CN115382575A - Preparation method of MXene-COF composite catalyst and application of MXene-COF composite catalyst in photocatalytic hydrogen production - Google Patents
Preparation method of MXene-COF composite catalyst and application of MXene-COF composite catalyst in photocatalytic hydrogen production Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The invention relates to a preparation method of an MXene-COF composite catalyst and application thereof in photocatalytic hydrogen production, wherein the preparation method comprises the following steps: (1) Preparation of Ti 3 C 2 T x The preparation method comprises the following steps of (1) preparing MXene nanosheets, (2) modifying the MXene nanosheets, (3) carrying out APTES-MXene-CHO functionalization, (4) mixing CHO-MXene, trialdehyde phloroglucinol and p-phenylenediamine, adding glacial acetic acid, 1,4-dioxane and mesitylene, uniformly mixing, carrying out freezing-air exhaust-unfreezing circulation degassing for at least three times, carrying out reaction at 120 +/-5 ℃ under a vacuum condition, and cooling to room temperature; performing Soxhlet extraction and purification, vacuum drying, and grinding to obtain the MXene-COF composite catalyst. The method will have excellent visibilityCOF with light capture capability and MXene with excellent conductivity are connected through covalent bonds to obtain the composite catalyst capable of being used for photocatalytic hydrogen production.
Description
Technical Field
The invention relates to a composite catalyst, in particular to a preparation method of an MXene-COF composite catalyst and application thereof in photocatalytic hydrogen production, and belongs to the technical field of photocatalysis.
Background
With the rapid development of global economy and industry, energy and environmental crisis become a major problem that plagues people. Converting renewable energy into chemical energy is a potential alternative. Great interest has been brought to scientists by converting inexhaustible solar energy into chemical energy sources essential to life. The photocatalytic hydrolysis hydrogen production has the advantages of low cost and reproducibility.
MXene serving as a novel two-dimensional layered structure material has high electronic conductivity, good hydrophilicity and energy storage capacity, and has good application prospect in the field of photocatalytic hydrogen production. But shows lower photocatalytic hydrogen production efficiency due to the rapid recombination of charges in the materials. MXene with conductivity is compounded by selecting a material with the capacity of capturing visible light, so that the transfer of photo-generated charges is improved, the photolytic water splitting capacity is improved, and high-efficiency hydrogen production is realized.
Disclosure of Invention
The invention aims to provide a preparation method of an MXene-COF composite catalyst, which connects COF with excellent visible light capturing capability and MXene with excellent conductive capability through covalent bonds to obtain the composite catalyst capable of being used for photocatalytic hydrogen production.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of an MXene-COF composite catalyst comprises the following steps:
(1) Preparation of Ti 3 C 2 T x MXene nano-sheet
Mixing Ti 3 AlC 2 Etching the powder by using LiF and HCl solution, stirring and reacting under the water bath condition of 35 +/-2 ℃ until the reaction is complete, and centrifuging to remove the solution to obtain MXene nanosheets;
(2) Modification of MXene nanosheets
Ultrasonically and uniformly mixing the MXene nanosheet obtained in the step (1) with ethanol, dropwise adding a mixed solution of ethanol and 3-Aminopropyltriethoxysilane (APTES) into the mixed solution of MXene and ethanol, and fully stirring to form APTES-MXene;
(3) — CHO functionalization of APTES-MXene
Mixing trialdehyde phloroglucinol (Tp), glacial acetic acid, 1,4-dioxane and APTES-MXene obtained in the step (2), carrying out freezing-air extraction-unfreezing cycle degassing for at least three times in liquid nitrogen, and reacting for 1-1.5h under a vacuum condition to obtain CHO-MXene;
(4) According to the technical scheme, the method comprises the steps of carrying out Schiff base reaction on trialdehyde phloroglucinol and p-phenylenediamine to generate COF, uniformly mixing the trialdehyde phloroglucinol and the p-phenylenediamine according to the formula amount, uniformly mixing CHO-MXene, trialdehyde phloroglucinol (Tp) and the p-phenylenediamine by taking glacial acetic acid as a catalyst and appropriate amounts of 1,4-dioxane and mesitylene as solvents, carrying out cyclic degassing for at least three times through freezing-air extraction-thawing, reacting for 72-78h at 120 +/-5 ℃ under a vacuum condition, and cooling to room temperature;
(5) And (4) carrying out Soxhlet extraction and purification on the product obtained in the step (4) by using an organic solvent, drying in vacuum, and grinding to obtain the MXene-COF composite catalyst.
The MXene-COF composite catalyst provided by the invention is formed into a heterostructure by connecting MXene with conductive performance and COF with visible light capturing capacity through covalent bonds. The COF with high visible light capturing capacity and the MXene with good conductivity further improve the transfer of photo-generated charges through covalent bonds.
In the step (2), ethanol for mixing and ultrasonically processing MXene nano-sheets provides a solvent environment for reaction, and the ethanol is prepared in a proper amount.
Preferably, in the step (4), the volume ratio of the solvent 1,4-dioxane to mesitylene is 1:1, the dosage of 1,4-dioxane is 1.5mL, and the dosage of glacial acetic acid is 0.5mL.
Preferably, in the step (4), the mass ratio of MXene to COF is 1:2-24. Further, in the step (4), the mass ratio of MXene to COF is 1:2-4.
Preferably, the concentration of glacial acetic acid used in steps (3) and (4) is 6mol/L.
Preferably, in the step (5), after primary washing is carried out by using methanol and acetone, soxhlet extraction purification is carried out by sequentially using ethanol, tetrahydrofuran and dichloromethane; the drying in step (5) is carried out for 12h under vacuum at 80 ℃.
Preferably, in the step (2), the ratio of the ethanol to the 3-Aminopropyltriethoxysilane (APTES) is 10mL:0.5mL; in the step (3), the dosage ratio of the trialdehyde phloroglucinol to the glacial acetic acid to the 1,4-dioxane is 5mg:0.5mL:2mL; in the step (3), the mass ratio of Tp to APTES-MXene is 1:10.
the invention relates to an MXene-COF composite catalyst prepared by the preparation method.
The invention relates to an application of MXene-COF composite catalyst in the aspect of photocatalytic hydrogen production. Preferably, the photocatalytic reaction conditions are: under the irradiation of visible light of a xenon lamp at 300W +/-50W, ascorbic acid is used as a sacrificial agent to carry out photocatalytic hydrogen production.
The invention has the beneficial effects that: according to the invention, COF with excellent visible light capturing capability and MXene with excellent conductivity are connected through covalent bonds, and the conduction and hydrogen evolution capability of photo-charges are enhanced by the covalent bonds. COF and MXene are subjected to in-situ compounding through covalent bonds to form a hybrid material with a heterostructure, the hybrid material can be used as a catalyst for photocatalytic hydrogen production, has excellent hydrogen production efficiency and good circulation stability, and realizes efficient utilization of hydrogen production by hydrolysis.
Drawings
FIG. 1 shows different proportions of MXene-COF and physical mixed material MXene synthesized by the catalyst of the invention: the effect of COF (1:3) on photocatalytic hydrogen production is compared;
FIG. 2 is a powder X-ray diffraction Pattern (PXRD) of MXene-COF synthesized by the catalyst of the present invention, CHO-MXene, COF and MXene-COF (1:3), respectively;
FIG. 3 shows the nitrogen desorption isotherms at 77K for MXene-COF synthesized according to the present invention, CHO-MXene, COF and MXene-COF (1:3).
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The concentration of glacial acetic acid used in the following examples was 6mol/L.
Example 1: preparing a composite catalyst MXene-COF with photocatalytic hydrogen production performance (the mass ratio of MXene to COF is 1:2)
A preparation method of MXene-COF composite catalyst comprises the following steps:
(1) Under the condition of 35 ℃ water bath, 1g of Ti 3 AlC 2 Mixing and stirring powder (sold in the market), 1g LiF and HCl solution (9 mol/L,20 mL) for reaction for 24 hours, and centrifuging to remove HF to obtain MXene nanosheets;
(2) Modifying the MXene nanosheet obtained in the step (1) by using APTES, namely ultrasonically mixing the MXene nanosheet with 80mL of ethanol uniformly, dropwise adding a mixed solution of 10mL of ethanol and 0.5mL of 3-Aminopropyltriethoxysilane (APTES) into the mixed solution of MXene and ethanol, and stirring the obtained reaction solution on a magnetic stirrer for 6 hours at the rotating speed of 350rpm to form APTES-MXene;
(3) Adding 5mg of trialdehyde phloroglucinol, 0.5mL of glacial acetic acid and 2mL of 1, 4-dioxane into 50mg of APTES-MXene obtained in the step (2), performing freeze-pumping circulation for three times through liquid nitrogen, and reacting for 1h under a vacuum condition to obtain functionalized CHO-MXene;
(4) Reacting trialdehyde phloroglucinol and p-phenylenediamine with Schiff base to generate pure COF, uniformly mixing the trialdehyde phloroglucinol and the p-phenylenediamine according to the calculated mass ratio, mixing 10mg of CHO-MXene obtained in the step (3) with the uniformly mixed trialdehyde phloroglucinol and p-phenylenediamine according to the mass ratio of the CHO-MXene to the generated COF of 1:2, adding the mixture into a heat-resistant glass tube, adding 0.5mL of glacial acetic acid, 1.5mL of 1, 4-dioxane and 1.5mL of mesitylene, performing ultrasonic mixing uniformly, and performing freeze-pumping circulation on liquid nitrogen for three times to realize reaction at 120 ℃ under vacuum condition for 72 hours;
(5) And (3) primarily cleaning the initial product obtained in the step (4) by using 20mL of methanol and acetone each time, sequentially performing Soxhlet extraction and purification by using ethanol, tetrahydrofuran and dichloromethane, performing vacuum drying at 80 ℃ for 12h, and grinding to obtain MXene-COF (1:2) reddish brown solid powder.
Example 2: preparing the composite catalyst MXene-COF (the mass ratio is 1:3) with the photocatalytic hydrogen production performance
The experimental procedure is the same as that of example 1, except that CHO-MXene, mixed trialdehyde phloroglucinol and p-phenylenediamine are mixed according to the proportion of 1:3, and MXene-COF (1:3) reddish brown solid powder is obtained through reaction and grinding.
Example 3: preparing the composite catalyst MXene-COF (the mass ratio is 1:4) with the photocatalytic hydrogen production performance
The preparation method is consistent with the example 1, except that CHO-MXene is mixed with the mixed trialdehyde phloroglucinol and p-phenylenediamine according to the proportion of 1:4, and MXene-COF (1:4) reddish brown solid powder is obtained through reaction and grinding.
Example 4: preparing the composite catalyst MXene-COF (the mass ratio is 1:5) with the photocatalytic hydrogen production performance
The preparation method is consistent with the example 1, except that CHO-MXene is mixed with the mixed trialdehyde phloroglucinol and p-phenylenediamine according to the proportion of 1:5, and MXene-COF (1:5) reddish brown solid powder is obtained through reaction and grinding.
Example 5: preparing a composite catalyst MXene-COF with photocatalytic hydrogen production performance (mass ratio of 1
The preparation method is consistent with the example 1, except that CHO-MXene is mixed with the mixed trialdehyde phloroglucinol and p-phenylenediamine according to the proportion of 1.
The application example is as follows:
15mg of the composite catalysts prepared in examples 1, 2, 3, 4, and 5, 62.4mL of deionized water and 0.6mL of an aqueous chloroplatinic acid solution were added to a photocatalytic reactor, photo-reduction was performed for 15 minutes under full spectrum light, 140mg of ascorbic acid as a sacrificial agent was added, photocatalytic hydrogen production was performed under the irradiation of 300W visible light (with a filter) from a xenon lamp, photocatalytic hydrogen production amounts of examples 1, 2, 3, 4, and 5 were measured, differences in hydrogen production amounts of composite catalysts of different proportions were observed, and a composite catalyst having an optimum hydrogen production amount was selected.
Comparative example 1: adding 15mg of MXene, 62.4mL of deionized water and 0.6mL of chloroplatinic acid aqueous solution into a photocatalytic reactor, carrying out photoreduction for 15 minutes under full-spectrum light, adding 140mg of ascorbic acid serving as a sacrificial agent, carrying out photocatalytic hydrogen production under the irradiation of 300W visible light (with a filter) of a xenon lamp, and observing the photocatalytic hydrogen production performance of pure MXene.
Comparative example 2: adding 15mg COF, 62.4mL deionized water and 0.6mL chloroplatinic acid aqueous solution into a photocatalytic reactor, carrying out photoreduction for 15 minutes under full spectrum light, adding 140mg sacrificial agent ascorbic acid, carrying out photocatalytic hydrogen production under the irradiation of 300W visible light (with a filter) of a xenon lamp, and observing the photocatalytic hydrogen production performance of pure COF.
Comparative example 3: 15mg of physically mixed MXene: COF (1:3) and 62.4mL deionized water and 0.6mL chloroplatinic acid aqueous solution were added to a photocatalytic reactor, photo-reduced for 15 minutes under full spectrum light, added with 140mg sacrificial ascorbic acid, photo-catalytically produced hydrogen under xenon 300W visible light (plus filter) illumination, and observed for physically mixed MXene: the photocatalytic hydrogen production performance of COF.
FIG. 1 is a comparison of hydrogen production of MXene-COF in different proportions with that of comparative example, and it is obvious that MXene-COF (1:3) has the best hydrogen production effect, and the hydrogen evolution rate is 5.74mmol h -1 g -1 The corresponding hydrogen production effect of the catalyst with the physical mixing ratio of 1:3 is 0.95mmol h -1 g -1 The method proves that the covalent bond connection plays an important role in photocatalytic hydrogen production. And the hydrogen production rate of MXene-COF (1:3) is 3.15 times that of pure COF, and the excellent effect of the covalent bond connection of COF and CHO-MXene on photocatalytic hydrogen production is also demonstrated.
From the X-ray diffraction pattern of FIG. 2, two main diffraction peaks of MXene-COF at 2 theta =4.7 ° and 2 theta =61 ° are seen, which correspond to the {100} crystal face of COF and the {110} crystal face of CHO-MXene, respectively, and the successful combination of MXene and COF is confirmed.
