CN115090332B - MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis and preparation method and application thereof - Google Patents
MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis and preparation method and application thereof Download PDFInfo
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- CN115090332B CN115090332B CN202210907570.3A CN202210907570A CN115090332B CN 115090332 B CN115090332 B CN 115090332B CN 202210907570 A CN202210907570 A CN 202210907570A CN 115090332 B CN115090332 B CN 115090332B
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 58
- 239000002351 wastewater Substances 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 claims abstract description 29
- 230000015556 catabolic process Effects 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 24
- 231100000719 pollutant Toxicity 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 41
- 230000003197 catalytic effect Effects 0.000 claims description 23
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 23
- 229960001180 norfloxacin Drugs 0.000 claims description 23
- 230000007547 defect Effects 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 12
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004021 humic acid Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- SMOZAZLNDSFWAB-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,24-dihydroporphyrin-5-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C=1C=CC(N=1)=C(C=1C=CC(=CC=1)C(O)=O)C1=CC=C(N1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)C(O)=O)=C2N=C1C=C2 SMOZAZLNDSFWAB-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- -1 4-carboxyphenyl Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 230000003115 biocidal effect Effects 0.000 abstract description 6
- 150000001449 anionic compounds Chemical class 0.000 abstract description 3
- 229910001412 inorganic anion Inorganic materials 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000004032 porphyrins Chemical class 0.000 description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229960002446 octanoic acid Drugs 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000005473 octanoic acid group Chemical group 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
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- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention relates to a MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis, and a preparation method and application thereof. The catalyst has good removal effect on antibiotic pollutant wastewater, can resist the influence of inorganic anions in actual water, reduces the generation of degradation byproducts, and is more suitable for the treatment of the actual wastewater.
Description
Technical Field
The invention relates to a MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis, and a preparation method and application thereof, and belongs to the technical field of chemistry and environment.
Background
The photocatalytic oxidation technology mostly uses a semiconductor as a catalyst, uses sunlight as driving energy to generate oxidative active substances (such as hydroxyl free radicals, superoxide free radicals and the like), converts organic pollutants into non-toxic or low-toxic substances, and is a pollutant removal technology with strong oxidability, energy conservation, high efficiency and thoroughness. At present, photocatalytic oxidation technology represented by visible light catalytic technology is often used in wastewater treatment processes such as industrial organic wastewater, antibiotic pharmaceutical wastewater and the like. However, in the application process of the traditional photocatalyst, the light responsiveness is poor, the electron-hole recombination rate is high, the photon utilization rate is low, and the catalytic efficiency often cannot reach a theoretical value. In addition, the life of the active substances generated in the photocatalytic oxidation process is extremely short, quenching is easy to occur in the mass transfer process, and oxidative degradation of pollutants is greatly limited. Therefore, improvement of the photocatalyst performance is very important.
The oxide semiconductor photocatalyst has defects introduced into a certain concentration range on the surface or the body thereof, so that the efficiency of the photocatalyst can be effectively improved. Even narrowing the band gap of the semiconductor to a certain extent and expanding the effect of visible light absorption so as to achieve the purpose of improving the performance of the photocatalyst. More importantly, defects, especially oxygen vacancies, are easier to capture photo-generated electrons, so that the recombination of the photo-generated electrons and the holes is inhibited, and the photocatalytic degradation of pollutants is promoted.
The Metal Organic Frameworks (MOFs) are highly ordered porous crystalline materials, and have wide application prospects in various fields such as adsorption, separation, catalysis and the like. Porphyrin MOFs have shown widespread use in photocatalytic applications due to their semiconductor-like function. The organic linkers in porphyrin MOFs can collect light by acting as an antenna and further activate the metal cluster through the linker, causing it to undergo charge transition, thereby generating sufficient Reactive Oxygen Species (ROS). In addition, the porphyrin MOFs also show excellent adsorptivity, have rich pores, can well collect target organic matters in water, and isolate the influence of humic acid and salt ions in a complex environment by reducing the space distance between a catalytic site and the organic matters.
