CN114985014B - Preparation method and application of Zn-atz@COF-TD composite photocatalytic material - Google Patents
Preparation method and application of Zn-atz@COF-TD composite photocatalytic material Download PDFInfo
- Publication number
- CN114985014B CN114985014B CN202210722126.4A CN202210722126A CN114985014B CN 114985014 B CN114985014 B CN 114985014B CN 202210722126 A CN202210722126 A CN 202210722126A CN 114985014 B CN114985014 B CN 114985014B
- Authority
- CN
- China
- Prior art keywords
- atz
- cof
- reaction
- photocatalytic material
- composite 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.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 37
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 34
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 30
- -1 dicarboxylic acid compound Chemical class 0.000 claims description 29
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- FEHLIYXNTWAEBQ-UHFFFAOYSA-N 4-(4-formylphenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=C(C=O)C=C1 FEHLIYXNTWAEBQ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 17
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 16
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002798 polar solvent Substances 0.000 claims description 14
- 239000001384 succinic acid Substances 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- 150000001299 aldehydes Chemical class 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 238000002156 mixing Methods 0.000 claims description 8
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- AZDOLIXTFBPILY-UHFFFAOYSA-N butanedioic acid;dihydrate Chemical compound O.O.OC(=O)CCC(O)=O AZDOLIXTFBPILY-UHFFFAOYSA-N 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000011258 core-shell material Substances 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000012621 metal-organic framework Substances 0.000 abstract description 9
- 238000004729 solvothermal method Methods 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 239000013310 covalent-organic framework Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000011941 photocatalyst Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract 1
- 238000011946 reduction process Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 12
- 239000011218 binary composite Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000012792 core layer Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 238000002604 ultrasonography Methods 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
Classifications
-
- 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
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of composite photocatalytic materials, and particularly relates to a preparation method and application of a Zn-atz@COF-TD composite photocatalytic material. The catalytic material is a binary core-shell composite material, and the material is formed by wrapping a metal organic framework Zn-atz by a covalent organic framework COF-TD. The composite material is prepared by adopting a solvothermal method, zn-atz is subjected to hydroformylation, and is compounded with COF-TD through imine bonds, and the final material is obtained after washing and drying; the photocatalytic material prepared by the invention has better selectivity and visible light response capability, and still maintains stronger photocatalytic activity after multiple photocatalytic tests. The method has the advantages that no sacrificial agent is needed in the photocatalytic carbon dioxide reduction process, the method is environment-friendly, the problem that the traditional photocatalyst is low in photocatalytic carbon dioxide reduction efficiency due to weak carbon dioxide adsorption capacity is solved, and a new thought and a new method are provided for the research of the binary core-shell type composite catalyst.
Description
Technical Field
The invention belongs to the technical field of composite photocatalytic materials, and particularly relates to a preparation method of a Zn-atz@COF-TD composite photocatalytic material and application of the Zn-atz@COF-TD composite photocatalytic material in photocatalytic carbon dioxide reduction.
Background
Under the background of ' carbon peak, carbon neutralization ' and ' strategic target, the efficient conversion of carbon dioxide generated by the traditional fossil energy combustion into a high value-added chemical product which can be utilized becomes an urgent problem to be solved. Solar energy is a clean renewable energy source, and the main product carbon dioxide generated by burning fossil fuel is converted into hydrocarbon fuel with industrial value by using solar energy, so that the environment-friendly concept of green chemical industry is met, the energy crisis caused by continuous exhaustion of fossil fuel can be further relieved, and the sustainable development strategy under the 'double carbon' background is completely met.
Metal Organic Frameworks (MOFs) have great promise in gas adsorption and catalytic conversion due to their porous structure. The strategy for constructing porous structures is generally to select inorganic building blocks as nodes and rigid organic bridging ligands as linkers, often by chelating various metal ions with the organic building blocks by complexation to form columnar or blocky framework structures. However, MOFs materials are often associated with the disadvantage of poor stability, so it is important to design a metal-organic framework that can exist stably. It was found that 3-amino-1, 2, 4-triazole (Atz) as ligand may tend to form a robust network and that the interaction between the functionalized amino material and the carbon dioxide molecule may enhance the capture capacity of the carbon dioxide gas. Zinc ions are widely used in photoelectrocatalysis due to their good conductivity and rich storage.
Triazinyl covalent organic frameworks (COF-TD) are organic semiconductors with a rigid structure and well-defined crystallization. It has all the advantages that covalent organic frameworks have, for example: large specific surface area, easy structure adjustment, high chemical stability and the like. The limited light absorption range, the fast recombination rate of electron-hole pairs and the poor charge carrier transfer of COFs materials have limited their development in the field of photocatalysis.
Disclosure of Invention
The invention aims to overcome the defects of low carbon dioxide capturing capability, narrow visible light absorption range and low charge carrier transfer rate of the traditional photocatalytic material, and prepare the core-shell binary composite photocatalytic carbon dioxide reduction catalyst with high-efficiency catalytic capability.
