CN115646545A - Preparation of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material in photocatalytic total water decomposition - Google Patents
Preparation of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material in photocatalytic total water decomposition Download PDFInfo
- Publication number
- CN115646545A CN115646545A CN202211539811.XA CN202211539811A CN115646545A CN 115646545 A CN115646545 A CN 115646545A CN 202211539811 A CN202211539811 A CN 202211539811A CN 115646545 A CN115646545 A CN 115646545A
- Authority
- CN
- China
- Prior art keywords
- covalent organic
- btt
- bpy
- cof
- photocatalytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 125000005605 benzo group Chemical group 0.000 claims description 12
- QEIRCDAYPQFYBI-UHFFFAOYSA-N 6-(5-aminopyridin-2-yl)pyridin-3-amine Chemical compound N1=CC(N)=CC=C1C1=CC=C(N)C=N1 QEIRCDAYPQFYBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 7
- 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 description 7
- 238000005406 washing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000004687 hexahydrates Chemical class 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002715 modification method Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical group C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000011800 void material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 238000010586 diagram Methods 0.000 description 8
- 238000011160 research Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 benzo trithiophene Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of the material in photocatalytic total water decomposition. The covalent organic framework material has the advantages of mild preparation conditions, convenience in operation, definite void structure, ordered pore structure, large specific surface area, high porosity and low density, and has the semiconductor characteristics of absorbing visible light in a certain waveband and exciting photoelectrons. The structural unit of the covalent organic framework has a rigid pi-shaped framework and a plurality of reaction sites, and NaBH is utilized 4 The solution loads Pt on a photocatalytic material which generates H by taking water as a reactant through photocatalytic decomposition while utilizing solar energy without adding a sacrificial agent 2 And O 2 The method has great potential.
Description
Technical Field
The invention belongs to the field of material preparation and photocatalytic organic synthesis of new energy materials, and mainly relates to a synthetic scheme of a bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of the same in photocatalytic total water decomposition.
Background
With the increasing awareness of energy demand and environmental protection, covalent organic framework materials have become a hot point of research in recent scientific communities since the new century. The application of the covalent organic framework material in the aspect of photocatalytic hydrogen production is widely researched, but the research on photocatalytic total water decomposition without a sacrificial agent is less, and based on the research, the invention researches a novel bipyridyl group-connected benzotrithienyl covalent organic framework material for photocatalytic total water decomposition.
The terphenyl group covalent organic framework material connected by the bipyridyl group prepared by the invention is a covalent organic framework connected by imine bonds formed by condensation of aldehyde groups and amino groups, has good solvent stability and thermal stability, unique photoelectric property, good light absorption capacity, proper band gap width and band structure, meets the thermodynamic condition of photocatalytic total decomposition of water, and can catalytically decompose water into H under visible light 2 And O 2 The clean energy has great significance for solving the energy problem of the earth. Deserves continuous research.
Disclosure of Invention
The invention utilizes a solvothermal method to prepare a novel bipyridyl group-connected benzotrithienyl covalent organic framework material under relatively mild conditions, and uses NaBH 4 Pt is loaded on the photocatalytic material by the solution, and the covalent organic photocatalytic material prepared by the method is Pt @ BTT-BPY-COF. Catalytic decomposition of water to H in the visible range without the use of a sacrificial agent 2 And O 2 。
In order to achieve the purpose, the invention adopts the following technical scheme:
a benzo trithiophene covalent organic photocatalytic material connected with bipyridyl radicals is Pt @ BTT-BPY-COF, and the monomers for synthesizing a covalent organic framework are benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridyl; pt is modified on a covalent organic framework material BTT-BPY-COF by adopting a post-functional modification method.
A preparation method of a bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material comprises the following steps: synthesizing benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridine into a bipyridyl group-connected benzotrithienyl covalent organic framework material BTT-BPY-COF by adopting a solvothermal method; the Pt @ BTT-BPY-COF is prepared by modifying metal Pt on a covalent organic framework material BTT-BPY-COF by adopting a post-functional modification method, and the Pt source used for 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, quickly freezing and unfreezing 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 from room temperature to 120 ℃, preserving heat for 3 days, cooling to room temperature, filtering, washing and drying to obtain the product.
Further, the mass ratio of benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridine was 2:3.
further, the mixed solvent is mesitylene and dioxane, and the volume ratio of the mesitylene to the dioxane is 1:1.
further, the concentration of acetic acid used is 3 to 6M.
