PERYLENE IMIDE AND COMPOSITE PHOTOCATALYTIC MATERIAL THEREOF, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF IN REMOVING ORGANIC POLLUTANTS FROM WATER

Abstract

Melamine is calcined to obtain melem; melem, perylene tetracarboxylic dianhydride and a solvent are mixed to obtain a mixture, and the mixture is subjected to a solvothermal reaction in an inert atmosphere to obtain perylene imide; and the perylene imide is dispersed in an aqueous solution containing a bismuth source and a tungsten source, and is subjected to a hydrothermal reaction to obtain a perylene imide/bismuth tungstate composite photocatalytic material. By means of constructing an organic-inorganic composite photocatalytic material, the introduction of the organic photocatalytic material that responds to visible light may enable the composite material to have a wider spectral response range; and the introduction of an inorganic semiconductor catalyst enables the composite material to produce more oxidizing active free radicals, thereby enhancing the photocatalytic degradation performance of the composite material on organic pollutants. The constructed organic-inorganic composite photocatalytic material has an excellent catalytic performance.

Claims

1. A perylene imide, which is characterized in that the preparation method of the perylene imide comprising the following steps: calcining melamine to obtain melem; thereafter, mixing the melem, perylene tetracarboxylic dianhydride and a solvent to obtain a mixture, and then placing the mixture in an inert atmosphere to obtain perylene imide by solvothermal reaction.

2. The perylene imide according to claim 1, wherein the calcination is carried out in air and calcined at 400˜450° C. for 3-5 h; the solvothermal reaction is carried out in inert gas at 180-200° C. for 72-120 h.

3. The perylene imide according to claim 1, wherein the solvent is a mixture of DMF and ethylene glycol, and the molar ratio of melem to perylene tetracarboxylic dianhydride is 2:3.

4. A perylene imide/bismuth tungstate composite photocatalytic material, which is characterized in that the preparation method of the perylene imide/bismuth tungstate composite photocatalytic material comprising the following steps: 1) calcining melamine to obtain melem; thereafter, mixing the melem, perylene tetracarboxylic dianhydride and a solvent to obtain a mixture, and then placing the mixture in an inert atmosphere to obtain perylene imide by solvothermal reaction; 2) dispersing the perylene imide obtained in step 1) in an aqueous solution containing bismuth source and tungsten source to obtain the perylene imide/bismuth tungstate composite photocatalytic material by hydrothermal reaction.

5. The perylene imide/bismuth tungstate composite photocatalytic material according to claim 4, wherein the calcination is carried out in air and calcined at 400-450° C. for 3-5 h; the solvothermal reaction is carried out in inert gas at 180-200° C. for 72-120 h.

6. The perylene imide/bismuth tungstate composite photocatalytic material according to claim 4, wherein the solvent is a mixture of DMF and ethylene glycol, and the molar ratio of melem to perylene tetracarboxylic dianhydride is 2:3.

7. The perylene imide/bismuth tungstate composite photocatalytic material according to claim 4, wherein centrimethyl ammonium bromide is used as a template in the hydrothermal reaction; and the hydrothermal reaction is carried out at 120-180° C. for 12-24 h.

8. The perylene imide/bismuth tungstate composite photocatalytic material according to claim 4, wherein the bismuth source is bismuth nitrate pentahydrate, the tungsten source is sodium tungstate dihydrate, and the molar ratio of bismuth source to tungsten source is 2:1.

9. The application of the perylene imide/bismuth tungstate composite photocatalytic material according to claim 4 in removal of organic pollution in water.

10. The application of the perylene imide according to claim 1 in preparing a composite photocatalytic material for removing organic pollutants from water.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 is a transmission electron microscope photograph (a), an infrared spectrum (b) and a nuclear magnetic spectrum (c) of perylene imide (PI) of embodiment 1;

[0027] FIG. 2 shows a SEM photo of the perylene imide/bismuth tungstate composite photocatalytic material of embodiment 3 (PI@BWO);

[0028] FIG. 3 shows the TEM photo of perylene imide/bismuth tungstate composite photocatalytic material of embodiment 3 (PI@BWO);

[0029] FIG. 4 shows the effect diagram of the perylene imide/bismuth tungstate composite photocatalytic material of embodiment 3 (PI@BWO) of degradation of bisphenol A in water.

DETAILED DESCRIPTION OF THE INVENTION

[0030] In the invention, the preparation method of the perylene imide comprising the following steps: calcining melamine to obtain melem; thereafter, mixing the melem, perylene tetracarboxylic dianhydride and a solvent to obtain a mixture, and then placing the mixture in an inert atmosphere to obtain perylene imide by solvothermal reaction.

[0031] The preparation method of the perylene imide/bismuth tungstate composite photocatalytic material comprising the following steps:

[0032] 1) calcining melamine to obtain melem; thereafter, mixing the melem, perylene tetracarboxylic dianhydride and a solvent to obtain a mixture, and then placing the mixture in an inert atmosphere to obtain perylene imide by solvothermal reaction;

[0033] 2) dispersing the perylene imide obtained in step 1) in an aqueous solution containing bismuth source and tungsten source to obtain the perylene imide/bismuth tungstate composite photocatalytic material by hydrothermal reaction.