In order to solve the problems, the invention provides a preparation method of a Zn-atz@COF-TD core-shell type binary composite material. Through the covalently linked structural units, the composite material has good crystallinity and graded porosity, and the synergistic effect of MOFs and COFs composite materials in heterogeneous catalysis is discussed. A Zn-atz three-dimensional metal organic framework which can exist stably is synthesized by selecting divalent zinc ion salt, 3-amino-1, 2, 4-triazole and dicarboxylic acid compound in a polar solvent/deionized water mixed solution through solvothermal treatment; the COF-TD shell layer is constructed outside the Zn-atz core layer by periodic organic components of 4,4 '-biphenyl dicarboxaldehyde and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine through imine bonds.
In order to achieve the technical purpose, the invention comprises the following specific steps:
(1) Preparing a metal organic framework Zn-atz;
mixing 3-amino-1, 2, 4-triazole, divalent zinc ion salt, a dicarboxylic acid compound, a polar solvent and water, adding into a hydrothermal kettle, performing ultrasonic dispersion uniformly, putting the hydrothermal kettle into an oven for hydrothermal reaction, centrifuging, washing and drying after the reaction to obtain white solid powder; a material marked as Zn-atz; the divalent zinc ion salt comprises basic zinc carbonate or zinc nitrate hexahydrate; the dicarboxylic acid compound includes oxalic acid dihydrate, sodium bicarbonate or succinic acid; the polar solvent comprises methanol or N, N-dimethylformamide;
(2) Preparing an aldehyde Zn-atz precursor;
firstly, mixing o-dichlorobenzene with ethanol to obtain an o-dichlorobenzene/ethanol mixed solution; then mixing the Zn-atz material prepared in the step (1) with a mixed solution of 4,4' -biphenyl dicarboxaldehyde and o-dichlorobenzene/ethanol, adding acetic acid, marking the obtained solution as a mixed solution A, carrying out vacuum pumping treatment after the mixed solution A is uniformly dispersed by ultrasonic, carrying out oil bath reaction under the stirring condition, naturally cooling to room temperature after the reaction, and centrifuging, washing and drying to obtain an aldehyde Zn-atz precursor;
(3) Preparation of Zn-atz@COF-TD core-shell binary composite material (preparation of Zn-atz@COF-TD by solvothermal method):
mixing the aldehyde Zn-atz precursor prepared in the step (2) with 4,4 '-biphenyl dicarboxaldehyde, 4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, mesitylene and 1, 4-dioxane, adding acetic acid, uniformly dispersing by ultrasonic, vacuumizing, putting into an oven for reacting for a period of time, centrifuging, washing and drying to obtain yellow powder, namely the Zn-atz@COF-TD composite photocatalytic material.
Further, in the step (1), the mass ratio of the 3-amino-1, 2, 4-triazole, the divalent zinc ion salt and the dicarboxylic acid compound is (1-10): 1-5): 1; the volume ratio of the polar solvent to the deionized water is (0.1-10): 1; the dosage ratio of the 3-amino-1, 2, 4-triazole to the polar solvent is 0.4g to 20mL; the hydrothermal kettle takes tetrafluoroethylene as a lining; the temperature of the hydrothermal reaction is 120-200 ℃, and the reaction time is 12-72 h.
Preferably, when the divalent zinc ion salt is basic zinc carbonate, the dicarboxylic acid compound is oxalic acid dihydrate, and the polar solvent is methanol, the mass ratio of the 3-amino-1, 2, 4-triazole to the basic zinc carbonate to the oxalic acid dihydrate is 4:1:1; the volume ratio of the methanol to the deionized water is 8:1;
preferably, when the divalent zinc ion salt is zinc nitrate hexahydrate, the dicarboxylic acid compound is sodium bicarbonate, and the polar solvent is N, N-dimethylformamide, the mass ratio of the 3-amino-1, 2, 4-triazole to the zinc nitrate hexahydrate to the sodium bicarbonate is 2:7:1; the volume ratio of the N, N-dimethylformamide to the deionized water is 0.4:1;
preferably, when the divalent zinc ion salt is zinc nitrate hexahydrate, the dicarboxylic acid compound is succinic acid, the polar solvent is N, N-dimethylformamide, the mass ratio of the 3-amino-1, 2, 4-triazole, the zinc nitrate hexahydrate and the succinic acid is 1.35:5:1; the volume ratio of the N, N-dimethylformamide to the deionized water is 0.4:1;
the hydrothermal reaction temperature is 180 ℃ and the time is 48 hours.
Further, in the step (2), the mass ratio of the Zn-atz material to the 4,4' -biphenyl dicarboxaldehyde is (1-10) 1; the o-dichloroThe volume ratio of benzene, ethanol and acetic acid is (1-5) (10) -5 ～5×10 -5 ) The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the acetic acid is (1-5) M; the 4,4' -biphenyl dicarboxaldehyde: the dosage ratio of the o-dichlorobenzene is 0.084g to 20mL; the ultrasonic time is 5-15min; the temperature of the oil bath reaction is 80-90 ℃ and the time is 8-15 h.