Further, the method for post-functionally modifying Pt specifically comprises the following steps: mixing a covalent organic framework material BTT-BPY-COF with chloroplatinic acid hexahydrate and methanol, performing ultrasonic treatment, stirring for 1.5 to 3 hours, performing rotary evaporation on the stirred solution, and adding methanol and NaBH at a low temperature of-18 ℃ into the obtained powder 4 And continuously stirring the solution for 2 to 6h, and washing to obtain Pt @ BTT-BPY-COF.
The application comprises the following steps: the terphenyl covalent organic photocatalytic material Pt @ BTT-BPY-COF connected with the bipyridyl group is used for photocatalytic total decomposition of water driven by visible light.
The invention has the beneficial effects that:
1) The invention uses a solvothermal method to carry 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 to obtain a novel bisthiophene group-connected benzotrithiophenyl covalent organic framework material.
2) The synthesis method has simple process conditions and operation and strong repeatability; the used chemical reagents and equipment are reasonable in price, easy to obtain, high in applicability, high in industrial application value and easy to popularize and utilize.
3) The covalent organic framework prepared by the invention is a crystalline polymer, is a crystalline porous material which is connected by covalent bonds and has a periodic network structure, has a definite void structure, an ordered pore structure and a larger specific surface area (can reach 145.2873 m) 2 (g), uniform pore size distribution (the pore size distribution is between 1 to 3 nm), and the semiconductor has the semiconductor characteristics of absorbing visible light with a certain wave band and exciting photoelectrons. The invention selects two monomers with bipyridyl group and thiophene group, the formed imine bond has hydrolysis capability, the photocatalysis efficiency is improved together with the protonation of bipyridyl monomer, the structural unit of the covalent organic framework has a rigid pi-shaped framework and a plurality of reaction sites, the synergistic interaction of a plurality of active sites effectively promotes the separation and transfer of photo-generated charges, the photocatalysis performance is improved, and NaBH is utilized 4 The solution loads Pt on a photocatalytic material which generates H by taking water as a reactant through photocatalytic decomposition while utilizing solar energy without adding a sacrificial agent 2 And O 2 The method has great potential in the aspect.
Drawings
FIG. 1: a structural unit diagram of BTT-BPY-COF in example 1;
FIG. 2 is a schematic diagram: x-ray powder diffractogram of BTT-BPY-COF in example 1;
FIG. 3: fourier transform Infrared Spectrum of BTT-BPY-COF in example 1;
FIG. 4: scanning electron micrograph of BTT-BPY-COF in example 1;
FIG. 5 is a schematic view of: n at 77K of BTT-BPY-COF in example 1 2 Adsorption and desorption isotherm curves;
FIG. 6: pore size distribution of BTT-BPY-COF in example 1;
FIG. 7: scanning electron micrograph of Pt @ BTT-BPY-COF in example 2;
FIG. 8: photocatalytic total hydrolysis performance diagram of Pt @ BTT-BPY-COF in example 3;
FIG. 9: photocatalytic full-hydrolytic property cycle chart of 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 and understandable, the present invention is further described in detail below with reference to 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 involved in the embodiments of the present invention described below may be combined as long as they do not conflict with each other.
(1) A synthetic method of a bipyridyl group-connected benzotrithienyl covalent organic framework material BTT-BPY-COF comprises the following steps:
adding benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde (BTT) and 5,5 '-diamino-2, 2' -Bipyridine (BPY) into a mixed solution of mesitylene and dioxane, adding an acetic acid solution as a catalyst, sealing a solution system by using flame, placing the solution system in an oven at 120 ℃ for reaction for 3 days, and filtering, washing and drying to obtain the covalent organic framework material BTT-BPY-COF.
(2) The synthesis method of Pt @ BTT-BPY-COF comprises the following steps:
covalent organic framework materials BTT-BPY-COF and chloroplatinic acid hexahydrate (H) 2 PtCl 6 ▪6H 2 O) and methanol are mixed, ultrasonic treatment is carried out, the mixture is stirred for 1.5 to 3 hours, the stirred solution is subjected to rotary evaporation, and methanol and NaBH at the temperature of-18 ℃ are added into the obtained powder 4 And continuously stirring the solution for 2 to 6h, and washing to obtain Pt @ BTT-BPY-COF.
(3) Application of Pt @ BTT-BPY-COF in photocatalytic total water decomposition:
putting a catalyst Pt @ BTT-BPY-COF and deionized water into a reactor, keeping a reaction system in a vacuum state, stirring the reaction system, controlling the reaction temperature to be about 20 ℃, and carrying out photocatalytic total decomposition on water by using a 300W xenon lamp with a 420nm cutoff filter as a light source. Gas production was monitored using gas chromatography.
