CN115970658A - Preparation method and application of zero-valent iron-based covalent organic framework composite material - Google Patents
Preparation method and application of zero-valent iron-based covalent organic framework composite material Download PDFInfo
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- CN115970658A CN115970658A CN202211715945.2A CN202211715945A CN115970658A CN 115970658 A CN115970658 A CN 115970658A CN 202211715945 A CN202211715945 A CN 202211715945A CN 115970658 A CN115970658 A CN 115970658A
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- borohydride
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- DJOSTUFCDFIBRL-UHFFFAOYSA-N C1=CC(=CC=C1N)N.C(=O)C1=C(C(=C(C(=C1O)C=O)O)C=O)O Chemical compound C1=CC(=CC=C1N)N.C(=O)C1=C(C(=C(C(=C1O)C=O)O)C=O)O DJOSTUFCDFIBRL-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 150000002505 iron Chemical class 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 150000004763 sulfides Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
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- 239000011148 porous material Substances 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- PTNZGHXUZDHMIQ-UHFFFAOYSA-N 4-(dimethylamino)-1,5,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4a,5,5a,6-tetrahydro-4h-tetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2C(C)C(C(O)C3C(C(O)=C(C(N)=O)C(=O)C3N(C)C)(O)C3=O)C3=C(O)C2=C1O PTNZGHXUZDHMIQ-UHFFFAOYSA-N 0.000 description 38
- 229960004082 doxycycline hydrochloride Drugs 0.000 description 38
- 239000000243 solution Substances 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
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- 229910052717 sulfur Inorganic materials 0.000 description 9
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
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- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
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Images
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of material preparation, water treatment and water environment restoration, and relates to a preparation method and application of a functional material nZVI/TpPa-1 or SnZVI/TpPa-1 covalent organic framework composite material. The invention provides a preparation method of novel functional materials (nZVI/TpPa-1 and SnZVI/TpPa-1) taking nano zero-valent iron (nZVI) or vulcanized nano zero-valent iron (SnZVI) as an active site and a Covalent Organic Framework (COF) porous material as a carrier, and application of the functional materials in degrading tetracyclic antibiotics in water. The technical scheme of the invention has simple synthetic process and mild reaction condition; reduces the aggregation of nZVI; the prepared composite material has magnetism, and magnetic separation and recovery of the material are realized; the composite material has high pollutant degradation efficiency and wide applicable pH range, the degradation effect can obviously reach 55.38-99.86% in the range of pH = 3-8, and the composite material has wide practical application prospect.
Description
Technical Field
The invention belongs to the technical field of material preparation, water treatment and water environment restoration, and relates to a preparation method and application of a functional material nZVI/TpPa-1 or SnZVI/TpPa-1 covalent organic framework composite material, wherein the antibiotic is removed by using a nZVI or SnZVI reinforced Covalent Organic Framework (COF) derivative material.
Background
Pharmaceutical and Personal Care Products (PPCPs), as a class of emerging environmental micropollutants, are increasingly receiving widespread attention from the scientific community and the public due to potential environmental toxicological effects and human health risks. Among them, doxycycline hydrochloride (DOX-H), which is a tetracycline antibiotic having potent bactericidal and bacteriostatic effects, is used in human infusion therapy, and also in the livestock, fish, and other breeding industries in large doses and at high frequencies. In recent years, it has been frequently detected in drinking water, surface water and ground water. It follows that antibiotics have become one of the most important new pollutants in the aquatic environment. The efficiency of removing trace antibiotics at the tail end of sewage treatment is improved.
Covalent Organic Framework (COFs) is a novel porous and crystalline network polymer formed by stable covalent bonds, and has the advantages of high stability, regular pore structure, high porosity, large specific surface area, stable chemical performance, easiness in functionalization, lower density and the like, so that the COFs are widely applied to the fields of adsorption and catalysis of liquid and gas, drug delivery and sensors, detection of pollutants in water and the like. However, due to the lack of active sites in COFs themselves, their use in the field of degradation of pollutants is less. In addition, most COF materials also have the disadvantages of difficult recycling, complicated and time-consuming preparation method, and environmental unfriendliness. Therefore, there is a need to develop a COFs composite material that is easy to prepare, recyclable, and has efficient removal performance.
