CN109806842B - Thioether-functionalized covalent organic framework material with triazine structure and preparation method and application thereof - Google Patents
Thioether-functionalized covalent organic framework material with triazine structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a thioether functionalized covalent organic framework material with a triazine structure, and a preparation method and application thereof, and belongs to the technical field of material preparation. The covalent organic framework material structure simultaneously contains acylhydrazone bonds, triazine groups and ethyl thioether groups, and nitrogen and sulfur atom components in the structure are rich, so that the photocatalytic activity of the covalent organic framework material is enhanced to a certain extent, and the thioether functionalized covalent organic framework material based on the triazine structure has a good application prospect in the field of hydrogen production by photocatalytic decomposition of seawater.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a thioether functionalized covalent organic framework material with a triazine structure, and a preparation method and application thereof.
Background
About 97% of the water on earth is seawater (3.0-5.0% salt), which indicates that if salt seawater can be used directly as an energy source, seawater will provide an unlimited supply of water. The photocatalytic decomposition of seawater is an extremely important technical progress, can directly realize proton reduction by utilizing abundant solar energy, and obtains clean hydrogen energy, thereby being beneficial to relieving and even solving the current environmental problems and energy problems.
Therefore, the photocatalytic hydrogen production technology developed based on hydrogen energy is gradually paid attention and paid attention by researchers. Most of traditional catalytic hydrogen production materials are concentrated on inorganic semiconductor materials, microporous materials composed of some light elements are rarely reported, and a covalent organic framework material with a triazine structure and rich in N components has good photocatalytic hydrogen production activity, and particularly the photocatalytic hydrogen production activity can be improved by metal doping and other methods.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a thioether functionalized covalent organic framework material with a triazine structure, and a preparation method and application thereof. And can be applied to the photocatalytic decomposition of seawater to produce hydrogen.
In order to achieve the purpose, the invention adopts the following technical scheme:
a thioether-functionalized covalent organic framework material (TTR-COF) having a triazine structure, the structural unit of which is:
The preparation method of the thioether functionalized covalent organic framework material with the triazine structure comprises the following steps: adding 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine and 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tri [ benzaldehyde ] into a reaction tube of a 1, 4-dioxane/mesitylene/acetic acid mixed system, and reacting at 100-120 ℃ for 3-5 days to obtain the thioether functionalized covalent organic framework material TTR-COF with the triazine structure.
A preparation method of a thioether functionalized covalent organic framework material with a triazine structure specifically comprises the following steps:
(1) adding 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine and 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tri [ benzaldehyde ] into a reaction tube of a 1, 4-dioxane/mesitylene/acetic acid mixed system, and ultrasonically oscillating for 10 minutes;
(2) then quickly freezing and unfreezing the reaction tube in a liquid nitrogen bath, vacuumizing for three times to the internal pressure of 0 mbar, and carrying out flame sealing;
(3) after the temperature is raised to the room temperature, the reaction tube is placed at 100-120 ℃ for reaction for 3-5 days to generate yellow solid precipitate;
(4) and (3) carrying out suction filtration, collecting precipitates, washing with anhydrous tetrahydrofuran three times, then washing with acetone three times, and carrying out vacuum drying on yellow powder at 80 ℃ overnight to obtain the thioether-functionalized covalent organic framework material TTR-COF with the triazine structure.
In the preparation method, the molar ratio of the 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine to the 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tris [ benzaldehyde ] in the step (1) is 3: 2.
In the preparation method, the molar ratio of the 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tri [ benzaldehyde ] to the acetic acid in the step (1) is 1 (8-12).
In the preparation method, the volume ratio of the 1, 4-dioxane, the mesitylene and the acetic acid in the step (1) is 5:15: 4.
The thioether functionalized covalent organic framework material with the triazine structure has good response to visible light, and is applied to the aspect of hydrogen production by photocatalytic decomposition of seawater.
An application of the thioether functionalized covalent organic framework material with a triazine structure in the aspect of photocatalytic decomposition of seawater to produce hydrogen is disclosed, wherein a sacrificial donor is Triethanolamine (TEOA), and a cocatalyst is a noble metal Au ion.
The invention has the beneficial effects that:
1) according to the invention, 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine and 1,3, 5-tris- (4-formyl-phenyl) triazine are used as reaction raw materials, and the thioether functionalized covalent organic framework material with the triazine structure is synthesized by solvothermal reaction in a 1, 4-dioxane/mesitylene/acetic acid aqueous solution mixed system, has relatively high synthesis yield and good response to visible light, and has good potential application value in the field of hydrogen production by photocatalytic decomposition of seawater.
2) The equipment and chemical reagents used in the synthesis method are easy to obtain, the process operation is simple and convenient, the applicability is strong, the industrial application value is high, and the method is easy to popularize and utilize.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of TTR-COF obtained in example 1;
FIG. 2 shows NMR of TTR-COF obtained in example 113C CP/MAS NMR spectra;
FIG. 3 is a nitrogen adsorption/desorption graph of TTR-COF obtained in example 1;
FIG. 4 is a photo-catalytic cycle hydrogen production test chart of TTR-COF obtained in example 1 under pure water condition;
FIG. 5 is a photo-catalytic cycle hydrogen production test chart of TTR-COF obtained in example 1 under simulated seawater conditions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood and understandable, the present invention is further described in detail with reference to the following embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention. In addition, the technical features mentioned in the embodiments of the present invention described below may be combined as long as they do not conflict with each other.
Example 1
A preparation method of a thioether functionalized covalent organic framework material with a triazine structure comprises the following steps:
2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine (15.4 mg, 38.13. mu. mol) and 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tris [ benzaldehyde ] (10.0 mg, 25.42. mu. mol) were added to 1.2 mL of a 1, 4-dioxane/mesitylene/acetic acid mixed system (v: v: v = 5:15: 4) and placed in a 5 mL Pyrex tube (body length 20 cm, neck length 1 cm) and sonicated for 10 minutes. The Pyrex tubes were then snap frozen and thawed in a liquid nitrogen bath, evacuated three times to an internal pressure of 0 mbar and flame sealed. After warming to room temperature, the Pyrex tube was placed in an oven at 120 ℃ for 3 days to yield a yellow solid. The precipitate was collected by suction filtration, washed three times with anhydrous tetrahydrofuran and three times with acetone. And (3) drying the yellow powder at 80 ℃ in vacuum overnight to obtain the thioether-functionalized covalent organic framework material TTR-COF with the triazine structure.
The X-ray powder diffraction pattern of the thioether-functionalized covalent organic framework material TTR-COF with the triazine structure prepared in the example is shown in figure 1, and nuclear magnetic resonance13The C CP/MAS NMR spectrum is shown in FIG. 2, and the nitrogen adsorption and desorption graph is shown in FIG. 3. The crystallinity of TTR-COF was determined by powder X-ray diffraction (PXRD) analysis, the PXRD pattern showing TTR-COF at 2 theta = 2.4o，4.7 o，6.0 oAnd 26.3oPeaks are shown which correspond to the 100, 110, 200 and 001 crystal planes, respectively (figure 1). The solid state 13C NMR spectrum of TTR-COF showed a resonance signal of 160 ppm, which corresponds to a carbon atom on a hydrazone bond in the TTR-COF structure, and in addition the peak at 169 ppm is attributed to a carbon atom in the triazine ring, while the signals at 14 and 31 ppm confirm the presence of thioethers in the frameworkGroup (fig. 2). By N2Adsorption and desorption tests to investigate the porosity of TTR-COF having a specific surface and a pore volume of 138 m, respectively2 g-1And 0.09 cm3 g-1(FIG. 3).
Example 2 photocatalytic cycle hydrogen production test of TTR-COF under pure water condition
20 mg of TTR-COF prepared in example 1 was suspended as a photocatalyst in 50 mL of a solution containing 10% triethanolamine/pure water (V/V), 1.0 wt% of Au was added dropwise as a co-catalyst, the solution was dispersed in an ultrasonic bath for 5 minutes, and photocatalytic decomposition of pure water was performed under irradiation of visible light (420 nm or more) to produce hydrogen, and a cyclic experiment was performed for 5 times, each for 4 hours. The photocatalytic cycle hydrogen production test chart of TTR-COF under the condition of pure water is shown in figure 4. As can be seen from FIG. 4, the total amount of hydrogen production of TTR-COF appeared to be 1720. mu. mol g in the first run for 4 hours-1And the stable test can be carried out for 20 hours by carrying out a cycle experiment under the irradiation of visible light (lambda is more than or equal to 420 nm).
