CN111514934A - Petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof - Google Patents
Petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof Download PDFInfo
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- CN111514934A CN111514934A CN202010268006.2A CN202010268006A CN111514934A CN 111514934 A CN111514934 A CN 111514934A CN 202010268006 A CN202010268006 A CN 202010268006A CN 111514934 A CN111514934 A CN 111514934A
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- petal
- zinc
- perylene
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 43
- HZBPPYBVGWSHKN-UHFFFAOYSA-N [Zn].C1(=C(C(=C2C(=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)C(=O)O)C(=O)O)C(=O)O)C(=O)O Chemical compound [Zn].C1(=C(C(=C2C(=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)C(=O)O)C(=O)O)C(=O)O)C(=O)O HZBPPYBVGWSHKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 14
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000003751 zinc Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- SHSQKCAFISKHJW-UHFFFAOYSA-J tetralithium;perylene-3,4,9,10-tetracarboxylate Chemical compound [Li+].[Li+].[Li+].[Li+].C=12C3=CC=C(C([O-])=O)C2=C(C([O-])=O)C=CC=1C1=CC=C(C([O-])=O)C2=C1C3=CC=C2C(=O)[O-] SHSQKCAFISKHJW-UHFFFAOYSA-J 0.000 claims description 4
- SYDOGHLMDRZWGK-UHFFFAOYSA-J tetrapotassium;perylene-3,4,9,10-tetracarboxylate Chemical compound [K+].[K+].[K+].[K+].C=12C3=CC=C(C([O-])=O)C2=C(C([O-])=O)C=CC=1C1=CC=C(C([O-])=O)C2=C1C3=CC=C2C(=O)[O-] SYDOGHLMDRZWGK-UHFFFAOYSA-J 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- -1 barium perylene-3, 4,9, 10-tetracarboxylate Chemical compound 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- ZWDJILAIDVILCQ-UHFFFAOYSA-J tetrasodium;perylene-3,4,9,10-tetracarboxylate Chemical compound [Na+].[Na+].[Na+].[Na+].C=12C3=CC=C(C([O-])=O)C2=C(C([O-])=O)C=CC=1C1=CC=C(C([O-])=O)C2=C1C3=CC=C2C(=O)[O-] ZWDJILAIDVILCQ-UHFFFAOYSA-J 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 3
- 239000011261 inert gas Substances 0.000 claims 2
- 230000031700 light absorption Effects 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 abstract description 31
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 abstract description 31
- 238000000034 method Methods 0.000 abstract description 15
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000004220 aggregation Methods 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000004098 Tetracycline Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229960002180 tetracycline Drugs 0.000 description 3
- 229930101283 tetracycline Natural products 0.000 description 3
- 235000019364 tetracycline Nutrition 0.000 description 3
- 150000003522 tetracyclines Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical compound CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
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- C02F2305/00—Use of specific compounds during water treatment
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Abstract
The invention discloses a petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material and a preparation method thereof. The method ensures that the perylene materials are regularly arranged in the framework of the supermolecule assembly, solves the problem of high photo-induced charge recombination rate of the perylene materials caused by molecular aggregation, does not need to carry out complicated pretreatment work on the perylene materials, is simple and convenient to operate, has mild reaction conditions and low production cost, and can be used for large-scale preparation. The petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material synthesized by the method can degrade organic pollutants and catalyze the polymerization of acrylate monomers by utilizing 200-1200nm photocatalysis, and has huge potential in the aspects of environmental treatment and energy utilization.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to a petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material and a preparation method thereof.
Background
The photocatalytic material can convert green and rich solar energy into electric energy and then into chemical energy, can be used for preparing clean energy by photocatalytic decomposition of water, reduction of carbon dioxide and the like, can mineralize and degrade organic pollutants, and has great potential on solving two worldwide problems of energy shortage and environmental deterioration. The perylene material has the structural characteristic of five benzene ring fusion, is easy to obtain raw materials, and is a common industrial dye. The large conjugated system enables the compound to have wide spectral absorption, high electron mobility and good stability, and has strong potential in the field of photocatalysis. However, the molecular structure of the perylene material plane enables strong pi-pi stacking effect to exist among molecules of the perylene material, the perylene material is easy to aggregate to form a disordered aggregation state, the disordered aggregation state enables electron migration to be blocked, and the photo-generated charge recombination rate is increased, so that the photocatalytic activity is low, and the development of the perylene material in the field of photocatalysis is limited. The existing methods for improving the photocatalytic activity of perylene materials mainly comprise the following steps:
1. and (4) depositing the noble metal. The noble metal is deposited on the surface of the perylene material by a chemical reduction or photoreduction method to form a metal-semiconductor heterojunction. Because the noble metal has a higher work function, when the noble metal is contacted with the perylene material, photo-generated electrons can migrate from the perylene material to the noble metal, a Schottky barrier can be formed at the interface of the perylene material and the noble metal, the recombination of photo-generated charges is inhibited, the separation efficiency of the photo-generated charges is improved, and the photocatalytic activity is further improved. The method is simple and convenient to operate, the photocatalytic effect is obviously improved, however, the commonly used precious metals are gold, platinum, silver and the like, the price is high, and in addition, the precious metal nano particles are easy to fall off in the using process, so that the circulation stability of the material is poor.
