CN103566779B - Macropore suprabasil metal organic nano rod array pinning effect is utilized to prepare the method that metal has machine frame thing gas separation membrane - Google Patents
Macropore suprabasil metal organic nano rod array pinning effect is utilized to prepare the method that metal has machine frame thing gas separation membrane Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000000926 separation method Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 title claims abstract description 17
- 239000002073 nanorod Substances 0.000 title claims abstract description 17
- 230000000694 effects Effects 0.000 title claims abstract description 14
- 239000002070 nanowire Substances 0.000 claims abstract description 60
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 58
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 30
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 16
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract description 15
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims abstract description 9
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims abstract description 4
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 4
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 28
- 239000013384 organic framework Substances 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000010409 thin film Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000013110 organic ligand Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of macropore suprabasil metal organic nano rod array pinning effect that utilizes and prepare the method that metal has machine frame thing gas separation membrane.Step is as follows: 1) under magnetic stirring, aqueous ethanolamine is added in same volume copper nitrate, zinc nitrate or the cadmium nitrate aqueous solution, slow down mixing speed, obtain Kocide SD, zinc hydroxide or cadmium hydroxide nanowires solution, nanowire solution is directly filtered on multiaperture pellumina, forms one deck nano wire layer; 2) nano wire layer is joined in the aqueous solution containing trimesic acid, obtain Metal-organic frame nanometer stick array.3) nanometer stick array is joined in the organic ligand mixed solution containing copper nitrate, zinc nitrate or cadmium nitrate as inculating crystal layer, obtain Metal-organic frame laminated film.The present invention is diauxic growth Metal-organic frame laminated film on metal organic nano rod array directly, and the adhesive force of film and substrate is very strong, obtain composition metal organic framework film for gas separaion.
Description
Technical field
The present invention relates to the preparation method of Metal-organic frame nano-array, particularly relate to a kind of macropore suprabasil metal organic nano rod array pinning effect that utilizes and prepare the method that metal has machine frame thing gas separation membrane.
Technical background
Metal organic framework thin film has due to it chemical stability that high porosity becomes reconciled, and has good application prospect in many fields such as adsorbing separation, catalytic reaction, pharmaceutical carrier and optical materials.The preparation method of metal current organic framework film has a lot, wherein has more traditional solvent-thermal method, layer by layer, and sol-gal process, colloidal deposition method and more novel microwave process for synthesizing, electrochemical synthesis etc.But these methods still also exist many drawbacks: although as easier in solvent-thermal method preparation, its synthetic, based on powder, is difficult to produce fine and close film; Sol-gal process and the standby more difficult unification of film thickness of colloidal deposition legal system, uniformity is bad; Layer by layer step is more loaded down with trivial details, and the film growth cycle is long; Microwave process for synthesizing and electrochemical synthesis immature development, production cost is higher.In addition, also have a very large drawback to be exactly that the adhesive force of film and substrate is strong not, carrying out easily disengaging mutually in some application such as gas separaion.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of utilization to assist synthetic metals organic framework nanometer stick array pinning to do to prepare the method that metal has machine frame thing gas separation membrane by hydroxide nano line on perforated substrate.
A kind of utilization assists synthetic metals organic framework nanometer stick array pinning to do to prepare metal by hydroxide nano line on perforated substrate has the step of the method for machine frame thing gas separation membrane as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reaction responses, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reaction responses obtain 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, in ethanol water, the volume ratio of ethanol and water is 1:1.
Another kind utilizes macropore suprabasil metal organic nano rod array pinning effect to prepare metal has the step of the method for machine frame thing gas separation membrane as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM zinc nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 1 hour, obtain zinc hydroxide nano-wire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4), 120 DEG C of reaction responses, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reaction responses obtain 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, in ethanol water, the volume ratio of ethanol and water is 1:1.
Another kind utilizes macropore suprabasil metal organic nano rod array pinning effect to prepare metal has the step of the method for machine frame thing gas separation membrane as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in the same volume 4mM cadmium nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 1 hour, obtain cadmium hydroxide nanowires solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reaction responses, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reaction responses obtain 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, in ethanol water, the volume ratio of ethanol and water is 1:1.
The present invention obtains Metal-organic frame laminated film by carrying out diauxic growth at metal organic nano rod array.The adhesive force of the film that this legal system is standby and substrate is very strong, repeatable strong, expands the range of application of Metal-organic frame array.Especially the introducing of nanometer stick array, make the film of diauxic growth and nanometer stick array have a good pinning effect, the adhesive force of effective enhanced film and substrate, can be used for gas separaion.
Accompanying drawing explanation
Fig. 1 utilizes macropore suprabasil metal organic nano rod array pinning effect to prepare the flow chart that metal has machine frame thing gas separation membrane;
Fig. 2 assists synthetic metals aluminium organic framework nanometer stick array surface SEM photo by hydroxide nano line in the substrate of aluminium oxide macropore;
Fig. 3 assists synthetic metals aluminium organic framework nanometer stick array section S EM photo by hydroxide nano line in the substrate of aluminium oxide macropore;
Fig. 4 is the section S EM photo as a child obtaining film at metal organic nano rod array diauxic growth 12;
Fig. 5 is the section S EM photo as a child obtaining film at metal organic nano rod array diauxic growth 24;
Fig. 6 is that embodiment 3 gained metal has machine frame thing gas separation membrane to carry out unitary gas separaion acquired results;
Fig. 7 is that embodiment 3 gained metal has machine frame thing gas separation membrane to carry out the separating obtained result of binary gas.
Detailed description of the invention
A kind ofly utilize macropore suprabasil metal organic nano rod array pinning effect to prepare metal to have the step of the method for machine frame thing gas separation membrane as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, and 120 DEG C of reactions obtained 25 ~ 50 μm of thick metal organic framework thin film after 6 hours, and in ethanol water, the volume ratio of ethanol and water is 1:1.
Another kind utilizes macropore suprabasil metal organic nano rod array pinning effect to prepare metal has the step of the method for machine frame thing gas separation membrane as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM zinc nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain zinc hydroxide nano-wire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reactions obtained 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, and in ethanol water, the volume ratio of ethanol and water is 1:1.
Another kind utilizes macropore suprabasil metal organic nano rod array pinning effect to prepare metal has the step of the method for machine frame thing gas separation membrane as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in the same volume 4mM cadmium nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain cadmium hydroxide nanowires solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reactions obtained 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, and in ethanol water, the volume ratio of ethanol and water is 1:1.The present invention is further illustrated below in conjunction with example.
Embodiment 1
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM (pH=4), and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array, see Fig. 2, Fig. 3;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reactions obtained 25 μm of thick metal organic framework thin film after 6 ~ 24 hours, and in ethanol water, the volume ratio of ethanol and water is 1:1.
Embodiment 2
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM (pH=4), and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, and 120 DEG C of reactions obtained 35 μm of thick metal organic framework thin film after 12 hours, in ethanol water, the volume ratio of ethanol and water is 1:1, sees Fig. 4.
Embodiment 3
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM (pH=4), and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, and 120 DEG C of reactions obtained 50 μm of thick metal organic framework thin film after 24 hours, in ethanol water, the volume ratio of ethanol and water is 1:1, sees Fig. 5.
Embodiment 4
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM (pH=4), and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the zinc nitrate of 30mM, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, and 120 DEG C of reactions obtained 25 ~ 50 μm of thick metal organic framework thin film after 24 hours, and in ethanol water, the volume ratio of ethanol and water is 1:1.
Embodiment 5
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM (pH=4), and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the cadmium nitrate of 30mM, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, and 120 DEG C of reactions obtained 50 μm of thick metal organic framework thin film after 24 hours, and in ethanol water, the volume ratio of ethanol and water is 1:1.
Claims (3)
1. utilize macropore suprabasil metal organic nano rod array pinning effect to prepare the method that metal has machine frame thing gas separation membrane, it is characterized in that its step is as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM copper nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 12 ~ 36 hours, obtain Kocide SD nanowire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reaction responses, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reaction responses obtain 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, in ethanol water, the volume ratio of ethanol and water is 1:1.
2. utilize macropore suprabasil metal organic nano rod array pinning effect to prepare the method that metal has machine frame thing gas separation membrane, it is characterized in that its step is as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in same volume 4mM zinc nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 1 hour, obtain zinc hydroxide nano-wire solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reactions, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reaction responses obtain 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, in ethanol water, the volume ratio of ethanol and water is 1:1.
3. utilize macropore suprabasil metal organic nano rod array pinning effect to prepare the method that metal has machine frame thing gas separation membrane, it is characterized in that its step is as follows:
1) under magnetic stirring, 1.4mM aqueous ethanolamine is added in the same volume 4mM cadmium nitrate aqueous solution, after 1 minute, slow down mixing speed, and reaction vessel is sealed, after 16 hours, obtain cadmium hydroxide nanowires solution, directly filtered by nanowire solution 30ml and form the thick nano wire layer of one deck 900nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5cm, aperture 200nm, porosity 25 ~ 50%;
2) join containing 30ml by nano wire layer, concentration is in the trimesic acid aqueous solution of 1mM, pH=4, and 120 DEG C of reaction responses, after 24 hours, obtain metallic aluminium organic framework nanometer stick array;
3) being joined by nanometer stick array containing 40ml concentration is the copper nitrate of 30mM, zinc nitrate or cadmium nitrate, the trimesic acid of 20mM, solvent is in the mixed solution of ethanol water, 120 DEG C of reaction responses obtain 25 ~ 50 μm of thick metal organic framework thin film after 6 ~ 24 hours, in ethanol water, the volume ratio of ethanol and water is 1:1.
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