Further, in the step (2), the mass ratio of the Zn-atz material to the 4,4' -biphenyl dicarboxaldehyde is 3.6:1; the volume ratio of the o-dichlorobenzene to the ethanol to the acetic acid is 1:1:10 -5 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the acetic acid is 3M; the ultrasonic time is 10min; the temperature of the oil bath reaction is 80 ℃ and the time is 12 hours.
Further, in the step (3), the mass ratio of the aldehyde Zn-atz precursor, 4 '-biphenyl dicarboxaldehyde and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine is (1-5): 1; the volume ratio of the mesitylene to the 1, 4-dioxane is (1-10): 1, a step of; the dosage ratio of the 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine to the 1, 4-dioxane is 0.106g to 2mL; the dosage ratio of the 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine to the acetic acid is 0.106g:0.23mL; the hydrothermal reaction temperature is 80-180 ℃ and the reaction time is 24-72 h.
Further, in the step (3), the mass ratio of the aldehyde Zn-atz precursor, 4 '-biphenyl dicarboxaldehyde and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine is 2.4:0.9:1; the volume ratio of the mesitylene to the 1, 4-dioxane is 6:1, a step of; the temperature of the hydrothermal reaction is 120 ℃, and the reaction time is 72 hours.
Further, in the step (3), the washing is performed by centrifugation three times with tetrahydrofuran and ethanol.
The application is as follows: the Zn-atz@COF-TD composite material prepared by the method is applied to high-selectivity reduction of carbon dioxide into carbon monoxide under the drive of visible light.
The invention has the remarkable effects that:
(1) The invention creatively adopts the hydroformylation Zn-atz precursor, 4 '-biphenyl dicarboxaldehyde and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine for solvothermal reaction, which is the prior literatureNot reported, and the invention limits the mass ratio of the aldehyde Zn-atz precursor, 4 '-biphenyl dicarboxaldehyde and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine to be (1-5): 1; the proportion of the two-component composite material is important to be directly related to the construction of an external COF-TD shell layer of the two-component composite material, if the proportion of 4,4 '-biphenyl dicarboxaldehyde and 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine is too low, a periodic long-range network coating Zn-atz core layer cannot be completely formed, and the stability of the Zn-atz@COF-TD composite material is unfavorable; if the ratio of 4,4 '-biphenyldicarboxaldehyde to 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine is too high, the thickness of the external COF-TD shell layer is greater than 200nm to be optimal, which is unfavorable for the CO of the Zn-atz core layer 2 The capture of gas molecules thereby affects the photocatalytic performance. The present invention introduces a critical improvement in this condition.
(2) The Zn-atz@COF-TD core-shell binary composite material takes Zn-atz as a core, and bridges the COF-TD through imine bonds, so that the high adsorption capacity of Zn-atz to carbon dioxide under low partial pressure is reserved by the compounded Zn-atz@COF-TD, and along with the introduction of the COF-TD, the catalyst is endowed with a larger specific surface area and a proper band gap width, so that the composite material has good photocatalytic activity.
(3) According to the invention, the Zn-atz@COF-TD core-shell binary composite material is prepared by a solvothermal method, a type I heterojunction is constructed, metal zinc ions serve as an active center, a Zn-atz core layer serves as an electron donor, a COF-TD shell layer serves as an electron transfer medium, and the photocurrent transfer efficiency of the composite material is increased, the charge transfer resistance is reduced, and the catalytic activity in a photocatalytic reaction is further improved through a three-stage electron transfer mode of the active center-donor-medium.
(4) The Zn-atz@COF-TD core-shell binary composite photocatalyst constructed by the invention can reduce carbon dioxide in water under the irradiation of visible light, no sacrificial agent exists in the reaction process, and carbon dioxide molecules are converted into fuel gas carbon monoxide with high added value, and the selectivity is close to 100 percent.
Description of the drawings:
FIG. 1 is an XRD pattern of the Zn-atz, COF-TD, zn-atz@COF-TD catalytic material prepared in example 1;
FIG. 2 is an SEM image of Zn-atz, COF-TD, zn-atz@COF-TD catalytic material prepared in example 1;
FIG. 3 is an electrochemical photo-voltaic diagram of Zn-atz, COF-TD, zn-atz@COF-TD catalytic materials prepared in example 1;
FIG. 4 is a graph of carbon dioxide adsorption capacity of the COF-TD, zn-atz@COF-TD catalytic material prepared in example 1;
FIG. 5 is a graph showing the comparison of the photocatalytic carbon dioxide reduction performance of Zn-atz, COF-TD, zn-atz@COF-TD catalytic materials prepared in example 1;
FIG. 6 is a graph showing the photocatalytic carbon dioxide reduction stability test performance of the Zn-atz@COF-TD catalytic material prepared in example 1.
Detailed Description
In order to facilitate understanding of the relevant aspects of the present invention, the present invention will be further described with reference to specific examples, but it should be understood that the scope of application of the present invention is not limited to the following examples.
