CN114797972A - Thiourea-PDI polymer photocatalyst and preparation method and application thereof - Google Patents
Thiourea-PDI polymer photocatalyst and preparation method and application thereof Download PDFInfo
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- CN114797972A CN114797972A CN202210377975.0A CN202210377975A CN114797972A CN 114797972 A CN114797972 A CN 114797972A CN 202210377975 A CN202210377975 A CN 202210377975A CN 114797972 A CN114797972 A CN 114797972A
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- thiourea
- photocatalyst
- pdi
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- perylene
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 239000002351 wastewater Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 150000002989 phenols Chemical class 0.000 abstract description 3
- 238000006053 organic reaction Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000593 degrading effect Effects 0.000 description 7
- 239000012425 OXONE® Substances 0.000 description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 6
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 6
- -1 Perylene imide Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000005385 peroxodisulfate group Chemical group 0.000 description 5
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical group [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- 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
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- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
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- C02F2101/00—Nature of the contaminant
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- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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Abstract
The invention discloses a thiourea-PDI polymer photocatalyst, which is prepared by taking perylene-3, 4,9, 10-tetracarboxylic dianhydride and thiourea as raw materials, anhydrous zinc acetate as a catalyst, imidazole as a solvent, carrying out organic reaction at 180-200 ℃, carrying out acid washing and filtering after the reaction is finished, washing to be neutral, and drying; the thiourea-PDI polymer photocatalyst has the advantages of high catalytic efficiency, wide pH application range and good stability; the thiourea-PDI polymer photocatalyst is combined with peroxymonosulfate or peroxydisulfate, is applied to degradation of organic pollutants of phenols, and has a good degradation effect.
Description
Technical Field
The invention relates to an organic polymer photocatalyst, in particular to a thiourea-PDI polymer photocatalyst and a preparation method and application thereof.
Background
Perylene imide (PDI) is a unique organic semiconductor, easy to synthesize, with strong electron affinity, tunable optoelectronic properties, and high physical and chemical stability. The PDI photocatalyst can independently complete the whole photocatalytic process from light absorption, carrier separation to catalytic reaction, however, its practical application still faces the challenges of slow transfer of photo-generated electrons and holes, fast recombination speed of electron holes, low catalytic activity, etc. Therefore, there are two main approaches to improve the photocatalytic oxidation activity of PDI by modifying PDI to improve the efficiency of separation of photo-generated electrons from holes: the oxidation activity is improved by preparing a series of PDI derivatives with supermolecular self-assembly structures and compounds thereof or adding an oxidant. Since self-assembled PDI is a weak interaction of hydrogen bonding, PDI is easily hydrolyzed under alkaline conditions and recycling performance is reduced.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a thiourea-PDI polymer photocatalyst with high catalytic efficiency and wide pH application range; the second object of the present invention is to provide a method for preparing the catalyst; the third purpose of the invention is to provide the application of the photocatalyst.
The technical scheme is as follows: the invention discloses a thiourea PDI polymer photocatalyst, which has a structural formula as follows:
the photocatalyst is synthesized by taking perylene-3, 4,9, 10-tetracarboxylic dianhydride and thiourea as raw materials, wherein the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the thiourea is 1:0.5 to 1.
The crystallinity of the photocatalyst is 12.8-63.5%. The higher the crystallinity of the photocatalyst is, the higher the surface unit cell order degree is, the electron transfer is facilitated, and the better the catalytic effect is.
The preparation method of the thiourea PDI polymer photocatalyst comprises the following steps:
(1) perylene-3, 4,9, 10-tetracarboxylic dianhydride and thiourea are used as raw materials, anhydrous zinc acetate is used as a catalyst, and imidazole is used as a solvent, and the reaction is carried out at 140-200 ℃;
(2) carrying out acid washing on the mixed material after the reaction in the step (1) to wash out acidic soluble impurities;
(3) and (3) filtering the acid-washed material obtained in the step (2), washing to be neutral, and drying to obtain the thiourea-PDI polymer photocatalyst.