Embodiment 1

[0034] The invention first adopts the method of high-temperature calcination to synthesize melem. First, weigh 5 g of melamine and place it in a 25 ml porcelain crucible with a cover; then, cover it and place it in muffle furnace, and set the heating rate to 5° C./min (room temperature rises to 425 ° C.), calcine at 425° C. for 4 h in air atmosphere, after cooling to room temperature, centrifuge the light yellow product and wash it with absolute ethanol for 3 times, and then dry it in a 60° C. vacuum drying oven for 12 h to obtain melem. Then, perylene imide is synthesized by solvothermal method. First, 88.1 mg of melem and 235.8 mg of perylene tetracarboxylic dianhydride are weighed and add in a 10 mL milled reaction bottle, then add 10 mL mixed solvent of DMF/EG (volume ratio: 1:1) and disperse it by ultrasonic for 1 h; then, inject argon for protection, check the air tightness, and put it in a 200° C. blast drying oven for 120 h. After the reaction, cool to room temperature, the dark red product is filtered with 0.45 μm organic phase microporous membrane to obtain a filter cake which is washed with DMF, acetone and absolute ethanol for 3 times respectively, and then dried in a 60° C. vacuum drying oven for 24 hours to obtain perylene imide. The transmission electron microscope diagram is shown in FIG. 1a, and the infrared and nuclear magnetic spectra are tested. The infrared spectrum shows that imide cyclocarbonyl at 1687.6 cm.sup.−1 and the appearance of C—N stretching vibration characteristic peak at 1363.6 cm.sup.−1 can prove the successful synthesis of perylene imide. In addition, the solid .sup.13C nuclear magnetic spectrum shows that 180.2 ppm corresponds to imide ring C═O, 165.6 and 162.7 ppm correspond to C—N.sub.3 and C═N of heptane structure respectively, and 110˜140 ppm correspond to Ar—C in perylene structure, which can further prove the structure of perylene imide.

Embodiment 2

[0035] Preparation of perylene imide/bismuth tungstate composite photocatalytic material (PI@BWO), the specific steps are as follows:

[0036] The invention uses centrimethyl ammonium bromide (CTAB) as a template to grow bismuth tungstate nano sheets on the surface of perylene imide by hydrothermal method, so as to obtain perylene imide/bismuth tungstate composite photocatalytic material (PI@BWO). First, weigh 48.5 mg of bismuth nitrate pentahydrate and 16.5 mg of sodium tungstate dihydrate, add 35 ml of deionized water dissolved with 5 mg of centrimethyl ammonium bromide, magnetic stirring and dispersion for 30 min; then, weigh 30 mg perylene imide (preparation of embodiment 1) in the above mixed solution, continue stirring for 30 min to obtain uniformly dispersed dark red suspension, and then ultrasonic dispersion for 1 h; finally, transfer the mixed solution to a 50 mL polytetrafluoroethylene lined high-pressure reactor and react in a 120° C. blast drying oven for 24 h. After the reaction, stop heating, and feed the product after the reactor is naturally cooled to room temperature. Perylene imide/bismuth tungstate nanocomposite photocatalyst is obtained by centrifugation and washing with deionized water for 3 times (PI@BWO), dry in a 60° C. blast oven for 24 hours. The loading amount of bismuth tungstate nanosheets in the composite photocatalytic material obtained in this embodiment is too small, and bismuth tungstate nanosheets grow only locally on the surface of perylene imide organic compound.

Embodiment 3

[0037] First, weigh 97.0 mg of bismuth nitrate pentahydrate and 33.0 mg of sodium tungstate dihydrate, add 35 ml of deionized water dissolved with 10 mg of centrimethyl ammonium bromide, magnetic stirring and dispersion for 30 min; Then, weigh 30 mg perylene imide in the above mixed solution, continue stirring for 30 min to obtain a uniformly dispersed dark red suspension, and then ultrasonic dispersion for 1 h; Finally, the mixed solution is transferred to a 50 ml polytetrafluoroethylene lined high-pressure reactor and reacted in a 120° C. blast drying oven for 24 hours. After the reaction, the heating is stopped. After the reactor is naturally cooled to room temperature, the product is centrifuged and washed with deionized water for 3 times to obtain perylene imide/bismuth tungstate composite photocatalytic material (PI@BWO), dry in a 60° C. blast oven for 24 hours. FIG. 2 shows SEM photo of perylene imide/bismuth tungstate composite photocatalytic material (PI@BWO); FIG. 3 is a transmission electron microscope photograph. It can be seen from the figure that bismuth tungstate nanosheets in the composite photocatalytic material obtained in this embodiment are uniformly loaded on the surface of perylene imide.