Example 1:
(1) Preparation of Metal organic frameworks Zn-atz
Sequentially weighing 0.400g of 3-amino-1, 2, 4-triazole, 0.100g of basic zinc carbonate and 0.100g of oxalic acid dihydrate into a hydrothermal kettle with a tetrafluoroethylene lining of 100 mL; respectively adding 20mL of methanol and 2.5mL of deionized water, and uniformly dispersing in an ultrasonic instrument with the power of 1000W for 20 min; carrying out hydrothermal reaction at 180 ℃ for 48 hours, centrifuging, washing with absolute ethyl alcohol for 3 times, and vacuum drying at 60 ℃ to obtain 0.516g white solid powder which is marked as Zn-atz material;
(2) Preparation of aldehyde Zn-atz precursor
Weighing 0.300g of Zn-atz material and 0.084g of 4,4' -biphenyl dicarboxaldehyde, adding the materials into a pressure-resistant bottle containing o-dichlorobenzene/ethanol (1:1, 20mL:20 mL) mixed solution, adding 0.2 mu L of 3M acetic acid as a catalyst, carrying out ultrasonic treatment for 10min, vacuumizing, carrying out oil bath reaction at 80 ℃ for 12h under stirring, naturally cooling, centrifuging, washing with absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 8h to obtain 0.258g of aldehyde Zn-atz precursor;
(3) Preparation of Zn-atz@COF-TD core-shell type binary composite material
The method for preparing Zn-atz@COF-TD by adopting a solvothermal method comprises the following steps of: putting 0.25g of the hydroformylation Zn-atz precursor prepared in the step (2) into a pressure-resistant bottle, weighing 0.095g of 4,4 '-biphenyl dicarboxaldehyde and 0.106g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, using 12mL of mesitylene and 2mL of 1, 4-dioxane as solvents, carrying out ultrasonic dispersion uniformly under the catalysis of 0.230mL of acetic acid, vacuumizing, putting the reaction system into a baking oven at 120 ℃ for reaction for 72 hours, centrifuging, washing 3 times with tetrahydrofuran, washing 3 times with absolute ethyl alcohol, and carrying out vacuum drying at 60 ℃ for 8 hours to obtain 0.327g of yellow powder, and recording as Zn-atz@COF-TD;
the preparation steps of the COF-TD are as follows: the preparation procedure was the same as in step (3) of example 1, except that the hydroformylation Zn-atz precursor was not added; finally, 0.115g of yellow powder was obtained, designated COF-TD.
Example 2:
(1) Preparation of carbonate-modified Zn-atz
Sequentially weighing 0.200g of 3-amino-1, 2, 4-triazole, 0.745g of zinc nitrate hexahydrate and 0.105g of sodium bicarbonate in a hydrothermal kettle with a tetrafluoroethylene lining of 100 mL; respectively adding 10mL of DMF and 25mL of deionized water, and uniformly dispersing in an ultrasonic instrument with the power of 1000W for 20 min; hydrothermal reaction at 180℃for 48h, centrifuging the resulting product, washing with DMF: deionized water (1:1) 3 times, vacuum drying at 80℃to give 0.372g of a white solid powder, designated Zn-atz (NaHCO) 3 )；
(2) Hydroformylation Zn-atz (NaHCO) 3 ) Preparation of the precursor
0.300g Zn-atz (NaHCO) 3 ) And 0.084g of 4,4' -biphenyl dicarboxaldehyde are put into a pressure-resistant bottle, then mixed solution of o-dichlorobenzene/ethanol (1:1, 20mL:20 mL) is added into the pressure-resistant bottle, finally 0.2 mu L of 3M acetic acid is added as a catalyst, ultrasonic treatment is carried out for 10min, vacuum pumping is carried out, oil bath reaction is carried out for 12h at 80 ℃ under the stirring condition, after natural cooling, centrifugation is carried out, absolute ethanol is used for washing for 3 times, and vacuum drying oven drying is carried out at 60 ℃ for 8h, thus obtaining 0.224g of hydroformylation Zn-atz (NaHCO) 3 ) A precursor;
(3)Zn-atz(NaHCO 3 ) Preparation of @ COF-TD core-shell binary composite material
Zn-atz (NaHCO) was prepared by solvothermal method as in example 1 3 ) @ COF-TD: 0.20g of hydroformylation Zn-atz (NaHCO) 3 ) Putting the precursor into a pressure-resistant bottle, weighing 0.095g of 4,4 '-biphenyl dicarboxaldehyde and 0.106g of 4,4' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, using 12mL of mesitylene and 2mL of 1, 4-dioxane as solvents, adding 0.230mL of acetic acid for catalysis, performing ultrasonic dispersion uniformly, vacuumizing, putting into a 120 ℃ oven for reaction for 72h, centrifuging the obtained product, washing 3 times with tetrahydrofuran, washing 3 times with absolute ethyl alcohol, vacuum-drying at 60 ℃ for 8h to obtain 0.283g of light yellow powder, and recording as Zn-atz (NaHCO) 3 )@COF-TD。
Example 3:
(1) Preparation of succinic acid modified Zn-atz
0.200g of 3-amino-1, 2, 4-triazole, 0.745g of zinc nitrate hexahydrate and 0.148g of succinic acid are weighed into a tetrafluoroethylene lining hydrothermal kettle; respectively adding 10mL of DMF and 25mL of deionized water, and uniformly dispersing in an ultrasonic instrument with the power of 1000W for 20 min; carrying out hydrothermal reaction at 180 ℃ for 48 hours, centrifuging and separating the obtained product, washing DMF (dimethyl formamide) with deionized water (1:1) for 3 times, and vacuum drying at 80 ℃ to obtain 0.582g of off-white solid powder which is marked as Zn-atz (succinic acid);