The synthetic route is as follows:
in the step (1), perylene-3, 4,9, 10-tetracarboxylic dianhydride and thiourea undergo a polymerization reaction at 140-200 ℃ under the catalytic action of anhydrous zinc acetate to generate a thiourea-PDI polymer, the temperature is reduced to room temperature, and the mixed material is solid after the reaction. Adding acid solutions such as hydrochloric acid and nitric acid into the step (2) for acid washing, adding the acid solutions, and stirring to dissolve imidazole and some impurities, wherein the target product is insoluble solid; imidazole and some acid soluble impurities can be removed by acid washing.
Preferably, in the step (1), the reaction temperature is 180-200 ℃. The reaction temperature affects the pi-pi stacking degree of the photocatalyst, the reactant temperature is high, and the pi-pi stacking degree is higher. The higher the pi-pi stacking degree, i.e., the higher the degree of order, the better the photocatalytic activity.
In the preferable step, the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the anhydrous zinc acetate is 1: 0.5-1. The anhydrous zinc acetate plays a role of a cocatalyst, and the more the anhydrous zinc acetate is used, the faster the reaction rate is.
Preferably, in the step (3), the drying temperature is 50-80 ℃.
The photocatalyst is applied to degrading organic pollutants of phenols.
The application method comprises the following steps: adding the catalyst into the sewage containing the phenol organic pollutants, turning on a visible light source, and adding the peroxymonosulfate or peroxydisulfate to perform a visible light catalytic degradation reaction.
Under the irradiation of visible light, electrons of the thiourea-PDI polymer are transferred from a valence band to a conduction band, so that a photogenerated hole is formed in the valence band, and a superoxide radical is formed in the conduction band. When peroxymonosulfate (peroxodisulfate) is added, photoelectrons can effectively activate peroxymonosulfate PMS (peroxodisulfate PDS) to generate sulfate radical, superoxide radical and HSO 5 - (S 2 O 8 2- ) Can also generate sulfate radicals. In the thiourea-PDI/PMS (PDS)/Vis system, the superoxide radical and HSO are used 5 - (S 2 O 8 2- ) Can form hydroxyl radicals and singlet oxygen. Therefore, a plurality of active species such as holes, singlet oxygen, superoxide radicals, hydroxyl radicals and sulfate radicals in a thiourea-PDI/PMS (PDS)/Vis system generate chain reaction and interaction reaction, and contribute to degrading phenolic organic pollutants together.
Preferably, the peroxymonosulfate is potassium hydrogen persulfate or sodium hydrogen persulfate; the peroxodisulfate is potassium persulfate or sodium persulfate.
The photocatalyst also comprises dark adsorption before turning on a visible light source after being added into the sewage containing the phenol organic pollutants. The oxidation reaction is carried out after the photocatalyst and the organic pollutant reach adsorption balance, which is beneficial to the contact of the pollutant and the catalyst and increases the reactive sites.
The phenolic organic matter is bisphenol A, bisphenol F and bisphenol S.
The invention mechanism is as follows: electrical characterization of thiourea-PDI polymers under visible light illuminationThe photon will be transferred from the valence band to the conduction band, thereby forming a photogenerated hole in the valence band and a superoxide radical in the conduction band. When peroxymonosulfate (peroxodisulfate) is added, photoelectrons can effectively activate peroxymonosulfate PMS (peroxodisulfate PDS) to produce sulfate radical, superoxide radical and HSO 5 - (S 2 O 8 2- ) Can also generate sulfate radicals. In the thiourea-PDI/PMS (PDS)/Vis system, the superoxide radical and HSO are used 5 - (S 2 O 8 2- ) Can form hydroxyl radicals and singlet oxygen. Therefore, a plurality of active species such as holes, singlet oxygen, superoxide radicals, hydroxyl radicals and sulfate radicals in a thiourea-PDI/PMS (PDS)/Vis system generate chain reaction and interaction reaction, and contribute to degrading phenolic organic pollutants together.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) the thiourea-PDI polymer photocatalyst has the advantages of high catalytic efficiency, wide pH application range and good stability; (2) the preparation method of the catalyst is simple; (3) the catalyst is combined with peroxymonosulfate or peroxydisulfate, is applied to degradation of organic pollutants of phenols, and has good degradation effect.
