Carbon nitride modified with perylenetetracarboxylic dianhydride / graphene oxide aerogel composite material, preparation method and application thereof

Abstract

A preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material includes: (1) preparing carbon nitride nanosheets by calcination using dicyandiamide as raw material; (2) reacting perylenetetracarboxylic dianhydride and carbon nitride nanosheets in imidazole to prepare carbon nitride modified with perylenetetracarboxylic dianhydride; (3) dispersing said carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide into deionized water, freeze-drying after the reaction to obtain carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material.

Claims

1. A preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material, characterized in comprising the following steps: (1) preparing carbon nitride nanosheets by calcination using dicyandiamide as raw material; (2) reacting perylenetetracarboxylic dianhydride and carbon nitride nanosheets in imidazole to prepare carbon nitride modified with perylenetetracarboxylic dianhydride; (3) dispersing said carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide into deionized water, freeze-drying after the reaction to obtain carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material.

2. The preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material according to claim 1, wherein in step (1), the calcination is carried out at 400 to 700 C. for 3 to 6 hours under the protection of argon, the rate of temperature rise during calcination is 2 to 15 C. per minute.

3. The preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material according to claim 1, wherein in step (2), the mass ratio of perylenetetracarboxylic dianhydride, carbon nitride nanosheets and imidazole is 1:30:120; the reaction is carried out at 130 to 160 C. for 4 to 7 hours.

4. The preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material according to claim 1, wherein in step (2), after the reaction, the product is added to an aqueous solution of K.sub.2CO.sub.3, refluxed for 1 to 3 hours, cooled to room temperature, then centrifuged, washed with hydrochloric acid, and then washed with water and ethanol until neutral, and finally vacuum dried for 3 to 6 hours to prepare carbon nitride modified with perylenetetracarboxylic dianhydride.

5. The preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material according to claim 1, wherein in step (3), the mass ratio of said nitride modified with perylenetetracarboxylic dianhydride and said graphene oxide is 3:1; taking ultrasonic treatment after dispersing in deionized water, the reaction is carried out at 160 to 200 C. for 5 to 8 hours; said freeze-drying is keeping in a freeze drying oven for 1 to 2 days.

6. Carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material prepared by the preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material according to claim 1.

7. A preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material, characterized in comprising the following steps: (1) preparing carbon nitride nanosheets by calcination using dicyandiamide as raw material; (2) reacting perylenetetracarboxylic dianhydride and carbon nitride nanosheets in imidazole to prepare carbon nitride modified with perylenetetracarboxylic dianhydride; (3) dispersing said carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide into deionized water to obtain carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material.

8. The preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material according to claim 7, wherein in step (1), the calcination is carried out at 400 to 700 C. for 3 to 6 hours under the protection of argon, the rate of temperature rise during calcination is 2 to 15 C. per minute; in step (2), the mass ratio of perylenetetracarboxylic dianhydride, carbon nitride nanosheets and imidazole is 1:30:120; the reaction is carried out at 130 to 160 C. for 4 to 7 hours; in step (3), the mass ratio of said nitride modified with perylenetetracarboxylic dianhydride and said graphene oxide is 3:1; taking ultrasonic treatment after dispersing in deionized water, the reaction is carried out at 160 to 200 C. for 5 to 8 hours.

9. Carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material prepared by the preparation method of carbon nitride modified with perylenetetracarboxylic dianhydride/graphene oxide aerogel composite material according to claim 7.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is the SEM image of graphitic carbon nitride;

(2) FIG. 2 is the TEM image of graphitic carbon nitride;

(3) FIG. 3 is the TEM image of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride;

(4) FIG. 4 is the SEM image of 3D aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide;

(5) FIG. 5 is the TEM image of 3D aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide;

(6) FIG. 6 is effect of photocatalytic degradation NO by the composites;

(7) FIG. 7 is cycling runs for the photocatalytic degradation of NO over 3D aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

(8) Preparation of graphitic carbon nitride. Specific steps are as follows:

(9) 10 g of dicyandiamide were played into a porcelain crucible, calcined for 5 hours at 600 C. at the heating rate of 10 C. per minute under argon protection, to obtain a yellow carbon nitride, and ground into powder; FIG. 1 and FIG. 2 were the SEM image and TEM image of the carbon nitride, respectively, which can be seen that carbon nitride was thin sheet structure.

(10) Preparation of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride. Specific steps are as follows:

(11) 0.05 g of perylenetetracarboxylic dianhydride, 1.0 g of carbon nitride and 4.0 g of imidazole were respectively added into a round-bottomed flask, in which imidazole was acted as solvent and melted into liquid under high temperature. The reaction was carried out in an oil bath and heated at 150 for 6 hours under a nitrogen gas atmosphere. After the reaction was completed, cooled to room temperature naturally, the product was transferred to a flask containing 150 ml of K.sub.2CO.sub.3 solution, refluxed for 2 hours, after the reaction was cooled to room temperature, the product was centrifuged, washed with hydrochloric acid until to neutralize the remaining lye, and then washed with water and ethanol to neutral, vacuum dried for 5 hours to obtain graphitic carbon nitride modified with perylenetetracarboxylic dianhydride; FIG. 3 is the TEM image of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride, which can be seen that it is a thin sheet-like structure.

(12) Preparation of aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide. Specific steps are as follows:

(13) 90 mg of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and 30 mg of graphene oxide were dispersed in 20 ml of water, stirred for 2 hours with ultrasonic agitation, and uniformly dispersed. The uniformly dispersed suspension was transferred to a Teflon-lined stainless autoclave and react at 190 C. for 6 hours. After the reaction was completed, the column was naturally cooled to room temperature to obtain a columnar hydrogel which was washed three times with deionized water. The hydrogel was then placed in a watch glass, and transferred to a freeze-drying oven for freeze-drying 2 days to finally obtain a columnar aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide; FIG. 4 and FIG. 5 are the SEM and TEM images of aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide, which showed that the material was macroporous structure and the carbon nitride and graphene were well compounded.

Example 2

(14) Photocatalytic degradation of NO. Specific steps are as follows:

(15) A batch reactor (2.2 liters in volume) containing one quartz glass was used for the photocatalytic degradation of nitric oxide; 50 mg of a aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide was placed in the batch reactor, the door was closed, the reactor was evacuated, the flow rate of high purity air (1 liter) and nitric oxide (concentration of 100 ppm) was adjusted so that the flow rate of the mixed gas was 2.4 liters per minute, until the concentration of nitrogen oxide concentration stabilized at 600 ppb for fifteen minutes, a xenon light was turned on to initiate the photodegradation reaction. The aerogel of graphitic carbon nitride modified with perylenetetracarboxylic dianhydride and graphene oxide composite photocatalyst can be recycled many times, With good stability, recycling after 4 times, still have a good catalytic effect.

(16) FIG. 6 is the effect of photocatalytic degradation NO by the composites;

(17) FIG. 7 is the photocatalytic material recycling effect.

(18) Through the above analysis shows that the aerogels in this present invention were synthesized through a simple method and has a good photocatalytic effect for NO removal; and can be recycled many times, and the preparation process is simple, the raw materials are easy to obtain. This composite photocatalyst has the application prospects in the treatment of nitric oxide gas pollution.