Nanometer zero-valent iron (nZVI) is a repair material for degrading various pollutants due to high reactivity, low price, easy availability, high safety and no secondary pollution to the environment. Meanwhile, nZVI is also one of the first nanomaterials engineered for environmental remediation. However, nZVI is easy to agglomerate and oxidize in the environment, and has a small specific surface area, and the advantage of nZVI cannot be fully exerted by using nZVI alone, which further hinders the wide application of nZVI technology in practical water treatment and groundwater remediation engineering. In recent years, sulfur doping is considered to be a very useful method for modifying nZVI, which can improve electron transfer on the iron surface and improve electron efficiency as well as improve material stability, but still has the problems of easy agglomeration, small specific surface area and the like due to electrostatic attraction between SnZVI particles. Therefore, in order to further improve the reaction activity and stability of the nZVI particles, high-activity nZVI and SnZVI can be loaded on a carrier with a porous structure, so that on one hand, the effective specific surface area of the nanoparticles can be increased, and thus the adsorption of pollutant molecules is enhanced; on the other hand, the agglomeration of the nZVI and the SnZVI particles can be effectively prevented. In addition, the loading material can also be used as a transmission medium of pollutant molecules, and can also have the functions of strengthening electron transfer or assisting in pre-enrichment of pollutants. The COFs have the characteristics of large specific surface area, stable chemical property, low density and the like, and are completely suitable for serving as load materials of nZVI and SnZVI. However, most of the previous studies have used COFs only as highly effective adsorbents. However, adsorption is limited to the physical conversion of contaminants from a liquid phase to a solid phase, where the contaminants accumulate without being degraded, which also makes practical application of COFs as adsorbents challenging. The functional COF composite material (nZVI/TpPa-1 and SnZVI/TpPa-1) coupling the reducibility of zero-valent iron and sulfurized zero-valent iron integrates the reduction and adsorption functions, and the material can be separated from a system through magnetic separation after the material is used. At present, the application of nZVI/TpPa-1 or SnZVI/TpPa-1 in the treatment of PPCPs is not seen.
The invention content is as follows:
the invention aims to provide a preparation method of novel functional materials (nZVI/TpPa-1 and SnZVI/TpPa-1) which take nano zero-valent iron (nZVI) or vulcanized nano zero-valent iron (SnZVI) as an active site and take a Covalent Organic Framework (COF) porous material as a carrier and application of the functional materials in degrading tetracycline antibiotics in water aiming at the current situation that the removal method of tetracycline antibiotics wastewater such as doxycycline hydrochloride is few.
The technical scheme provided by the invention is that the preparation method of the zero-valent iron-based covalent organic framework composite material is characterized by comprising the following steps:
step (1) preparation of covalent organic framework TpPa-1: mixing 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde (Tp) and p-phenylenediamine (Pa-1) under the condition of acidity (pH = 3-5), adding an organic mixed solvent, taking acetic acid as a catalyst, carrying out ultrasonic treatment for 10-60 min, uniformly mixing, transferring the obtained acidic organic ligand mixed solution into a polytetrafluoroethylene high-pressure hydrothermal reaction kettle, reacting for 2-4 days in an oven at 100-150 ℃, cooling to room temperature, washing, centrifuging, and drying for 12-36 h to obtain TpPa-1.
Loading active components in the step (2): adding a metal iron salt and the TpPa-1 obtained in the step (1) into a reaction solvent, stirring for 1-5 h, and uniformly mixing to obtain a TpPa-1/metal iron salt mixed solution; continuously stirring under the atmosphere of reducing gas, and adding borohydride serving as a reducing agent to slowly mix with the TpPa-1/metal salt mixed solution; and simultaneously adding soluble sulfide salt, reacting for 0.3-5 h, immediately washing after the reaction is finished, freeze-drying for 12-36 h to obtain the nZVI/TpPa-1 or SnZVI/TpPa-1 composite functional material, grinding into powder for later use, filling inert gas, and storing at low temperature.
Preferably, in the step (1), the molar ratio of the 4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde (Tp) to the p-phenylenediamine (Pa-1) is 2:3.
preferably, in the step (1), the organic mixed solvent is one or more of mesitylene, dioxane and dimethyl sulfoxide; the volume ratio of the organic mixed solvent to the mixture of the 4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde (Tp) and the p-phenylenediamine (Pa-1) is 1:1.
preferably, in the step (2), the metallic iron salt is one or more of ferric nitrate, ferric chloride and ferrous sulfate; the addition amount of the metal iron salt is as follows: the mass ratio of TpPa-1 is 0.1-4: 1.
preferably, in the step (2), the reaction solvent is water or a mixed solution of water and ethanol in any proportion.
Preferably, in the step (2), the reducing gas is one or more of nitrogen, argon and hydrogen.
Preferably, in the step (2), the borohydride is any one of sodium borohydride, lithium borohydride, potassium borohydride and magnesium borohydride; the addition amount of the borohydride is as follows: the mol ratio of Fe is 1-4: 1.
preferably, in step (2), the soluble sulfide solution is sodium sulfide (Na) 2 S), sodium thiosulfate (Na) 2 S 2 O 3 ) And sodium dithionite (Na) 2 S 2 O 4 ) An aqueous solution of one of (1).
Preferably, in the step (2), the molar ratio of the soluble sulfide salt to the metal iron salt is 0.00125-1: 1.
the zero-valent iron-based covalent organic framework composite material prepared by the invention can be used for treating water bodies containing heavy metals, pesticides, azo dyes, halogenated organics and/or nitro-organics besides tetracycline antibiotics such as doxycycline hydrochloride and the like.
Specifically, the heavy metals include anionic heavy metals (arsenic, chromium, selenium, antimony, uranium, technetium, etc.) and cationic heavy metals (copper, cobalt, mercury, gold, silver, nickel, zinc, lead, etc.); the pesticide specifically includes, for example: fenpropathrin, organophosphates, carbamates, pyrethroids, DDT, hexachloro cyclohexane, atrazine, etc.; such azo dyes are, for example: congo red, methyl orange, methyl blue, methylene blue, gold orange II, etc.; such halogenated organic compounds are, for example: methyl chloride, chloroform, carbon tetrachloride, ethyl chloride, vinyl chloride, ethylene dichloride, ethylene trichloride, ethylene tetrachloride, chlorobenzene, polybrominated diphenyl ether, tetrabromobisphenol A, and the like; the organic nitro compound is, for example: nitrobenzene, nitrochlorobenzene, nitrophenol, and the like.
In order to verify the removal effect of the zero-valent iron-based composite functional material on organic matters, the zero-valent iron-based composite functional material is put into a water environment containing tetracycline antibiotics to trigger degradation reaction, and experiments prove that the effect is remarkable. The invention has the beneficial effects that:
(1) According to the invention, the TpPa-1 is added in the synthesis process of the nano zero-valent iron and the vulcanized nano zero-valent iron, so that the nZVI or the SnZVI directly grows on the surface of the TpPa-1, the synthesis process is simple, the reaction condition is mild, and the method is economical and effective.
(2) The zero-valent iron-based covalent organic framework composite material (nZVI/TpPa-1 and SnZVI/TpPa-1) prepared by the method reduces the aggregation of nZVI.
(3) The nanometer zero-valent iron covalent organic framework composite material (nZVI/TpPa-1 and SnZVI/TpPa-1) prepared by the method has magnetism, realizes magnetic separation and recovery of the material, has high pollutant degradation efficiency, especially has higher degradation speed on antibiotic doxycycline hydrochloride, and has the degradation rate which is 44.24 percent higher than that of nZVI.
(4) The composite material has wide applicable pH range, has a degradation effect remarkably reaching 55.38-99.86% in the range of pH = 3-8, and has wide practical application prospect.