Drawings
FIG. 1 is a scanning electron microscope photograph of the thiourea-PDI polymer prepared in example 2;
FIG. 2 is a transmission electron microscope photograph of the thiourea-PDI polymer prepared in example 2, showing micron-sized stripes;
FIG. 3 is an XRD pattern of a thiourea-PDI polymer photocatalyst prepared in example 2 of the present invention;
FIG. 4 is a Fourier-infrared plot of a thiourea-PDI polymer photocatalyst prepared in example 2 of the present invention;
FIG. 5 is a graph comparing the effect of example 4, example 5 and comparative examples 1-6 in degrading bisphenol A;
FIG. 6 is a graph comparing the effect of the thiourea-PDI polymer photocatalyst prepared in example 2 in degrading bisphenol A under different pH conditions;
FIG. 7 is a plot of the reaction rate constants for the degradation of bisphenol A by the thiourea-PDI polymer photocatalyst prepared in example 2 at different concentrations of oxone.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The invention relates to a thiourea-PDI polymer photocatalyst, and a preparation method thereof comprises the following steps:
(1) adding 2mmol of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 2mmol of thiourea and 2mmol of anhydrous zinc acetate, then adding 5g of imidazole, reacting at 140 ℃ for 5 hours, and cooling to room temperature after the reaction is finished;
(2) adding 1mol/L hydrochloric acid into the mixed material after the reaction in the step (1) and stirring;
(3) and (3) filtering the material subjected to acid washing in the step (2), washing to be neutral, drying at 60 ℃, and grinding to obtain thiourea PDI polymer photocatalyst powder.
Example 2
The invention relates to a thiourea-PDI polymer photocatalyst, and a preparation method thereof comprises the following steps:
(1) adding 2mmol of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 2mmol of thiourea and 2mmol of anhydrous zinc acetate, then adding 5g of imidazole, reacting at 180 ℃ for 5 hours, and cooling to room temperature after the reaction is finished;
(2) adding 1mol/L hydrochloric acid into the mixed material after the reaction in the step (1) and stirring;
(3) and (3) filtering the material subjected to acid washing in the step (2), washing to be neutral, drying at 60 ℃, and grinding to obtain thiourea-PDI polymer photocatalyst powder.
Example 3
The invention relates to a thiourea-PDI polymer photocatalyst, and a preparation method thereof comprises the following steps:
(1) adding 2mol of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 1mmol of thiourea and 1mmol of anhydrous zinc acetate, then adding 10g of imidazole, reacting at 200 ℃ for 2 hours, and cooling to room temperature after the reaction is finished;
(2) adding 1mol/L hydrochloric acid into the mixed material after the reaction in the step (1) and stirring;
(3) and (3) filtering the material subjected to acid washing in the step (2), washing to be neutral, drying at 60 ℃, and grinding to obtain thiourea-PDI polymer photocatalyst powder.
Performance characterization
The thiourea-PDI polymer photocatalyst of example 2 was scanned under an electronic scanning mirror and was in the form of a long strip as shown in fig. 1. Further scanning under a transmission electron microscope, as shown in fig. 2, exhibits a micron-scale long strip.
FIG. 3 is an XRD pattern of the thiourea-PDI polymer photocatalysts prepared in examples 1 and 2, from which T-PDI prepared at 180 ℃ has better pi-pi stacking degree, and the higher the pi-pi stacking degree, i.e., the higher the degree of order, the better the photocatalytic activity. The T-PDI polymer prepared at the reaction temperature of 180 ℃ has a diffraction peak at 27.2 ℃ higher than that of thiourea-PDI polymer prepared at the reactant temperature of 140 ℃, so that the T-PDI polymer prepared at 180 ℃ has a pi-pi stacking degree better than that of the T-PDI polymer prepared at 140 ℃. The crystallinity of the thiourea-PDI polymers prepared in examples 1 and 2 was calculated by crystallinity fitting using the Jade software, and the crystallinity of the thiourea-PDI polymer prepared at the reactant temperature of 140 ℃ was 12.8%, and the crystallinity of the thiourea-PDI polymer prepared at the reactant temperature of 180 ℃ was 63.5%, so that the unit cell order of the T-PDI polymer prepared at 180 ℃ was superior to that of the T-PDI polymer prepared at 140 ℃.
Fig. 4 is a fourier-infrared graph of the thiourea-PDI polymer photocatalysts prepared in examples 1 and 2, from which it can be seen that the thiourea-PDI polymer has stretching vibration peaks of amide and C ═ S.
Example 4
25mg of the thiourea-PDI photocatalyst prepared in example 1 was put into 50mL of bisphenol A solution with a concentration of 5mg/L, and stirred in the dark for 30min, after reaching the adsorption equilibrium, a xenon lamp (lambda >420nm) with an optical filter was turned on, 46mg of potassium hydrogen peroxymonosulfate was added at this time, and the mixture was mixed uniformly to perform the visible light photocatalytic degradation reaction.
Example 5
25mg of the thiourea-PDI photocatalyst prepared in example 2 was put into 50mL of bisphenol A solution with a concentration of 5mg/L, and stirred in the dark for 30min, after reaching the adsorption equilibrium, a xenon lamp (lambda >420nm) with an optical filter was turned on, 46mg of potassium hydrogen peroxymonosulfate was added at this time, and the mixture was mixed uniformly to perform the visible light photocatalytic degradation reaction.
Comparative example 1
On the basis of example 5, no thiourea-PDI was added, no light was applied, and other conditions were unchanged.
Comparative example 2
On the basis of example 5, thiourea-PDI and potassium monopersulfate were not added, and the other conditions were not changed.
Comparative example 3
On the basis of example 5, no potassium monopersulfate was added, and no light irradiation was performed, and the other conditions were not changed.
Comparative example 4
On the basis of example 5, thiourea-PDI is not added, and other conditions are not changed.
Comparative example 5
No light was applied to the substrate of example 5, and other conditions were not changed.
Comparative example 6
Potassium monopersulfate was not added to the mixture in example 5, and the other conditions were not changed.
The content of bisphenol A in the solutions of example 4, example 5 and comparative examples 1 to 6 was measured, and the measurement results are shown in FIG. 5; as can be seen from the figure, under the combined action of thiourea-PDI, potassium hydrogen peroxymonosulfate and visible light, the degradation effect is optimal, and the removal rate of bisphenol A reaches 100% in 17.5 min. Example 5 shows better effect of degrading bisphenol A than example 4 because thiourea-PDI of example 5 is prepared by reaction at 180 ℃ and pi-pi stacking degree and crystallinity are higher than those of thiourea-PDI of example 4 (prepared by reaction at 140 ℃), thus the catalytic effect is better.
Example 6
25mg of the thiourea-PDI photocatalyst prepared in example 2 is taken and placed in 50mL of bisphenol A solution with the concentration of 5mg/L and the pH of 3, 5, 7, 9 and 11 respectively, the mixture is stirred for 30min under dark conditions, after the adsorption equilibrium is reached, a xenon lamp (lambda is more than 420nm) added with an optical filter is turned on, at the moment, 46mg of potassium hydrogen peroxymonosulfate is added, the mixture is uniformly mixed, and the visible light catalytic degradation reaction is carried out.
In example 6, the content of bisphenol a in the solution was measured under different pH conditions, and the measurement results are shown in fig. 6; as can be seen from the figure, the effect of degrading bisphenol A under alkaline conditions is better, the degradation effect of bisphenol A is optimal when the pH of the solution is 11, and bisphenol A can be efficiently degraded in the full pH range.
