CN107556329B - A kind of porous metals organic framework materials and preparation method thereof - Google Patents
A kind of porous metals organic framework materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of porous metals organic frame Cu3(BTC)2Material and preparation method thereof.The size range in the material hole is 200 nm-850 nm；Preparation method is by Cu (NO3)2·3H2O is dissolved into p-aminobenzene sulfonic acid solution, stirs certain time；By trimesic acid ethanol solution and dissolved with Cu (NO3)2·3H2The solution of O mixes, stirring；It again by the mixed solution insulation reaction, is centrifuged, washing is dried to obtain porous metals organic frame Cu3(BTC)2Material.The characteristics of preparation method is that the continuous finely regulating to pore size at the nanoscale is realized under the synergistic effect of p-aminobenzene sulfonic acid and ammonium hydroxide, the case where to breach size of the previous most of length by changing organic ligand chain to regulate and control duct, and this method has the characteristics that easy to operate, product quality is high, mild condition, short preparation period, is suitble to large-scale production.
Description
Technical field
The invention belongs to metal organic frame Cu3(BTC)2The preparation field of material, and in particular to a kind of porous metals are organic
Frame Cu3(BTC)2Material and preparation method thereof.
Background technique
Cu3(BTC)2For a kind of MOF material, due to their controllable pore structures and superelevation specific surface area and excellent urge
Change, absorption etc. characteristics, catalysis oxidation, gas absorption with separate, sensor, magnetic material and in terms of have
Biggish purposes, thus Cu3(BTC)2Material has obtained relatively broad concern.Because MOFs material possessed these are excellent
Performance and the size in itself duct have a close relationship, thus the size for changing the duct of MOFs material is that current hot spot is asked
Topic.The duct for changing MOFs material at present substantially regulates and controls duct using the length for changing organic ligand chain, but
It is that qualified organic ligand is difficult to find in actual operation, and can make MOFs material with the extension of organic ligand chain
Structural instability, it is often more important that the size finely regulating in duct, and low yield can not be made by this method.Therefore it closes
In the rare report of the finely regulating of the Nano grade of MOFs material.Current mesoporous or even macropore MOFs be still research difficult point and
Hot spot.
The application realizes the Cu with different size pore sizes by the synergistic effect of ammonium hydroxide and p-aminobenzene sulfonic acid3
(BTC)2The preparation of material, it is often more important that the size in these ducts can be made to realize the essence under Nano grade by this method
Fine tuning control.Cu is adjusted in this way3(BTC)2The pore size of material is not yet reported, and this method has behaviour
Make simple, product quality height, mild condition, short preparation period, be suitble to the features such as large-scale production.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of porous metals organic frame Cu3(BTC)2Material
Material and preparation method thereof.It is organic to metal under Nano grade to realize by the synergistic effect of p-aminobenzene sulfonic acid and ammonium hydroxide
Frame Cu3(BTC)2The pore size of material carries out fine regulation, and this method has that easy to operate, product quality is high,
Mild condition, is suitble to the features such as large-scale production at short preparation period.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of porous metals organic frame Cu3(BTC)2Material, the size in hole are 200 nm-850 nm.
Above-mentioned porous metal organic frame Cu3(BTC)2The preparation method of material, comprising the following steps:
(1) p-aminobenzene sulfonic acid is dissolved into deionized water, is stirred；Its pH value of solution is adjusted to 9, then again with ammonium hydroxide
Stirring；Then Cu (NO is added into the solution after adjusting pH value3)2·3H2O, dissolution；
(2) it weighs a certain amount of trimesic acid to be dissolved into ethyl alcohol, stir；By trimesic acid solution and step (1)
Solution mixed, stir；Mixed solution is fitted into water heating kettle, in certain temperature held for some time, then will be obtained
Blue precipitate centrifugation, washing, be dried to obtain porous metals organic frame Cu3(BTC)2Material.
More specifically, above-mentioned porous metal organic frame Cu3(BTC)2The preparation method of material, specific steps are as follows:
(1) 0.0433 ~ 0.0866g p-aminobenzene sulfonic acid is dissolved into 12 mL deionized waters, stirs 30 min；Use ammonia
Water adjusts p-aminobenzene sulfonic acid pH value of solution to 4.5 ~ 9, is then stirred for 10 min；Then to the p-aminophenyl sulphur after adjusting pH value
0.875 g Cu (NO is added in acid solution3)2·3H2O, dissolution；
(2) it weighs 0.42 g trimesic acid to be dissolved into 12 mL ethyl alcohol, stirs 30 min；Trimesic acid is molten
Liquid and the solution of step (1) are mixed, and 30min is stirred；Mixed solution is fitted into 100 mL water heating kettles, is kept the temperature at 120 DEG C
Then obtained blue precipitate is centrifuged by 12 h, washing is dried to obtain porous metals organic frame Cu3(BTC)2Material.
