CN103570755A - Method of assisted-synthesizing metallic aluminum organic framework object nanorod array on aluminum oxide macroporous substrate through hydroxide nanowire - Google Patents
Method of assisted-synthesizing metallic aluminum organic framework object nanorod array on aluminum oxide macroporous substrate through hydroxide nanowire Download PDFInfo
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Abstract
The invention discloses a method for preparing a metallic organic framework object gas separation membrane by means of a pinning effect of a metallic organic nanorod array on a macroporous substrate. The method comprises the following steps: 1) under magnetic stirring, adding ethanol amine aqueous liquor into cupric nitrate aqueous liquor, zinc nitrate aqueous liquor and cadmium nitrate aqueous liquor in same volume; slowing the stirring speed to obtain corresponding copper hydroxide, zipper hydroxide or cadmium hydroxide nanowire liquors; and directly filtering the nanowire liquors to form a nanowire layer on a porous aluminum oxide membrane; and 2) adding the nanowire layer into the aqueous liquor containing trimesic acid, and carrying out thermal treatment to obtain the metallic aluminum organic framework object nanorod array. According to the invention, the metallic aluminum-organic framework object nanorod array with an orthohexagonal section can be directly grown on the aluminum oxide macroporous substrate. The method is simple to operate, and the metallic aluminum organic framework object nanorod array prepared is good in array direction, can stably exist and can growth secondarily as a seed layer. The method expands the application range of the metallic organic framework object thin film.
Description
Technical field
The present invention relates to the preparation method of metal organic frame thing nano-array, relate in particular to a kind of method of assisting synthetic metallic aluminium organic frame thing nanometer stick array in the substrate of aluminum oxide macropore by hydroxide nano line.
Technical background
Metal organic frame thing, because it has the chemical stability that high porosity is become reconciled, has good application prospect in many fields such as fractionation by adsorption, catalyzed reaction, pharmaceutical carrier and optical materials.This wherein structure and the pattern of metal organic frame thing its performance is had to this tremendous influence, and the metal organic frame thing that contains aluminium element is due to its good hexagonal structure and good orientation and being paid close attention to by everybody.The metal organic frame thing that preparation contains aluminium element at present need to just can complete mostly under strong acid condition.
summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method of assisting synthetic metal organic frame thing nanometer stick array on perforated substrate by hydroxide nano line is provided.
In the substrate of aluminum oxide macropore, by a method for the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array of hydroxide nano line, step is as follows:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM copper nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain copper hydroxide nano wire solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
The another kind of hydroxide nano line that passes through in the substrate of aluminum oxide macropore assists the step of the method for synthesizing metallic aluminium organic frame thing nanometer stick array as follows:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM zinc nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain zinc hydroxide nano-wire solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
The another kind of hydroxide nano line that passes through in the substrate of aluminum oxide macropore assists the step of the method for synthesizing metallic aluminium organic frame thing nanometer stick array as follows:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in the same volume 4 mM cadmium nitrate aqueous solution, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain cadmium hydroxide nanowires solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
The present invention generates metallic aluminium organic frame thing nanometer stick array by auxiliary the reaction with organic ligand of hydroxide nano line in the substrate of aluminum oxide macropore.The standby array of this legal system is orientated, simple to operate, can stable existence, and repeatable strong, expanded the range of application of metal organic frame thing array.Especially the introducing of nano wire layer can obtain by simple filter method in macropore substrate, can effectively promote the synthetic of nano-array.
Accompanying drawing explanation
Fig. 1 is by the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array schema of hydroxide nano line in the substrate of aluminum oxide macropore;
Fig. 2 is by the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array of hydroxide nano line surface SEM photo in the substrate of aluminum oxide macropore;
Fig. 3 is by the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array section SEM photo of hydroxide nano line in the substrate of aluminum oxide macropore;
Fig. 4 is by the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array of hydroxide nano line surface SEM photo in the substrate of aluminum oxide macropore;
Fig. 5 is by the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array of hydroxide nano line surface SEM photo in the substrate of aluminum oxide macropore.
Embodiment
A kind of as follows by the step of the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array of hydroxide nano line in the substrate of aluminum oxide macropore:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM copper nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain copper hydroxide nano wire solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
Another kind of as follows by the step of the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array of hydroxide nano line in the substrate of aluminum oxide macropore:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM zinc nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain zinc hydroxide nano-wire solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
Another kind of as follows by the step of the auxiliary synthetic metallic aluminium organic frame thing nanometer stick array of hydroxide nano line in the substrate of aluminum oxide macropore:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in the same volume 4 mM cadmium nitrate aqueous solution, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain cadmium hydroxide nanowires solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
Below in conjunction with example, further illustrate the present invention.
Embodiment 1
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM copper nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain copper hydroxide nano wire solution, nano wire solution 15 ml direct filtration are formed to the thick nano wire layer of one deck 400 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, in the trimesic acid aqueous solution that concentration is 1mM (pH=4), 120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
Embodiment 2
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM copper nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain copper hydroxide nano wire solution, nano wire solution 30ml direct filtration is formed to the thick nano wire layer of one deck 900 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, in the trimesic acid aqueous solution that concentration is 1mM (pH=4), 120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array, see Fig. 2, Fig. 3.
Embodiment 3
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM copper nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain copper hydroxide nano wire solution, nano wire solution 60 ml direct filtration are formed to the thick nano wire layer of one deck 2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, in the trimesic acid aqueous solution that concentration is 1mM (pH=4), 120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
Embodiment 4
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM zinc nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain zinc hydroxide nano-wire solution, nano wire solution 30 ml direct filtration are formed to the thick nano wire layer of one deck 900 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, in the trimesic acid aqueous solution that concentration is 1mM (pH=4), 120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array, see Fig. 4.
Embodiment 5
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM zinc nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain zinc hydroxide nano-wire solution, nano wire solution 60 ml direct filtration are formed to the thick nano wire layer of one deck 2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, in the trimesic acid aqueous solution that concentration is 1mM (pH=4), 120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
Embodiment 6
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in the same volume 4 mM cadmium nitrate aqueous solution, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain cadmium hydroxide nanowires solution, nano wire solution 30 ml direct filtration are formed to the nano wire layer that one deck 900nm is thick on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, in the trimesic acid aqueous solution that concentration is 1mM (pH=4), 120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array, see Fig. 5.
Claims (3)
1. in the substrate of aluminum oxide macropore, by hydroxide nano line, assist a method for synthetic metallic aluminium organic frame thing nanometer stick array, it is characterized in that its step is as follows:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM copper nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain copper hydroxide nano wire solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatment 24 hours, obtains metallic aluminium organic frame thing nanometer stick array.
2. in the substrate of aluminum oxide macropore, by hydroxide nano line, assist a method for synthetic metallic aluminium organic frame thing nanometer stick array, it is characterized in that its step is as follows:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in same volume 4 mM zinc nitrate aqueous solutions, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain zinc hydroxide nano-wire solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
3. in the substrate of aluminum oxide macropore, by hydroxide nano line, assist a method for synthetic metallic aluminium organic frame thing nanometer stick array, it is characterized in that its step is as follows:
1) under magnetic agitation, the 1.4 mM thanomin aqueous solution are added in the same volume 4 mM cadmium nitrate aqueous solution, after 1 minute, slow down stirring velocity, and reaction vessel is sealed, after 12～36 hours, obtain cadmium hydroxide nanowires solution, nano wire solution 15～60 ml direct filtration are formed to the thick nano wire layer of one deck 400～2000 nm on multiaperture pellumina, the diameter of multiaperture pellumina is 2.5 cm, aperture 200 nm, porosity 25～50%;
2) nano wire layer is joined and contains 30ml, concentration is 1mM, and in the trimesic acid aqueous solution of pH=4,120 ℃ of thermal treatments, after 24 hours, obtain metallic aluminium organic frame thing nanometer stick array.
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| JP2017057439A (en) * | 2015-09-14 | 2017-03-23 | 新日鐵住金株式会社 | Method of manufacturing metal-porous polymer metal complex composite material, and metal-porous polymer metal complex composite material |
| CN108421541A (en) * | 2018-03-16 | 2018-08-21 | 南京大学 | A kind of preparation method and application of carbonization Zn bases MOFs extraction coatings |
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Application publication date: 20140212 |