Preparation method of COF-5 crystal

Abstract

A preparation method for covalent organic framework 5 (COF-5) includes: adding 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid to a mixed solution of 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture in the anhydrous and oxygen-free environment; and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene:1,4-phenylenebisboronic acid:1,3,5-trimethylbenzene:1,4-dioxane is 0.02-0.8 mmol:0.08-1.4 mmol:10-15 mL:10-15 mL; sealing the mixture in an airtight container; and obtaining a uniform dispersion solution after shaking the container for wholly mixing the components; heating the dispersion solution to a temperature ranging from 80-100° C.; reacting for a period of time ranging from 72-120 h; and obtaining a precipitate after the reaction; and washing the precipitate, drying the precipitate in vacuum, and heating the precipitate at a temperature ranging from 200-300° C. for a period of time ranging from 1-3 h with a protective atmosphere to obtain COF-5 crystal.

Claims

1. A method for preparing one-dimensional rod-shaped covalent organic framework 5 (COF-5) crystals, the method comprising: 2.1) adding 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid to a mixed solution of 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture in the anhydrous and oxygen-free environment; and a ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane is 0.1-0.3 mmol: 0.1-0.5 mmol: 10-15 mL: 10-15 mL; 2.2) sealing the mixture in an airtight container; obtaining a uniform dispersion solution after shaking the container for wholly mixing the components; 2.3) heating the dispersion solution to a temperature; reacting for a period of time; obtaining a precipitate after the reaction; and 2.4) washing the precipitate by using a washing reagent; drying the precipitate in vacuum; heating the precipitate at a temperature for a period of time in the presence of a protective gas to obtain the one-dimensional rod-shaped COF-5 crystals.

2. The method of claim 1, wherein in 2.3), a heating temperature is in the range of 80-100° C., and a reaction time is from 72 to 120 h.

3. The method of claim 1, wherein in 2.4), a heating temperature is in the range of 200-300° C., and a reaction time is from 1 to 3 h.

4. The method of claim 1, wherein in 2.4), the washing reagent is any one of acetone, methanol, benzene, ether, and N,N-Dimethylformamide.

5. The method of claim 1, wherein in 2.4), the protective gas is any one of nitrogen, argon, and helium.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1: XRD pattern of zero-dimensional spherical COF-5 crystal prepared in Example 1;

(2) FIG. 2: FT-IR diagram of zero-dimensional spherical COF-5 crystal prepared in Example 2;

(3) FIG. 3: SEM image of zero-dimensional spherical COF-5 crystal prepared in Example 3;

(4) FIG. 4: TEM image of zero-dimensional spherical COF-5 crystal prepared in Example 4;

(5) FIG. 5: XRD pattern of one-dimensional rod-like COF-5 crystal prepared in Example 5;

(6) FIG. 6: FT-IR diagram of one-dimensional rod-like COF-5 crystal prepared in Example 6;

(7) FIG. 7: SEM image of one-dimensional rod-like COF-5 crystal prepared in Example 7;

(8) FIG. 8: SEM image of one-dimensional rod-like COF-5 crystal prepared in Example 8;

(9) FIG. 9: XRD pattern of two-dimensional sheet-like COF-5 crystal prepared in Example 9;

(10) FIG. 10: FT-IR diagram of two-dimensional sheet-like COF-5 crystal prepared in Example 10;

(11) FIG. 11: SEM image of two-dimensional sheet-like COF-5 crystal prepared in Example 11;

(12) FIG. 12: SEM image of two-dimensional sheet-like COF-5 crystal prepared in Example 12;

(13) FIG. 13: TEM image of two-dimensional sheet-like COF-5 crystal prepared in Example 13;

(14) FIG. 14: Gas sensitivity of two-dimensional sheet-like COF-5 crystal of Example 9 to high concentration of ammonia; and

(15) FIG. 15: Gas sensitivity of two-dimensional sheet-like COF-5 crystal of Example 9 to low concentration of ammonia.

DETAILED DESCRIPTION

(16) The following Examples 1-4 will in detail describe the specific implementation of zero-dimensional spherical COF-5 crystal involved in the disclosure with reference and FIGS. 1-4.