(2) Preparation of aldehyde Zn-atz (succinic acid) precursor
Weighing 0.300g of Zn-atz (succinic acid) and 0.084g of 4,4' -biphenyl dicarboxaldehyde, adding into a pressure-resistant bottle containing o-dichlorobenzene/ethanol (1:1, 20mL:20 mL) mixed solution, adding 0.2 mu L of 3M acetic acid as a catalyst, carrying out ultrasonic treatment for 10min, vacuumizing, carrying out oil bath reaction at 80 ℃ for 12h under stirring conditions, after natural cooling, centrifuging, washing with absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 8h to obtain 0.265g of hydroformylation Zn-atz (succinic acid) precursor;
(3) Preparation of Zn-atz (succinic acid) @ COF-TD core-shell binary composite material
The preparation method of Zn-atz (succinic acid) @ COF-TD was the same as in example 1, weighing 0.25g of the hydroformylation Zn-atz (succinic acid) precursor, placing into a pressure-resistant bottle, weighing 0.095g of 4,4 '-biphenyl dicarboxaldehyde and 0.106g of 4,4' - (1, 3, 5-triazine-2, 4, 6-tri) triphenylamine, using 12mL of mesitylene and 2mL of 1, 4-dioxane as solvents, introducing 0.230mL of acetic acid, dispersing uniformly by ultrasound, vacuumizing, placing into a 120 ℃ oven for reaction for 72 hours, centrifuging, washing 3 times with tetrahydrofuran, washing 3 times with absolute ethanol, and vacuum-drying at 60 ℃ for 8 hours to obtain 0.317g of dark yellow powder, which is recorded as Zn-atz (succinic acid) @ COF-TD.
Performance test:
the invention prepares Zn-atz@COF-TD, zn-atz (NaHCO) respectively by a solvothermal method 3 ) @COF-TD and Zn-atz (succinic acid) @ COF-TD catalytic material. Taking Zn-atz@COF-TD as an example, the following performance test is performed:
(1) Photocatalytic carbon dioxide reduction performance test of Zn-atz@COF-TD core-shell binary composite material
Weighing 0.020g Zn-atz@COF-TD sample in a top-illuminated quartz photo-reaction kettle, adding 100mL deionized water, completely sealing the bottle mouth of the photo-reaction kettle by using a rubber plug, introducing carbon dioxide for 15min by using a needle head, removing air in the photo-reaction kettle, maintaining the whole reaction system under the carbon dioxide atmosphere, setting 20A by using a xenon lamp as a reaction light source, circulating condensed water at 20 ℃ by using the light source current, reacting for 4h, and obtaining a carbon dioxide reduction product of carbon monoxide with the yield of 2.665 mu mol g -1 h -1 。
(2) Photocatalytic carbon dioxide reduction stability test of Zn-atz@COF-TD core-shell binary composite material
After the performance of Zn-atz@COF-TD is measured for 4 hours, argon is introduced for 15 minutes, unreacted carbon dioxide and products in a reaction system are thoroughly discharged, carbon dioxide is introduced for 15 minutes, a cycle experiment is carried out under the same condition as in (4) of the example 1, and the stability of the Zn-atz@COF-TD composite material is tested; after each cycle is completed, the reaction system is thoroughly cleaned by argon so as to eliminate the influence of products generated in the previous cycle; then, the reaction system is continuously cleaned by carbon dioxide for 15min, so that the system is kept under the atmosphere of carbon dioxide, and then the subsequent operation is carried out; a total of 3 cycles of experiments were carried out, the yields of carbon monoxide being 2.122. Mu. Mol g, respectively -1 h -1 、2.983μmol g -1 h -1 、0.832μmol g -1 h -1 。
Figure 1 is an XRD pattern of the three materials prepared. As can be seen from the graph, zn-atz has good crystallinity, while COF-TD has a large packet peak around 20 degrees; the composite material Zn-atz@COF-TD shows the same diffraction peak as the COF-TD at 2.2 degrees, and the diffraction peak same as Zn-atz is reserved at 10.5 degrees, 12.6 degrees and 13.6 degrees, which shows that the composite material has the diffraction peaks of two monomer materials, and the crystal form structure of the monomer is reserved. And no significant shift was found in the main peak, indicating that a higher long range order was maintained.
Fig. 2 is an SEM image of the three materials produced. As can be seen from the figure, zn-atz (b) has a regular tetrahedral structure, each face being very smooth; COF-TD (a) is a pellet with wrinkles on the surface; and the Zn-atz@COF-TD (c)/(d) after compounding is a polyhedron with surface wrinkles, wherein the Zn-atz main body framework structure is clearly visible, the wrapped COF-TD takes Zn-atz as a template for primary growth, a coating cover is evenly coated for vertical growth, and the thickness of a shell layer is about 200nm, so that the Zn-atz is successfully wrapped by the COF-TD, and a core-shell binary structure is formed.
