CN109776814A

CN109776814A - A kind of acid imide covalent organic frame material and its preparation method and application

Info

Publication number: CN109776814A
Application number: CN201910204961.7A
Authority: CN
Inventors: 李留义; 陈鑫; 于岩
Original assignee: Fuzhou University
Current assignee: Fuzhou University
Priority date: 2019-03-18
Filing date: 2019-03-18
Publication date: 2019-05-21
Anticipated expiration: 2039-03-18
Also published as: CN109776814B

Abstract

The present invention proposes a kind of acid imide covalent organic frame material and its preparation method and application, preparation method is by pyromellitic acid anhydride and 2, 4, 6- tri- (4- aminophenyl) -1, 3, 5- triazine is added in mesitylene/N- methyl pyrrole network alkanone/isoquinolin dicyandiamide solution, reheating is reacted, obtain acid imide covalent organic frame material PI-COF-TT, the covalent organic frame large specific surface area of acid imide of the invention, stability is high, be conducive to and metallic ion coordination in duct rich in hetero atom, the present invention is by covalent organic frame material and metal ion with semiconductor property, high-selectivity reduction carbon dioxide prepares carbon monoxide under the irradiation of visible light, there is potential using value in terms of environmentally conscious materials.

Description

A kind of acid imide covalent organic frame material and its preparation method and application

Technical field

The invention belongs to field of new energy technologies, and in particular to a kind of acid imide covalent organic frame material and its preparation side Method and application.

Background technique

Currently, world energy consumption mostlys come from fossil fuel, and excessive carbon emission causes very big burden to environment, Therefore we need to develop some green energy resources to control greenhouse effects bring and influence.According to studies have shown that we can lead to Cross CO₂Photocatalytic conversion is at CO, HCHO, HCOOH, CH₃OH and CH₄Equal hydrocarbons reduce CO in atmosphere to reach₂Contain Amount, and current energy crisis is effectively relieved.But CO₂Inertia is larger, and needing, which just can be carried out using suitable photochemical catalyst, turns Change.

With the development of research, more and more new materials are by development and application in photocatalysis field, especially porous material. COFs material is as a kind of novel porous materials, because of the advantages that its specific surface area is high, chemical property is stable and is easy to functionalization, It is usually used in the research of heterogeneous catalysis, and COFs material is applied to CO at present₂The report in photo catalytic reduction field is also seldom.Cause This based on COFs class catalyst there is stability height and active site the advantages such as to be uniformly dispersed, we will be to COFs material In photo catalytic reduction CO₂On application probed into, the development for being COFs material in terms of the energy provides new thinking.

Summary of the invention

The purpose of the present invention is to provide a kind of preparation methods of acid imide covalent organic frame material, obtain specific surface area Greatly, stability is high, is conducive to the acid imide covalent organic frame material (PI- with metallic ion coordination rich in hetero atom in duct COF-TT), and be applied under the irradiation of visible light high-selectivity reduction carbon dioxide prepare carbon monoxide.

For achieving the above object, the present invention adopts the following technical scheme:

A kind of preparation method of acid imide covalent organic frame material, comprising the following steps: by 0.15mol Pyromellitic Acid Dianhydride and 0.1mol 2,4,6- tri- (4- aminophenyl) -1,3,5- triazine are added to mesitylene/N- methyl pyrrole network alkanone/different In the dicyandiamide solution of quinoline (v/v/v=1:1:0.1, total volume are 1.05 mL), PI-COF- is obtained after reacting 5 days in 200 DEG C TT。

The application of above-mentioned PI-COF-TT: it is thrown by the PI-COF-TT and containing acetonitrile/water/triethanolamine mixed solvent Enter in reactor, add nickel ion and 2,2- bipyridyl makees co-catalyst, by the solvent burden ratio in regulation catalyst system, leads to Enter CO₂, make reactor full of CO₂And seal, with 300W xenon lamp simulated visible light, keep reactor 6 small under 30-50 DEG C of illumination When, with the gas componant after gas chromatographic detection light-catalyzed reaction.By analyzing photocatalysis product CO and H₂Content explanation, In this photocatalytic system, PI-COF and nickel ion can be catalyzed with high selectivity by CO altogether₂It is reduced into CO, and selectivity reaches 95%。

Further, the source of above-mentioned nickel ion is nickelous perchlorate.