Example 3 photocatalytic cycle hydrogen production test of TTR-COF under simulated seawater conditions
20 mg of TTR-COF prepared in example 1 as a photocatalyst was suspended in 50 mL of a solution containing 10% triethanolamine/seawater (V/V), 1.0 wt% of Au as a co-catalyst was added dropwise, the solution was dispersed in an ultrasonic bath for 5 minutes, photocatalytic decomposition of seawater was performed under irradiation of visible light (420 nm or more) to produce hydrogen, and a cyclic experiment was performed for 5 times, each for 4 hours. The photocatalytic cycle hydrogen production test chart of TTR-COF under simulated seawater conditions is shown in figure 5. As shown in FIG. 5, the average total hydrogen evolution amount per photocatalytic cycle of TTR-COF under visible light irradiation (lambda ≧ 420 nm) can reach 500. mu. mol g-1。
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (7)
1. A thioether functionalized covalent organic framework material with a triazine structure is characterized in that the structural unit is as follows:
the preparation method of the thioether functionalized covalent organic framework material with the triazine structure comprises the following steps: adding 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine and 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tri [ benzaldehyde ] into a 1, 4-dioxane/mesitylene/acetic acid mixed system, and reacting at 100-120 ℃ for 3-5 days to obtain the thioether functionalized covalent organic framework material with the triazine structure.
2. The preparation method of the thioether-functionalized covalent organic framework material with the triazine structure as claimed in claim 1, which comprises the following steps:
(1) adding 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine and 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tri [ benzaldehyde ] into a reaction tube of a 1, 4-dioxane/mesitylene/acetic acid mixed system, and ultrasonically oscillating for 10 minutes;
(2) then quickly freezing and unfreezing the reaction tube in a liquid nitrogen bath, vacuumizing for three times to the internal pressure of 0 mbar, and carrying out flame sealing;
(3) after the temperature is raised to the room temperature, the reaction tube is placed at 100-120 ℃ for reaction for 3-5 days to generate yellow solid precipitate;
(4) and (3) carrying out suction filtration, collecting the precipitate, washing with anhydrous tetrahydrofuran three times, then washing with acetone three times, and carrying out vacuum drying on the yellow powder at 80 ℃ overnight to obtain the thioether functionalized covalent organic framework material with the triazine structure.
3. The method of claim 2, wherein the thioether-functionalized covalent organic framework material having a triazine structure comprises: in the step (1), the molar ratio of the 2, 5-bis (2- (ethylthio) ethoxy) terephthaloyl hydrazine to the 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tris [ benzaldehyde ] is 3: 2.
4. The method of claim 2, wherein the thioether-functionalized covalent organic framework material having a triazine structure comprises: in the step (1), the molar ratio of 4,4',4' ' - (1,3, 5-triazine-2, 4, 6-triyl) tri [ benzaldehyde ] to acetic acid is 1 (8-12).
5. The method of claim 2, wherein the thioether-functionalized covalent organic framework material having a triazine structure comprises: in the step (1), the volume ratio of the 1, 4-dioxane, the mesitylene and the acetic acid is 5:15: 4.
6. The use of the thioether-functionalized covalent organic framework material with a triazine structure as defined in claim 1 for photocatalytic decomposition of seawater to produce hydrogen.
7. The application of the thioether-functionalized covalent organic framework material with a triazine structure in the aspect of photocatalytic decomposition of seawater to produce hydrogen is characterized in that: the sacrificial donor used was Triethanolamine (TEOA) and the promoter was a noble metal Au ion.
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| CN113512162B (en) * | 2021-04-30 | 2022-04-15 | 华中科技大学 | Thioether-based covalent organic framework material and preparation method and application thereof |
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| CN113845665B (en) * | 2021-09-28 | 2022-11-08 | 天津大学 | Full-conjugated organic triazine framework material and preparation method and application thereof |
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| CN115029731B (en) * | 2022-07-18 | 2024-02-09 | 齐齐哈尔大学 | Heteroatom doped covalent organic framework material and preparation method and application thereof |
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