However, in the photocatalysis process of the porphyrin MOFs, metal sites are easily masked by organic ligands, and cannot play a role in catalysis, so that the electron transfer efficiency in the photocatalysis process is low; meanwhile, the sources of free radicals and non-free radicals in the system are single, the actual catalytic effect is poor, and the photocatalytic effect in high-salt wastewater is poor.
Therefore, it is necessary to develop a novel porphyrin MOFs photocatalyst with high photocatalytic efficiency, which can be used for degrading pollutants in complex water environments.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis, and a preparation method and application thereof.
Summary of the invention:
the invention prepares the Hf-TCPP MOFs by a simple hydrothermal method, uses monocarboxylic acids with different chain lengths to regulate the defect degree, introduces defects into the porphyrin MOFs, increases the pore diameter of the porphyrin MOFs, enhances the capability of capturing electrons of a catalyst, enhances the separation of photo-generated electrons and holes, and obtains a novel MOFs photocatalyst which can generate more free radicals and non-free radicals when being used for removing organic pollutants in wastewater by visible light catalysis, especially in high-salt wastewater, can promote the degradation of pollutants, and is suitable for the degradation of pollutants in complex water environment. The catalyst has good removal effect on antibiotic pollutant wastewater, can resist the influence of inorganic anions in actual water, reduces the generation of degradation byproducts, and is more suitable for the treatment of the actual wastewater.
Detailed description of the invention:
in order to achieve the above purpose, the invention is realized by the following technical scheme:
MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis, wherein the MOFs photocatalyst is prepared from Hf 4+ And meso-tetra (4-carboxyphenyl) porphin H 2 TCPP coordinates, defects are manufactured by monocarboxylic acid, crystals with regular morphology are obtained through one-step hydrothermal synthesis, and the microscopic morphology is a three-dimensional porous structure.
The preparation method of the MOFs photocatalyst comprises the following steps:
HfCl is added 4 Meso-tetra (4-carboxyphenyl) porphine H 2 TCPP, a monocarboxylic acid and N,stirring the mixture of the N-dimethylformamide DMF to obtain a mixed system; and heating the mixed system, cooling, filtering, washing and drying to obtain the defect-rich Hf-TCPP MOFs photocatalytic material.
According to a preferred embodiment of the invention, hfCl is present in the mixture 4 Is present in a concentration of 0.5-3.3g/L, meso-tetra (4-carboxyphenyl) porphine H 2 The concentration of TCPP is 0.5-3.3g/L.
According to a preferred embodiment of the invention, hfCl is present in the mixture 4 With meso-tetra (4-carboxyphenyl) porphine H 2 The TCPP molar ratio is (1-2): (1-2).
According to a preferred embodiment of the invention, DMF is used in an amount of 100-500mL in the mixture.
According to a preferred embodiment of the invention, the monocarboxylic acid is formic acid, butyric acid or caprylic acid with a volume fraction of 88%.
Most preferably, the monocarboxylic acid is 88% formic acid by volume.
According to the invention, hfCl is preferably 4 The molar ratio of Hf to monocarboxylic acid is: (1-3): (300-900).
Preferably, hfCl 4 The molar ratio of Hf to monocarboxylic acid is: (1-3): (400-620).
Most preferably, hfCl 4 The molar ratio of Hf to monocarboxylic acid is: 1.5:612.
When the monocarboxylic acid is formic acid, the obtained Hf-TCPP MOFs photocatalytic material is named Hf-TCPP-FA, when the monocarboxylic acid is butyric acid, the obtained Hf-TCPP MOFs photocatalytic material is named Hf-TCPP-BA, and when the monocarboxylic acid is octanoic acid, the obtained Hf-TCPP MOFs photocatalytic material is named Hf-TCPP-OA.
According to the invention, the mixing system is preferably prepared as follows:
HfCl is added 4 Adding the powder into N, N-dimethylformamide DMF, and dissolving completely by ultrasonic treatment for 8-15min, and adding meso-tetra (4-carboxyphenyl) porphine H 2 And performing ultrasonic treatment on TCPP for 8-15min, and then adding monocarboxylic acid to perform ultrasonic mixing for 8-15min to obtain a mixed system.
The monocarboxylic acid is uniformly dispersed in the MOFs structure in the synthesis process and is removed along with the displacement reaction; forming the defect-rich Hf-TCPP MOFs photocatalytic material.
According to the invention, the heating temperature of the mixed system is preferably 90-180 ℃, and the mixed system is washed by DMF and acetone respectively after cooling.
According to the invention, the temperature of the drying treatment is preferably 60-180 ℃ and the drying time is 6-24h.
The MOFs photocatalyst is applied to catalytic degradation of pollutants in high-salt and/or humic acid-containing complex water, and is added into a pollutant solution, and after dark state adsorption saturation, visible light is irradiated to the MOFs photocatalyst under room temperature condition to perform visible light catalytic degradation.
According to the present invention, preferably, the light irradiation light source is a xenon lamp.
According to the invention, the mass-volume ratio of the MOFs photocatalyst to the water body is as follows: 5-50mg:50-200mL.
According to the invention, the concentration of pollutants in the water body is 5-30mg/L, the pollutants are Norfloxacin (NOR) antibiotics, and the catalytic degradation time is 0.5-3h.
According to the invention, the pH of the application system is preferably from 4 to 9.
According to the invention, the salt in the high-salt water body is sodium chloride, sodium sulfate, sodium bicarbonate or sodium nitrate, and the concentration of the salt is 5-500mM.
According to the invention, the catalytic system preferably has the capacity of resisting complex environmental interference, and the degradation effect of NOR is not obviously inhibited in the presence of 2-10mg/L humic acid.
According to the invention, the Hf-TCPP MOFs photocatalytic material is recycled by centrifugal collection after photocatalytic degradation, washing with deionized water, soaking and washing with absolute ethyl alcohol, centrifugal collection again and freeze drying.
According to the invention, the centrifugal collection rotation speed is 5000r/min, the deionized water washing times are 3 times, and the circulation times are 6 times.
Through the recovery and utilization discovery, after the catalyst material is recovered and utilized for 6 times, the catalyst still has good photocatalytic performance, which proves that the Hf-TCPP MOFs photocatalytic material has recycling property, stability and recyclability.
After the defect is introduced into the porphyrin MOFs, the Hf-O cluster has stronger electropositivity, more anions can be enriched, and ionic bonds Hf-Cl are formed, so that not only are the anions and organic pollutants isolated, but also free anions are prevented from quenching free radicals. In the photocatalytic process, the coexisting anions can act as additional electron donors, transporting electrons into the Hf-O cluster, forming more lower-valence Hf (III). The lower valence metal has the ability to react further with dissolved oxygen, generating more superoxide radicals.
The invention has the technical characteristics and advantages that:
1. the Hf-TCPP MOFs photocatalytic material rich in defects of the invention is prepared from Hf and H 2 TCPP coordination, utilizing monocarboxylic acid to make defect, synthesizing three-dimensional porous visible light catalytic material, providing new method and thinking for synthesizing MOFs photocatalyst with porous defect.
2. The defect-rich Hf-TCPP MOFs photocatalytic material has the advantages that the adsorption capacity of the defect-rich Hf-TCPP MOFs photocatalytic material on pollutants is obviously enhanced, the free radical and non-free radical content is obviously improved, the free radical variety is rich, and the anti-biological pollutants in the water body can be rapidly removed.
3. The Hf-TCPP MOFs photocatalytic material rich in defects is used as a visible light catalyst, generates a large amount of free radicals and non-free radicals when being subjected to photocatalysis, is particularly suitable for degrading pollutants in complex water environment, and has good effect of removing antibiotic organic pollutant wastewater; can resist the influence of inorganic anions in the actual water body, and is more suitable for the treatment of the actual wastewater.
4. The defect-rich Hf-TCPP MOFs photocatalytic material can realize efficient degradation of high-salinity water environmental pollutants, and can promote generation of more free radicals under the condition of high salinity of 500mM, so that degradation of the pollutants is promoted.
5. The defect-rich Hf-TCPP MOFs photocatalytic material has good visible light response capability and excellent catalytic performance, can effectively degrade antibiotic organic pollutants, and realizes reasonable development and utilization of visible light energy.