Embodiment 4

[0038] First, weigh 145.5 mg of bismuth nitrate pentahydrate and 49.5 mg of sodium tungstate dihydrate, add 35 ml of deionized water dissolved with 15 mg of centrimethyl ammonium bromide, magnetic stirring and dispersion for 30 min; Then, weigh 30 mg perylene imide in the above mixed solution, continue stirring for 30 min to obtain a uniformly dispersed dark red suspension, and then ultrasonic dispersion for 1 h; Finally, the mixed solution is transferred to a 50 ml polytetrafluoroethylene lined high-pressure reactor and reacted in a 120° C. blast drying oven for 24 hours. After the reaction, the heating is stopped. After the reactor is naturally cooled to room temperature, the product is centrifuged and washed with deionized water for 3 times to obtain perylene imide/bismuth tungstate composite photocatalytic material (PI@BWO), dry in a 60° C. blast oven for 24 hours. In the composite photocatalytic material obtained in this embodiment, bismuth tungstate nanosheets are agglomerated, and there are few bismuth tungstate nanosheets uniformly loaded on the surface of perylene imide.

Embodiment 5

[0039] Photocatalytic degradation experiment of perylene imide/bismuth tungstate composite photocatalytic material (PI@BWO) of bisphenol A in water: weigh 25 mg of perylene imide/bismuth tungstate composite photocatalytic material obtained in embodiment 3 or embodiment 4 and embodiment 5 above (PI@BWO), put it into 50 ml bisphenol A aqueous solution with a concentration of 10 mg/L and stir it for 1 h without light to achieve adsorption desorption equilibrium. After equilibrium, the prepared photocatalytic material is irradiated with a 300 W xenon lamp cold light source, and the degradation experiment is started. 1 mL is sampled every 30 min, the signal intensity of the water sample at the wavelength of 280 nm is measured by high performance liquid chromatography with an ultraviolet detector, and the concentration of bisphenol A in the corresponding water sample is calculated. Referring to the standard curve, the residual concentration of bisphenol A in the corresponding water sample is obtained. FIG. 3 shows the relationship between the concentration and time of residual bisphenol A obtained by photocatalytic degradation of bisphenol A in water using the perylene imide/bismuth tungstate composite photocatalytic material obtained by embodiment 3 (PI@BWO). It can be seen from the figure that while adding PI@BWO photocatalytic material and under the condition of illumination, the removal rate of bisphenol A in aqueous solution reached more than 99% after 180 minutes of illumination. Compared with the effect of the perylene imide/bismuth tungstate composite photocatalytic material (PI@BWO) obtained in embodiment 2 and embodiment 4, the photocatalytic effect of the composite photocatalytic material obtained in embodiment 3 is the best. Table 1 shows the removal rate of bisphenol Ain aqueous solution after 180 minutes of illumination with the same experimental method above for different catalysts.

TABLE-US-00001 TABLE 1 Removal rate of bisphenol A by different catalysts Removal Rate embodiment 3 99.7% embodiment 2 96.1% embodiment 4 86.0% embodiment 1 77.6% BWO 77.8%

[0040] BWO is prepared by weighing 97.0 mg bismuth nitrate pentahydrate and 33.0 mg sodium tungstate dihydrate, adding 35 ml deionized water with 10 mg centrimethyl ammonium bromide, magnetic stirring and dispersion for 30 min, and then ultrasonic dispersion for 1 h; Finally, the mixed solution is transferred to a 50 ml polytetrafluoroethylene lined high-pressure reactor and reacted in a 120° C. blast drying oven for 24 hours. After the reaction, stop heating. After the reactor is naturally cooled to room temperature, the product is centrifuged and washed with deionized water for 3 times to obtain bismuth tungstate photocatalytic material (BWO), which is dried in a 60° C. blast oven for 24 hours.

[0041] The invention discloses an organic-inorganic composite photocatalytic material with visible light response based on perylene imide organic compound. First, perylene imide is prepared by solvothermal method (PI); then, the precursor of bismuth tungstate is evenly distributed on the surface of perylene imide by ultrasonic dispersion; further, bismuth tungstate nano sheets are grown on the surface of perylene imide by hydrothermal method to obtain a new organic-inorganic composite photocatalytic material. When using this material for catalytic reaction, the combination of organic photocatalytic material and inorganic two-dimensional nano sheets can not only accelerate electron hole separation and improve photocatalytic efficiency, moreover, the introduction of nano sheets can also provide large specific surface area and rich active sites to promote the adsorption and surface catalysis of organic pollutants by composite photocatalysts.

[0042] In conclusion, the invention constructs an organic-inorganic hybrid photocatalytic material composed of perylene imide organic compound with visible light response and two-dimensional bismuth tungstate nano sheet. This design is not only conducive to the separation and migration of photogenerated electron hole pairs, but also improves the adsorption capacity of small molecules of organic pollutants, at the same time, provides a large number of surface catalytic active sites. In terms of catalytic performance, the above prepared perylene imide/bismuth tungstate organic-inorganic nanocomposite photocatalytic material (PI@BWO) shows effective degradation of bisphenol A in water.