Example 1

(17) A preparation method of a zero-dimensional spherical COF-5 crystal provided in Example 1 comprises the following steps:

(18) (A1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.02 mmol: 0.08 mmol: 12.5 mL: 12.5 mL;

(19) (A2) the mixture was sealed in an airtight container and then a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(20) (A3) the dispersion solution was heated to 100° C., and then reacted for 72 h; a precipitate was obtained after the reaction; and

(21) (A4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 200° C. for 3 h with an argon protective gas to obtain a zero-dimensional spherical COF-5 crystal.

Example 2

(22) A preparation method of a zero-dimensional spherical COF-5 crystal provided in Example 2 comprises the following steps:

(23) (A1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.04 mmol: 0.12 mmol: 13 mL: 12 mL;

(24) (A2) the mixture was sealed in an airtight container and then a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(25) (A3) the dispersion solution was heated to 85° C., and then reacted for 84 h; a precipitate was obtained after the reaction; and

(26) (A4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 220° C. for 1 h with an argon protective gas to obtain a zero-dimensional spherical COF-5 crystal.

Example 3

(27) A preparation method of a zero-dimensional spherical COF-5 crystal provided in Example 3 comprises the following steps:

(28) (A1) In the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.05 mmol: 0.1 mmol: 10 mL: 15 mL;

(29) (A2) The mixture was sealed in an airtight container and then a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(30) (A3) The dispersion solution was heated to 80° C., and then reacted for 72 h; a precipitate was obtained after the reaction; and

(31) (A4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 250° C. for 2 h with an argon protective gas to obtain a zero-dimensional spherical COF-5 crystal.

Example 4

(32) A preparation method of a zero-dimensional spherical COF-5 crystal provided in Example 4 includes the following steps:

(33) (A1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.06 mmol: 0.15 mmol: 15 mL: 10 mL;

(34) (A2) the mixture was sealed in an airtight container and then a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(35) (A3) the dispersion solution was heated to 95° C., and then reacted for 120 h; and a precipitate was obtained after the reaction;

(36) (A4) the precipitate was washed with acetone and then dried in vacuum; and the precipitate was heated at 300° C. for 2 h with an argon protective gas to obtain a zero-dimensional spherical COF-5 crystal.

(37) Further, zero-dimensional spherical COF-5 crystals prepared in the above examples were characterized and tested:

(38) As shown in FIG. 1, the positions and relative intensities of the diffraction peaks obtained from actual tests (experimental values) in the XRD pattern are highly matched with those of the theoretical calculations (simulation values). Therefore, the synthesized product of the disclosure is COF-5 crystal.

(39) As shown in FIGS. 2-4, the COF-5 crystals obtained in different examples of the disclosure have the zero-dimensional spherical morphology with large dimensions of predominantly 1 μm.

(40) In addition, in Step 2 a vortex mixer was used for the shaking treatment for all of the above examples, and the shaking time was about 1 min; the temperature of the vacuum drying treatment in Step 4 was in the range of 60-90° C., and the drying time was from 24-36 h; Step 2 and Step 3 were carried out under the sealed conditions.

(41) The following Examples 5 to 8 will describe in detail the specific implementation of one-dimensional rod-like COF-5 crystal involved in the disclosure with reference and FIGS. 5-8.

Example 5

(42) A preparation method of a one-dimensional rod-like COF-5 crystal provided in Example 5 comprises the following steps:

(43) (B1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.1 mmol: 0.1 mmol: 12.5 mL: 12.5 mL;

(44) (B2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication; a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(45) (B3) the dispersion solution was heated to 85° C., and then reacted for 72 h. A precipitate was obtained after the reaction; and

(46) (B4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 200° C. for 1 h with an argon protective gas to obtain a one-dimensional rod-like COF-5 crystal.

Example 6

(47) A preparation method of a one-dimensional rod-like COF-5 crystal provided in Example 6 comprises the following steps:

(48) (B1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.2 mmol: 0.3 mmol: 12 mL: 13 mL;

(49) (B2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication; a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(50) (B3) the dispersion solution was heated to 100° C., and then reacted for 84 h; and a precipitate was obtained after the reaction; and

(51) (B4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 220° C. for 1 h with an argon protective gas to obtain a one-dimensional rod-like COF-5 crystal.