FIG. 3 shows the nitrogen adsorption and desorption curves of COF, CHO-MXene and MXene-COF (1:3), and it can be seen that CHO-MXene is type III adsorption curve and MXene-COF (1:3) retains the type I adsorption curve of COF. The specific surface area of pure CHO-MXene is only 42.2m 2 g -1 The specific surface area of the pure COF is 404.45m 2 g -1 The specific surface area of the compounded MXene-COF reaches 484.32m 2 g -1 。
In the present specification, the embodiments are described in a progressive manner, and each embodiment focuses on differences from other embodiments, and the same or similar parts between the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The MXene-COF composite catalyst, the preparation method and the application thereof in photocatalytic hydrogen production are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A preparation method of an MXene-COF composite catalyst is characterized by comprising the following steps:
(1) Preparation of Ti 3 C 2 T x MXene nano-sheet
Mixing Ti 3 AlC 2 Etching the powder by using LiF and HCl solution, stirring and reacting under the water bath condition of 35 +/-2 ℃ until the reaction is complete, and centrifuging to remove the solution to obtain MXene nanosheets;
(2) Modification of MXene nanosheets
Ultrasonically and uniformly mixing the MXene nanosheet obtained in the step (1) with an appropriate amount of solvent ethanol, dropwise adding a mixed solution of ethanol and 3-Aminopropyltriethoxysilane (APTES) into the mixed solution of MXene and ethanol, and fully stirring to form APTES-MXene;
(3) CHO functionalization of APTES-MXene
Mixing trialdehyde phloroglucinol (Tp), glacial acetic acid, 1,4-dioxane and APTES-MXene obtained in the step (2), carrying out freezing-air extraction-unfreezing cycle degassing for at least three times in liquid nitrogen, and reacting for 1-1.5h under a vacuum condition to obtain CHO-MXene;
(4) According to the technical scheme, the method comprises the steps of carrying out Schiff base reaction on trialdehyde phloroglucinol and p-phenylenediamine to generate COF, uniformly mixing the trialdehyde phloroglucinol and the p-phenylenediamine according to the formula amount, uniformly mixing CHO-MXene, trialdehyde phloroglucinol (Tp) and the p-phenylenediamine by taking glacial acetic acid as a catalyst and appropriate amounts of 1,4-dioxane and mesitylene as solvents, carrying out cyclic degassing for at least three times through freezing-air extraction-thawing, reacting for 72-78h at 120 +/-5 ℃ under a vacuum condition, and cooling to room temperature;
(5) And (4) carrying out Soxhlet extraction and purification on the product obtained in the step (4) by using an organic solvent, drying in vacuum, and grinding to obtain the MXene-COF composite catalyst.
2. The method for preparing MXene-COF composite catalyst according to claim 1, characterized in that: in the step (4), the volume ratio of the solvent 1,4-dioxane to mesitylene is 1:1, the dosage of 1,4-dioxane is 1.5mL, and the dosage of glacial acetic acid is 0.5mL.
3. The method for preparing a MXene-COF composite catalyst according to claim 1, characterized in that: in the step (4), the mass ratio of CHO-MXene to COF is 1:2-24.
4. The method for preparing MXene-COF composite catalyst according to claim 1, characterized in that: in the step (4), the mass ratio of CHO-MXene to COF is 1:2-4.
5. The method for preparing MXene-COF composite catalyst according to claim 1, characterized in that: the concentration of glacial acetic acid used in the steps (3) and (4) is 6mol/L.
6. The method for preparing MXene-COF composite catalyst according to claim 1, characterized in that: in the step (5), firstly, methanol and acetone are used for preliminary cleaning, and then ethanol, tetrahydrofuran and dichloromethane are sequentially used for Soxhlet extraction and purification; the drying in the step (5) is vacuum drying at 80 ℃ for 12h.
7. The method for preparing MXene-COF composite catalyst according to claim 1, characterized in that:
in the step (2), the dosage ratio of ethanol to 3-Aminopropyltriethoxysilane (APTES) is 10mL:0.5mL;
in the step (3), the dosage ratio of the trialdehyde phloroglucinol to the glacial acetic acid to the 1,4-dioxane is 5mg:0.5mL:2mL;
in the step (3), the mass ratio of Tp to APTES-MXene is 1:10.
8. an MXene-COF composite catalyst obtained by the production method according to claim 1.
9. An application of the MXene-COF composite catalyst of claim 1 in photocatalytic hydrogen production.
10. Use according to claim 1, characterized in that: the photocatalytic reaction conditions are as follows: under the irradiation of visible light of a xenon lamp 300W +/-50W, ascorbic acid is used as a sacrificial agent to carry out photocatalytic hydrogen production.
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