Fig. 3 is an electrochemical photo-voltaic diagram of the prepared photocatalyst. The photocurrent intensity of Zn-atz@COF-TD is obviously superior to that of Zn-atz and COF-TD, which also verifies that Zn-atz@COF-TD has good electron-hole separation efficiency; probably because Zn-atz and COF-TD constitute special heterojunction, in the structure, metal zinc ions serve as active centers, a Zn-atz nuclear layer serves as an electron donor, a COF-TD shell layer serves as an electron transfer medium, a built-in electric field beneficial to carrier transmission is formed through a three-stage electron transfer mode of active center-donor-medium, and photocurrent characteristics of the composite material are improved.
FIG. 4 is a graph of carbon dioxide adsorption capacity versus the COF-TD, zn-atz@COF-TD catalytic material prepared. At P/p0=1.0, the absorption of carbon dioxide by COF-TD and Zn-atz@cof-TD was 4.3cm, respectively 3 g -1 And 39.0cm 3 g -1 Clearly, this indicates that Zn-atz@COF-TD has a more excellent carbon dioxide adsorption capacity than COF-TD; the carbon dioxide absorption capacity is improved by about 10 times, so that the number of carbon dioxide molecules on the surface of the catalyst is greatly improved, and more dioxygen is providedThe carbon-melting molecules are combined with the photo-generated electrons to participate in the reduction reaction; it is speculated that the catalyst increases the carbon dioxide absorption capacity of the catalyst, thereby increasing the CO near the catalytic surface 2 Thereby affecting the surface reaction kinetics and improving the rate of the catalytic reaction.
FIG. 5 is a graph showing the comparison of photocatalytic carbon dioxide reduction performance of the prepared catalyst. The CO yield was calculated using the following formula: yco=co yield/(catalyst amount x reaction time). As can be seen from the graph, the CO yields of Zn-atz, COF-TD and Zn-atz@COF-TD were 0.673. Mu. Mol g, respectively -1 h -1 、1.314μmol g -1 h -1 、2.665μmol g -1 h -1 The yield of the composite material is 4 times higher than that of the monomer Zn-atz and 2 times higher than that of the monomer COF-TD, and the composite material accords with the result obtained by predicting the carbon dioxide adsorption curve. In order to verify the reliability of the test results, 2 repeated experiments were performed on the photocatalytic carbon dioxide reduction performance of Zn-atz@COF-TD under the same conditions, and the test results showed that the CO yield of Zn-atz@COF-TD1 was 2.660. Mu. Mol g -1 h -1 The CO yield of Zn-atz@COF-TD2 was 2.510. Mu. Mol g -1 h -1 The deviation value of the test result is within the experimental error allowance, which indicates that the obtained result is true and reliable.
FIG. 6 is a graph showing the photocatalytic carbon dioxide reduction stability test performance of a Zn-atz@COF-TD catalytic material. In order to confirm the stability of the composite catalyst prepared by the present invention, a cyclic experiment was performed with yields of 2.665. Mu. Mol g, respectively -1 h -1 、2.122μmol g -1 h -1 、2.983μmol g -1 h -1 And 0.832. Mu. Mol g -1 h -1 After 3 runs, the catalytic activity of Zn-atz@COF-TD is kept good, and the catalytic activity of the 4 th experiment is obviously reduced, which indicates that the catalyst can stably exist for more than ten hours.
The above description will enable those skilled in the art to more fully understand the invention, but is not intended to limit it in any way. Accordingly, it will be understood by those skilled in the art that the present invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and technical essence of the invention are included in the protection scope of the invention patent.
Claims (10)
1. The preparation method of the Zn-atz@COF-TD composite photocatalytic material is characterized by comprising the following steps of:
(1) Mixing 3-amino-1, 2, 4-triazole, divalent zinc ion salt, a dicarboxylic acid compound, a polar solvent and deionized water, adding into a hydrothermal kettle, performing ultrasonic dispersion uniformly, putting the hydrothermal kettle into an oven for hydrothermal reaction, centrifuging, washing and drying after the reaction to obtain white solid powder; a material marked as Zn-atz; the divalent zinc ion salt comprises basic zinc carbonate or zinc nitrate hexahydrate; the dicarboxylic acid compound includes oxalic acid or succinic acid dihydrate; the polar solvent comprises methanol or N, N-dimethylformamide;
(2) Firstly, mixing o-dichlorobenzene with ethanol to obtain an o-dichlorobenzene/ethanol mixed solution; then mixing the Zn-atz material prepared in the step (1) with a mixed solution of 4,4' -biphenyl dicarboxaldehyde and o-dichlorobenzene/ethanol, adding acetic acid, marking the obtained solution as a mixed solution A, carrying out vacuum pumping treatment after the mixed solution A is uniformly dispersed by ultrasonic, carrying out oil bath reaction under the stirring condition, naturally cooling to room temperature after the reaction, and centrifuging, washing and drying to obtain an aldehyde Zn-atz precursor;
(3) Mixing the aldehyde Zn-atz precursor prepared in the step (2) with 4,4' -biphenyl dicarboxaldehyde, 4' ' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine, mesitylene and 1, 4-dioxane, adding acetic acid, uniformly dispersing by ultrasonic, vacuumizing, putting into an oven for reacting for a period of time, centrifuging, washing and drying to obtain yellow powder, namely the Zn-atz@COF-TD composite photocatalytic material.