Drawings
FIG. 1 is a scanning electron micrograph of an nZVI/TpPa-1 composite.
FIG. 2 is a Fourier transform infrared spectrum of TpPa-1 and nZVI/TpPa-1.
FIG. 3 is an X-ray diffraction diagram of nZVI, tpPa-1 and nZVI/TpPa-1 composites.
FIG. 4 is a graph showing the removal of doxycycline hydrochloride from nZVI, tpPa-1, and nZVI/TpPa-1 composites; the abscissa represents the removal time (min), and the ordinate represents the DOX-H removal rate (%).
FIG. 5 is a graph showing the removal of doxycycline hydrochloride from nZVI/TpPa-1 composites at various ratios; the abscissa represents the removal time (min), and the ordinate represents the DOX-H removal rate (%).
Detailed Description
The invention provides a zero-valent iron-based/covalent organic framework composite material capable of efficiently treating medical wastewater containing doxycycline hydrochloride tetracycline antibiotics.
The technical solutions of the present invention will be further described with reference to the drawings in the following embodiments, it should be noted that the following embodiments are only used for further illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above disclosure and still fall within the scope of the present invention.
Example 1:
(1) Tp and Pa-1 (n/n =2 3) were dispersed in 3mL mesitylene/dioxane (v/v = 1) using Schiff base reaction, ultrasonically dispersed for 30min using 3M acetic acid as a catalyst, and sealed for reaction at 120 ℃ for 3 days. The red solid is obtained by centrifugal separation, then is washed by DMF and acetone for a plurality of times and is dried for 48 hours in vacuum at the temperature of 60 ℃ to obtain TpPa-1.
(2) Mixing ferric chloride and the TpPa-1 obtained in the step (1) according to the weight ratio of Fe: the mass ratio of TpPa-1 is 1:1.5 is added into 200mL deionized water, stirred for 2h and mixed evenly to obtain a TpPa-1/metal iron salt mixed solution; under the atmosphere of nitrogen, continuously stirring, slowly mixing 50mL of sodium borohydride solution serving as a reducing agent with the TpPa-1/metal salt mixed solution, reacting for 0.5h, immediately washing after the reaction is finished, and freeze-drying for 24h to obtain the nZVI/TpPa-1 (1.5) composite functional material, grinding into powder for later use, filling inert gas, and storing at low temperature.
Example 2:
(1) Tp and Pa-1 (n: n =2 = 3) were dispersed in 3mL mesitylene/dioxane (v/v = 1) using Schiff base reaction, ultrasonically dispersed for 30min using 3M acetic acid as a catalyst, and sealed for reaction at 120 ℃ for 3 days. The red solid is obtained by centrifugal separation, then is washed by DMF and acetone for a plurality of times and is dried for 48 hours in vacuum at the temperature of 60 ℃ to obtain TpPa-1.
(2) Mixing ferric chloride and the TpPa-1 obtained in the step (1) according to the weight ratio of Fe: the mass ratio of TpPa-1 is 1:1, adding the mixture into 200mL of deionized water, stirring for 2 hours and uniformly mixing to obtain a TpPa-1/metal iron salt mixed solution; under the atmosphere of nitrogen, continuously stirring, slowly mixing 50mL of sodium borohydride solution serving as a reducing agent with the TpPa-1/metal salt mixed solution, reacting for 0.5h, immediately washing after the reaction is finished, and freeze-drying for 24h to obtain the nZVI/TpPa-1 (1.
Example 3:
(1) Tp and Pa-1 (n/n =2 3) were dispersed in 3mL mesitylene/dioxane (v/v = 1) using schiff base reaction, dispersed with ultrasound for 30min using 3M acetic acid as a catalyst, and reacted in a sealed state at 120 ℃ for 3 days. The red solid is obtained by centrifugal separation, then is washed by DMF and acetone for a plurality of times and is dried for 48 hours in vacuum at the temperature of 60 ℃ to obtain TpPa-1.