Example 1
A synthetic method of a bipyridyl group-connected benzotrithienyl covalent organic framework material BTT-BPY-COF comprises the following specific synthetic 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 about 5 mL, length 20 cm, diameter 1 cm), 0.5 mL of mesitylene and 0.5 mL of dioxane were added and sonicated for 20 minutes to disperse uniformly, and then 0.1 mL of 6M acetic acid solution was added. The Pyrex tube was then snap 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. And (3) carrying out suction filtration to collect precipitates, washing the precipitates with dichloromethane, acetone and tetrahydrofuran respectively for three times, and carrying out vacuum drying at 60 ℃ overnight to obtain solid powder BTT-BPY-COF. FIGS. 1 to 6 are respectively a structural unit diagram, an X-ray powder diffraction diagram, a Fourier transform infrared spectrogram, a scanning electron microscope diagram and N under the condition of 77K of BTT-BPY-COF 2 Adsorption and desorption isotherm curves and pore size distribution maps.
Example 2
The synthesis method of the Pt @ BTT-BPY-COF comprises the following specific synthesis steps:
will covalently organicPutting a mixed solution of BTT-BPY-COFs (30 mg), 10mg/mL chloroplatinic acid solution (90 mu L) and methanol (3 mL) in a round-bottom flask for ultrasonic treatment for 20min, then putting the mixed solution on a magnetic stirrer for stirring for 1.5h, carrying out rotary evaporation on the stirred solution to obtain BTT-BPY-COF containing Pt metal ions, adding methanol (3 mL) at the temperature of-18 ℃ and 1.5M NaBH into the obtained powder 4 Stirring the mixed solution for 2h, washing with a large amount of deionized water, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain NaBH (1 mL) 4 The content of Pt in the reduced Pt @ BTT-BPY-COF is theoretically calculated to be 1.0 wt%. FIG. 7 is a scanning electron microscope photograph of Pt @ BTT-BPY-COF, which shows that the structure of BTT-BPY-COF is not destroyed after Pt is loaded, and the structure of BTT-BPY-COF is a hollow rod-like structure formed by stacking nanowires before and after the loading of BTT-BPY-COF.
Example 3
The application of a covalent organic framework material Pt @ BTT-BPY-COF in photocatalytic total water decomposition comprises the following specific steps:
weighing 20mg Pt @ BTT-BPY-COF, adding 50 mL deionized water, stirring and mixing uniformly, carrying out ultrasonic treatment on the mixture in an ultrasonic machine for 20min, and putting the mixture into a quartz glass reactor. The performance of Pt @ BTT-BPY-COF total decomposition water is tested by three times of vacuum pumping, 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 gas components after the photocatalytic reaction by using gas chromatography. FIG. 8 is a graph of photocatalytic total water splitting performance of Pt @, BTT-BPY-COF, from which it can be seen that the amounts of hydrogen and oxygen generated after four hours are 2.28. Mu. Mol and 1.10. Mu. Mol, and the molar ratio is about 2: FIG. 9 is a diagram of photocatalytic total decomposition water cycle performance of Pt @ BTT-BPY-COF, one hour is adopted as one cycle, and it can be seen from the diagram that the amount of hydrogen and oxygen can still reach 0.70 μmol and 0.24 μmol after eight cycles, and the catalytic activity of the material can be basically maintained.
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. Numerous modifications and alterations of 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 (8)
1. A bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material is characterized in that: the covalent organic photocatalytic material is Pt @ BTT-BPY-COF, and the monomer for synthesizing the covalent organic framework is 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 a covalent organic framework material BTT-BPY-COF by adopting a post-functional modification method.
2. The method for preparing a bipyridyl-group-linked benzotrithienyl covalent organic photocatalytic material as claimed in claim 1, wherein the method comprises the following steps: synthesizing benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridine into a bipyridine group-connected benzo trithiophene group covalent organic framework material BTT-BPY-COF by adopting a solvothermal method; the Pt @ BTT-BPY-COF is prepared by modifying metal Pt on a covalent organic framework material BTT-BPY-COF by adopting a post-functional modification method, and the source of Pt used for post-functional modification is chloroplatinic acid hexahydrate.
3. The method of claim 2, wherein: 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, quickly freezing and unfreezing 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 from room temperature to 120 ℃, preserving heat for 3 days, cooling to room temperature, filtering, washing and drying to obtain the product.
4. The production method according to claim 2 or 3, characterized in that: the mass ratio of benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde and 5,5 '-diamino-2, 2' -bipyridine was 2:3.
5. the method of claim 3, wherein: the mixed solvent is mesitylene and dioxane, and the volume ratio of the mesitylene to the dioxane is 1:1.
