CN106396736A - Method for growing three-dimensional covalent organic frame material on surface of alpha-Al2O3 ceramic - Google Patents
Method for growing three-dimensional covalent organic frame material on surface of alpha-Al2O3 ceramic Download PDFInfo
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Abstract
The present invention discloses a method for growing a three-dimensional covalent organic frame material on the surface of an alpha-Al2O3 ceramic. According to the present invention, an organic monomer is linked on a substrate through a covalent bond to form a material having a crystal structure, wherein the material is the three-dimensional covalent organic frame material; and the covalent organic skeleton compound of the present invention has the three-dimensional structure and is firstly used for the growth on the surface of the alpha-Al2O3 ceramic substrate.
Description
Technical field
The present invention relates to one kind is in α-Al2O3The method of ceramic surface growing three-dimensional covalent organic frame material (hereinafter referred to as 3D COFs).
Background technology
Covalent organic frame material (covalent organic frameworks, COFs) it is the new organic porous material of a class, it is the crystal formation porous material that organic precursor is formed by Covalent bonding together, there is good chemical stability and heat endurance, since Yaghi in 2005 and its partner synthesize first COFs material using topology design principle, COFs material attracts the eyeball of numerous scientific research personnel always, its compound with regular structure, duct is homogeneous, specific surface area is big, store in gas and separate, chemical reaction is catalyzed, there is potential application prospect (bibliography 1 in the fields such as opto-electronic conversion：X.Feng,X.Ding,D.Jiang,Chem.Soc.Rev.41(2012)6010.).
COFs material is with one-dimensional, two dimension, presented in three-dimensional, wherein report that more is two-dimensional material, when preparing COFs material, three-dimensional COFs material is obtained with planar molecule copolymerization by the autohemagglutination or tetrahedron molecule of tetrahedron molecule, difficulty due to synthesis, three-dimensional COFs material quantity is extremely limited, wherein COF-320 is the crystal with space net structure that Yaghi et al. was obtained by tetrahedron molecule and planar molecule copolymerization in 2013 first, compared with two-dimensional material, it has more superior performance, as specific surface area is higher, structure is more stable, it is more beneficial in catalysis, gas storage and the application of energy storage aspect.Additionally, existing COFs material is existed with powder mostly, it is insoluble in water or organic solvent, is unfavorable for manufacturing further function element.If can by COFs material, Direct precipitation is grown in substrate surface in the form of a film, not only can widen its application field, and can accelerate its application step.(bibliography 2：Y.B.Zhang,J.Su,H.Furukawa,Y.Yun,F.Gandara and O.M.Yaghi,J.Am.Chem.Soc.135(2013)16336.)
α-Al2O3It is a kind of ceramic base material cheap and easy to get, intensity is high, specific surface area is big, heat-resist, is widely used in gas separation, the field such as purifying, catalytic reaction.If by 3D COFs in the form of a film direct growth to α-Al2O3Ceramic surface, then can convenient material following process, the gas absorption performance of device can be greatly improved again.
Content of the invention
In order to reduce cost, accelerate the target of application, 3D COFs material in situ is grown into porous α-Al by first2O3Ceramic surface.
For realizing the object of the invention, using concrete technical scheme it is：
One kind is in α-Al2O3The method of ceramic surface growing three-dimensional covalent organic frame material (hereinafter referred to as 3D COFs).Described α-Al2O3, need in advance to α-Al2O3Surface is chemically modified modification, and method is as shown in Equation 1.With 3- aminopropyl triethoxysilane to α-Al2O3Ceramic surface carries out grafting modification, silicon ethyoxyl and α-Al2O3The hydroxyl on surface by be condensed dealcoholysis realize key and.Modified substrate surface carries amino, the biphenyl dialdehyde (BPDA) required with 3D COFs synthesis can react, makes 3D COFs film situ-formed graft be grown in α-Al2O3Ceramic surface.