Drawings
FIG. 1 is an SEM image of photocatalytic materials of different MOFs;
FIG. 2 is an XRD spectrum of a different MOFs photocatalytic material;
FIG. 3 is an XPS spectrum of different MOFs photocatalytic materials;
FIG. 4 is a graph showing degradation of NOR by different MOFs photocatalytic materials in the visible light catalytic system of experimental example 2;
FIG. 5 is a graph showing degradation of different MOFs photocatalytic materials on NOR in a visible light catalytic high-salt system of application experiment example 2;
FIG. 6 is a graph showing the degradation of NOR by the visible light catalytic system of Experimental example 1 at different pH values;
FIG. 7 is a graph showing the degradation of NOR in the presence of different capture agents in application experiment 1;
FIG. 8 is an ESR spectrum of the different active materials and defects in application experiment example 1;
FIG. 9 is a graph showing the effect of anions at different concentrations on catalytic degradation in application experiment 1;
FIG. 10 is a graph showing the effect of humic acid of different concentrations on catalytic degradation in application experiment example 1;
FIG. 11 is a graph showing the effect of recyclability of MOFs photocatalytic material in example 1 of the present invention.
Detailed Description
The invention will now be further illustrated by, but is not limited to, the following specific examples in connection with the accompanying drawings.
The starting materials used in the examples were all conventional commercial products.
Example 1
Preparation of MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis:
(1) 481mg of HfCl 4 ，500mg H 2 TCPP was dissolved in 300mL DMF and was prepared as HfCl 4 The molar ratio to the monocarboxylic acid is as follows: 1.5:612 addition ofFormic acid with a volume fraction of 88%, and finally the mixture was transferred to a 500mL round bottom flask;
(2) The mixture was heated at 120 ℃ for 24h, cooled to room temperature, and after centrifugation the product was harvested and washed with DMF;
(3) Adding the product into 1.25% hydrochloric acid solution, heating at 90 ℃ for 12h, and repeating for 3 times;
(4) The product was filtered, washed with DMF and methanol, respectively, and soaked in methanol for 24h, repeated 2 times;
(5) And (3) filtering the product, and drying the product in a vacuum oven at 100 ℃ for 12 hours to obtain dark purple crystals, thereby obtaining the defect-rich Hf-TCPP MOFs photocatalytic material, which is named as Hf-TCPP-FA.
As can be seen from FIG. 1, the Hf-TCPP-FA photocatalytic material has a three-dimensional porous structure, and XRD and XPS of the Hf-TCPP-FA photocatalytic material are shown in FIG. 2 and 3, respectively. The application of the Hf-TCPP-FA photocatalytic material is used for removing organic pollutants in high-salt wastewater by visible light catalysis, and specifically comprises the following steps:
adding Hf-TCPP-FA photocatalytic material into high-salt wastewater containing pollutants, stirring the high-salt wastewater under the condition of room temperature and pH of 4.0-9.0 and the irradiation condition of a visible light source, and rapidly generating a large amount of free radicals and non-free radicals by a system to catalyze and degrade the pollutants for 1h, wherein 5mg of Hf-TCPP-FA photocatalytic material is added into each 100mL of wastewater, and the concentration of the pollutants in the wastewater is 10mg/L.
Application experiment example 1:
the Hf-TCPP-FA photocatalytic material in example 1 is added into simulated wastewater with norfloxacin antibiotic concentration of 10mg/L, 5mg of Hf-TCPP-FA photocatalytic material is added into each 100mL of wastewater, and is irradiated by a Shi Jiake light source to form a photocatalytic system, and the pH, salinity, anions and humic acid concentration of the system are respectively changed for testing:
1. influence of different pH conditions on the catalytic System
The effect of different pH conditions on the catalytic system is shown in FIG. 6, and the result shows that under the irradiation condition of a visible light source, in the initial pH range of pH 3-9, the degradation of NOR is obviously inhibited when the pH is 3, and the degradation effect of NOR is obviously improved along with the rise of the pH, so that the catalyst has better effect in an alkaline environment.