6. the method of claim 3, wherein: the concentration of the acetic acid is 3-6M.
7. A method of making according to claim 2, wherein: the method for post-functionally modifying Pt specifically comprises the following steps: mixing a covalent organic framework material BTT-BPY-COF with chloroplatinic acid hexahydrate and methanol, performing ultrasonic stirring for 1.5 to 3 hours, performing rotary evaporation on the stirred solution, and adding methanol and NaBH at the temperature of-18 ℃ into the obtained powder 4 The solution is stirred for 2 to 6 hours and washed to obtain Pt @ BTT-BPY-COF.
8. Use of the bipyridyl group-linked benzotrithienyl covalent organic photocatalytic material of claim 1 in visible light-driven photocatalytic total decomposition water without a sacrificial agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211539811.XA CN115646545A (en) | 2022-12-03 | 2022-12-03 | Preparation of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material in photocatalytic total water decomposition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211539811.XA CN115646545A (en) | 2022-12-03 | 2022-12-03 | Preparation of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material in photocatalytic total water decomposition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115646545A true CN115646545A (en) | 2023-01-31 |
Family
ID=85017517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211539811.XA Pending CN115646545A (en) | 2022-12-03 | 2022-12-03 | Preparation of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material in photocatalytic total water decomposition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115646545A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328845A (en) * | 2023-03-16 | 2023-06-27 | 兰州大学 | Pt unit point catalyst for olefin hydrosilylation and preparation method thereof |
| CN116948123A (en) * | 2023-08-07 | 2023-10-27 | 广东工业大学 | Alkynyl functionalized COF material, free radical COF material with strong electron donor-acceptor structure, and preparation method and application thereof |
| CN117430770A (en) * | 2023-12-21 | 2024-01-23 | 四川大学 | Light response oxidase material based on COF, and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011025790A1 (en) * | 2009-08-24 | 2011-03-03 | Lumiphore, Inc. | Macrocyclic hopo chelators |
| CN108889334A (en) * | 2018-06-05 | 2018-11-27 | 华中科技大学 | A kind of application containing heteroatomic triazine covalent organic frame material in photocatalysis |
| CN110157008A (en) * | 2019-06-25 | 2019-08-23 | 哈尔滨理工大学 | A kind of diplopore covalent organic framework material of imines key connecting and its preparation and application |
| CN112156758A (en) * | 2020-09-15 | 2021-01-01 | 清华大学 | Porous material and preparation method and application thereof |
| CN112592474A (en) * | 2020-12-01 | 2021-04-02 | 福州大学 | Benzotriazole covalent organic framework material and preparation method and application thereof |
| CN112642482A (en) * | 2020-12-16 | 2021-04-13 | 福州大学 | Metal-anchored hollow covalent organic framework material and preparation method and catalytic application thereof |
| CN114409862A (en) * | 2022-02-17 | 2022-04-29 | 上海交通大学 | 2,4, 6-trimethylpyridine-based vinyl-bridged two-dimensional covalent organic framework material and preparation method thereof |
| CN114591477A (en) * | 2022-04-15 | 2022-06-07 | 福州大学 | Preparation and application of imine-connected dibenzothiophene sulfone-based covalent organic framework material |
-
2022
- 2022-12-03 CN CN202211539811.XA patent/CN115646545A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011025790A1 (en) * | 2009-08-24 | 2011-03-03 | Lumiphore, Inc. | Macrocyclic hopo chelators |
| CN108889334A (en) * | 2018-06-05 | 2018-11-27 | 华中科技大学 | A kind of application containing heteroatomic triazine covalent organic frame material in photocatalysis |
| CN110157008A (en) * | 2019-06-25 | 2019-08-23 | 哈尔滨理工大学 | A kind of diplopore covalent organic framework material of imines key connecting and its preparation and application |
| CN112156758A (en) * | 2020-09-15 | 2021-01-01 | 清华大学 | Porous material and preparation method and application thereof |
| CN112592474A (en) * | 2020-12-01 | 2021-04-02 | 福州大学 | Benzotriazole covalent organic framework material and preparation method and application thereof |
| CN112642482A (en) * | 2020-12-16 | 2021-04-13 | 福州大学 | Metal-anchored hollow covalent organic framework material and preparation method and catalytic application thereof |
| CN114409862A (en) * | 2022-02-17 | 2022-04-29 | 上海交通大学 | 2,4, 6-trimethylpyridine-based vinyl-bridged two-dimensional covalent organic framework material and preparation method thereof |
| CN114591477A (en) * | 2022-04-15 | 2022-06-07 | 福州大学 | Preparation and application of imine-connected dibenzothiophene sulfone-based covalent organic framework material |
Non-Patent Citations (2)
| Title |
|---|
