CN115646545B - Preparation of bipyridine group-connected benzotrithiophene-based covalent organic photocatalytic material and photocatalytic full-decomposition water application thereof - Google Patents
Preparation of bipyridine group-connected benzotrithiophene-based covalent organic photocatalytic material and photocatalytic full-decomposition water application thereof Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a preparation method of a bipyridyl group-connected benzotrithiophene covalent organic photocatalytic material and application of the material in photocatalytic total decomposition of water. The covalent organic framework material has the advantages of mild preparation conditions, convenient operation, definite void structure, ordered pore canal structure, large specific surface area, high porosity and low density, and has the semiconductor characteristics of absorbing visible light with a certain wave band and exciting light electrons. The structural unit of the covalent organic framework has a rigid pi-type framework and a plurality of reaction sites, pt is loaded on a photocatalytic material by utilizing NaBH 4 solution, and the material has great potential in the aspect of generating H 2 and O 2 by photocatalytic decomposition by taking water as a reactant while solar energy is utilized and no sacrificial agent is added.
Description
Technical Field
The invention belongs to the field of material preparation and photocatalysis organic synthesis of new energy materials, and is mainly applied to a synthesis scheme of a benzopyrimidine group connected covalent organic photocatalysis material and application of the material in photocatalysis total decomposition of water.
Background
In the recent century, covalent organic framework materials have become a hot spot of research in recent scientific community, with increasing awareness of energy demand and environmental protection. The application of the covalent organic framework material in the aspect of photocatalytic hydrogen production is widely studied, but the research on photocatalytic total water splitting without a sacrificial agent is less, and based on the application, the invention researches a novel benzo trithiophene covalent organic framework material connected with bipyridyl groups for photocatalytic total water splitting.
The prepared benzopyridyl group-connected covalent organic framework material is a covalent organic framework connected by imine bonds formed by condensing aldehyde groups and amine groups, has good solvent stability and thermal stability, unique photoelectric property and good light absorption capacity, has proper band gap width and energy band structure, meets the thermodynamic condition of photocatalytic total decomposition of water, can catalytically decompose water into clean energy sources such as H 2 and O 2 under visible light, and has great significance for solving the energy problem of the earth. Deserving of researchers.
Disclosure of Invention
The invention prepares a novel benzotrithienyl covalent organic framework material connected with bipyridyl groups by using a solvothermal method under a relatively mild condition, loads Pt on a photocatalytic material by using NaBH 4 solution, and prepares the covalent organic photocatalytic material Pt@BTT-BPY-COF. Water is catalytically decomposed in the visible range without the use of a sacrificial agent to produce H 2 and O 2.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
The covalent organic photocatalytic material is Pt@BTT-BPY-COF, and monomers for synthesizing covalent organic frameworks are benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridine; pt is modified on the covalent organic framework material BTT-BPY-COF by adopting a post-functional modification method.
A preparation method of a bipyridyl group-connected benzotrithiophene-based covalent organic photocatalytic material, which comprises the following steps: synthesizing a benzo trithiophene-base covalent organic framework material BTT-BPY-COF with a bipyridyl group connected by benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridine by adopting a solvothermal method; and modifying metal Pt on the covalent organic framework material BTT-BPY-COF by adopting a post-functional modification method to prepare Pt@BTT-BPY-COF, wherein a Pt source used for the post-functional modification is chloroplatinic acid hexahydrate.
Further, the preparation method of the covalent organic framework material BTT-BPY-COF specifically comprises the following steps: adding benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde, 5 '-diamino-2, 2' -bipyridine and acetic acid into a mixed solvent, rapidly freezing and thawing a reaction system in a liquid nitrogen bath, vacuumizing for three times until the internal pressure is 0 mbar, sealing, heating the sealed reaction system to 120 ℃ from room temperature, preserving heat for 3 days, cooling to room temperature, and performing suction filtration, washing and drying to obtain the catalyst.
Further, the mass ratio of benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde to 5,5 '-diamino-2, 2' -bipyridine was 2:3.
Further, the mixed solvent is mesitylene and dioxane, and the volume ratio of the mixed solvent is 1:1.
Further, the concentration of acetic acid used is 3-6M.
Further, the method for post-functional modification of Pt specifically includes: and mixing the covalent organic framework material BTT-BPY-COF, chloroplatinic acid hexahydrate and methanol for ultrasonic treatment, stirring for 1.5-3 hours, performing rotary evaporation on the stirred solution, adding low-temperature methanol at-18 ℃ and NaBH 4 solution into the obtained powder, continuously stirring for 2-6 hours, and washing to obtain Pt@BTT-BPY-COF.
Application: the bipyridyl group-connected benzo trithiophene covalent organic photocatalytic material Pt@BTT-BPY-COF is used for photocatalytic total decomposition of water driven by visible light.
The invention has the beneficial effects that:
1) The invention carries out catalytic reaction on benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridine in a mixed solvent of mesitylene and dioxane by a solvothermal method to obtain a novel diphenyl trithiophene-base covalent organic framework material connected with bipyridine groups, the prepared material has more micropore structures, narrower band gap width and proper energy band structure, and after the covalent organic framework material is loaded with metal Pt, photocatalytic total decomposition water-based energy research can be carried out under visible light.
2) The synthesis method has simple process conditions and operation and strong repeatability; the chemical reagent and the equipment used are reasonable in price, easy to obtain, strong in applicability, high in industrial application value and easy to popularize and use.
3) The covalent organic framework prepared by the invention is a crystalline polymer, is a crystalline porous material with a periodic network structure and connected by covalent bonds, has a definite void structure, an ordered pore canal structure and a large specific surface area (which can reach 145.2873m 2/g), has uniform pore size distribution (the pore size distribution is between 1 and 3 nm), and has the semiconductor characteristic of absorbing visible light with a certain wave band and exciting light electrons. According to the invention, two monomers with bipyridine groups and thiophene groups are selected, the formed imine bond has hydrolysis capability, the photocatalytic efficiency is improved together with the protonation of the bipyridine monomers, the structural unit of the covalent organic framework has a rigid pi-shaped framework and a plurality of reaction sites, the synergistic interaction of the plurality of active sites effectively promotes the separation and transfer of photo-generated charges, the photocatalytic performance is improved, the NaBH 4 solution is utilized to load Pt on a photocatalytic material, and the material has great potential in the aspect of generating H 2 and O 2 by photocatalytic decomposition of water serving as reactants while solar energy is utilized and no sacrificial agent is added.
Drawings
Fig. 1: a structural unit diagram of BTT-BPY-COF in example 1;
fig. 2: x-ray powder diffraction pattern of BTT-BPY-COF in example 1;
Fig. 3: fourier transform infrared spectrum of BTT-BPY-COF in example 1;
Fig. 4: scanning electron microscopy of BTT-BPY-COF in example 1;
Fig. 5: n 2 adsorption-desorption isotherms at 77K for BTT-BPY-COF in example 1;
fig. 6: pore size distribution profile of BTT-BPY-COF in example 1;
Fig. 7: scanning electron microscopy of Pt@BTT-BPY-COF in example 2;
fig. 8: photocatalytic full water splitting Performance map for Pt@BTT-BPY-COF in example 3;
Fig. 9: photocatalytic full solution Water Performance cycle chart for Pt@BTT-BPY-COF in example 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention will be described in further detail with reference to the following examples. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined as long as they do not collide with each other.
(1) A synthesis method of a bipyridyl group-connected benzotrithiophene-based covalent organic framework material BTT-BPY-COF comprises the following steps:
Benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde (BTT) and 5,5 '-diamino-2, 2' -Bipyridine (BPY) are added into a mixed solution of mesitylene and dioxane, an acetic acid solution is added as a catalyst, the solution system is sealed by flame and then placed into a baking oven at 120 ℃ for reaction for 3 days, and the covalent organic framework material BTT-BPY-COF is obtained through suction filtration, washing and drying.
(2) The synthesis method of Pt@BTT-BPY-COF comprises the following steps:
And mixing the covalent organic framework material BTT-BPY-COF, chloroplatinic acid hexahydrate (H 2PtCl6▪6H2 O) and methanol, performing ultrasonic treatment, stirring for 1.5-3 hours, performing rotary evaporation on the stirred solution, adding methanol and NaBH 4 solution at the temperature of minus 18 ℃ into the obtained powder, continuously stirring for 2-6 hours, and washing to obtain Pt@BTT-BPY-COF.
(3) Application of Pt@BTT-BPY-COF in photocatalytic total decomposition of water:
The catalyst Pt@BTT-BPY-COF and deionized water are placed into a reactor, a reaction system is in a vacuum state and is stirred, the reaction temperature is controlled to be about 20 ℃, and a 300W xenon lamp with a 420nm cut-off filter is used as a light source to perform photocatalysis full decomposition on water. Gas yield was measured using gas chromatography.
Example 1
A synthesis method of a bipyridyl group-connected benzotrithiophene covalent organic framework material BTT-BPY-COF comprises the following specific synthesis steps:
Benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde (13.22mg,0.04 mmol) and 5,5 '-diamino-2, 2' -bipyridine (11.17 mg,0.06mmol) were placed in a Pyrex tube (volume of about 5mL, length 20 cm, diameter 1 cm), and 0.5mL of mesitylene and 0.5mL of dioxane were added and sonicated for 20 minutes to disperse them uniformly, followed by the addition of 0.1 mL of 6M acetic acid solution. The Pyrex tube was then flash frozen and thawed in a 77K 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. The precipitate was collected by suction filtration, washed three times with dichloromethane, acetone, tetrahydrofuran, and dried under vacuum at 60 ℃ overnight to give solid powder BTT-BPY-COF. FIGS. 1 to 6 are respectively a BTT-BPY-COF structure unit diagram, an X-ray powder diffraction diagram, a Fourier transform infrared spectrogram, a scanning electron microscope diagram, an N 2 adsorption-desorption isothermal curve under 77K condition and a pore diameter distribution diagram.
Example 2
The synthesis method of the Pt@BTT-BPY-COF comprises the following specific synthesis steps:
A mixed solution of a covalent organic framework BTT-BPY-COFs (30 mg), a 10mg/mL chloroplatinic acid solution (90 mu L) and methanol (3 mL) is placed in a round bottom flask and is subjected to ultrasonic treatment for 20min, then the mixed solution is placed on a magnetic stirrer and stirred for 1.5h, the stirred solution is subjected to rotary evaporation to obtain a BTT-BPY-COF containing Pt metal ions, methanol (3 mL) at the temperature of minus 18 ℃ and a 1.5M NaBH 4 solution (1 mL) are added to the obtained powder, the mixed solution is stirred for 2h, washed by a large amount of deionized water and dried in a vacuum drying oven at the temperature of 60 ℃ for 12h, and the Pt@BTT-BPY-COF reduced by NaBH 4 is obtained in a theoretical calculation mode, wherein the Pt content in the Pt@BTT-BPY-COF is 1.0 wt%. FIG. 7 is a scanning electron microscope image of Pt@BTT-BPY-COF, and it can be seen from the image that the structure of the BTT-BPY-COF is not destroyed after Pt is loaded, and the structure of the BTT-BPY-COF is a hollow rod-shaped structure formed by stacking nanowires before and after the loading.
Example 3
The application of the covalent organic framework material Pt@BTT-BPY-COF in photocatalysis total decomposition water comprises the following specific steps:
20mg of Pt@BTT-BPY-COF is weighed, 50mL deionized water is added, stirred and mixed uniformly, and the mixture is subjected to ultrasonic treatment for 20min by an ultrasonic machine and is put into a quartz glass reactor. And (3) carrying out vacuum pumping for three times, irradiating for 4 hours by using a 300W xenon lamp with a 420nm cut-off filter as a light source in a vacuum state, and detecting the gas components after the photocatalytic reaction by using gas chromatography, so as to test the performance of Pt@BTT-BPY-COF total decomposed water. FIG. 8 is a graph of photocatalytic fully-exploded water performance of Pt@BTT-BPY-COF, from which it can be seen that the amount of hydrogen and oxygen produced after four hours is 2.28. Mu. Mol to 1.10. Mu. Mol, with a molar ratio of about 2:1, FIG. 9 is a graph of the photocatalytic total decomposition water cycle performance of Pt@BTT-BPY-COF, wherein one hour is adopted as one cycle, and the graph shows that the amounts of hydrogen and oxygen can still reach 0.70 mu mol and 0.24 mu mol after eight cycles, so that the catalytic activity of the material can be basically maintained.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description should not be deemed to be a limitation on the invention. Many modifications and alternatives to the present invention will be apparent to those of skill in the art upon reading the foregoing description. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (1)
1. The application of a bipyridyl group-connected benzotrithiophene-based covalent organic photocatalytic material in photocatalytic total decomposition water without a sacrificial agent for visible light driving is characterized in that: the covalent organic photocatalytic material is Pt@BTT-BPY-COF, and a solvothermal method is adopted to synthesize a benzo trithienyl covalent organic framework material BTT-BPY-COF connected with bipyridyl groups by benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridyl; modifying metal Pt on a covalent organic framework material BTT-BPY-COF by adopting a post-functional modification method to prepare Pt@BTT-BPY-COF, wherein a Pt source used for the post-functional modification is chloroplatinic acid hexahydrate;
the preparation method of the covalent organic framework material BTT-BPY-COF specifically comprises the following steps: adding benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde, 5 '-diamino-2, 2' -bipyridine and acetic acid into a mixed solvent, rapidly freezing and thawing a reaction system in a liquid nitrogen bath, vacuumizing for three times until the internal pressure is 0 mbar, sealing, heating the sealed reaction system to 120 ℃ from room temperature, preserving heat for 3 days, cooling to room temperature, and performing suction filtration, washing and drying to obtain the catalyst; the mass ratio of benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde to 5,5 '-diamino-2, 2' -bipyridine was 2:3, a step of; the mixed solvent is mesitylene and dioxane, and the volume ratio is 1:1, a step of; the concentration of the acetic acid is 3-6M;
the method for modifying Pt by the post-function specifically comprises the following steps: and mixing the covalent organic framework material BTT-BPY-COF, chloroplatinic acid hexahydrate and methanol for ultrasonic treatment, stirring for 1.5-3 hours, performing rotary evaporation on the stirred solution, adding methanol and NaBH 4 solution at-18 ℃ into the obtained powder, continuously stirring for 2-6 hours, and washing to obtain the Pt@BTT-BPY-COF.
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