The beneficial effects of the present invention are:
1) the metal organic frame Cu that duct can be finely continuously adjusted at the nanoscale is successfully prepared by the above method3
(BTC)2Material, the advantage one of this method are through the coordinative role of p-aminobenzene sulfonic acid and ammonium hydroxide to realize to metal
Organic frame Cu3(BTC)2The duct of this material has carried out fine regulation under Nano grade to breach and pass through in the past
Find the problem for the size regulation that suitable organic ligand is just able to achieve to metal-organic framework material；
2) advantage two of this method is that easy to operate, product quality is high, mild condition, short preparation period, is suitble to big rule
Mould production, the Cu (NO of the p-aminobenzene sulfonic acid by being dissolved in certain pH value3)2·3H2O solution and trimesic acid solution are mixed
It closes, can be obtained by porous metal organic frame Cu by the preparation of simple hydro-thermal3(BTC)2Material, and the size range in hole
For 200 nm-850 nm, opened up to be formed in the metal-organic framework material that duct can be finely continuously adjusted under nanoscale
One new field, has a very important significance.
Detailed description of the invention
The diffraction curve of XRD is a) Cu in Fig. 13(BTC)2The diffraction curve of crystal and b) porous Cu3(BTC)2Crystal
Diffraction curve；
Fig. 2 is the porous metals organic frame Cu that example 1 obtains3(BTC)2The shape appearance figure of material；
Fig. 3 is the porous metals organic frame Cu that example 2 obtains3(BTC)2The shape appearance figure of material；
Fig. 4 is the porous metals organic frame Cu that example 3 obtains3(BTC)2The shape appearance figure of material；
Fig. 5 is the porous metals organic frame Cu that example 4 obtains3(BTC)2The shape appearance figure of material.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
As shown in figure 1, figure 2, figure 3, figure 4 and figure 5, it is based on metal organic frame Cu3(BTC)2The porous C u that material is prepared3
(BTC)2Material now enumerates exemplary embodiments of the invention:
Embodiment 1
Porous metals organic frame Cu3(BTC)2The preparation method of material, comprising the following specific steps
(1) it is dissolved into the deionized water of 12 mL, is stirred with electronics capacity of balance 0.0866g p-aminobenzene sulfonic acid
30min；
(2) it also weighs 0.42 g trimesic acid simultaneously to be dissolved into the ethyl alcohol of 12 mL, stirs 30 min；
(3) pH that p-aminobenzene sulfonic acid solution is then adjusted with ammonium hydroxide, makes its pH value 4.5, is then stirred for 10 min；
(4) 0.875 g Cu (NO is dissolved to the p-aminobenzene sulfonic acid solution after adjusting pH value again3)2·3H2O；
(5) trimesic acid solution and step (4) solution are mixed, stirs 30 min；
(6) mixed solution is packed into the water heating kettle of 100 mL, in 120 DEG C of 12 h of heat preservation, the precipitating that then will be obtained
Centrifugation, washing, drying can be obtained by porous metal organic frame Cu3(BTC)2Material.
The blue powder being prepared by 1 method of embodiment is measured as by Miniflex600M X-ray diffractometer
Metal organic frame Cu3(BTC)2Material is scanned to obtain SEM figure through German karr Zeiss SUPAR55 field emission scanning electron microscope
As shown in figure 3, obtained porous metals organic frame Cu3(BTC)2Material is octahedra or bulk, and the size range in hole is 200
nm -300 nm。
Embodiment 2
Porous metals organic frame Cu3(BTC)2The preparation method of material, comprising the following specific steps
(1) it is dissolved into the deionized water of 12 mL with 0.0433 g p-aminobenzene sulfonic acid of electronics capacity of balance, stirring 30
min；
(2) it also weighs 0.42 g trimesic acid simultaneously to be dissolved into the ethyl alcohol of 12 mL, stirs 30 min.
(3) pH that p-aminobenzene sulfonic acid solution is then adjusted with ammonium hydroxide, makes its pH value 9, is then stirred for 10 min；
(4) 0.875 g Cu (NO is dissolved to the p-aminobenzene sulfonic acid solution after adjusting pH value again3)2·3H2O；
(5) trimesic acid solution and step (4) solution are mixed, stirs 30 min；
(6) mixed solution is packed into the water heating kettle of 100 mL, in 120 DEG C of 12 h of heat preservation, the precipitating that then will be obtained
Centrifugation, washing, drying can be obtained by porous metal organic frame Cu3(BTC)2Material.
