CN116162090A - Preparation of heptazinyl polymer photocatalyst and application of heptazinyl polymer photocatalyst in photocatalytic decomposition of water to produce oxygen - Google Patents
Preparation of heptazinyl polymer photocatalyst and application of heptazinyl polymer photocatalyst in photocatalytic decomposition of water to produce oxygen Download PDFInfo
- Publication number
- CN116162090A CN116162090A CN202310007006.0A CN202310007006A CN116162090A CN 116162090 A CN116162090 A CN 116162090A CN 202310007006 A CN202310007006 A CN 202310007006A CN 116162090 A CN116162090 A CN 116162090A
- Authority
- CN
- China
- Prior art keywords
- heptazinyl
- polymer
- water
- monomer
- photocatalytic decomposition
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 21
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002841 Lewis acid Substances 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229930192474 thiophene Natural products 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 241000872931 Myoporum sandwicense Species 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000006303 photolysis reaction Methods 0.000 description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001144 powder X-ray diffraction data Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/16—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a preparation method of a heptazinyl polymer photocatalyst and application thereof in photocatalytic decomposition of water to produce oxygen, and belongs to the field of organic polymer semiconductor photocatalysis. According to the invention, the monomer 1, the monomer 2, the Lewis acid and the solvent are mixed and reacted in inert atmosphere to obtain the heptazinyl polymer, the operation is simple, the reaction condition is mild, the material is easy to synthesize, the obtained polymer can be used for carrying out the reaction of photocatalytic decomposition of water to produce oxygen by taking water as an oxygen source and light as an energy source, and the thiophene structure is introduced into the structure, so that the photocatalytic decomposition of water to produce oxygen without a cocatalyst can be realized, and the method has a certain application prospect.
Description
Technical Field
The invention belongs to the technical field of organic polymer semiconductor photocatalysis, and particularly relates to preparation of a heptazine-based polymer photocatalyst and application of the heptazine-based polymer photocatalyst in photocatalytic decomposition of water to produce oxygen.
Background
With the continuous development of industrial level in China, the problem of energy shortage is increasingly prominent, and the development of clean energy sources, such as wind energy, solar energy and the like, is scheduled. Among them, the solar photocatalytic decomposition of water into hydrogen and oxygen and the conversion of solar energy into chemical energy for storage have been paid attention. The technology of photolysis of water to produce oxygen refers to the process of forming photo-generated charges in the catalyst under the action of light, separating the photo-generated charges to form holes and electrons, and oxidizing water by the holes to produce oxygen. However, in the process, the photolysis water is subjected to oxygen generation, the kinetics are slow, the improvement of the photolysis water efficiency is restricted, the method is a great challenge at present, and the improvement of the oxidation capacity of a catalyst and the electronic circulation process are key to the improvement of the photolysis water oxygen generation efficiency.
Disclosure of Invention
The invention aims to provide a preparation and application of a heptazinyl polymer photocatalyst, which utilizes sulfur on a thiophene skeleton to promote the adsorption of the catalyst and water, so that the oxidation capacity and the electron circulation process of the catalyst are improved, and the photocatalytic decomposition of water to produce oxygen under the condition of no intervention of a cocatalyst is realized. The method is simple in synthesis and easy to operate, has excellent catalytic effect on decomposing water to produce oxygen by photocatalysis, and has potential application value.
In order to achieve the above purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to protect a heptazinyl polymer, which is prepared by mixing and reacting a monomer 1, a monomer 2, lewis acid and a solvent under an inert atmosphere.
Further, the molar ratio of the monomer 1 to the monomer 2 is 1 (1-6). The monomer 1 is trichloroheptazine, and the monomer 2 is any one of thiophene, 2' -bithiophene and 2,2':5',2' ' -trithiophene.
Further, the molar ratio of the monomer 1 to the Lewis acid is 1 (1-5). The Lewis acid is AlCl 3 。
Further, the solvent is any one of dichloromethane and dichloroethane.
Further, the inert atmosphere includes any one of nitrogen and argon.
Further, the reaction temperature is 35-90 ℃ and the reaction time is 1-3 days.
The second purpose of the invention is to protect the application of the heptazinyl polymer, namely, the obtained heptazinyl polymer is used as a photocatalyst to carry out photocatalytic decomposition water oxygen production reaction in a water-sacrificial agent system under the condition of no cocatalyst.
Further, the sacrificial agent is AgNO 3 、FeCl 3 、NaIO 3 Any one of the following.
Further, the temperature of the reaction for decomposing water into oxygen by photocatalysis is 10-25 ℃ and the time is 30-60 min.
Compared with the prior art, the invention has the following advantages:
(1) The invention discloses a preparation method of a heptazinyl polymer photocatalyst, which utilizes the characteristic of sulfur in thiophene to promote the adsorption of the catalyst and water, thereby improving the oxidation capacity of the catalyst and the electronic circulation process and realizing the photocatalytic decomposition of water to produce oxygen under the condition of no cocatalyst.
(2) The invention has simple synthesis, low cost and easy operation, and the obtained polymer has good catalytic effect on decomposing water to produce oxygen by photocatalysis and has potential application value.
Drawings
FIG. 1 is a schematic illustration of the reaction of the present invention to prepare a heptazinyl polymer.
FIG. 2 is a powder XRD pattern of the heptazinyl polymer prepared in examples 1-3.
FIG. 3 is a FI-IR diagram of the heptazinyl polymer prepared in examples 1-3.
FIG. 4 is an XPS plot of the heptazinyl polymers prepared in examples 1-3.
FIG. 5 is an SEM image of the heptazinyl polymers (a-c) prepared in examples 1-3.
FIG. 6 is a graph showing the comparative activity of the heptazinyl polymers prepared in examples 1-3 in photocatalytic decomposition of water to oxygen.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1 preparation of heptazinyl Polymer TP-1
To a round bottom flask was added trichloroheptazine (220 mg,0.78 mmol), aluminum trichloride (422 mg,3.17 mmol), thiophene (197 mg,2.34 mmol) and dichloroethane (5 mL) and reacted 48 h under argon heated to 90 ℃. Then cooled to room temperature, ice water was added to a round bottom flask, stirred, filtered, and purified 48 h with THF in a soxhlet extractor, and finally dried in vacuo at 100 ℃ to give heptazinyl polymer TP-1.
Example 2 preparation of heptazinyl Polymer TP-2
To a round bottom flask was added heptazine trichloride (220 mg,0.78 mmol), aluminum trichloride (422 mg,3.17 mmol), 2' -bithiophene (388 mg,2.34 mmol) and dichloroethane (5 mL), and the reaction was heated to 90℃under argon to 48 h. Then cooled to room temperature, ice water was added to the round bottom flask, stirred, filtered, and purified 48 h with THF in a soxhlet extractor, and finally dried in vacuo at 100 ℃ to give heptazinyl polymer TP-2.
EXAMPLE 3 preparation of heptazinyl Polymer TP-3
To a round bottom flask was added trichloroheptazine (220 mg,0.78 mmol), aluminum trichloride (422 mg,3.17 mmol), 2':5',2 "-trithiophene (580 mg,2.34 mmol) and dichloroethane (5 mL), and the mixture was heated to 90℃under argon to react 48 h. Then cooled to room temperature, ice water was added to the round bottom flask, stirred, filtered, and purified 48 h with THF in a soxhlet extractor, and finally dried in vacuo at 100 ℃ to give heptazinyl polymer TP-3.
Fig. 2 is an XRD pattern of the prepared heptazinyl polymer. As can be seen, the polymers are amorphous structures.
FIG. 3 is a FI-IR diagram of the prepared heptazinyl polymer. 800-cm in the figure -1 、~1370 cm -1 And 1600-1600 cm -1 The presence of a heptazine ring backbone in the polymer is demonstrated by the oscillation peaks of (a).
Fig. 4 is an XPS diagram of the prepared heptazinyl polymer. Peaks in the C1 s spectrum of 284.8, 285.4 and 288.4 eV correspond to C-C, N- (C) in the heptazine ring skeleton respectively 3 And c=n bond; peaks in the N1 s spectrum, namely 398.7 and 400.3 eV, correspond to C=N and N- (C) in the heptazine ring skeleton respectively 3 A key. The results of the C1 s and N1 s spectra indicate the presence of heptazine structures in the polymer. Peaks of 163.8 to 164.9 and eV in the S2 p spectrum correspond to S2 p3/2 and S2 p1/2 of sulfur species on thiophene respectively, so that the existence of a thiophene structure is proved.
Fig. 5 is an SEM image of the prepared heptazinyl polymer. The heptazinyl polymer is shown as a bulk material.
Application examples
50 mg heptazinyl polymer was ultrasonically dispersed in 100 mL water, then transferred to a reactor with 0.16 g FeCl added 3 As a sacrificial agent, the reactor was irradiated with a xenon lamp with a 420 nm cut-off piece under an argon atmosphere, the reaction temperature was controlled at 12 ℃, and the oxygen content generated in the reactor was detected by gas chromatography every 30 min.