(2) Mixing ferric chloride and the TpPa-1 obtained in the step (1) according to the weight ratio of Fe: the mass ratio of TpPa-1 is 1:2, adding the mixture into 200mL of deionized water, stirring for 2 hours and uniformly mixing; under the atmosphere of nitrogen, continuously stirring, slowly mixing 50mL of sodium borohydride solution serving as a reducing agent with the TpPa-1/metal salt mixed solution, reacting for 0.5h, immediately washing after the reaction is finished, and freeze-drying for 24h to obtain the nZVI/TpPa-1 (1.
Example 4:
(1) Tp and Pa-1 (n/n =2 3) were dispersed in 3mL mesitylene/dioxane (v/v = 1) using Schiff base reaction, ultrasonically dispersed for 30min using 3M acetic acid as a catalyst, and sealed for reaction at 120 ℃ for 3 days. The red solid is obtained by centrifugal separation, and then is washed by DMF and acetone for a plurality of times and dried in vacuum for 48 hours at the temperature of 60 ℃ to obtain TpPa-1.
(2) Mixing ferric chloride and the TpPa-1 obtained in the step (1) according to the weight ratio of Fe: the mass ratio of TpPa-1 is 1:2.5, adding the mixture into 200mL of deionized water, stirring for 2 hours, and uniformly mixing to obtain a TpPa-1/metal iron salt mixed solution; under the atmosphere of nitrogen, continuously stirring, slowly mixing 50mL of sodium borohydride solution serving as a reducing agent with the TpPa-1/metal salt mixed solution, reacting for 0.5h, immediately washing after the reaction is finished, and freeze-drying for 24h to obtain the nZVI/TpPa-1 (1.
Example 5:
(1) Tp and Pa-1 (n/n =2 3) were dispersed in 3mL mesitylene/dioxane (v/v = 1) using Schiff base reaction, ultrasonically dispersed for 30min using 3M acetic acid as a catalyst, and sealed for reaction at 120 ℃ for 3 days. The red solid is obtained by centrifugal separation, then is washed by DMF and acetone for a plurality of times and is dried for 48 hours in vacuum at the temperature of 60 ℃ to obtain TpPa-1.
(2) Mixing ferric chloride and the TpPa-1 obtained in the step (1) according to the weight ratio of Fe: the mass ratio of TpPa-1 is 1:1.5, adding the mixture into 200mL of deionized water, stirring for 2h, and uniformly mixing to obtain a TpPa-1/metal iron salt mixed solution (1), continuously stirring under the atmosphere of nitrogen, and simultaneously respectively adding 50mL of the mixed solution containing different sulfur sources: na (Na) 2 S·9H 2 O(2.14mM)、Na 2 S 2 O 4 (1.07mM)、Na 2 S 2 O 3 ·5H 2 Slowly mixing the mixed solution (2) of sodium borohydride with O (1.07 mM) and the mixed solution (1), continuously reacting for 1h, immediately washing after the reaction is finished, and freeze-drying for 24h to obtain SnZVI/TpPa-1 composite functional materials with S/Fe =0.050 and different sulfur sources, respectively grinding the materials into powder for later use, filling inert gas into the powder, and storing the powder at low temperature.
Example 6:
(1) Tp and Pa-1 (n/n =2 3) were dispersed in 3mL mesitylene/dioxane (v/v = 1) using schiff base reaction, dispersed with ultrasound for 30min using 3M acetic acid as a catalyst, and reacted in a sealed state at 120 ℃ for 3 days. The red solid is obtained by centrifugal separation, then is washed by DMF and acetone for a plurality of times and is dried for 48 hours in vacuum at the temperature of 60 ℃ to obtain TpPa-1.
(2) Mixing ferric chloride and the TpPa-1 obtained in the step (1) according to the weight ratio of Fe: the mass ratio of TpPa-1 is 1:1.5, adding the mixture into 200mL of deionized water, stirring for 2h, and uniformly mixing to obtain a TpPa-1/metal iron salt mixed solution (1); continuously stirring under the atmosphere of nitrogen, slowly mixing 50mL of sodium borohydride mixed solution (2) containing vulcanizing agents (0.214-12.84 mM) with different concentrations with the mixed solution (1), keeping the reaction for 1h, immediately washing after the reaction is finished, freeze-drying for 24h to obtain SnZVI/TpPa-1 composite functional materials with different sulfur-iron ratios, respectively grinding the materials into powder for later use, filling inert gas, and storing at low temperature.
Comparative example 1:
synthesis of TpPa-1
Tp and Pa-1 (n/n =2 3) were dispersed in 3mL mesitylene/dioxane (v/v = 1) using Schiff base reaction, ultrasonically dispersed for 30min using 3M acetic acid as a catalyst, and sealed for reaction at 120 ℃ for 3 days. The red solid is obtained by centrifugal separation, then is washed by DMF and acetone for a plurality of times and is dried for 48 hours in vacuum at the temperature of 60 ℃ to obtain TpPa-1.
Comparative example 2:
synthesis of nZVI:
weighing 5.8g FeCl at normal temperature 3 ·6H 2 Dissolving O in 200mL of deionized water in a 500mL three-neck flask, turning on a stirrer at the rotation speed of 300r/min, and stirring for 2 hours; 3.0g of NaBH are weighed 4 Dissolved in a glass bottle containing 50mL of deoxygenated triple water. Three-neck flask with human N therein 2 Continuous aeration for 30min 4 The solution was added dropwise at 4mL/min by a peristaltic pump and stirred for another 30min after the addition. The obtained material is washed three times by using deoxidized absolute ethyl alcohol, washed three times by using deoxidized water, and freeze-dried for 24 hours. And filling nitrogen into the dried nZVI, sealing the nZVI in a bottle (the content of the nitrogen is 90-100 percent), and storing the nZVI at the temperature of 4 ℃.
A series of characterizations were performed on the nZVI, tpPa-1, nZVI/TpPa-1 composite materials obtained in the above examples and comparative examples by scanning electron microscopy, fourier transform infrared spectroscopy, X-ray powder diffraction, and the like.
FIG. 1 is SEM images of nZVI/TpPa-1 composite functionalized material samples obtained in example 1 of the present invention at different magnifications. As can be seen from FIGS. 1 (a-c), the overall spherical nZVI particles of the composite material are attached to coral-shaped COFs, and the existence of COF reduces the aggregation of nZVI to a great extent and increases the specific surface area of nZVI.
FIG. 2 shows Fourier transform infrared light obtained from TpPa-1 and nZVI/TpPa-1 composite functionalized material samples obtained in example 1 of the present inventionSpectra. The material of TpPa-1 and nZVI/TpPa-1 is in the range of 3420cm -1 、1590cm -1 、1260cm -1 The characteristic peaks observed in the composite functional material are respectively the tensile vibration of N-H, C = O and C-N, and the nZVI/TpPa-1 composite functional material is at 580cm -1 A characteristic peak of Fe-O that TpPa-1 does not have is the oxidation formation of nZVI, which indicates that the material nZVI successfully grows on the TpPa-1, and indicates the successful synthesis of nZVI/TpPa-1.
FIG. 3 is the X-ray powder diffraction patterns of nZVI, tpPa-1 and nZVI/TpPa-1 composite functionalized material samples obtained in comparative example 2 and example 1 of the invention. The composite material nZVI/TpPa-1 has diffraction peaks at 27 degrees and 45.17 degrees, and as shown in the figure, the characteristic diffraction peak at 27 degrees is derived from the fact that the TpPa-1 is caused by the pi-pi superposition of COFs, and the weak peak at 45.17 degrees is derived from the (110) surface of nZVI corresponding to Fe, thereby proving that the nZVI is successfully loaded on the TpPa-1 to form the nZVI/TpPa-1 composite material.
