CN111514934B - Petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof - Google Patents
Petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material and preparation method thereof Download PDFInfo
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- CN111514934B CN111514934B CN202010268006.2A CN202010268006A CN111514934B CN 111514934 B CN111514934 B CN 111514934B CN 202010268006 A CN202010268006 A CN 202010268006A CN 111514934 B CN111514934 B CN 111514934B
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- tetracarboxylic acid
- perylene
- zinc
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- perylene tetracarboxylic
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 41
- 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 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 20
- -1 acrylic ester Chemical class 0.000 claims abstract description 13
- 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 12
- 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
- 238000001035 drying Methods 0.000 claims description 9
- 239000012266 salt solution Substances 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
- 239000002904 solvent Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 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
- GXLHNWGZJLJFKU-UHFFFAOYSA-N [K].OC(=O)C1=CC=C2C3=C4C(=CC=C(C(O)=O)C4=C(C=C3)C(O)=O)C3=C2C1=C(C=C3)C(O)=O Chemical compound [K].OC(=O)C1=CC=C2C3=C4C(=CC=C(C(O)=O)C4=C(C=C3)C(O)=O)C3=C2C1=C(C=C3)C(O)=O GXLHNWGZJLJFKU-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
- 238000005119 centrifugation Methods 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
- 229910052786 argon Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims 3
- 239000011261 inert gas Substances 0.000 claims 2
- WSRHMJYUEZHUCM-UHFFFAOYSA-N perylene-1,2,3,4-tetracarboxylic acid Chemical compound C=12C3=CC=CC2=CC=CC=1C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C2=C1C3=CC=C2C(=O)O WSRHMJYUEZHUCM-UHFFFAOYSA-N 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 27
- 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 27
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000004220 aggregation Methods 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000006798 recombination Effects 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 6
- 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
- 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
- 239000012046 mixed solvent Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000008569 process Effects 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
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000001338 self-assembly Methods 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 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
- 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
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- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 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
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001105 regulatory effect 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 239000011787 zinc oxide Substances 0.000 description 1
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- 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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Abstract
The invention discloses a petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material and a preparation method thereof. The method ensures that the perylene materials are regularly arranged in the skeleton of the supermolecule assembly, solves the problem of high photo-generated charge recombination rate of the perylene materials caused by molecular aggregation, does not need complex pretreatment work on the perylene materials, has simple and convenient operation, mild reaction conditions and low production cost, and can be prepared in a large scale. The petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material synthesized by the method can utilize 200-1200nm photocatalysis to degrade organic pollutants and catalyze polymerization of acrylic ester monomers, and has great 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 perylene tetracarboxylic acid supermolecule assembly photocatalytic material and a preparation method thereof.
Background
The photocatalytic material can convert green and abundant solar energy into electric energy and then into chemical energy, can prepare clean energy by photocatalytic decomposition of water, reduction of carbon dioxide and the like, can mineralize and degrade organic pollutants, and has great potential in solving two worldwide problems of energy shortage and environmental deterioration. The perylene material has the structural characteristic of condensed five benzene rings, and the raw materials are easy to obtain, thus being a common industrial dye. The large conjugated system has 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 has strong pi-pi stacking effect among molecules, and is easy to aggregate to form disordered aggregation state, and the disordered aggregation state can prevent electron migration, so that the photo-generated charge recombination rate is increased, the photo-catalytic activity is low, and the development of the perylene material in the field of photocatalysis is limited. The prior method for improving the photocatalytic activity of the perylene material mainly comprises the following steps:
1. and (5) precious metal deposition. Precious metals are deposited on the surface of perylene materials by a chemical reduction or photo-reduction method to form a metal-semiconductor heterojunction. Because the noble metal has a higher work function and is contacted with the perylene material, the photo-generated electrons can migrate from the perylene material to the noble metal, and a Schottky barrier can be formed at the interface of the two materials, so that the recombination of photo-generated charges is inhibited, the separation efficiency of the photo-generated charges is improved, and the photo-catalytic activity is further improved. The method is simple and convenient to operate, the photocatalysis effect is obviously improved, but common noble metals are gold, platinum, silver and the like, the price is relatively high, noble metal nano particles are easy to fall off in the using process, and the material has poor circulation stability.
2. And (5) compounding semiconductors. And (3) compounding the semiconductor with the perylene material, which is matched with the energy band structure, to form a semiconductor-semiconductor heterojunction. Because of the matched energy band structure, photo-generated charges can be transferred at the interface of two materials, so that photo-generated electrons are mainly concentrated on the conduction band of one semiconductor, and photo-generated holes are mainly concentrated on the valence band of the other semiconductor, thereby inhibiting the recombination of the photo-generated charges and improving the photo-catalytic activity. The method leads the photo-generated electrons and the holes to be respectively positioned on different semiconductors, greatly improves the separation efficiency of photo-generated charges, but has few semiconductor types which can be selected and are matched with the energy band structure of perylene materials, and the construction of a compact interface which is favorable for charge transfer between the two semiconductors is difficult.
3. And (3) self-assembling perylene molecules. The self-assembly method can lead perylene materials to form ordered and regular structures through intermolecular interaction, greatly inhibit the defects caused by molecular aggregation and improve the separation efficiency of photo-generated charges. The particle size and morphology of the material can be easily regulated and controlled by changing the conditions of concentration, temperature and the like. However, the self-assembly of perylene molecules requires complex pretreatment of perylene molecules to make them possess certain reactive groups or to improve their solubility, and complicated pretreatment steps and the resulting high cost are disadvantageous for practical production.
The invention aims to solve the problem of high photogenerated charge recombination rate of perylene materials by searching a method which is relatively low in price and relatively simple and convenient in synthesis process, and the invention provides the perylene photocatalytic material which is wide in spectral response range and can be prepared in a large quantity, thus being a valuable invention result.
Disclosure of Invention
The invention aims to provide a petal-shaped zinc perylene tetracarboxylic acid supermolecule 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 constructs a petal-shaped supermolecule assembly by the interaction of perylene molecules and zinc ions in solution and taking the zinc ions as nodes and perylene molecules as a framework. The perylene molecules are arranged in an orderly manner in the supermolecule assembly, so that aggregation effect among molecules is greatly inhibited, photo-generated charges can be transferred through a supermolecule framework, and the photocatalytic activity is greatly improved. The method does not need to carry out complex pretreatment process on perylene molecules, can prepare a large amount, and meets the actual production requirement.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
according to 1:4~4:1 preparing perylene tetracarboxylic acid ligand solution and zinc salt solution with the concentration of 0.1-10 mM in a molar ratio, transferring the zinc salt solution into a reaction kettle, starting stirring, and dropwise adding the perylene tetracarboxylic acid ligand solution at the speed of 5-30 ml/min by a precise metering pump under the condition of 5-60 ℃ and nitrogen or argon atmosphere at the rotating speed of 200-600 r/min. After the perylene tetracarboxylic acid ligand solution is completely dripped, stirring is closed, aging is carried out for 1-20 days at the temperature of 5-60 ℃, and then the petal-shaped perylene tetracarboxylic acid zinc supermolecule assembly photocatalytic material is obtained through centrifugation, filtration and drying processes.
The perylene tetracarboxylic acid ligand is at least one of perylene-3, 4,9, 10-tetracarboxylic acid potassium, perylene-3, 4,9, 10-tetracarboxylic acid sodium, perylene-3, 4,9, 10-tetracarboxylic acid barium and perylene-3, 4,9, 10-tetracarboxylic acid lithium.
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 carried out for 5-20 min at a rotation speed of 5000-15000 r/min; washing is to use a solvent for preparing perylene tetracarboxylic acid ligand solution and zinc salt solution for 3-5 times; drying means drying at 30-60 ℃ and a vacuum degree of 1-20 pa for 48h.
Technical advantages of the invention
1. The perylene tetracarboxylic acid zinc supermolecule assembly makes perylene molecules arranged in an ordered structure, greatly inhibits the aggregation problem of perylene molecules, and solves the problem of photo-generated charge recombination caused by molecular aggregation. Simultaneously, the photo-generated charges can be transferred in the supramolecular framework, so that the separation efficiency of the photo-generated charges is improved, and the photocatalytic activity of the perylene material is improved.
2. The preparation method of the petal-shaped perylene tetracarboxylic acid zinc supermolecule assembly photocatalytic material does not need to carry out complex pretreatment process on perylene molecules, has mild reaction conditions, can prepare a large amount of perylene tetracarboxylic acid zinc supermolecule assemblies, and is beneficial to actual production.
3. The petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material can utilize 200-1200nm photocatalysis to degrade organic pollutants and catalyze polymerization of acrylic ester 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 perylene tetracarboxylic acid supermolecule assembly photocatalytic material prepared in example 1; FIG. 2 is a powder X-ray diffraction pattern (XRD) of the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material prepared in example 1; FIG. 3 is an ultraviolet visible diffuse reflectance spectrum (UV-vis DRS) of a petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material prepared in example 1; FIG. 4 is a graph showing a cycle experiment of the photocatalytic material of the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly prepared in example 1.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration only and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and adaptations of the invention as described above will be within the skill of the art.
Example 1
1.4500g of potassium perylene-3, 4,9, 10-tetracarboxylic acid was dissolved in 250 ml deionized water, 3.660g of zinc acetate was dissolved in 500 ml deionized water; transferring zinc acetate solution into a reaction kettle, opening and stirring at the rotating speed of 200r/min, dropwise adding perylene-3, 4,9, 10-tetracarboxylic acid potassium solution with a precise metering pump under the condition of nitrogen atmosphere and 60 ℃, wherein the dropwise adding speed is 5ml/min, closing and stirring after the dropwise adding is finished, aging for 1 day under the condition of 60 ℃, centrifuging the mixed solution for 5min at the rotating speed of 5000r/min, washing with deionized water for 3 times, and finally drying for 48h under the condition of 60 ℃ and the vacuum degree of 20pa to obtain petal-shaped perylene zinc tetracarboxylic acid supermolecule assembly photocatalytic material.
Example 2
0.1130g of perylene-3, 4,9, 10-tetracarboxylic acid lithium is dissolved in a mixed solvent of 250 ml 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 zinc sulfate solution into a reaction kettle, opening and stirring at the rotating speed of 400r/min, dropwise adding perylene-3, 4,9, 10-tetracarboxylic acid lithium solution with a precise metering pump at the temperature of 30 ℃ in an argon atmosphere, stopping stirring after the dropwise adding is finished, aging for 10 days at the temperature of 30 ℃, centrifuging the mixed solution at the rotating speed of 10000r/min for 5min, washing with a mixed solvent of deionized water and ethanol for 4 times, and finally drying for 48h at the temperature of 30 ℃ and the vacuum degree of 10pa to obtain petal-shaped perylene tetracarboxylic acid zinc supermolecule assembly photocatalytic material.
Example 3
0.0129g of perylene-3, 4,9, 10-tetracarboxylic sodium is dissolved in a mixed solvent of 250 ml deionized water and methanol, wherein the volume ratio of the deionized water to the methanol is 8:2, 0.0148g zinc nitrate was dissolved in the same solvent; transferring zinc nitrate solution into a reaction kettle, opening and stirring at 600r/min, dropwise adding perylene-3, 4,9, 10-sodium tetracarboxylic acid solution at the temperature of 5 ℃ by using a precise metering pump under the condition of argon atmosphere, 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 at the speed of 15000r/min for 10min, washing with a mixed solvent of deionized water and methanol for 5 times, and finally drying for 48 hours at the temperature of 50 ℃ and the vacuum degree of 1pa to obtain petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material.
Example 4
100mg of petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material is added into 200 mL tetracycline solution, the tetracycline concentration is 10 mg/L, and the light intensity is 20 mW/cm 2 The light source of the (2) is irradiated for 60 min, the concentration of the tetracycline is detected by an ultraviolet spectrophotometer, and the degradation rate is calculated.
Example 5
300mg of petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material and 10ml of N, N-dimethylformamide are added into a 50ml quartz photopolymerization reactor, and high-purity argon is introduced for 30min to remove oxygen. Then, 5ml methyl methacrylate, 0.15 ml tetramethyl ethylenediamine and 0.08 ml alpha-bromophenyl ethyl acetate were added sequentially, and high purity argon was introduced for 30min after each addition to exclude oxygen. Finally, at a light intensity of 20 mW/cm 2 Under the irradiation of an LED light source, the polymerization reaction is carried out for 10 hours at 25 ℃. After the polymerization was completed, the mixture was centrifuged, the polymer and the catalyst were separated, the supernatant was added dropwise to methanol to precipitate the separated product, and the obtained polymer was dried under vacuum at 80℃to constant weight.
Claims (7)
1. The preparation method of the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material is characterized by comprising the following steps of:
(1) According to 1: 4-4: 1, respectively weighing perylene tetracarboxylic acid ligand and zinc salt precursor in a molar ratio, respectively dissolving the perylene tetracarboxylic acid ligand and the zinc salt precursor in a solvent at the temperature of 5-60 ℃ to prepare perylene tetracarboxylic acid ligand solution and zinc salt solution;
(2) Transferring zinc salt solution into a reaction kettle, keeping the constant temperature of 5-60 ℃, starting stirring, and dropwise adding perylene tetracarboxylic acid ligand solution under the protection of inert gas by using a precise metering pump to react;
(3) After the perylene tetracarboxylic acid ligand solution is completely dripped, stirring is closed, and aging is carried out for 1-20 days at the temperature of 5-60 ℃;
(4) Centrifuging, washing and drying the aged product to obtain petal-shaped perylene tetracarboxylic acid zinc supermolecule assembly photocatalytic material, wherein the chemical general formula of the material 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 96,9 and z is more 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 body is petal-shaped; the light absorption range is 200-1200nm.
2. The method for preparing the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material according to claim 1, characterized by comprising the steps of:
the perylene tetracarboxylic ligand in the step (1) is at least one of perylene-3, 4,9, 10-tetracarboxylic acid potassium, perylene-3, 4,9, 10-tetracarboxylic acid sodium, perylene-3, 4,9, 10-tetracarboxylic acid barium and perylene-3, 4,9, 10-tetracarboxylic acid lithium.
3. The method for preparing the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material according to claim 1, characterized by comprising the steps of:
the zinc salt precursor in the step (1) is at least one of zinc acetate, zinc nitrate and zinc sulfate.
4. The method for preparing the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material according to claim 1, characterized by comprising the steps of:
the solvent in the step (1) is at least one of water, ethanol, methanol, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
5. The method for preparing the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material according to claim 1, characterized by comprising the steps of:
the concentration of the perylene tetracarboxylic ligand solution in the step (1) is 0.1-10 mM, and the concentration of the zinc salt solution is 0.1-10 mM.
6. The method for preparing the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material according to claim 1, characterized by comprising the steps of:
the stirring speed in the step (2) is 200-600 r/min, the inert gas is nitrogen or argon, and the dripping speed of the precise metering pump is 5-30 ml/min.
7. The method for preparing the petal-shaped zinc perylene tetracarboxylic acid supermolecule assembly photocatalytic material according to claim 1, characterized by comprising the steps of:
the centrifugation in the step (4) means centrifugation for 3-5 min at a rotation speed of 5000-15000 r/min; washing is to use a solvent for preparing perylene tetracarboxylic acid ligand solution and zinc salt solution for 3-5 times; drying means drying at 30-60 deg.c and vacuum degree of 1-20 pa for 48 hr.
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