The blue powder being prepared by 2 method of embodiment is measured as gold by Miniflex600M X-ray diffractometer
Belong to organic frame Cu3(BTC)2Material is scanned to obtain SEM figure such as through German karr Zeiss SUPAR55 field emission scanning electron microscope
Shown in Fig. 4, obtained porous metals organic frame Cu3(BTC)2Material is octahedra or bulk, and the size range in hole is 400
nm-500 nm。
Embodiment 3
Porous metal organic frame Cu3(BTC)2The preparation method of material, comprising the following specific steps
(1) it is dissolved into the deionized water of 12 mL, is stirred with 0.0433 g p-aminobenzene sulfonic acid of electronics capacity of balance
30min；
(2) it also weighs 0.42 g trimesic acid simultaneously to be dissolved into the ethyl alcohol of 12 mL, stirs 30 min；
(3) pH that p-aminobenzene sulfonic acid solution is then adjusted with ammonium hydroxide, makes its pH value 8.5, is then stirred for 10 min；
(4) 0.875 g Cu (NO is dissolved to the p-aminobenzene sulfonic acid solution after adjusting pH value again3)2·3H2O；It (5) will be equal
Benzenetricarboxylic acid solution and step (4) solution are mixed, and 30 min are stirred；
(6) mixed solution is packed into the water heating kettle of 100 ml, in 120 DEG C of 12 h of heat preservation, the precipitating that then will be obtained
Centrifugation, washing, drying can be obtained by porous metal organic frame Cu3(BTC)2Material.
The blue powder being prepared by 3 method of embodiment is measured as by Miniflex600M X-ray diffractometer
Metal organic frame Cu3(BTC)2Material is scanned to obtain SEM figure through German karr Zeiss SUPAR55 field emission scanning electron microscope
As shown in figure 5, obtained porous metals organic frame Cu3(BTC)2Material is octahedra or bulk, and the size range in hole is 500
nm-700 nm。
Embodiment 4
Porous metal organic frame Cu3(BTC)2The preparation method of material, comprising the following specific steps
(1) it is dissolved into the deionized water of 12 mL, is stirred with 0.0433 g p-aminobenzene sulfonic acid of electronics capacity of balance
30min；
(2) it also weighs 0.42 g trimesic acid simultaneously to be dissolved into the ethyl alcohol of 12 mL, stirs 30 min；
(3) pH that p-aminobenzene sulfonic acid solution is then adjusted with ammonium hydroxide, makes its pH value 8, is then stirred for 10 min；
(4) 0.875 g Cu (NO is dissolved to the p-aminobenzene sulfonic acid solution after adjusting pH value again3)2·3H2O；
(5) trimesic acid solution and step (4) solution are mixed, stirs 30 min；
(6) mixed solution is packed into the water heating kettle of 100 ml, in 120 DEG C of 12 h of heat preservation, the precipitating that then will be obtained
Centrifugation, washing, drying can be obtained by porous metal organic frame Cu3(BTC)2Material.
The blue powder being prepared by 4 method of embodiment is measured as by Miniflex600M X-ray diffractometer
Metal organic frame Cu3(BTC)2Material is scanned to obtain SEM figure through German karr Zeiss SUPAR55 field emission scanning electron microscope
As shown in figure 5, obtained porous metals organic frame Cu3 (BTC) 2 material is octahedra or bulk, the size range in hole are
700nm-850nm。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (2)
1. a kind of porous metals organic frame Cu3(BTC)2The preparation method of material, it is characterised in that: the porous metals are organic
Frame Cu3(BTC)2The shape of material is blocky or octahedral shape, and the size range in hole is 200 nm -850 nm；It is prepared
Method the following steps are included:
(1) p-aminobenzene sulfonic acid is dissolved into deionized water, is stirred；Its pH value of solution is adjusted to 9 with ammonium hydroxide, is then stirred for；
Then Cu (NO is added into the solution after adjusting pH value3)2·3H2O, dissolution；
(2) it weighs a certain amount of trimesic acid to be dissolved into ethyl alcohol, stir；By the molten of trimesic acid solution and step (1)
Liquid is mixed, stirring；Mixed solution is fitted into water heating kettle, in certain temperature held for some time, the indigo plant that then will obtain
Color precipitating centrifugation, washing are dried to obtain porous metals organic frame Cu3(BTC)2Material.
2. porous metals organic frame Cu according to claim 13(BTC)2The preparation method of material, it is characterised in that: institute
State preparation method specific steps are as follows:
(1) 0.0433 ~ 0.0866g p-aminobenzene sulfonic acid is dissolved into 12 mL deionized waters, stirs 30 min；With ammonium hydroxide tune
P-aminobenzene sulfonic acid pH value of solution is saved to 9, is then stirred for 10 min；Then into the p-aminobenzene sulfonic acid solution after adjusting pH value
0.875 g Cu (NO is added3)2·3H2O, dissolution；
(2) it weighs 0.42 g trimesic acid to be dissolved into 12 mL ethyl alcohol, stirs 30 min；By trimesic acid solution and
The solution of step (1) is mixed, and 30min is stirred；Mixed solution is fitted into 100 mL water heating kettles, in 120 DEG C of 12 h of heat preservation,
Then obtained blue precipitate is centrifuged, washing is dried to obtain porous metals organic frame Cu3(BTC)2Material.
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| CN111215033A (en) * | 2019-12-10 | 2020-06-02 | 江苏师范大学 | Porous CeO wrapped by N, S doped C2Synthesis method of nano rod |
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