2. And (5) compounding semiconductors. And (3) selecting a semiconductor with matched energy band structure to be compounded with the perylene material to form a semiconductor-semiconductor heterojunction. Due to the matched energy band structure, photoproduction charges can be transferred at the interface of two materials, so that photoproduction electrons are mainly concentrated on a conduction band of one semiconductor, and photoproduction holes are mainly concentrated on a valence band of the other semiconductor, so that the recombination of the photoproduction charges is inhibited, and the photocatalytic activity is improved. The method enables the photoproduction electrons and the holes to be respectively positioned on different semiconductors, so that the separation efficiency of photoproduction charges is greatly improved, but the types of the selectable semiconductors matched with the energy band structure of the perylene material are few, and the establishment of a compact interface which is beneficial to charge transfer between the two semiconductors is difficult.
3. Perylene molecules self-assemble. The self-assembly method can enable the perylene material to form an ordered and regular structure through the interaction between molecules, greatly inhibit the defects caused by molecular aggregation, and improve the separation efficiency of photo-generated charges. The self-assembly method can easily regulate and control the particle size and the morphology of the material by changing the conditions of concentration, temperature and the like. However, the self-assembly of perylene molecules requires complicated pretreatment of perylene molecules to have some reactive groups or to improve their solubility, and the complicated pretreatment steps and the resulting high cost are disadvantageous for practical production.
The invention provides a method with low price and simple synthesis process to solve the problem of high photo-induced charge recombination rate of perylene materials, and provides a perylene photocatalytic material with wide spectral response range and capable of being prepared in large scale, which is a valuable invention achievement.
Disclosure of Invention
The invention aims to provide a petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material and a preparation method thereof.
Aiming at the problems of the existing perylene photocatalyst, the invention adopts a self-assembly method, and the petal-shaped supermolecule assembly is constructed by the interaction of perylene molecules and zinc ions in a solution, taking the zinc ions as nodes and the perylene molecules as a framework. Perylene molecules are arranged in an ordered manner in the supermolecular assembly, the aggregation effect among the molecules is greatly inhibited, and photo-generated charges can be transferred through the supermolecular framework, so that the photocatalytic activity is greatly improved. In addition, the method does not need to carry out a complicated pretreatment process on perylene molecules, can be used for preparing a large amount of perylene molecules, and meets the requirement of actual production.
In order to realize the purpose, the invention adopts the technical scheme that:
according to the following steps of 1: 4-4: 1, preparing a perylene tetracarboxylic acid ligand solution with the concentration of 0.1-10 mM and a zinc salt solution, transferring the zinc salt solution into a reaction kettle, opening and stirring at the rotating speed of 200-600 r/min, and dropwise adding the perylene tetracarboxylic acid ligand solution at the speed of 5-30 ml/min by using a precision metering pump under the condition of 5-60 ℃ and in a nitrogen or argon atmosphere. And after the perylene tetracarboxylic acid ligand solution is dropwise added, stopping stirring, aging for 1-20 days at 5-60 ℃, and then centrifuging, filtering and drying to obtain the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material.
The perylene tetracarboxylic acid ligand is at least one of potassium perylene-3, 4,9, 10-tetracarboxylate, sodium perylene-3, 4,9, 10-tetracarboxylate, barium perylene-3, 4,9, 10-tetracarboxylate and lithium perylene-3, 4,9, 10-tetracarboxylate.
The zinc salt is at least one of zinc acetate, zinc nitrate, zinc sulfate and zinc oxide.
The solvent of the perylene tetracarboxylic acid ligand solution and the zinc salt solution is at least one of water, ethanol, methanol, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
The centrifugation is to centrifuge for 5-20 min at the rotating speed of 5000-15000 r/min; washing refers to washing for 3-5 times by using a solvent prepared with a perylene tetracarboxylic acid ligand solution and a zinc salt solution; the drying is carried out for 48 hours under the conditions that the temperature is 30-60 ℃ and the vacuum degree is 1-20 pa.
Technical advantages of the invention
1. The perylene tetracarboxylic acid zinc supermolecule assembly enables perylene molecules to be arranged in an ordered structure, greatly inhibits the aggregation problem of the perylene molecules, and solves the problem of photo-generated charge recombination caused by molecular aggregation. Meanwhile, photoproduction charges can be transferred in the supermolecular framework, so that the separation efficiency of the photoproduction charges is improved, and the photocatalytic activity of the perylene material is improved.
2. The preparation method of the petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material does not need to carry out a complex pretreatment process on perylene molecules, has mild reaction conditions, can be prepared in large quantities, and is beneficial to actual production.
3. The petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material can degrade organic pollutants by 200-1200nm photocatalysis and catalyze the polymerization of acrylate molecules, and has great potential in solving the problems of environmental deterioration and energy shortage.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material prepared in example 1; FIG. 2 is a powder X-ray diffraction pattern (XRD) of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material prepared in example 1; FIG. 3 is a UV-VIS DRS (UV-vis-DRS) spectrum of a petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material prepared in example 1; fig. 4 is a cycle experiment chart of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material prepared in example 1.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art may make insubstantial modifications and adaptations to the invention described above.
Example 1
Dissolving 1.4500g of potassium perylene-3, 4,9, 10-tetracarboxylate in 250 ml of deionized water, and dissolving 3.660g of zinc acetate in 500 ml of deionized water; transferring the zinc acetate solution into a reaction kettle, starting stirring at the rotating speed of 200r/min, dropwise adding the potassium perylene-3, 4,9, 10-tetracarboxylate solution by using a precision metering pump under the conditions of nitrogen atmosphere and 60 ℃, wherein the dropwise adding speed is 5ml/min, stopping stirring after the dropwise adding is finished, aging for 1 day at the temperature of 60 ℃, centrifuging the mixed solution for 5min at the rotating speed of 5000r/min, washing for 3 times by using deionized water, and finally drying for 48 hours at the temperature of 60 ℃ and the vacuum degree of 20pa to obtain the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material.
Example 2
0.1130g of lithium perylene-3, 4,9, 10-tetracarboxylate is dissolved in 250 ml of a mixed solvent of deionized water and ethanol, wherein the volume ratio of the deionized water to the ethanol is 9: 1, 0.322g zinc sulfate was dissolved in the same solvent; transferring the zinc sulfate solution into a reaction kettle, starting stirring at the rotating speed of 400r/min, dropwise adding the lithium perylene-3, 4,9, 10-tetracarboxylate solution by using a precision metering pump under the condition of argon atmosphere and at the temperature of 30 ℃, wherein the dropwise adding speed is 15ml/min, stopping stirring after the dropwise adding is finished, aging for 10 days at the temperature of 30 ℃, centrifuging the mixed solution for 5min at the rotating speed of 10000r/min, washing for 4 times by using a mixed solvent of deionized water and ethanol, and finally drying for 48 hours at the temperature of 30 ℃ and the vacuum degree of 10pa to obtain the petal-shaped supermolecular zinc perylene tetracarboxylic acid assembly photocatalytic material.
Example 3
0.0129g of perylene-3, 4,9, 10-sodium tetracarboxylic acid is dissolved in 250 ml of mixed solvent of deionized water and methanol, and the volume ratio of the deionized water to the methanol is 8: 2, 0.0148g of zinc nitrate was dissolved in the same solvent; transferring a zinc nitrate solution into a reaction kettle, opening and stirring at the rotating speed of 600r/min, dropwise adding a perylene-3, 4,9, 10-sodium tetracarboxylic acid solution by using a precision metering pump under the condition of argon atmosphere and at the temperature of 5 ℃, wherein the dropwise adding speed is 30ml/min, closing and stirring after the dropwise adding is finished, aging for 20 days at the temperature of 5 ℃, centrifuging the mixed solution for 10min at the rotating speed of 15000r/min, washing for 5 times by using a mixed solvent of deionized water and methanol, and finally drying for 48 hours at the temperature of 50 ℃ and the vacuum degree of 1pa to obtain the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material.
Example 4
100mg of petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material is added into 200 mL of tetracycline solution, the concentration of tetracycline is 10 mg/L, and the light intensity is 20 mW/cm2Irradiating for 60 min under the LED light source, detecting the concentration of the tetracycline by using an ultraviolet spectrophotometer, and calculating the degradation rate.
Example 5
Adding 300mg of petal-shaped zinc perylenetetracarboxylic acid supermolecule assembly photocatalytic material and 10ml of N, N-dimethylformamide into a 50ml quartz photopolymerization reactor, introducing high-purity argon for 30min to remove oxygen, then sequentially adding 5ml of methyl methacrylate, 0.15 ml of tetramethylethylenediamine and 0.08 ml of α -ethyl bromophenylacetate, introducing high-purity argon for 30min to remove oxygen after each addition, and finally, introducing the high-purity argon with the light intensity of 20 mW/cm for 30min to remove oxygen2Under the irradiation of the LED light source, the polymerization reaction is carried out for 10 hours in the environment of 25 ℃. After the polymerization is completed, the mixed solution is centrifuged to separate the polymer from the catalystThe supernatant was precipitated dropwise in methanol to isolate the product, and the obtained polymer was vacuum-dried at 80 ℃ to constant weight.
Claims (9)
1. A petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material is characterized in that the chemical general formula is as follows: ZnxCyOzHw, wherein x is more than or equal to 1 and less than or equal to 4, y is more than or equal to 24 and less than or equal to 96, z is more than or equal to 9 and less than or equal to 33, H is more than or equal to 16 and less than or equal to 34, and the shape of the assembly is in a petal shape.
2. The petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material as claimed in claim 1, wherein the light absorption range is 200-1200 nm.
3. A preparation method of a petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material is characterized by comprising the following steps: (1) according to the following steps of 1: 4-4: 1, respectively weighing a perylene tetracarboxylic acid ligand and a zinc salt precursor according to a molar ratio, respectively dissolving the perylene tetracarboxylic acid ligand and the zinc salt precursor in a solvent at 5-60 ℃, and preparing a perylene tetracarboxylic acid ligand solution and a zinc salt solution; (2) transferring the zinc salt solution into a reaction kettle, keeping the temperature constant at 5-60 ℃, starting stirring, and dropwise adding a perylene tetracarboxylic acid ligand solution by using a precision metering pump under the protection of inert gas to react; (3) after the perylene tetracarboxylic acid ligand solution is completely dripped, stopping stirring, and aging for 1-20 days at 5-60 ℃; (4) and centrifuging, washing and drying the aged product to obtain the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material.
4. The preparation method of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material as claimed in claim 3, characterized in that: the perylene tetracarboxylic acid ligand in the step (1) is at least one of potassium perylene-3, 4,9, 10-tetracarboxylate, sodium perylene-3, 4,9, 10-tetracarboxylate, barium perylene-3, 4,9, 10-tetracarboxylate and lithium perylene-3, 4,9, 10-tetracarboxylate.
5. The preparation method of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material as claimed in claim 3, characterized in that: the zinc salt precursor in the step (1) is at least one of zinc acetate, zinc nitrate, zinc sulfate and zinc oxide.
6. The preparation method of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material as claimed in claim 3, characterized in that: the solvent in the step (1) is at least one of water, ethanol, methanol, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
7. The preparation method of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material as claimed in claim 3, characterized in that: the concentration of the perylene tetracarboxylic acid ligand solution in the step (1) is 0.1-10 mM, and the concentration of the zinc salt solution is 0.1-10 mM.
8. The preparation method of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material as claimed in claim 3, characterized in that: the stirring speed in the step (2) is 200-600 r/min, the inert gas is nitrogen or argon, and the dropping speed of the precision metering pump is 5-30 ml/min.
9. The preparation method of the petal-shaped zinc perylenetetracarboxylic acid supramolecular assembly photocatalytic material as claimed in claim 3, characterized in that: centrifuging in the step (4) for 3-5 min at the rotating speed of 5000-15000 r/min; washing refers to washing for 3-5 times by using a solvent prepared with a perylene tetracarboxylic acid ligand solution and a zinc salt solution; the drying is carried out for 48 hours under the conditions that the temperature is 30-60 ℃ and the vacuum degree is 1-20 pa.
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