Example 7

(52) A preparation method of a one-dimensional rod-like COF-5 crystal provided in Example 7 comprises the following steps:

(53) (B1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.3 mmol: 0.5 mmol: 10 mL: 15 mL;

(54) (B2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication; a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(55) (B3) the dispersion solution was heated to 80° C., and then reacted for 96 h; a precipitate was obtained after the reaction; and

(56) (B4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 250° C. for 2 h with an argon protective gas to obtain a one-dimensional rod-like COF-5 crystal.

Example 8

(57) A preparation method of one-dimensional rod-like COF-5 crystal provided in Example 8 comprises the following steps:

(58) (B1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.3 mmol: 0.3 mmol: 15 mL: 10 mL;

(59) (B2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication; a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(60) (B3) the dispersion solution was heated to 95° C., and then reacted for 120 h; a precipitate was obtained after the reaction; and

(61) (B4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 300° C. for 2 h with an argon protective gas to obtain one-dimensional rod-like COF-5 crystal.

(62) Furthermore, one-dimensional rod-like COF-5 crystals prepared in the above Examples 5-8 were characterized and tested:

(63) As shown in FIG. 5, the positions and relative intensities of the diffraction peaks obtained from actual tests (experimental values) are highly matched with those of the theoretical calculations (simulation values) in the XRD pattern. As shown in FIG. 6, each infrared absorption peak in the FT-IR spectrum corresponds to the characteristic absorption peak of the functional group contained in the COF-5 crystal. These data all indicate that the synthesized product of the disclosure is COF-5 crystal.

(64) As shown in FIGS. 7 and 8, the COF-5 crystals obtained in different examples of the disclosure have the one-dimensional rod-like morphology, the crystal size is relatively large, and one-dimensional rod-like COF-5 crystal obtained at the reaction temperature of 80° C. has a larger and more uniform crystal size compared with that synthesized at the reaction temperature of 95° C. Therefore, the size of the synthesized one-dimensional rod-like COF-5 crystals can be controlled by regulating the reaction temperature.

(65) In addition, the frequency of the ultrasonic treatment in step 2 was 70 Hz in the above Examples 5-8, and the ultrasonic time was from 5-10 min; t a vortex mixer was used for the shaking treatment, and the shaking time was about 1 min; the temperature of the vacuum drying treatment in Step 4 was in the range of 60-90° C., and the drying time was from 24-36 h; Step 2 and Step 3 were carried out under sealed conditions.

(66) The following Examples 9-13 will describe in detail the specific implementation of two-dimensional sheet-like COF-5 crystal involved in the disclosure with reference to FIGS. 9-15.

Example 9

(67) A preparation method of a two-dimensional sheet-like COF-5 crystal provided in Example 9 comprises the following steps:

(68) (C1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.4 mmol: 0.6 mmol: 12.5 mL: 12.5 mL;

(69) (C2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication; a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(70) (C3) the dispersion solution was heated to 95° C.; and then reacted for 72 h; a precipitate was obtained after the reaction; and

(71) (C4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 200° C. for 3 h with an argon protective gas to obtain a two-dimensional sheet-like COF-5 crystal.

Example 10

(72) A preparation method of a two-dimensional sheet-like COF-5 crystal provided in Example 10 comprises the following steps:

(73) (C1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.5 mmol: 0.9 mmol: 12 mL: 13 mL;

(74) (C2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication; a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(75) (C3) the dispersion solution was heated to 85° C., and then reacted for 84 h, and then reacted for 84 h; and a precipitate was obtained after the reaction; and

(76) (C4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 220° C. for 1 h with an argon protective gas to obtain a two-dimensional sheet-like COF-5 crystal.

Example 11

(77) A preparation method of a two-dimensional sheet-like COF-5 crystal provided in Example 11 comprises the following steps:

(78) (C1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.6 mmol: 1.0 mmol: 10 mL: 15 mL;

(79) (C2) The mixture was sealed in an airtight container. Then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication. A uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(80) (C3) The dispersion solution was heated to 100° C., and then reacted for 72 h. A precipitate was obtained after the reaction;

(81) (C4) The precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 250° C. for 2 h with an argon protective gas to obtain a two-dimensional sheet-like COF-5 crystal.

Example 12

(82) The preparation method of a two-dimensional sheet-like COF-5 crystal provided in Example 12 comprises the following steps:

(83) (C1) in the anhydrous and oxygen-free environment, the 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.7 mmol: 1.3 mmol: 15 mL: 10 mL;

(84) (C2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication. A uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(85) (C3) the dispersion solution was heated to 80° C., and then reacted for 120 h; a precipitate was obtained after the reaction; and

(86) (C4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 300° C. for 2 h with the argon protective gas to obtain a two-dimensional sheet-like COF-5 crystal.

Example 13

(87) A preparation method of a two-dimensional sheet-like COF-5 crystal provided in Example 13 comprises the following steps:

(88) (C1) in the anhydrous and oxygen-free environment, 2,3,6,7,10,11-hexahydroxytriphenylene and 1,4-phenylenebisboronic acid were added to 1,3,5-trimethylbenzene and 1,4-dioxane to form a mixture, and the addition ratio of 2,3,6,7,10,11-hexahydroxytriphenylene: 1,4-phenylenebisboronic acid: 1,3,5-trimethylbenzene: 1,4-dioxane was 0.8 mmol: 1.4 mmol: 13 mL: 12 mL;

(89) (C2) the mixture was sealed in an airtight container; then the container was put into an ultrasonic cleaner for processing, and was shaken after ultrasonication; and a uniform dispersion solution was obtained after shaking the container for wholly mixing the components;

(90) (C3) the dispersion solution was heated to 85° C., and then reacted for 120 h; and a precipitate was obtained after the reaction; and

(91) (C4) the precipitate was washed with acetone and then dried in vacuum, and finally the precipitate was heated at 250° C. for 1 h with the argon protective gas to obtain a two-dimensional sheet-like COF-5 crystal.

(92) Further, two-dimensional sheet-like COF-5 crystals prepared in the above Examples 9 to 13 were characterized and tested:

(93) As shown in FIG. 9, the positions and relative intensities of the diffraction peaks obtained from actual tests (experimental values) in the XRD pattern are highly matched with those of the theoretical calculations (simulation values). As shown in FIG. 10, each infrared absorption peak in the FT-IR spectrum corresponds to the characteristic absorption peak of the functional group contained in the COF-5 crystal. These data all indicate that the synthesized product of the disclosure is COF-5 crystal.

(94) As shown in FIGS. 11 and 12, COF-5 crystals obtained in different examples of the disclosure have the sheet-like morphology with slightly wrinkle. The sheets with relatively uniform size are stacked on each other. Two-dimensional sheet-like COF-5 crystals obtained under different experimental conditions have no obvious difference in the morphology and size. In order to observe the morphology of two-dimensional sheet-like COF-5 crystals more clearly, two-dimensional sheet-like COF-5 crystals were fully dispersed by ultrasonication and were diluted with acetone for TEM test. As shown in FIG. 13, a small amount of thin two-dimensional sheet-like crystal structure with stacking relationship between the flakes can be seen, indicating that the material is formed by stacking many sheet-like crystals. It is difficult to obtain a single-layer sheet-like crystal due to the certain interaction force between the sheets.

(95) As shown in FIGS. 14 and 15, the gas sensitivity test of two-dimensional sheet-like COF-5 crystal shows a good gas sensitivity response to ammonia at a high concentration range of 5-25 ppm and a low concentration range of 100-1000 ppb at 50° C.

(96) In addition, the frequency of the ultrasonic treatment in step 2 was 70 Hz in the above Examples 9-13, and the ultrasonic time was from 5-10 min; a vortex mixer was used for the shaking treatment, and the shaking time was about 1 min; the temperature of the vacuum drying treatment in Step 4 was in the range of 60-90° C., and the drying time was from 24-36 h; Step 2 and Step 3 were carried out under sealed conditions.

(97) It will be obvious to those skilled in the art that changes and modifications may be made, and therefore, the aim in the appended claims is to cover all such changes and modifications.