The product obtained in the example was subjected to a doxycycline hydrochloride removal experiment in water:
(1) Preparing a doxycycline hydrochloride stock solution: accurately weighing 0.5g of doxycycline hydrochloride, diluting with deionized water to a volume of 100mL volumetric flask, and transferring to a brown reagent bottle for later use. In order to reduce errors, the whole process needs to be protected from light, and the solution is prepared and used.
(2) Drawing a doxycycline hydrochloride standard curve (100 mg/L): preparing 5g/L stock solution, putting 2mL of the prepared stock solution into a 100mL volumetric flask, and performing constant volume by using deionized water to obtain the doxycycline hydrochloride solution with the concentration of 100 mg/L. Respectively taking 0.1 mL, 0.5 mL, 1.0 mL, 3.0 mL, 5.0 mL, 8.0 mL and 10.0mL of the doxycycline hydrochloride standard solution with the concentration of 100mg/L in a 10mL colorimetric tube, diluting to a constant volume to a marked line, sealing and shaking up to obtain a solution with the concentration of the doxycycline hydrochloride from 1.0mg/L to 100 mg/L. The absorbance of the solution was measured at a wavelength of 345nm using an ultraviolet-visible spectrophotometer, and a doxycycline hydrochloride standard curve was plotted, as shown in fig. 3.
Application example 1
The nZVI/TpPa-1 in the examples used in this application example provides a method for removing DOX-H from an aqueous environment.
50mL of DOX-H (100 mg/L) solution was taken in a 50mL brown glass bottle, and pH =4 was adjusted. 20mg of the series of composite materials produced in example 1, comparative example 1 and comparative example 2 were added, respectively. Then shaken in a constant temperature shaker at 25 ℃ for 20min at a speed of 100rpm. The solution was collected through a 0.22 μm filter, and the DOX-H concentration was measured on an ultraviolet spectrophotometer with the wavelength of the absorbed light set at 345nm. The result shows that after 20min of reaction, DOX-H is completely removed, and the removal rate is 100%. The graph is drawn according to experimental data and can be seen in fig. 4.
Application example 2
The nZVI/TpPa-1 with different proportions used in the application optimizes the method for removing DOX-H in the water environment.
50mL of DOX-H (100 mg/L) solution was taken in a 50mL brown glass bottle, and pH =4 was adjusted. 20mg of the series of composites produced in example 1, example 2, example 3, example 4 were added, respectively. Then shaken in a constant temperature shaker at 25 ℃ for 20min at a speed of 100rpm. Then the solution is collected after passing through a filter membrane of 0.22 mu m, the DOX-H concentration is measured on an ultraviolet spectrophotometer, and the wavelength of the absorbed light wave is set to 345nm. After 20min of reaction, DOX-H was completely removed, and the removal rate was 100%. The graph is drawn according to experimental data as shown in fig. 5.
Application example 3
The application uses SnZVI/TpPa-1, wherein S/Fe =0.050, the sulfur source is sodium sulfide, and an optimized method for removing DOX-H in water environment is adopted.
50mL of DOX-H (100 mg/L) solution was taken in a 50mL brown glass bottle, and pH =4 was adjusted. 20mg of SnZVI/TpPa-1 composite material prepared by taking sodium sulfide as a sulfur source is added respectively. Then shaken in a constant temperature shaker at 25 ℃ for 20min at 100rpm. Then the solution is collected after passing through a filter membrane of 0.22 mu m, the DOX-H concentration is measured on an ultraviolet spectrophotometer, and the wavelength of the absorbed light wave is set to 345nm. After 20min of reaction, DOX-H was completely removed, and the removal rate was 100%.
Application example 4
The application uses SnZVI/TpPa-1, wherein S/Fe =0.050, the sulfur source is sodium hydrosulfite, and an optimized method for removing DOX-H in water environment is adopted.
50mL of DOX-H (100 mg/L) solution was taken in a 50mL brown glass bottle, and pH was adjusted to =4. 20mg of SnZVI/TpPa-1 composite material prepared by taking sodium hydrosulfite as a sulfur source is added respectively. Then shaken in a constant temperature shaker at 25 ℃ for 20min at 100rpm. Then the solution is collected after passing through a filter membrane of 0.22 mu m, the DOX-H concentration is measured on an ultraviolet spectrophotometer, and the wavelength of the absorbed light wave is set to 345nm. After 20min of reaction, DOX-H was completely removed, and the removal rate was 100%.
Application example 5
The application uses SnZVI/TpPa-1, wherein S/Fe =0.050, the sulfur source is sodium thiosulfate, and an optimized method for removing DOX-H in the water environment is adopted.
50mL of DOX-H (100 mg/L) solution was taken in a 50mL brown glass bottle, and pH =4 was adjusted. 20mg of SnZVI/TpPa-1 composite material prepared by taking sodium thiosulfate as a sulfur source is added respectively. Then shaken in a constant temperature shaker at 25 ℃ for 20min at 100rpm. Then the solution is collected after passing through a filter membrane of 0.22 mu m, the DOX-H concentration is measured on an ultraviolet spectrophotometer, and the wavelength of the absorbed light wave is set to 345nm. After 20min of reaction, DOX-H was completely removed, and the removal rate was 100%.
The embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above embodiments, and any modifications, equivalents, and improvements made by those skilled in the art within the spirit and principle of the present invention should be within the protection scope of the present invention.
Claims (8)
1. A preparation method of a zero-valent iron-based covalent organic framework composite material is characterized by comprising the following steps:
(1) Preparation of covalent organic framework TpPa-1: mixing 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde and p-phenylenediamine under an acidic condition, adding an organic mixed solvent, taking acetic acid as a catalyst, carrying out ultrasonic treatment for 10-60 min, uniformly mixing, transferring the obtained mixed solution into a high-pressure hydrothermal reaction kettle, reacting for 2-4 days at 100-150 ℃, cooling to room temperature, washing, centrifuging, and drying for 12-36 h to obtain TpPa-1.
(2) Loading of active components: adding a metal iron salt and the TpPa-1 obtained in the step (1) into a reaction solvent, stirring for 1-5 h, and uniformly mixing to obtain a TpPa-1/metal iron salt mixed solution; continuously stirring under the atmosphere of reducing gas, and adding borohydride serving as a reducing agent to slowly mix with the TpPa-1/metal salt mixed solution; and simultaneously adding soluble sulfide salt, reacting for 0.3-5 h, immediately washing after the reaction is finished, and freeze-drying for 12-36 h to obtain the nZVI/TpPa-1 or SnZVI/TpPa-1 composite functional material.
2. The method of claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of the 4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde to the p-phenylenediamine is 2:3.
3. the method of claim 1, wherein the method comprises the following steps: in the step (1), the organic mixed solvent is one or more of mesitylene, dioxane and dimethyl sulfoxide; the volume ratio of the organic mixed solvent to the mixture of the 4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde and the p-phenylenediamine is 1:1.
4. the method of claim 1, wherein the method comprises the following steps: in the step (2), the metal iron salt is one or more of ferric nitrate, ferric chloride and ferrous sulfate; the addition amount of the metal iron salt is as follows: the mass ratio of TpPa-1 is 0.1-4: 1.
5. the method of claim 1, wherein the method comprises the following steps: in the step (2), the reaction solvent is water or a mixed solution of water and ethanol in any proportion.
6. The method of claim 1, wherein the method comprises the following steps: in the step (2), the reducing gas is one or more of nitrogen, argon and hydrogen.
7. The method of claim 1, wherein the method comprises the steps of: in the step (2), the borohydride is any one of sodium borohydride, lithium borohydride, potassium borohydride and magnesium borohydride; the addition amount of the borohydride is as follows: the mol ratio of Fe is 1-4: 1.
8. the method of claim 1, wherein the method comprises the following steps: in the step (2), the soluble sulfide salt solution is an aqueous solution of one of sodium sulfide, sodium thiosulfate and sodium dithionite; the molar ratio of the soluble sulfide salt solution to the metal iron salt is 0.00125-1: 1.
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