CN108704491A - The method that steam gel method prepares laminated metal organic framework film - Google Patents
The method that steam gel method prepares laminated metal organic framework film Download PDFInfo
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Abstract
The present invention relates to a kind of methods that steam gel method prepares laminated metal organic framework film, using dipping-pulling method, the sol-gel layer of one layer of offer source metal is first provided in carrier surface, obtain the carrier of the disposition activity point with laminated metal organic framework film, the carrier is placed directly in the solvent-free reaction kettle containing the corresponding pure organic ligand substance of a certain amount of this kind of metal-organic framework materials, under the conditions of certain temperature is solvent-free, the organic ligand in kettle is set to form steam by heating, complex reaction is generated with the source metal gel layer of carrier surface and obtains the laminated metal organic framework film of continuous uniform.Not only preparation process is simple for the method that the present invention uses, but also the environmental-friendly preparation under organic solvent-free, amplifies convenient for upgrading scale, can solve traditional lamella metal organic framework film and prepare existing difficult and challenge, have broad application prospects.
Description
Technical field
The present invention relates to a kind of methods that steam gel method prepares laminated metal organic framework film.
Background technology
In recent years, as the aggravation of energy shortage and people's environmental consciousness are increasingly enhanced, compared to traditional highly energy-consuming, height
Isolation technics is polluted, membrane separation technique is with low energy consumption, separative efficiency is high, it is apparent to be easily achieved continuously separation, low-carbon emission etc.
Advantage obtains more and more be widely applied in fields such as gas separation, sea water desalination, pervaporation, water pollution processing.Its
In, the performance of gas separation membrane is always subjected to the interactional limit of permeation flux and selectivity because of " trade-off " effect
System, i.e. Robinson's upper limit.
How molecular sieve nanometer sheet prepares large area and very thin thickness as ideal gas separation membrane construction material
Nanometer sheet molecular screen membrane be the key that break through permeation flux with selectivity interactional limitation.But it prepares at this stage
There is greatly challenge in the nanometer sheet molecular screen membrane of large area and high separability energy.
Tsapatsis seminars mix polymer with MFI molecular sieves, and nano level molecular sieve nanometer is obtained based on stripping
Piece has certain adjacency pair dimethylbenzene Fen Lixingneng [ with the molecular screen membrane that nanometer sheet is constructed;Varoon K,Zhang X,
Elyassi B,et al.Dispersible exfoliated zeolite nanosheets and their
application as a selective membrane.Science,2011,334:72-75.].But have found so far
Two-dimentional zeolite molecular sieve material is only more than ten kind, and molecular sieve stratified material is easy in synthetic method controllability and layers apart method
Property etc. there is limitation, correlative study do not obtain always apparent breakthrough.
Metal organic framework (MOFs) material is developed in recent years a kind of by metal is with organoligand coordination
At porous new material, with zeolite molecular sieve have similar topological structure because skeleton structure and pore size can pass through
It is reasonably adjusted between organic ligand and inorganic metal, surface can also be functionalized processing, compared to traditional zeolite point
Son sieve, metal-organic framework materials have more abundant skeleton structure and adjustable pore size.The organic bone of two-dimensional layer metal
Frame is the branch of metal-organic framework materials, compared to the two-dimentional zeolite molecular sieve of only more than ten kinds, two-dimensional layer metal organic framework
Diversity and multi-functional abundant material depot is provided for molecular sieve nanometer sheet.Wherein, zeolite imidazole skeleton class conduct
A kind of important branch of metal organic framework, in addition to the various pore passage structure of metal-organic framework materials and be easy to modification
The characteristics of framework counterpart, while also there is the micropore for being less than 0.5nm and excellent chemical stability and thermal stability, and it is two-dimentional
Zeolite imidazole skeleton similarly has these excellent specific properties.If can be by the two-dimentional zeolite imidazole skeleton layers apart of stratiform to nanometer
Scale, so that it may which nanometer sheet molecular screen membrane is obtained with assembling.
In recent years, how by laminated metal organic backbone layers apart and prepare nanometer sheet molecular screen membrane by researcher
Greatly concern.Currently, preparation 2D ultrathin nanometer chip seperation films include mainly：" top-down from top to bottom " and " from lower and
The method of upper bottom-up ".Recently, Peng Deng Rens [PengY,Li Y,BanY,et al.Metal-organic
framework nanosheets as building blocks for molecular sieving
membranes.Science,2014,346:1356-1359.Peng Y,Li Y,Ban Y,et al.Two‐Dimensional
Metal–Organic Framework Nanosheets for Membrane‐Based Gas
Separation.Angewandte Chemie International Edition,2017,56:9757-9761.]Using
The method of " top-down " obtains ultrathin nanometer chip gas separation membrane, mainly by organic solvent pitch layer, wet ball grinding with
And ultrasonic method, multilayer zeolite imidazole skeleton material is removed, the ultrathin membrane no more than 100nm is obtained on 200 DEG C of chip carrier,
And there is higher gas separating property.The preparation method can not equally avoid the limitation of " top-down " method, that is, prepare
Journey is complicated, condition is harsh, time-consuming, low output, and lamella size is small, and this method is easy to damage nanometer sheet, and nanoscale twins
It easily stacks, and then influences gas separating property, reduce the repeatability of separation film preparation, be unfavorable for further developmental research and answer
With.Nanometer sheet equally can also in the solution be obtained using the method for " bottom-up ".Tania Deng Rens [Rodenas T,Luz
I,Prieto G,et al.Metal–organic framework nanosheets in polymer composite
materials for gas separation.Nature Materials,2015,14:48-55.]By different solvents interface
Super thin metal organic backbone nanometer sheet is prepared, and itself and organic matter are mixed with preferable gas separating property hybridized film.
But the organic solvent that the process needs more toxicity big, the low output of the nanometer sheet of preparation, and the hybridized film infiltration prepared is logical
It measures low.There are no a kind of technology of laminated metal organic framework film for the preparation high quality being simple and efficient environmental protection and sides so far
Method.
Invention content
The problems such as present invention is complicated for current laminated metal organic backbone film preparation, difficult, repeatability is not high, it is proposed that
A kind of steam gel method prepares the new method of laminated metal organic framework film.The preparation method is not necessarily to organic solvent, has green
Environmental protection, operating process is simple, yield is high, can large area film forming, the high advantage of repeatability, before there is amplification well and application
Scape.
The present invention inventive concept be：It is solidifying by the colloidal sol-for lifting one layer of offer source metal of introducing in carrier surface first
Disposition activity point of the glue-line as laminated metal organic framework film, obtains the disposition activity point with laminated metal organic framework film
Carrier；Then the carrier is placed directly within to the solvent-free reaction kettle of the ligand pure material containing this kind of metal-organic framework materials
In, under certain temperature condition of no solvent, directly so that the organic ligand in kettle is formed steam by heating, the steam of generation is carrying
Body surface face coordinates and is formed the organic bone in two-dimensional nano chip laminated metal of continuous uniform with the contacted with ions of source metal gel layer
Frame film.
Technical scheme is as follows, and a kind of steam gel method preparation laminated metal organic framework film is with zinc or cobalt
Central ion, using benzimidazole as organic ligand, the zeolite imidazole skeleton class laminated metal organic framework film of formation, load used
Body is the porous alumina ceramic pipe that average pore size is 200nm~2 μm or potsherd or non-porous glass chip carrier.
A kind of preparation side of steam gel method preparation laminated metal organic framework film is claimed in another object of the present invention
Method includes the following steps：S1. being prepared in the sol-gel layer of the previously-introduced one layer of offer source metal of carrier surface has metal
The carrier of gel layer；
S2., carrier with metal gel layer is overhang to the stainless steel cauldron of the polytetrafluoroethylene (PTFE) added with benzimidazole
In, at 180~200 DEG C, reaction 4-12h obtains two-dimensional layer metal organic framework film.
The source metal gel-sol layer is zinc sol-gel layer or cobalt sol-gel layer.It can be according to being lifted
The gel layer in different metal source (zinc or cobalt), the organic bone of two-dimensional layer metal of corresponding available different metal source (zinc or cobalt)
Frame film.
Metal-sol liquid is prepared with the following method in the step S1：Ethylene glycol monomethyl ether and acetate are stirred under water-bath
It mixes, a certain amount of ethanol amine is slowly added dropwise, stir to get uniform metal-sol liquid at ambient temperature.More specifically, second
Glycol methyl ether is 20 in molar ratio with acetate:1,70 DEG C of bath temperature, ethanol amine：Acetate is 2 in molar ratio:1, in room temperature
Under the conditions of stir and obtain uniform metal-sol liquid for 24 hours, metal-sol liquid is introduced into carrier by the method that lifting or spin coating is used in combination
Surface, dry 1h, obtains the carrier with homogeneous metal gel layer at 120 DEG C；Wherein acetate is zinc acetate and/or acetic acid
Cobalt.
In the above method, metal-sol liquid is lifted in carrier surface or spin coating certain time, generally 2s-60s are practical
According to the time of coating difference in production, the two-dimensional layer metal organic framework film of different-thickness can be obtained.
In the step S2, the benzimidazole being added in the stainless steel cauldron of polytetrafluoroethylene (PTFE) is excessive, and
It need to ensure to have the carrier of metal gel active layer cannot be contacted with benzimidazole.
Compared with prior art, the beneficial effects of the present invention are：
Steam gel method provided by the invention prepares laminated metal organic backbone film method, and not only preparation process is simple, but also
The environmental-friendly preparation under organic solvent-free, it is high with yield, can the high advantage of large area film forming, repeatability, convenient for upgrading rule
Mould amplifies, and can solve to prepare present in traditional lamella metal organic framework film preparation process difficult, complicated, repeated not high
Problem has broad application prospects.
Description of the drawings
Fig. 1 a are the electron microscope on empty carrier surface.
Fig. 1 b are the electron microscope of the carrier surface of sol-gel layer modification.
Fig. 2 a are the Electronic Speculum on the cobalt-based two-dimensional layer metal organic framework film surface generated by the induction of cobalt sol-gel layer
Figure.
Fig. 2 b are the Electronic Speculum in the cobalt-based two-dimensional layer metal organic framework film section generated by the induction of cobalt sol-gel layer
Figure.
Fig. 2 c are the XRD diagram of 1 synthetic sample of embodiment.
Fig. 3 a are the Electronic Speculum on the zinc-base two-dimensional layer metal organic framework film surface generated by the induction of zinc sol-gel layer
Figure.
Fig. 3 b are the Electronic Speculum in the zinc-base two-dimensional layer metal organic framework film section generated by the induction of zinc sol-gel layer
Figure.
Specific implementation mode
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method is conventional method used by invention, and experiment equipment used, material, reagent etc. commercially obtain.
1 two-dimensional layer Co of embodiment2(bim)4The preparation of nanometer chip film
(1) porous carrier selected is the porous alumina ceramic pipe of average pore size about 200nm.Using preceding porous carrier
It is washed for several times through deionized water and EtOH Sonicate, then 400 DEG C of roasting 2h in Muffle furnace, are cooled to room temperature and are placed in drier
For use.
(2) alumina ceramic carrier inner surface introduces cobalt sol layer.The cobalt acetate of 9.3624g is added to 50ml ethylene glycol
In methyl ether, after stirring 0.5h under 70 DEG C of water-baths, 4.6ml ethanol amines is slowly added dropwise as stabilizer, stir at ambient temperature
Uniform cobalt sol solutions are obtained for 24 hours.Then it is dipped into the alumina ceramic carrier inner surface of lifting coating in (1) and forms cobalt
Sol layer, the dry 1h at 120 DEG C obtain the porous carrier with uniform cobalt gel layer, and comparison porous carrier (such as Fig. 1 a) should
Gel layer can modify the apparent defect of carrier surface (such as Fig. 1 b), while provide uniform metal work to prepare nanometer chip film
Property site.
(3) alumina ceramic carrier surface growth two-dimensional layer Co2(bim)4Nanometer chip film.To there is cobalt gel in (2)
The porous carrier of layer is overhang in the stainless steel cauldron added with the polytetrafluoroethylene (PTFE) of benzimidazole, it is ensured that there is metal gel to live
Property layer carrier cannot be contacted with benzimidazole, at 200 DEG C react 4-12h after ceramic tube is taken out, slowly rinsed with methanol
Film surface spontaneously dries, and obtains the stratiform Co with horizontal direction oriented growth2(bim)4Nanometer chip film (such as Fig. 2 b), X
X ray diffraction confirms that there is the film prepared the c- axis of height to be orientated (such as Fig. 2 c).
2 two-dimensional layer Zn of embodiment2(bim)4The preparation of nanometer chip film
(1) porous carrier selected is the porous alumina ceramic pipe of average pore size about 200nm.Its processing step is the same as implementation
1 step of example (1)；
(2) alumina ceramic carrier inner surface introduces zinc sol layer.The zinc acetate of 8.2621g is added to 50ml ethylene glycol
In methyl ether, after stirring 0.5h under 70 DEG C of water-baths, 4.6ml ethanol amines is slowly added dropwise as stabilizer, stir at ambient temperature
Uniform cobalt sol solutions are obtained for 24 hours.Then it is dipped into the alumina ceramic carrier inner surface of lifting coating in (1) and forms zinc
Sol layer, dry 1h, obtains the porous carrier with uniform gel of zinc layer at 120 DEG C；
(3) alumina ceramic carrier surface growth two-dimensional layer Zn2(bim)4Nanometer chip film.With 1 step of embodiment (3),
The difference is that by (2) with gel of zinc layer porous carrier overhang added with benzimidazole polytetrafluoroethylene (PTFE) it is stainless
In steel reaction kettle.As shown in figure 3, by steam gel method, the stratiform Zn of horizontal direction oriented growth can be still obtained2
(bim)4Nanometer chip film.
3 two-dimensional layer of embodiment (Zn/Co)2(bim)4The preparation of nanometer chip film
(1) porous carrier selected is the porous alumina ceramic pipe of average pore size about 200nm.Its processing step is the same as implementation
1 step of example (1)；
(2) alumina ceramic carrier inner surface introduces zinc/cobalt mixed sols layer.The cobalt acetate of zinc acetate sum is added to
In 50ml ethylene glycol monomethyl ethers, ethylene glycol monomethyl ether in coagulant liquid is maintained：(zinc acetate+cobalt acetate) molar ratio is 20：1,70
Under DEG C water-bath after stirring 0.5h, 4.6ml ethanol amines are slowly added dropwise as stabilizer, stir at ambient temperature obtain for 24 hours it is uniform
Zinc/cobalt mixed sols liquid.Then it is molten to be dipped into the alumina ceramic carrier inner surface formation zinc cobalt of lifting coating in (1)
Glue-line, dry 1h, obtains the porous carrier with uniform zinc/cobalt gel layer at 120 DEG C；
(3) alumina ceramic carrier surface growth two-dimensional layer (Zn/Co)2(bim)4Nanometer chip film.With 1 step of embodiment
Suddenly (3), the difference is that the porous carrier with zinc/cobalt gel layer in (2) is overhang the polytetrafluoro added with benzimidazole
In the stainless steel cauldron of ethylene.
4 two-dimensional layer of embodiment (Co)2(bim)4The gas permeability test of nanometer chip film
(Co) of two-dimensional layered structure prepared by the embodiment of the present invention2(bim)4Nanometer chip film is at 30 DEG C of 0.1MPa
Test its one-component gas flux and its rationality gas separation selectivity with gas-kinetic diameter variation：Hydrogen leads to
Amount is 17.2 × 10-8mol m-2s-1Pa-1, H2/CO2、H2/N2、H2/CH4Ideal separation factor be respectively 58.7,49.7,
68.6.Illustrate (Co) of two-dimensional layered structure prepared by steam gel method2(bim)4Nanometer chip film has gas excellent separation
Effect.
The preferable specific implementation mode of the above, only the invention, but the protection domain of the invention is not
It is confined to this, any one skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it
It is interior.
Claims (8)
1. a kind of steam gel method prepares laminated metal organic framework film, which is characterized in that the ion centered on zinc or cobalt, with benzene
And imidazoles is organic ligand, the zeolite imidazole skeleton class laminated metal organic framework film of formation, carrier used is average pore size
Porous alumina ceramic pipe or potsherd for 200nm~2 μm or non-porous glass chip carrier.
2. a kind of preparation method of laminated metal organic framework film as described in claim 1, includes the following steps：
S1. the carrier with metal gel layer is prepared in the sol-gel layer of the previously-introduced one layer of offer source metal of carrier surface；
S2. the carrier with metal gel layer is overhang in the stainless steel cauldron added with the polytetrafluoroethylene (PTFE) of benzimidazole,
At 180~200 DEG C, reaction 4-12h obtains two-dimensional layer metal organic framework film.
3. according to the method described in claim 2, it is characterized in that, the source metal gel-sol layer is zinc sol-gel
Layer or cobalt sol-gel layer.
4. according to the method described in claim 2, it is characterized in that, metal-sol liquid is prepared with the following method in step S1：
Ethylene glycol monomethyl ether and acetate are stirred under water-bath, a certain amount of ethanol amine is slowly added dropwise, stirs to get at ambient temperature
Uniform metal-sol liquid.
5. according to the method described in claim 4, it is characterized in that, the step S1 is specially：By ethylene glycol monomethyl ether and acetic acid
Salt is 20 in molar ratio:1 stirs under 70 DEG C of water-baths, while a certain amount of ethanol amine, ethanol amine is slowly added dropwise：Acetate is massaged
You are than being 2:1, it stirs obtain uniform metal-sol liquid for 24 hours at ambient temperature, be used in combination the method for lifting or spin coating by metal
Sol solutions are introduced into carrier surface, and dry 1h, obtains the carrier with homogeneous metal gel layer at 120 DEG C；Wherein acetate
For zinc acetate and/or cobalt acetate.
6. according to the method described in claim 2, it is characterized in that, metal-sol liquid is lifted or spin coating according in carrier surface
The time of time coating obtains the two-dimensional layer metal organic framework film of different-thickness.
7. according to the method described in claim 5, it is characterized in that, the time is 2s-60s.
8. anti-in the stainless steel of polytetrafluoroethylene (PTFE) according to the method described in claim 2, it is characterized in that, in the step S2
It answers and excessive benzimidazole is added in kettle.
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Cited By (5)
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| CN110833769A (en) * | 2019-11-20 | 2020-02-25 | 大连理工大学 | Layered zirconium phosphate-based molecular sieve membrane and preparation method thereof |
| CN111589311A (en) * | 2020-05-29 | 2020-08-28 | 大连理工大学 | Method for preparing metal organic framework molecular sieve membrane by supercritical fluid technology |
| CN112458489A (en) * | 2020-11-23 | 2021-03-09 | 浙江工商大学 | Novel catalyst material and preparation method and application thereof |
| CN112657351A (en) * | 2020-12-01 | 2021-04-16 | 大连理工大学 | Method for preparing high-orientation MOF nano-sheet membrane by utilizing self-rotation of layered metal hydroxide |
| CN114471174A (en) * | 2021-02-25 | 2022-05-13 | 大连理工大学 | Preparation method of in-pore synthesized ZIF-8 membrane |
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