2. The preparation method of the Zn-atz@COF-TD composite photocatalytic material according to claim 1, wherein in the step (1), the mass ratio of the 3-amino-1, 2, 4-triazole to the divalent zinc ion salt to the dicarboxylic acid compound is (1-10): (1-5): 1; the volume ratio of the polar solvent to the deionized water is (0.1-10): 1; the dosage ratio of the 3-amino-1, 2, 4-triazole to the polar solvent is 0.4g:20mL; the hydrothermal kettle takes polytetrafluoroethylene as a lining; the temperature of the hydrothermal reaction is 120-200 ℃, and the reaction time is 12-72 h.
3. The method for preparing a Zn-atz@cof-TD composite photocatalytic material according to claim 2, characterized in that when the divalent zinc ion salt is basic zinc carbonate, the dicarboxylic acid compound is oxalic acid dihydrate, the polar solvent is methanol: the mass ratio of the 3-amino-1, 2, 4-triazole to the basic zinc carbonate to the oxalic acid dihydrate is 4:1:1; the volume ratio of the methanol to the deionized water is 8:1;
when the divalent zinc ion salt is zinc nitrate hexahydrate, the dicarboxylic acid compound is succinic acid, and the polar solvent is N, N-dimethylformamide: the mass ratio of the 3-amino-1, 2, 4-triazole to the zinc nitrate hexahydrate to the succinic acid is 1.35:5:1; the volume ratio of the N, N-dimethylformamide to the deionized water is 0.4:1.
4. The method for preparing the Zn-atz@COF-TD composite photocatalytic material according to claim 2, wherein the hydrothermal reaction temperature is 180 ℃ and the time is 48h.
5. The preparation method of the Zn-atz@COF-TD composite photocatalytic material according to claim 1, wherein in the step (2), the mass ratio of the Zn-atz material to 4,4' -biphenyl dicarboxaldehyde is (1-10): 1; the volume ratio of the o-dichlorobenzene to the ethanol to the acetic acid is (1-5) (10) -5 ~5×10 -5 ) The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the acetic acid is (1-5) M; the 4,4' -biphenyl dicarboxaldehyde: the dosage ratio of the o-dichlorobenzene is 0.084g to 20mL; the ultrasonic time is (5-15) min; the temperature of the oil bath reaction is 80-90 ℃ and the time is (8-15) h.
6. The method for preparing a Zn-atz@COF-TD composite photocatalytic material according to claim 5, wherein in the step (2), the Zn-atz material is mixed with 4,4' -biphenylThe mass ratio of the dicarboxaldehyde is 3.6:1; the volume ratio of the o-dichlorobenzene to the ethanol to the acetic acid is 1:1:10 -5 The method comprises the steps of carrying out a first treatment on the surface of the The acetic acid concentration was 3M; the ultrasonic time is 10min; the temperature of the oil bath reaction is 80 ℃ and the time is 12h.
7. The preparation method of the Zn-atz@COF-TD composite photocatalytic material according to claim 1, wherein in the step (3), the mass ratio of the hydroformylation Zn-atz precursor, 4' -biphenyl dicarboxaldehyde and 4,4' ' - (1, 3, 5-triazine-2, 4, 6-tri-yl) triphenylamine is (1-5): 1-5:1; the volume ratio of the mesitylene to the 1, 4-dioxane is (1-10): 1; the dosage ratio of the 4, 4'' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine to the 1, 4-dioxane is 0.106 g/2 mL; the dosage ratio of the 4, 4'' - (1, 3, 5-triazine-2, 4, 6-triyl) triphenylamine to the acetic acid is 0.106g:0.23mL; the hydrothermal reaction temperature is 80-180 ℃ and the reaction time is 24-72 h.
8. The method for preparing a Zn-atz@COF-TD composite photocatalytic material according to claim 7, wherein in the step (3), the volume ratio of mesitylene to 1, 4-dioxane is 6:1; the temperature of the hydrothermal reaction is 120 ℃, and the reaction time is 72h.
9. The method for preparing a Zn-atz@cof-TD composite photocatalytic material according to claim 1, wherein in step (3), the washing is performed by using tetrahydrofuran and ethanol for three times.