2. Analysis of active species in photocatalytic systems
To verify the active species in the photocatalytic system, quenching experiments and electron paramagnetic resonance Experiments (ESR) were performed. As a result, as shown in FIG. 7, isopropanol and furfuryl alcohol were used as OH and furfuryl alcohol, respectively 1 O 2 After addition of isopropanol and furfuryl alcohol quenchers, the system concentration after addition of isopropanol and furfuryl alcohol was 10mmol/L, respectively, and degradation of NOR was significantly inhibited. As shown in FIG. 8, the ESR results indicate that a large amount of OH and OH can be generated during the photocatalytic process 1 O 2 (OH and OH) 1 O 2 Is the main active substance of NOR degradation under the irradiation of visible light.
3. Effect of different anions on photoreaction System
To verify against the influence of natural environment background, different anions and Cl-, SO-with different concentrations are added into the simulated wastewater 4 2- And NO 3 The effect on the reaction system, as shown in figure 9, the addition of anions has a significant promoting effect on the overall degradation system. This is mainly because, after addition of the salt ions, the content of OH increases significantly, which has the characteristic of non-selective attack and can accelerate the degradation of NOR.
4. Influence of high-salt water on different catalysts
In order to verify the influence of the high-salt water body, different salts are added into the simulated wastewater, and the influence of the different salts on the photocatalytic system is explored. As shown in FIG. 9, in 500mM high-salt water, the degradation effect of NOR is improved to a certain extent, and the performance of the Hf-TCPP MOFs photocatalytic material with abundant defects is improved most obviously.
5. Influence of humic acid with different concentrations on photoreaction system
In order to verify the influence of the natural environment background resistance, the influence of humic acid with different concentrations on a reaction system is explored. As shown in FIG. 10, in 2-10mg/L humic acid water, the degradation effect of NOR is not obviously inhibited, which indicates that the Hf-TCPP MOFs photocatalytic material has the capability of resisting complex environmental interference.
6. Recyclability of catalyst
To verify the stability of the catalyst, the effect of the catalyst in 6 cycles of pure water and high brine, respectively, was studied. As shown in FIG. 11, after 6 cycles, the performance of the Hf-TCPP-FA photocatalytic material for NOR removal was slightly degraded, indicating that the catalyst had good recyclability.
Example 2
The preparation of the Hf-TCPP MOFs photocatalytic material described in example 1 is different in that:
the remaining operation and amount were exactly the same as in example 1, except that 88% by volume of formic acid was replaced with butyric acid, and the resultant product was designated as Hf-TCPP-BA.
SEM image of Hf-TCPP-BA is shown in FIG. 1, XRD is shown in FIG. 2, and XPS is shown in FIG. 3.
Example 3
The preparation of the Hf-TCPP MOFs photocatalytic material described in example 1 is different in that:
the remaining operation and amount were exactly the same as in example 1 except that formic acid having a volume fraction of 88% was replaced with octanoic acid, and the resultant product was designated as Hf-TCPP-OA.
SEM image of Hf-TCPP-OA is shown in FIG. 1, XRD is shown in FIG. 2, and XPS is shown in FIG. 3.
Comparative example 1
The photocatalytic material according to example 1 was prepared with the difference that:
the remaining operation and amount were exactly the same as in example 1 without adding formic acid, and the resultant product was designated as Hf-TCPP.
The SEM image of Hf-TCPP is shown in FIG. 1, the XRD image is shown in FIG. 2, and the XPS image is shown in FIG. 3.
Application experiment example 2:
samples of the photocatalytic materials of examples 1 to 3 and comparative example 1 were taken at a concentration of 5mg in 100mL of a 10mg/L NOR solution, and adsorbed at room temperature. At the end of adsorption (30 min), photocatalytic degradation was performed. In the degradation process, 1mL of sample is taken at intervals of 5-15min, and the concentration of the sample is measured by a high performance liquid chromatograph, so that the catalytic behavior of the process is studied.
