uniformly distributed in Metal-organic frame hole, metal
The continuous free from flaw of organic framework film.
8. the Metal-organic frame that kayexalate is modified as claimed in claims 6 or 7
Film application in alkali metal ion separates.
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