Further, the mass ratio of above-mentioned PI-COF-TT, 2,2- bipyridyl and nickelous perchlorate are 15:15:1.

The beneficial effects of the present invention are:

(1) hetero atom is more in the duct PI-COF-TT of imide bond connection, can be cooperated with metal ion.PI-COF- TT and nickel ion can be catalyzed with high selectivity by CO altogether₂It is reduced into CO.

(2) for PI-COF-TT by being covalently keyed, chemical stability is high, utilizes acetonitrile and water washing, 80 o after catalysis reaction It is after C is dried overnight, i.e., reusable.

Detailed description of the invention

The preparation that Fig. 1 is the PI-COF-TT of embodiment 1 synthesizes schematic diagram；

Fig. 2 is embodiment 1, the solid state nmr carbon spectrogram of product is made in comparative example 1, comparative example 2；

Fig. 3 is that PI-COF-1, PI-COF-2 and PI-COF-TT make CO₂The active comparison diagram of photo-reduction catalyst；

Fig. 4 is that PI-COF-TT made from embodiment 1 makees CO₂The yield of photo-reduction catalyst changes over time figure；

Fig. 5 is that the PI-COF-TT of recycling makees CO₂Photo-reduction catalyst circulation figure.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, right below in conjunction with attached drawing, that is, embodiment The present invention is further elaborated.It should be appreciated that described herein, the specific embodiments are only for explaining the present invention, not For limiting the present invention.

Embodiment 1

Pyromellitic acid anhydride (0.15 mmol) and 2,4,6- tri- (4- aminophenyl) -1,3,5- triazine (0.10 mmol) are set In Pyrex pipe, N-Methyl pyrrolidone/mesitylene/isoquinolin (volume ratio 1:1:0.1, total volume 1.05 is added ML), it is ultrasonically treated 10 minutes.Then Pyrex pipe is rapidly frozen in liquid nitrogen bath, the internal pressure for being evacuated to 0 mbar is gone forward side by side The sealing of row flame.After being warming up to room temperature, Pyrex pipe is placed in 200 DEG C of baking oven 5 days.8 h are impregnated with anhydrous THF to live Change, is then precipitated again with THF collected by suction.The powder of acquisition is dried in vacuum overnight in 80 oC, obtains PI-COF-TT.

Comparative example 1

Pyromellitic acid anhydride (0.15 mmol) and three (4- aminophenyl) ammonia (0.10 mmol) are placed in Pyrex pipe, added Enter N-Methyl pyrrolidone/mesitylene/isoquinolin (v/v/v=1:1:0.1, total volume are 1.05 mL), is ultrasonically treated 10 points Clock.Then Pyrex pipe is rapidly frozen in liquid nitrogen bath, is evacuated to the internal pressure of 0 mbar and carries out flame sealing.Heating To room temperature, Pyrex pipe is placed in 200 DEG C of baking oven 5 days.8 h are impregnated with anhydrous THF to be activated, and then use THF again Collected by suction precipitating.The powder of acquisition is dried in vacuum overnight in 80 oC, obtains PI-COF-1.

Comparative example 2

Pyromellitic acid anhydride (0.15 mmol) and three (4- aminophenyl) benzene (0.10 mmol) are placed in Pyrex pipe, added Enter N-Methyl pyrrolidone/mesitylene/isoquinolin (v/v/v=1:1:0.1, total volume are 1.05 mL), is ultrasonically treated 10 points Clock.Then Pyrex pipe is rapidly frozen in liquid nitrogen bath, is evacuated to the internal pressure of 0 mbar and carries out flame sealing.Heating To room temperature, Pyrex pipe is placed in 200 DEG C of baking oven 5 days.8 h are impregnated with anhydrous THF to be activated, and then use THF again Collected by suction precipitating.The powder of acquisition is dried in vacuum overnight in 80 oC, obtains PI-COF-2.

Application performance test:

15 mg PI-COF-1, PI-COF-2 and PI-COF-TT are weighed respectively, are separately added into 1 mg Ni [(ClO)₄]₂With 15 Mg 2,2'- bipyridyl, put into special quartz glass reactor, add acetonitrile/water/triethanolamine (3:1:1 v/v/v, always Volume=5 mL).After reactor vacuumizes, it is passed through CO₂And ventilation 15 minutes is kept, make reactor full of CO₂And it seals.With 300 W xenon lamp simulated visible light makes reactor at illumination 6 hours at 303 ~ 323 K, at interval of 2 hours with gastight syringe (100 μ L) acquire the gas generated in reactor.With the gas componant after Shimadzu GC-2014 gas chromatographic detection light-catalyzed reaction, root According to CO and H₂Content detect the CO of PI-COF-1, PI-COF-2 and PI-COF-TT₂Photo catalytic reduction performance can be obtained from Fig. 3, Three kinds of PI-COF have similar chemical structure, but component units are different.PI-COF-1 and PI- containing ammonia and phenyl ring segment COF-2 spatially has the distortion of certain angle, there is steric effect during the reaction.And the PI- with triazine segment COF-TT spatially shows as big planar structure, is conducive to metal ion and COF is catalyzed photo-reduction CO altogether₂, Fig. 4 illustrates PI-COF-TT can be by CO under illumination condition₂It is reduced into CO, and selectively up to 95%.

The PI-COF-TT photocatalysis performance of recycling is tested:

It by the PI-COF-TT recycling after reaction, is washed respectively three times using acetonitrile and pure water, 80 oC are dried overnight i.e. recyclable. The PI-COF-TT of 15 mg recycling is weighed, then carries out photocatalysis performance test, can be obtained from Fig. 5, PI-COF-TT is after simple Reason can be recycled, and recycles repeatedly rear catalytic activity and do not weaken.

The foregoing is merely presently preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto, Ge Geshi The succession of example also less has any impact to 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

1. a kind of preparation method of acid imide covalent organic frame material, it is characterised in that: step includes: by Pyromellitic Acid two Acid anhydride and 2,4,6- tri- (4- aminophenyl) -1,3,5- triazine are added to mesitylene/N- methyl pyrrole network alkanone/isoquinolin solvent In system, reheating is reacted, and obtains acid imide covalent organic frame material PI-COF-TT.

2. preparation method according to claim 1, it is characterised in that: the mole of the pyromellitic acid anhydride is 0.15mol, the mole of 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines are 0.1mol.

3. preparation method according to claim 1, it is characterised in that: mesitylene, N- methyl pyrrole network alkanone, isoquinolin Volume ratio is 1;1:0.1, total dosage are 1.05ml.

4. preparation method according to claim 1, it is characterised in that: the reaction temperature is 200 DEG C, the reaction time 5 It.

5. acid imide covalent organic frame material PI-COF-TT made from a kind of preparation method as described in claim 1.

6. a kind of application of the acid imide covalent organic frame material PI-COF-TT as described in 3 claims 1, it is characterised in that: By the PI-COF-TT and containing in acetonitrile/water/triethanolamine mixed solvent investment reactor, nickel ion and 2 are added, 2- bipyridyl makees co-catalyst, by regulating and controlling the solvent burden ratio in catalyst system, and the irradiation through visible light, with high selectivity will Carbon dioxide reduction is at carbon monoxide.

7. the application of acid imide covalent organic frame material PI-COF-TT according to claim 4, it is characterised in that: mixed The volume ratio of acetonitrile, water and triethanolamine is 3:1:1 in bonding solvent.

8. the application of acid imide covalent organic frame material PI-COF-TT according to claim 4, it is characterised in that: institute The source for stating nickel ion is nickelous perchlorate.

9. the application of acid imide covalent organic frame material PI-COF-TT according to claim 4, it is characterised in that: The mass ratio of PI-COF-TT, 2,2- bipyridyl and nickelous perchlorate is 15:15:1.

10. the application of acid imide covalent organic frame material PI-COF-TT according to claim 4, it is characterised in that: The temperature of photocatalytic reduction of carbon oxide reaction is 30-50 DEG C.