Formula 1：To α-Al2O3Surface is chemically modified modification
The molecule that described 3- aminopropyl triethoxysilane can also be had similar structures by other substitutes, and its common trait is：Contain amino-NH simultaneously2Molecule (wherein R is methyl or ethyl) with silane epoxide-Si (OR).
Described chemical modification modified condition is：40～100 DEG C of temperature, time 8～24h, modified α-Al2O3Base material can be used for subsequent reactions after ethanol washing, vacuum drying.In modifying process, reactant mass concentration in a solvent is：3- aminopropyl triethoxysilane：0.5-1wt%；α-Al2O3Base material：0.5-10wt%.
Described 3D COFs, it is characterized by：By modified for the described chemical modification α-Al crossing2O3Mix with TAM, diphenyl-dimethanal, with Isosorbide-5-Nitrae-dioxane as solvent, add 1ml 3M vinegar aqueous acid, vacuumize, screw plug seal, through pyroreaction in α-Al2O3Surface in situ grows COF-320 film, and method is as shown in Equation 2.Generating reactant mass concentration in a solvent in COF-320 thin-film process is：TAM：0.5-5wt%；Biphenyl dialdehyde：0.5-5wt%；α-the Al that surface modification is crossed2O3：0.5-10wt%.Wherein, TAM and the molar feed ratio of biphenyl dialdehyde are locked as 1：2.
Formula 2：In the modified α-Al crossing2O3Surface in situ grows COF-320 film
The molecule that described diphenyl-dimethanal can also be had similar structures by other substitutes, and its common trait is：Molecule containing phenyl ring and two or more aldehyde radical simultaneously.
Described pyroreaction condition is：Time 48-120h, temperature 100-180 DEG C.
Comprise the following steps that：
The first step：α-Al2O3The surface modifying method of base material：
By α-Al2O3Base material is immersed in 5h in hydrochloric acid solution.After washing is dried, base material is mixed with 3- aminopropyl triethoxysilane, toluene, under argon gas protection, react 3h in 100 DEG C, now substrate surface has been grafted amino group, vacuum room temperature drying for standby after ethanol washing several times.
Second step：Using solvent-thermal method in α-Al2O3Substrate surface grows COF-320 film：
By the modified α-Al crossing2O3Load reactor with TAM, biphenyl dialdehyde, with Isosorbide-5-Nitrae-dioxane and 3M acetum as solvent, under vacuum condition, be heated to 120 DEG C, react 72h.Product oxolane and acetone respectively soak, wash room temperature vacuum drying 12h after several times, and obtaining superficial growth has the α-Al of COF-320 film2O3.
Of the present invention in α-Al2O3Ceramic surface grow 3D COFs film method have the advantages that three below aspect:
1) base material selected is α-Al cheap and easy to get2O3Pottery, reduces production cost；
2) modifying process and subsequent synthetic run are simple and convenient, and 3D COFs film can equably be grown in substrate surface；
3) overcome the unmanageable obstacle of COFs material, simultaneously the 3D COFs film of high-specific surface area and stability and porous α-Al2O3Ceramic base material strong-combine by force and would be even more beneficial to improve the performances such as the gas absorption of multiple device, catalysis；
Brief description
Fig. 1 (a) .COF-320 film is in α-Al2O3The pattern of substrate surface；
Fig. 1 (b) COF-320 film is in α-Al2O3The infrared scan figure of substrate surface.
Specific embodiment
With reference to specific embodiment, the present invention is further described, but protection scope of the present invention is not limited to that.
Embodiment 1
The first step：α-Al2O3The surface modifying method of base material：
By α-Al2O3Base material is immersed in (1.0mol/L) 5h in 50mL hydrochloric acid solution.After washing is dried, base material is mixed with 3- aminopropyl triethoxysilane (98mg), toluene (20mL), react 3h in 100 DEG C under argon gas protection, now substrate surface has been grafted amino group.After ethanol washs 3 times, vacuum drying at room temperature 24h is stand-by.
Second step：In α-Al2O3Substrate surface grows 3D COFs film：
By the modified α-Al crossing2O3With tetra- (4-anilyl) methane (TAM) of 100mg, 100mg 4,4 '-biphenyldialdehyde (BPDA) load reactor (the solvent holding bottle of 25ml), add the 1 of 5mL, 4- dioxane, 1mL 3M vinegar aqueous acid, as solvent, reaction vessel is positioned over freezing (temperature 77K) in liquid nitrogen, vacuumize (vacuum is 4.0Pa), sealing orifice, reacts 72h by 120 DEG C.Product oxolane and acetone soaks respectively, wash 3 times after under room temperature vacuum (vacuum is 1bar) (temperature 100 DEG C) 12h is dried, obtaining superficial growth has the α-Al of COF-320 film2O3, call pipe fitting in the following text.
As shown in Figure 1：We use scanning electron microscopic observation COF-320 film in α-Al2O3The pattern of substrate surface, obtain is the uniform film that thickness is 1 microns.
Embodiment 2
The pipe fitting that embodiment 1 is obtained carries out mixed gas separation mensure, and step is as follows：
The first step, measures N at 25 DEG C of pipe fitting2Infiltration rate；
Second step, measures O at 25 DEG C of pipe fitting2Infiltration rate；
3rd step, obtains N at 25 DEG C of pipe fitting2/O2Separation；
Finally give N at 25 DEG C of pipe fitting2/O2Separation be 4.7, more than the separation 3.7 of preferable Knudsen diffusion, possess N2/O2Separating property.
Embodiment 3-6
In α-Al2O3During substrate surface growth COFs film, the molecule that biphenyl dialdehyde is had similar structures by partly other substitutes, and, according to condition described in table 2, other reaction conditions, with the synthetic method in embodiment 1 for difference from Example 1.
Table 2
With the surrogate response Internet of Things phthaladehyde such as terephthalic aldehyde, isophthalic aldehyde, according to the condition of embodiment 1, only terephthalic aldehyde can obtain corresponding COFs film, and other analogs can not obtain corresponding COFs film.
Embodiment 6-10
Difference from Example 1 presses table 3 condition in α-Al2O3Substrate surface grows COFs film, and with embodiment 1, the pipe fitting obtaining carries out N according to the operation of embodiment 2 for other operations2/O2Separation measure.
Table 3
The reactant using embodiment 1 according to table 3 condition in α-Al2O3During substrate surface growth COFs film, only embodiment 6-8 can grow COFs film, simply the N of film2/O2Separation assume difference, the base material that only embodiment 6 obtains has N2/O2Separating power, the base material that efficiency obtains less than embodiment 1；Embodiment 9,10 can not grow corresponding film.
Claims (9)
1. one kind is in α-Al2O3The method of ceramic surface growing three-dimensional covalent organic frame material, its
It is characterised by：Comprise the following steps that：
(1) by α-Al2O3Ceramic base material and reactant are added in reaction vessel, add solvent；
Mix, reaction vessel is positioned over freezing in liquid nitrogen, vacuumizes, sealing orifice,
Under the conditions of 100-150 DEG C, react 48-72 hour；
(2) after reaction terminates, product is used organic solvent washing 3 times respectively, remove unreacted
Reactant；
(3) dried process obtains final product to the product after carrying out washing treatment under vacuum.
2. preparation method according to claim 1 it is characterised in that：Step (1) is used
Reactant be the first compound tetra- (4-anilyl) methane (TAM) and another kindization
Compound 4,4 '-biphenyldialdehyde (BPDA)；
The first compound is 1 with the consumption mass ratio of another kind of compound:1-1:1.5.
3. preparation method according to claim 1 it is characterised in that：In step (1)
Solvent be 1-5M acetic acid, 1,4 dioxane, oxolane, n-butanol, o-dichlorohenzene or
N, one of N dimethyl acetamide or more than two kinds, it is with respect to tetra- (4-anilyl)
The consumption of methane (TAM) is 0.5-5wt%.
4. preparation method according to claim 1 it is characterised in that：
Reaction vessel is freezed described in (1) by step, vacuumizes, and the process of sealing orifice is：
Reaction vessel is positioned over freezing in liquid nitrogen, vacuumizes, sealing orifice；
Reaction bulb is positioned in liquid nitrogen and is refrigerated to below 77K, vacuumize true in guarantee reaction bulb
Reciprocal of duty cycle is less than or equal to 5Pa.
5. preparation method according to claim 1 it is characterised in that：
Organic solvent used by step (2) be 1,4 dioxane, oxolane, n-butanol,
O-dichlorohenzene or N, one of N dimethyl acetamide or two or more.
6. preparation method according to claim 1 it is characterised in that：Step (3) is washed
Product after process is in 80-100 DEG C of dried process of heated under vacuum of below 1bar
24-72 hour obtains final product.
7. preparation method according to claim 1 it is characterised in that：
Described α-Al2O3Ceramic base material needs in advance to α-Al2O3Surface is chemically modified and changes
Property, make modified substrate surface carry amino, can be occurred with biphenyl dialdehyde (BPDA) anti-
Should, make required film situ-formed graft be grown in α-Al2O3Ceramic surface.
8. preparation method according to claim 7 it is characterised in that：
The described modified reagent adopting is to contain amino-NH simultaneously2With silane epoxide-Si (OR)
Molecule, wherein R are methyl or ethyl.
9. the preparation method according to claim 7 or 8 it is characterised in that：
Described chemical modification modified condition is：40～100 DEG C of temperature, time 8～24h, change
α-Al after property2O3Base material can be used for subsequent reactions after ethanol washing, vacuum drying, modified
During reactant mass concentration in a solvent be：The modified reagent adopting：0.5-1wt%；
α-Al2O3Base material：0.5-10wt%.
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Cited By (3)
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| CN107983173A (en) * | 2017-11-01 | 2018-05-04 | 北京化工大学 | A kind of high throughput covalent organic framework composite membrane and preparation method thereof |
| CN110743382A (en) * | 2019-09-12 | 2020-02-04 | 武汉绿帆世纪科技有限公司 | PVDF-MOF-COF composite film based on in-situ growth and preparation method thereof |
| CN114628777A (en) * | 2021-05-29 | 2022-06-14 | 海南大学 | Preparation method of interface-modified solid electrolyte material |
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| CN104710191A (en) * | 2013-12-16 | 2015-06-17 | 中国科学院大连化学物理研究所 | Method for growing covalent organic framework film on alpha Al2O3 ceramic surface |
| CN104892879A (en) * | 2014-03-04 | 2015-09-09 | 中国科学院大连化学物理研究所 | Method for growing microporous polymer SNW film on alpha-Al2O3 ceramic surface |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107983173A (en) * | 2017-11-01 | 2018-05-04 | 北京化工大学 | A kind of high throughput covalent organic framework composite membrane and preparation method thereof |
| CN107983173B (en) * | 2017-11-01 | 2020-10-27 | 北京化工大学 | High-flux covalent organic framework composite membrane and preparation method thereof |
| CN110743382A (en) * | 2019-09-12 | 2020-02-04 | 武汉绿帆世纪科技有限公司 | PVDF-MOF-COF composite film based on in-situ growth and preparation method thereof |
| CN110743382B (en) * | 2019-09-12 | 2021-11-05 | 武汉加科思链科技有限公司 | PVDF-MOF-COF composite film based on in-situ growth and preparation method thereof |
| CN114628777A (en) * | 2021-05-29 | 2022-06-14 | 海南大学 | Preparation method of interface-modified solid electrolyte material |
| WO2022252486A1 (en) * | 2021-05-29 | 2022-12-08 | 海南大学 | Preparation method for interface-modified solid electrolyte material |
| CN114628777B (en) * | 2021-05-29 | 2023-06-23 | 海南大学 | Preparation method of interface modified solid electrolyte material |
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