Example 7
Taking 25mg of the thiourea-PDI photocatalyst prepared in the example 2, placing the thiourea-PDI photocatalyst in 50mL of bisphenol A solution with the concentration of 5mg/L, stirring for 30min under a dark condition, turning on a xenon lamp (lambda is more than 420nm) added with an optical filter after reaching adsorption balance, adding potassium hydrogen peroxymonosulfate, mixing uniformly, and carrying out visible light photocatalytic degradation reaction; the concentration of potassium monopersulfate in the solution was 1.0mM, 1.5mM, and 2.0mM, respectively.
The reaction rate constants of example 7 were measured at different potassium monopersulfate concentrations, and the results are shown in FIG. 7.
Reaction rate constant determination method:
ln(C 0 /C t ) T is linear, k is the first order reaction rate constant, C 0 As the initial concentration of bisphenol A in solution, C t The concentration of bisphenol A in the solution at reaction time t min.
As can be seen from FIG. 7, the reaction rate increases with increasing potassium monopersulfate concentration.
Claims (10)
1. A thiourea-PDI polymer photocatalyst having the structural formula:
the photocatalyst is synthesized by taking perylene-3, 4,9, 10-tetracarboxylic dianhydride and thiourea as raw materials, wherein the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the thiourea is 1:0.5 to 1.
2. The photocatalyst as claimed in claim 1, wherein the photocatalyst has a crystallinity of 12.8 to 63.5%.
3. A method for preparing the photocatalyst of claim 1 or 2, comprising the steps of:
(1) reacting perylene-3, 4,9, 10-tetracarboxylic dianhydride and thiourea serving as raw materials at 140-200 ℃ for 2-5 hours by taking anhydrous zinc acetate as a catalyst and imidazole as a solvent;
(2) carrying out acid washing on the mixed material after the reaction in the step (1) to wash out acidic soluble impurities;
(3) and (3) filtering the acid-washed material obtained in the step (2), washing to be neutral, and drying to obtain the thiourea PDI polymer photocatalyst.
4. The method for preparing a photocatalyst as claimed in claim 3, wherein in the step (1), the reaction temperature is 180 to 200 ℃.
5. The method for preparing a photocatalyst according to claim 3, wherein in the step (1), the molar ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride to the anhydrous zinc acetate is 1:0.5 to 1.
6. The method for preparing the photocatalyst according to claim 4, wherein the drying temperature in the step (3) is 50 to 80 ℃.
7. Use of a photocatalyst as claimed in claim 1 or 2 for the degradation of phenolic organic contaminants.
8. The application of claim 7, wherein the application method comprises: adding the catalyst into the sewage containing the phenol organic pollutants, turning on a visible light source, and adding the peroxymonosulfate or peroxydisulfate to perform a visible light catalytic degradation reaction.
9. The use of claim 8, wherein the catalyst further comprises dark adsorption after addition to the wastewater containing the phenolic organic contaminants and before turning on the visible light source.
10. The use of claim 7, wherein the phenolic organic is bisphenol A, bisphenol F, or bisphenol S.
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| CN108579806A (en) * | 2018-03-29 | 2018-09-28 | 清华大学 | A kind of preparation method and applications of acid imide-urea polymer |
| CN111569940A (en) * | 2020-04-20 | 2020-08-25 | 南京师范大学 | PDI supramolecular photocatalyst and preparation method and use method thereof |
| CN112718009A (en) * | 2020-12-23 | 2021-04-30 | 南京师范大学 | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof |
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| CN104789774A (en) * | 2014-01-21 | 2015-07-22 | 中国科学院过程工程研究所 | Method used for selective recovery of gold in aqueous solutions via reduction and adsorption coupling |
| CN108579806A (en) * | 2018-03-29 | 2018-09-28 | 清华大学 | A kind of preparation method and applications of acid imide-urea polymer |
| CN111569940A (en) * | 2020-04-20 | 2020-08-25 | 南京师范大学 | PDI supramolecular photocatalyst and preparation method and use method thereof |
| CN112718009A (en) * | 2020-12-23 | 2021-04-30 | 南京师范大学 | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof |
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