FIG. 6 is a graph showing the comparative activity of the prepared heptazinyl polymer in photocatalytic decomposition of water to oxygen. The results in the figure show that the heptazinyl polymer has good activity and stability of photocatalytic decomposition of water to oxygen.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A preparation method of a heptazinyl polymer is characterized in that: mixing the monomer 1, the monomer 2, lewis acid and a solvent in inert atmosphere for reaction to obtain the heptazinyl polymer;
wherein the monomer 1 is trichloroheptazine, and the monomer 2 is any one of thiophene, 2' -bithiophene and 2,2':5',2' ' -trithiophene.
2. The method for preparing a heptazinyl polymer according to claim 1, wherein: the molar ratio of the monomer 1 to the monomer 2 is 1 (1-6).
3. The method for preparing a heptazinyl polymer according to claim 1, wherein: the molar ratio of the monomer 1 to the Lewis acid is 1 (1-5).
4. A process for the preparation of a heptazinyl polymer according to claim 1 or 3, wherein: the Lewis acid is AlCl 3 。
5. The method for preparing a heptazinyl polymer according to claim 1, wherein: the solvent is any one of dichloromethane and dichloroethane.
6. The method for preparing a heptazinyl polymer according to claim 1, wherein: the reaction temperature is 35-90 ℃ and the reaction time is 1-3 days.
7. A heptazinyl polymer prepared by the method of any one of claims 1-6.
8. Use of the heptazinyl polymer prepared by the method of claim 7 for photocatalytic decomposition of water to oxygen, wherein: the heptazinyl polymer is used as a photocatalyst, and under the condition of no catalyst promoter, the water-sacrificial agent system is subjected to photocatalytic decomposition to produce the water oxygen reaction.
9. The use according to claim 8, characterized in that: the sacrificial agent is AgNO 3 、FeCl 3 、NaIO 3 Any one of the following.
10. The use according to claim 8, characterized in that: the temperature of the reaction for decomposing water into oxygen by photocatalysis is 10-25 ℃ and the time is 30-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310007006.0A CN116162090B (en) | 2023-01-04 | 2023-01-04 | Preparation of heptazinyl polymer photocatalyst and application of heptazinyl polymer photocatalyst in photocatalytic decomposition of water to produce oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310007006.0A CN116162090B (en) | 2023-01-04 | 2023-01-04 | Preparation of heptazinyl polymer photocatalyst and application of heptazinyl polymer photocatalyst in photocatalytic decomposition of water to produce oxygen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116162090A true CN116162090A (en) | 2023-05-26 |
| CN116162090B CN116162090B (en) | 2024-06-28 |
Family
ID=86419341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310007006.0A Active CN116162090B (en) | 2023-01-04 | 2023-01-04 | Preparation of heptazinyl polymer photocatalyst and application of heptazinyl polymer photocatalyst in photocatalytic decomposition of water to produce oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116162090B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010132953A1 (en) * | 2009-05-22 | 2010-11-25 | Commonwealth Scientific And Industrial Research Organisation | Heptaazaphenalene derivatives and use thereof in organic electroluminescent device |
| US20110297925A1 (en) * | 2009-02-17 | 2011-12-08 | Merck Patent Gmbh | Organic electronic device |
| KR101746672B1 (en) * | 2016-03-18 | 2017-06-13 | 주식회사 아루이 | Catalyst for dehydrogenation reaction, the method for synthesizing the same and the decomposition method of form acid using the same |
| CN112961327A (en) * | 2021-02-04 | 2021-06-15 | 中国科学技术大学 | Covalent heptazine polymers, process for their preparation and catalytic process for the production of hydrogen peroxide |
| CN114920908A (en) * | 2022-05-27 | 2022-08-19 | 福州大学 | Organic conjugated polymer containing fluorenone and application thereof in alpha-ketoester synthesis |
-
2023
- 2023-01-04 CN CN202310007006.0A patent/CN116162090B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110297925A1 (en) * | 2009-02-17 | 2011-12-08 | Merck Patent Gmbh | Organic electronic device |
| WO2010132953A1 (en) * | 2009-05-22 | 2010-11-25 | Commonwealth Scientific And Industrial Research Organisation | Heptaazaphenalene derivatives and use thereof in organic electroluminescent device |
| KR101746672B1 (en) * | 2016-03-18 | 2017-06-13 | 주식회사 아루이 | Catalyst for dehydrogenation reaction, the method for synthesizing the same and the decomposition method of form acid using the same |
| CN112961327A (en) * | 2021-02-04 | 2021-06-15 | 中国科学技术大学 | Covalent heptazine polymers, process for their preparation and catalytic process for the production of hydrogen peroxide |
| CN114920908A (en) * | 2022-05-27 | 2022-08-19 | 福州大学 | Organic conjugated polymer containing fluorenone and application thereof in alpha-ketoester synthesis |
Non-Patent Citations (3)
| Title |
|---|
| HAO CHENG等: "Rational Design of Covalent Heptazine Frameworks with Spatially Separated Redox Centers for High-Efficiency Photocatalytic Hydrogen Peroxide Production", ADVANCED MATERIALS, vol. 34, 23 November 2021 (2021-11-23), pages 2107480 * |
| KANG LIU等: "An N-rich metal–organic framework with an rht topology: high CO2and C2hydrocarbons uptake and selective capture from CH4", CHEMISTRY COMMUNICATION, vol. 50, 25 March 2014 (2014-03-25), pages 5031 - 5033 * |
| 王千;高慧敏;任世杰;: "含硫共轭微孔聚合物的制备及光催化水分解性能研究", 高分子通报, no. 06, 13 June 2018 (2018-06-13), pages 62 - 69 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116162090B (en) | 2024-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111203231B (en) | Indium zinc sulfide/bismuth vanadate composite material and preparation method and application thereof | |
| CN110975918B (en) | Indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and preparation method and application thereof | |
| CN113663704B (en) | Indium zinc sulfide/graphite phase carbon nitride composite material and preparation and application thereof | |
| CN111437824B (en) | 3D layered micro-flower structure CoWO4@Bi2WO6Z-type heterojunction composite catalyst and preparation method and application thereof | |
| CN112473717B (en) | Nickel monoatomic/functionalized graphite-phase carbon nitride composite catalyst | |
| CN110756203A (en) | Ni2P/Mn0.3Cd0.7S photocatalytic water splitting composite catalyst and preparation method and application thereof | |
| CN110586183A (en) | Method for preparing TiO by using supercritical carbon dioxide2Method for preparing/COF catalytic material | |
| CN114534783B (en) | Method for preparing single-atom Pt-embedded covalent organic framework photocatalyst and application thereof | |
| CN113351210A (en) | Cu-based catalyst and application thereof in photocatalytic water hydrogen production-5-HMF oxidation coupling reaction | |
| CN112295604B (en) | Metal organic framework nanosheet, preparation method thereof and application of nanosheet in efficient photocatalytic reduction of carbon dioxide | |
| CN112961327B (en) | Covalent heptazine polymers, process for their preparation and catalytic process for the production of hydrogen peroxide | |
| CN114308132A (en) | Protonated CdS-COF-366-M composite photocatalyst and preparation method thereof | |
| CN112547125B (en) | CdS/NiPc photocatalyst for water photolysis and preparation method thereof | |
| CN113680366A (en) | Graphite-phase carbon nitride-based composite photocatalyst and preparation method and application thereof | |
| CN116162090B (en) | Preparation of heptazinyl polymer photocatalyst and application of heptazinyl polymer photocatalyst in photocatalytic decomposition of water to produce oxygen | |
| CN115286757B (en) | Covalent organic framework material based on multi-nitrogen olefin connection and preparation method and application thereof | |
| CN111672541A (en) | Loaded with MoS2Preparation method and application of hollow covalent triazine-based framework material of quantum dot | |
| CN114713264B (en) | Photocatalytic carboxylation conversion of chlorophenols and carbon dioxide on carbon nitride nanotubes | |
| CN114308126B (en) | K (K)4Nb6O17Micron flower/Co-TCPP MOF hydrogen evolution catalyst and preparation method and application thereof | |
| CN116173987A (en) | CdIn 2 S 4 /CeO 2 Heterojunction photocatalyst, preparation method and application thereof | |
| CN115532298A (en) | Preparation method of diatom cluster photocatalyst | |
| CN111871462B (en) | Iron-cobalt organic catalyst, preparation method thereof and CO conversion method thereof 2 Use of benzazepine for the synthesis of benzazepine | |
| CN117986509B (en) | Flower-shaped COF-based photocatalyst and preparation method and application thereof | |
| CN115121238B (en) | TiO (titanium dioxide) 2 nanotube/Ti 3 C 2 Preparation method and application of ultrathin nano-sheet composite photocatalyst | |
| CN115838471B (en) | Preparation of triazole nitrogen-based polymer and application of triazole nitrogen-based polymer in photocatalytic reaction |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |