CN112718009B - PDI/MOF heterojunction photocatalyst and preparation method and use method thereof - Google Patents
PDI/MOF heterojunction photocatalyst and preparation method and use method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 96
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 36
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 15
- 229940000635 beta-alanine Drugs 0.000 claims abstract description 12
- 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 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 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 description 33
- NTHXOOBQLCIOLC-UHFFFAOYSA-N iohexol Chemical compound OCC(O)CN(C(=O)C)C1=C(I)C(C(=O)NCC(O)CO)=C(I)C(C(=O)NCC(O)CO)=C1I NTHXOOBQLCIOLC-UHFFFAOYSA-N 0.000 claims description 30
- 229960001025 iohexol Drugs 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 6
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
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- 230000007613 environmental effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- XTUBPKVLOAIMQY-UHFFFAOYSA-H chromium(3+);terephthalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1.[O-]C(=O)C1=CC=C(C([O-])=O)C=C1.[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 XTUBPKVLOAIMQY-UHFFFAOYSA-H 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000002872 contrast media Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment 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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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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Abstract
The invention discloses a PDI/MOF heterojunction photocatalyst, a preparation method and a use method thereof, wherein the photocatalyst comprises the following raw material components: PDI, MIL-101 (Cr) and acid in a mass ratio of 1:0.11-1:37. The PDI/MOF heterojunction photocatalyst is prepared from perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine, imidazole and MOF serving as raw materials by adopting an organic synthesis method, a water bath heating method is adopted to obtain the PDI/MOF heterojunction photocatalyst, and the application method of the photocatalyst is provided.
Description
Technical Field
The invention relates to a heterojunction photocatalyst and a preparation method and a use method thereof, in particular to a PDI/MOF heterojunction photocatalyst and a preparation method and a use method thereof.
Background
PDI is an n-type organic semiconductor that has a relatively narrow band gap (-1.69 eV) and therefore absorbs visible light. The PDI can be added with acid to carry out molecular self-assembly so as to form an ordered structure, and is fixed by pi-pi stacking and weak interaction of hydrogen bonds. Self-assembled PDI (SA-PDI) has superior photocatalysis than bulk PDI due to the red shift of the absorption sidebands and shorter electron transport channelsBut because of its narrower band gap, it causes easy recombination of electrons and holes, so the photocatalytic oxidation capability of SA-PDI is limited. Most of the inventions related to PDI are related to the construction of heterojunction photocatalysts that prevent recombination of electrons and holes to improve photocatalytic performance. However, the composite material cannot generate hydroxyl radicals (OH) due to the intrinsic valence and conduction band positions of PDI, so that the photocatalytic activity is poor. PDI is capable of activating persulfates under visible light, but has limited reactive sites. Persulfates (PS) are a white, odorless, readily water-soluble inorganic compound, as well as a stable acidic oxidizer. The activated PS releases a large amount of sulfate radicals (SO 4 · - ) And OH, the existing method for activating persulfate comprises ultraviolet activation, thermal activation, transition metal activation and the like, but the activation methods have the problems of high energy consumption, high cost, easiness in causing secondary pollution and the like.
Metal Organic Framework (MOF) materials are three-dimensional network structure materials formed by chemical bonds between secondary structural units consisting of inorganic metal ions and organic ligands. These materials have a larger specific surface area, a lower skeletal density, a larger porosity, a higher chemical stability and more reactive sites. In recent years, great achievement in removing organic pollutants in the environment is achieved by utilizing the good adsorption and photocatalytic properties of MOF, and the full application of MOF materials in the field of environmental science is marked. Among the numerous MOF materials, chromium terephthalate [ MIL-101 (Cr) ] has high thermal and chemical stability, high solubility resistance, and MIL-101 (Cr) is often used as a good catalyst support. MILs-101 (Cr), however, can only excite electrons in uv light due to its wide bandgap width. And most MIL-101 (Cr) preparation needs hydrofluoric acid, which has great harm to the environment.
Iohexol (IOH) is a typical iodinated X-ray contrast agent, which is often detected in surface water, has high biostability and hydrophilicity, and cannot be decomposed and metabolized by the human body. After ingestion by humans, IOH will drain into public drainage systems in a very short period of time, posing a threat to the ecological environment and human health. The traditional water treatment process is difficult to ensure that the IOH wastewater is discharged up to the standard, so that searching for an efficient and stable IOH wastewater treatment technology becomes a problem to be solved urgently.
Disclosure of Invention
The invention aims to: the invention provides a PDI/MOF heterojunction photocatalyst with high degradation efficiency, energy conservation, no secondary pollution and environmental protection, and the invention also provides a simple preparation process of the PDI/MOF heterojunction photocatalyst, and a third purpose of the invention is to provide a using method of the PDI/MOF heterojunction photocatalyst.
The technical scheme is as follows: the PDI/MOF heterojunction photocatalyst provided by the invention comprises the following raw material components: PDI, MIL-101 (Cr) and acid in a mass ratio of 1:0.11-1:37.
Further, the acid is HNO 3 . The mass ratios of SA-PDI to MOF are 9:1,9:3,9:5,9:7 and 9:9 are designated PM-1, PM-3, PM-5, PM-7 and PM-9, respectively.
The preparation method of the PDI/MOF heterojunction photocatalyst comprises the following steps:
(1) Organic synthesis is carried out on perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole, ethanol and HCl are added and stirred, and a stirring product is prepared;
(2) Filtering, washing to neutrality and drying the stirred product to obtain PDI powder;
(3) Vacuum activating MIL-101 (Cr) material at 145-155 ℃;
(4) Preparing PDI powder into PDI solution, sequentially adding triethylamine, MIL-101 (Cr), HNO 3 And stirring, filtering, washing to neutrality and drying to obtain the PDI/MOF heterojunction photocatalyst.
Preferably, in step (1), the mass ratio of perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole is 1:1.8:10-15. In the step (1), perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole are organically synthesized in a nitrogen atmosphere at the temperature of 100-110 ℃. In the step (1), the mass ratio of ethanol to HCl is 150-160:18.
In the step (2), the pore diameter of the filtering membrane is 0.22-0.45 μm, and the drying temperature is 50-70 ℃.
In the step (4), the drying temperature is 50-70 ℃.
The application method of the PDI/MOF heterojunction photocatalyst in degrading iohexol in water comprises the following steps: adding a PDI/MOF heterojunction photocatalyst into the iohexol solution; adding persulfate to perform visible light catalytic reaction, wherein the mass ratio of the photocatalyst to iohexol is 20-300:1, and the mass ratio of the photocatalyst to persulfate is 25:5.37-53.7.
Dark adsorption is carried out before the visible light catalytic reaction, and the visible light catalytic reaction is carried out after the adsorption equilibrium is reached.
The PDI/MOF heterojunction photocatalyst provided by the invention has the advantages of simple preparation process and high yield, and the system can activate persulfate under visible light to carry out high-efficiency catalytic degradation on iohexol in water.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The photocatalyst does not need hydrofluoric acid, has no secondary pollution, is practical, has strong operability, saves energy and is environment-friendly;
(2) According to the preparation method of the photocatalyst, PDI is obtained through organic synthesis, and the PDI/MOF heterojunction photocatalyst is obtained through a water bath heating method, so that the preparation process is simple, the preparation conditions are mild, the large-scale production is easy to realize, the cost is low, and the large-scale preparation is easy to realize;
(3) The photocatalyst of the invention activates the persulfate to use, utilize visible light, compared with traditional ultraviolet light to activate persulfate, the energy consumption is low, with low costs.
Drawings
FIG. 1 is a transmission electron microscope image of SA-PDI;
FIG. 2 is a transmission electron microscope image of MOF;
FIG. 3 is a transmission electron microscopy image of a PDI/MOF heterojunction photocatalyst;
FIG. 4 is a graph showing the comparison of the effect of activated PS degradation of 5mg/L iohexol in the presence of visible light for different materials prepared according to the present invention;
FIG. 5 is a graph of the degradation mechanism of the PDI/MOF heterojunction photocatalyst activated persulfate system under visible light of the present invention.
Detailed Description
The technical scheme of the invention is further described below by referring to examples.
Example 1
The PDI/MOF heterojunction photocatalyst of the embodiment is a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light.
The preparation method of the PDI/MOF heterojunction photocatalyst comprises the following steps:
(1) Placing perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole in a four-neck flask according to a mass ratio of 1:1.8:10 under nitrogen atmosphere at a temperature of 110 ℃ for organic synthesis, adding ethanol and HCl according to a mass ratio of 150:18, and stirring to obtain a stirring product;
(2) Filtering, washing to neutrality and drying the stirred product to obtain PDI powder, wherein the pore diameter of a filtering membrane is 0.22 mu m, and the drying temperature is 60 ℃;
(3) Vacuum activating MIL-101 (Cr) material at 150 ℃;
(4) 50mL of LPDI stock solution was prepared, triethylamine was added thereto, stirred for 30min, MOF was added thereto and then 5mL of HNO was added thereto 3 Heating the solution to 60 ℃ and stirring for 60min to form a PDI/MOF heterojunction photocatalyst, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃, wherein PDI, MOF and HNO are added 3 The mass ratio of (2) is 1:0.78:37;
(5) And placing PDI/MOF in 50mL of iohexol solution, stirring for 30min under dark condition, opening a xenon lamp (lambda >420 nm) added with an optical filter after reaching adsorption balance, adding sodium persulfate at the moment, and uniformly mixing to obtain a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light, wherein the mass ratio of PDI/MOF to iohexol is 20:1, and the mass ratio of PDI/MOF to persulfate is 25:35.8.
Example 2
The PDI/MOF heterojunction photocatalyst of the embodiment is a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light.
The preparation method of the PDI/MOF heterojunction photocatalyst comprises the following steps:
(1) Placing perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole in a four-neck flask according to a mass ratio of 1:1.8:10 under nitrogen atmosphere at a temperature of 100 ℃ for organic synthesis, adding ethanol and HCl according to a mass ratio of 160:18, and stirring to obtain a stirring product;
(2) Filtering, washing to neutrality and drying the stirred product to obtain PDI powder, wherein the pore diameter of a filtering membrane is 0.45 μm, and the drying temperature is 50 ℃;
(3) Vacuum activating MIL-101 (Cr) material at 145 ℃;
(4) 50mL of PDI stock solution was prepared, triethylamine was added, stirring was performed for 30min, MOF was added and then 3mL of HNO was added 3 Heating the solution to 60 ℃ and stirring for 60min to form a PDI/MOF heterojunction photocatalyst, centrifuging, washing, and drying in a vacuum drying oven at 50 ℃, wherein PDI, MOF and HNO are added 3 The mass ratio of (2) is 1:0.34:37;
(5) And placing PDI/MOF in 50mL of iohexol solution, stirring for 30min under dark condition, opening a xenon lamp (lambda >420 nm) added with an optical filter after reaching adsorption balance, adding sodium persulfate at the moment, and uniformly mixing to obtain a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light, wherein the mass ratio of PDI/MOF to iohexol is 300:1, and the mass ratio of PDI/MOF to persulfate is 25:17.9.
Example 3
The PDI/MOF heterojunction photocatalyst of the embodiment is a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light.
The preparation method of the PDI/MOF heterojunction photocatalyst comprises the following steps:
(1) Placing perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole in a four-neck flask according to a mass ratio of 1:1.8:15 under nitrogen atmosphere at a temperature of 105 ℃ for organic synthesis, adding ethanol and HCl according to a mass ratio of 155:18, and stirring to obtain a stirring product;
(2) Filtering, washing to neutrality and drying the stirred product to obtain PDI powder, wherein the pore diameter of a filtering membrane is 0.22 mu m, and the drying temperature is 70 ℃;
(3) Vacuum activating MIL-101 (Cr) material at 155 ℃;
(4) Formulation 50mL of PDI stock solution, triethylamine was added, stirred for 30min, MOF was added and then 7mL of HNO was added 3 Heating the solution to 60 ℃ and stirring for 60min to form a PDI/MOF heterojunction photocatalyst, centrifuging, washing, and drying in a vacuum drying oven at 70 ℃, wherein PDI, MOF and HNO are added 3 The mass ratio of (2) is 1:0.56:37;
(5) And placing PDI/MOF in 50mL of iohexol solution, stirring for 30min under dark condition, opening a xenon lamp (lambda >420 nm) added with an optical filter after reaching adsorption balance, adding sodium persulfate at the moment, and uniformly mixing to obtain a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light, wherein the mass ratio of PDI/MOF to iohexol is 100:1, and the mass ratio of PDI/MOF to persulfate is 25:53.7.
Example 4
The PDI/MOF heterojunction photocatalyst of the embodiment is a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light.
The preparation method of the PDI/MOF heterojunction photocatalyst comprises the following steps:
(1) Placing perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole in a four-neck flask according to a mass ratio of 1:1.8:12 under nitrogen atmosphere at a temperature of 110 ℃ for organic synthesis, adding ethanol and HCl according to a mass ratio of 150:18, and stirring to obtain a stirring product;
(2) Filtering, washing to neutrality and drying the stirred product to obtain PDI powder, wherein the pore diameter of a filtering membrane is 0.22 mu m, and the drying temperature is 60 ℃;
(3) Vacuum activating MIL-101 (Cr) material at 150 ℃;
(4) 50mL of PDI stock solution was prepared, triethylamine was added, stirring was performed for 30min, MOF was added and then 5mL of HNO was added 3 Heating the solution to 60 ℃ and stirring for 60min to form a PDI/MOF heterojunction photocatalyst, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃, wherein PDI, MOF and HNO are added 3 The mass ratio of (2) is 1:0.11:37;
(5) And placing PDI/MOF in 50mL of iohexol solution, stirring for 30min under dark condition, opening a xenon lamp (lambda >420 nm) added with an optical filter after reaching adsorption balance, adding sodium persulfate at the moment, and uniformly mixing to obtain a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light, wherein the mass ratio of PDI/MOF to iohexol is 100:1, and the mass ratio of PDI/MOF to persulfate is 25:10.7.
Example 5
The PDI/MOF heterojunction photocatalyst of the embodiment is a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light.
The preparation method of the PDI/MOF heterojunction photocatalyst comprises the following steps:
(1) Placing perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole in a four-neck flask according to a mass ratio of 1:1.8:10 under nitrogen atmosphere at a temperature of 110 ℃ for organic synthesis, adding ethanol and HCl according to a mass ratio of 150:18, and stirring to obtain a stirring product;
(2) Filtering, washing to neutrality and drying the stirred product to obtain PDI powder, wherein the pore diameter of a filtering membrane is 0.22 mu m, and the drying temperature is 60 ℃;
(3) Vacuum activating MIL-101 (Cr) material at 155 ℃;
(4) 50mL of PDI stock solution was prepared, triethylamine was added, stirring was performed for 30min, MOF was added and then 5mL of HNO was added 3 Heating the solution to 60 ℃ and stirring for 60min to form a PDI/MOF heterojunction photocatalyst, centrifuging, washing, and drying in a vacuum drying oven at 60 ℃, wherein PDI, MOF and HNO are added 3 The mass ratio of (2) is 1:1:37;
(5) And placing PDI/MOF in 50mL of iohexol solution, stirring for 30min under dark condition, opening a xenon lamp (lambda >420 nm) added with an optical filter after reaching adsorption balance, adding sodium persulfate at the moment, and uniformly mixing to obtain a PDI/MOF heterojunction photocatalyst activated persulfate system under visible light, wherein the mass ratio of PDI/MOF to iohexol is 100:1, and the mass ratio of PDI/MOF to persulfate is 25:5.4.
Comparative example 1
In this comparative example, SA-PDI was used as a photocatalyst, and other raw materials, ratios, preparation methods and detection methods were the same as those of example 1, with the removal rate of iohexol reaching 39.7% at 35 min.
Comparative example 2
In this comparative example, MOF was used as a photocatalyst, and other raw materials, ratios, preparation methods and detection methods were the same as in example 1, with a removal rate of iohexol of 6.9% at 35 min.
FIG. 1 is a transmission electron microscope image of SA-PDI, showing a stripe cluster shape.
Fig. 2 is a transmission electron microscope image of a MOF heterojunction photocatalyst, which is in the shape of a regular octahedron.
FIG. 3 is a transmission electron microscopy image of a PDI/MOF heterojunction photocatalyst; it can be seen from the figure that the PDI is successfully complexed with the MOF.
FIG. 4 is a graph showing the comparison of the effect of activated PS degradation of 5mg/L iohexol in the presence of visible light for different materials prepared according to the present invention; from the graph, when PDI is equal to MOF=9:7, the degradation effect is optimal, and the iohexol removal rate reaches 100% at 35 min.
By comparing comparative examples 1-2 with example 1, the removal rate of SA-PDI and MOF to degrade IOH under visible light is lower than the scope of the invention.
FIG. 5 is a graph of the degradation mechanism of the PDI/MOF heterojunction photocatalyst activated persulfate system under visible light of the present invention. PDI/MOF photocatalysis is a typical type I heterojunction, with the Valence (VB) and Conduction (CB) bands of the MOF being more positive and more negative than SA-PDI, respectively. Thus, when holes (h + ) And electrons (e) - ) When energy is obtained under the irradiation of visible light, h is generated by light + Can migrate from VB of MOF to VB of SA-PDI, while light induced e - Can be transferred from the CB of the MOF to the CB of the SA-PDI. In fact, all charge carriers are accumulated on the SA-PDI, which is detrimental to charge carrier separation. Therefore, PS is added as an electron acceptor and hinders e - /h + Recombination in SA-PDI is an advantageous strategy. PS can directly capture electrons, generating SO at CB of PDI 4 · - . In addition, partial electron reduction O 2 And generates superoxide radical (O) at CB of SA-PDI 2 - ) Further generating singlet oxygen 1 O 2 ). In addition, CB electrons of PDI reduce S 2 O 8 2- SO generation 4 · - Or reduce H 2 O generates OH. At the same time, the photo-generated electrons can directly destroy PSSome O-O bonds, thereby generating SO 4 · - . Subsequently, a series of free radical chain reactions may occur to form SO 4 · - 、·OH、·O 2 - And 1 O 2 . Finally, h + 、·OH、 1 O 2 、·O 2 - And SO 4 · - All contribute to degradation of IOH.
Claims (8)
1. The preparation method of the PDI/MOF heterojunction photocatalyst is characterized by comprising the following steps of:
(1) Organic synthesis is carried out on perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole, ethanol and HCl are added and stirred, and a stirring product is prepared;
(2) Filtering, washing the stirred product to be neutral and drying to obtain PDI powder;
(3) Vacuum activating MIL-101 (Cr) material at 145-155 ℃;
(4) Preparing the PDI powder into PDI solution, sequentially adding triethylamine, MIL-101 (Cr) and HNO 3 And stirring, filtering, washing to neutrality and drying to obtain the PDI/MOF heterojunction photocatalyst.
2. The method for preparing the PDI/MOF heterojunction photocatalyst according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of the perylene-3, 4,9, 10-tetracarboxylic dianhydride, the beta-alanine and the imidazole is 1:1.8:10-15.
3. The method for preparing the PDI/MOF heterojunction photocatalyst according to claim 1, wherein the method comprises the following steps: in the step (1), the perylene-3, 4,9, 10-tetracarboxylic dianhydride, beta-alanine and imidazole are organically synthesized in a nitrogen atmosphere at the temperature of 100-110 ℃.
4. The method for preparing the PDI/MOF heterojunction photocatalyst according to claim 1, wherein the method comprises the following steps: in the step (2), the pore size of the filtering membrane is 0.22-0.45 μm.
5. The method for preparing the PDI/MOF heterojunction photocatalyst according to claim 1, wherein the method comprises the following steps: in the steps (2) and (4), the drying temperature is 50-70 ℃.
6. The method for preparing the PDI/MOF heterojunction photocatalyst according to claim 1, wherein the method comprises the following steps: the material comprises the following raw material components: PDI, MIL-101 (Cr) and acid with the mass ratio of 1:0.11-1:37, wherein the acid is HNO 3 。
7. A method of using the PDI/MOF heterojunction photocatalyst prepared by the preparation method of claim 1 to degrade iohexol in water, comprising the steps of: adding a PDI/MOF heterojunction photocatalyst into the iohexol solution; adding persulfate to perform visible light catalytic reaction, wherein the mass ratio of the photocatalyst to iohexol is 20-300:1, and the mass ratio of the photocatalyst to persulfate is 25:5.37-53.7.
8. The method for using the PDI/MOF heterojunction photocatalyst for degrading iohexol in water according to claim 7, wherein the method comprises the following steps: and carrying out dark adsorption before the visible light catalytic reaction, and carrying out the visible light catalytic reaction after reaching adsorption equilibrium.
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