10. Use of a Zn-atz@cof-TD composite photocatalytic material prepared according to any one of claims 1 to 9 in photocatalytic carbon dioxide reduction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210722126.4A CN114985014B (en) | 2022-06-24 | 2022-06-24 | Preparation method and application of Zn-atz@COF-TD composite photocatalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210722126.4A CN114985014B (en) | 2022-06-24 | 2022-06-24 | Preparation method and application of Zn-atz@COF-TD composite photocatalytic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114985014A CN114985014A (en) | 2022-09-02 |
| CN114985014B true CN114985014B (en) | 2023-11-10 |
Family
ID=83036935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210722126.4A Active CN114985014B (en) | 2022-06-24 | 2022-06-24 | Preparation method and application of Zn-atz@COF-TD composite photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114985014B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115501915B (en) * | 2022-10-21 | 2023-10-27 | 江南大学 | Bimetal organic framework/covalent organic framework composite photocatalyst with core-shell structure and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560125A (en) * | 2019-09-06 | 2019-12-13 | 北京交通大学 | N-g-C3N4Preparation method and application of visible light catalytic material |
| CN113275041A (en) * | 2021-06-22 | 2021-08-20 | 哈尔滨理工大学 | Preparation of COF-316/CAT-1 composite material and photocatalytic carbon dioxide reduction |
-
2022
- 2022-06-24 CN CN202210722126.4A patent/CN114985014B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110560125A (en) * | 2019-09-06 | 2019-12-13 | 北京交通大学 | N-g-C3N4Preparation method and application of visible light catalytic material |
| CN113275041A (en) * | 2021-06-22 | 2021-08-20 | 哈尔滨理工大学 | Preparation of COF-316/CAT-1 composite material and photocatalytic carbon dioxide reduction |
Non-Patent Citations (3)
| Title |
|---|
| "Boosting charge carriers separation and migration efficiency via fabricating all organic van der Waals heterojunction for efficient photoreduction of CO2";Xianghai Song et al.;《Chemical EngineeringJournal》;第408卷;第1-12页 * |
| "Visible-light-driven sustainable conversion of carbon dioxide to methanol using a metal-free covalent organic framework as a recyclable photocatalyst";Pekham Chakrabortty et al.;《Catalysis Science & Technology》;第12卷;第3484-3497页 * |
| Laurence LE CAMPION et al.."PHOTOCATALYTIC DEGRADATION OF 5-NITRO-1,2,4-TRIAZOL-3-ONE NTO IN AQUEOUS SUSPENTION OF TiO2. COMPARISON WITH FENTON OXIDATION".《Cheraosphere》.1999,第38卷(第7期),第1561-1570页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114985014A (en) | 2022-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107552083B (en) | A kind of FeP/C3N4Composite photo-catalyst and its preparation method and application | |
| CN113275041B (en) | Preparation of COF-316/CAT-1 composite material and photocatalytic carbon dioxide reduction | |
| CN111389442A (en) | P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof | |
| CN114985014B (en) | Preparation method and application of Zn-atz@COF-TD composite photocatalytic material | |
| CN110624550A (en) | In-situ carbon-coated copper-nickel alloy nanoparticle photocatalyst and preparation method and application thereof | |
| CN116139867B (en) | MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof | |
| CN115594861B (en) | Transition metal organic framework material with photosensitive characteristic, and preparation method and application thereof | |
| Zhang et al. | Cobalt-based metal–organic frameworks for the photocatalytic reduction of carbon dioxide | |
| CN114849785B (en) | Preparation of triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst | |
| CN112892608A (en) | Water-stable composite material for photodegradation of organic pollutants and preparation method thereof | |
| CN114210328B (en) | Rh monoatomic-modified PCN photocatalyst and preparation method and application thereof | |
| CN111599970A (en) | Magnesium oxide/iron composite material modified diaphragm and preparation method thereof | |
| CN110743583A (en) | 0D/2D iron phosphide/cadmium sulfide composite photocatalyst and preparation method and application thereof | |
| CN111495431B (en) | Photocatalyst and preparation method thereof | |
| Zhang et al. | Assembling CeO 2 nanoparticles on ZIF-8 via the hydrothermal method to promote the CO 2 photoreduction performance | |
| CN114984937A (en) | Spatially separated double-vacancy titanium dioxide homojunction catalyst and preparation method and application thereof | |
| CN109569726B (en) | MOFs/CNT photocatalyst and preparation method thereof | |
| CN109569659B (en) | Photocatalytic auxiliary agent for reducing carbon dioxide and preparation method thereof | |
| CN114762829A (en) | Simple preparation method of Z-type heterojunction photocatalytic material | |
| CN112717958A (en) | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst | |
| CN112570030A (en) | Bi4O5Br2Preparation method and application of/Fe-MIL composite material photocatalyst | |
| CN115044055B (en) | Preparation and application of nitrogen coordinated CoFe-PBA nano-frame material | |
| CN113735065B (en) | Method for producing hydrogen peroxide by using modified amino functionalized zirconium-based metal-organic framework composite photocatalyst | |
| CN112958124B (en) | Indium-doped molybdenum carbide nanoflower core-shell structure photocatalyst and preparation and application thereof | |
| CN113198510B (en) | Preparation method and application of graphite-phase carbon nitride nanotube/nickel-cobalt layered double-metal oxide hierarchical hollow heterojunction |
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 |