The effect of different photocatalytic materials on NOR removal is shown in fig. 4;
different Hf-TCPP MOFs photocatalytic materials are used in different high-salt water bodies (500 mM NaCl, na) 2 SO 4 、NaNO 3 And 50mM NaHCO 3 ) The performance of the medium removal NOR is shown in fig. 5: (a) Hf-TCPP, (b) Hf-TCPP-FA, (c) Hf-TCPP-BA, (d) Hf-TCPP-OA;
the effect of different catalytic materials on NOR removal in different concentrations of anionic environment is shown in fig. 9: (a) NaCl, (b) Na 2 SO 4 ，(c)NaHCO 3 ，(d)NaNO 3 。
Claims (6)
1. The application of MOFs photocatalyst capable of removing organic pollutants in high-salt wastewater through visible light catalysis is applied to catalytic degradation of pollutants in high-salt and/or humic acid-containing complex water, MOFs photocatalyst is added into pollutant solution, after dark state adsorption saturation, visible light is irradiated to the MOFs photocatalyst under room temperature condition, and visible light catalytic degradation is carried out;
the MOFs photocatalyst is prepared by using Hf 4+ And meso-tetra (4-carboxyphenyl) porphin H 2 TCPP coordination, utilizing monocarboxylic acid to manufacture defects, synthesizing by a one-step hydrothermal method to obtain crystals with regular morphology, wherein the microstructure is a three-dimensional porous structure,
the preparation method comprises the following steps:
HfCl is added 4 Meso-tetra (4-carboxyphenyl) porphine H 2 Stirring the mixture of TCPP, monocarboxylic acid and N, N-dimethylformamide DMF to obtain a mixed system; heating the mixed system, cooling, filtering, washing and drying to obtain the Hf-TCPP MOFs photocatalytic material rich in defects;
in the mixture, hfCl 4 Is present in a concentration of 0.5-3.3g/L, meso-tetra (4-carboxyphenyl) porphine H 2 The concentration of TCPP is 0.5-3.3g/L, hfCl 4 With meso-tetra (4-carboxyphenyl) porphine H 2 The TCPP molar ratio is (1-2): (1-2) the amount of DMF in the mixture was 100-500mL and the monocarboxylic acid was 88% by volumeFormic acid, hfCl 4 The molar ratio of Hf to monocarboxylic acid is: (1-3) (400-620), wherein the heating temperature of the mixed system is 90-180 ℃, the mixed system is respectively washed by DMF and acetone after being cooled, the drying treatment temperature is 60-180 ℃, and the drying time is 6-24h.
2. The use according to claim 1, characterized in that HfCl 4 The molar ratio of Hf to monocarboxylic acid is: 1.5:612.
3. The use according to claim 1, wherein the mixed system is prepared as follows:
HfCl is added 4 Adding the powder into N, N-dimethylformamide DMF, and dissolving completely by ultrasonic treatment for 8-15min, and adding meso-tetra (4-carboxyphenyl) porphine H 2 And performing ultrasonic treatment on TCPP for 8-15min, and then adding monocarboxylic acid to perform ultrasonic mixing for 8-15min to obtain a mixed system.
4. The use according to claim 1, wherein the light irradiation light source is a xenon lamp, and the mass-to-volume ratio of the MOFs photocatalyst to the water body is: 5-50mg:50-200mL, the concentration of pollutants in the water body is 5-30mg/L, the pollutants are Norfloxacin (NOR) antibiotics, the catalytic degradation time is 0.5-3h, and the pH of an application system is 4-9.
5. The use according to claim 1, wherein the system is promoted to degrade in a high-salt water body, wherein the salt in the high-salt water body is sodium chloride, sodium sulfate, sodium bicarbonate or sodium nitrate, and the salt concentration is 5-500mM; the catalytic system has the capability of resisting complex environmental interference, and the degradation effect of NOR is not obviously inhibited in the presence of 2-10mg/L humic acid.
6. The use according to claim 1, wherein the recycling of the Hf-TCPP MOFs photocatalytic material is achieved by centrifugation at 5000r/min, washing with deionized water, soaking with absolute ethanol, and freeze-drying after centrifugation again, the number of times of centrifugation is 3, and the number of times of circulation is 6.
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