| LU DAI ET AL.: "Enhancement of Visible-Light-Driven Hydrogen Evolution Activity of 2D π-Conjugated Bipyridine-Based Covalent Organic Frameworks via Post-Protonation", 《ANGEWANDTE》, no. 62, pages 1 - 8 * |
| 杨延: "吡啶基COFs纳米片的制备及可见光催化全解水产氢应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 2, pages 015 - 131 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116328845A (en) * | 2023-03-16 | 2023-06-27 | 兰州大学 | Pt unit point catalyst for olefin hydrosilylation and preparation method thereof |
| CN116948123A (en) * | 2023-08-07 | 2023-10-27 | 广东工业大学 | Alkynyl functionalized COF material, free radical COF material with strong electron donor-acceptor structure, and preparation method and application thereof |
| CN116948123B (en) * | 2023-08-07 | 2024-04-23 | 广东工业大学 | Alkynyl functionalized COF material, free radical COF material with strong electron donor-acceptor structure, and preparation method and application thereof |
| CN117430770A (en) * | 2023-12-21 | 2024-01-23 | 四川大学 | Light response oxidase material based on COF, and preparation method and application thereof |
| CN117430770B (en) * | 2023-12-21 | 2024-02-23 | 四川大学 | Light response oxidase material based on COF, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115646545A (en) | Preparation of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material and application of bipyridyl group-connected benzotrithienyl covalent organic photocatalytic material in photocatalytic total water decomposition | |
| CN107175125B (en) | Activation method of MOFs base oxygen reduction electrocatalyst | |
| CN112592474B (en) | Benzotriazole covalent organic framework material and preparation method and application thereof | |
| CN113087923B (en) | Azine-connected benzotrithienyl covalent organic framework material and preparation method and application thereof | |
| CN113019459B (en) | Titanium dioxide porphyrin-based covalent organic framework composite material and preparation method and application thereof | |
| CN113072672B (en) | Preparation of benzotrithiophene-benzothiazolyl covalent organic framework material and application of benzotrithiophene-benzothiazolyl covalent organic framework material in photocatalytic water decomposition to produce oxygen | |
| CN107899618B (en) | Macrocyclic compound photosensitive dye and titanium dioxide-based hybrid material, preparation method thereof and application thereof in photocatalysis | |
| CN112495421B (en) | Preparation method of nitrogen-doped carbon quantum dot modified nitrogen-rich graphite type carbon nitride photocatalyst | |
| Zeng et al. | Metal-free synthesis of pyridyl conjugated microporous polymers for photocatalytic hydrogen evolution | |
| CN114849785B (en) | Preparation of triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst | |
| CN111939878A (en) | Ternary composite aerogel and preparation method and application thereof | |
| CN113318788A (en) | Cu-NH2Preparation of-MIL-125/TpPa-2 composite material and hydrogen production by photolysis of water | |
| CN115197383A (en) | Thiazolyl covalent organic framework material and application thereof | |
| CN112354545B (en) | Copper sulfide composite potassium tantalate niobate with p-n heterojunction structure and preparation method thereof | |
| CN110227544B (en) | Honeycomb structured porphyrin COP and g-C3N4Synthesis of composite material and application of composite material in aspect of photocatalytic degradation of dye | |
| CN111393663A (en) | Perylene bisimide base coordination polymer, preparation method and application thereof | |
| CN115463667B (en) | Preparation method of composite photocatalytic nitrogen fixation material with iridium loaded by cuprous oxide of different crystal planes | |
| CN116120505A (en) | Halogen-containing pyrenyl covalent organic framework polymer photocatalyst, and preparation method and application thereof | |
| CN114011467B (en) | Mercaptopropionic acid-linked titanium dioxide covalent organic framework composite material and preparation method and application thereof | |
| CN114016076B (en) | Nickel-based metal organic framework material and application thereof in electrocatalytic methanol oxidation | |
| CN114085388B (en) | Covalent organic framework material containing oxadiazole connecting element | |
| CN116217849A (en) | Pyrenyl covalent organic framework polymer photocatalyst, preparation method thereof and application thereof in photocatalytic water splitting hydrogen production | |
| CN115403782A (en) | Two-dimensional metal organic framework material containing sulfur and nitrogen groups, conjugated bimetal organic framework material, and preparation method and application thereof | |
| Song et al. | Fabricating carbon nitride-based 3D/0D intramolecular donor–acceptor catalysts for efficient photoreduction of CO 2 | |
| CN113398968A (en) | MOF-derived TiO2Porous g-C3N4Composite photocatalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |