CN113842953A - NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst and preparation method thereof - Google Patents
NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst and preparation method thereof Download PDFInfo
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- 239000013215 MIL-88B Substances 0.000 title claims abstract description 75
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000011258 core-shell material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 50
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002073 nanorod Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 15
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229960001553 phloroglucinol Drugs 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000007605 air drying Methods 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 84
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 14
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 14
- 229960000583 acetic acid Drugs 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000012362 glacial acetic acid Substances 0.000 claims description 14
- 229960000502 poloxamer Drugs 0.000 claims description 14
- 229920001983 poloxamer Polymers 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- -1 iron ions Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000004321 preservation Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 10
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000012360 testing method 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
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004098 Tetracycline Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229960002180 tetracycline Drugs 0.000 description 3
- 229930101283 tetracycline Natural products 0.000 description 3
- 235000019364 tetracycline Nutrition 0.000 description 3
- 150000003522 tetracyclines Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000013082 iron-based metal-organic framework Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 229940123317 Sulfonamide antibiotic Drugs 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B01J35/39—
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/396—
-
- B01J35/40—
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
-
- 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
- C02F2305/026—Fenton's reagent
-
- 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
Abstract
The invention provides NH2A preparation method of-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst, which is prepared by reacting NH2-MIL-88b (fe) nanorods and trialdehyde phloroglucinol are dispersed in tetrahydrofuran to obtain a solution a; taking p-phenylenediamine to fully disperse in tetrahydrofuran to obtain a solution B; slowly adding the solution B into the solution A; placing the mixed solution in a polytetrafluoroethylene-lined hydrothermal reaction kettle, and then placing the kettle in a forced air drying oven for heat preservation; taking out the hydrothermal reaction kettle from the oven, naturally cooling to room temperature, and then carrying out production in the hydrothermal reaction kettleThe product is fully washed by tetrahydrofuran, filtered and then placed in a vacuum oven to be dried to constant weight, and the product is obtained. And NH prepared by the method2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst. The invention prepares NH2The MIL-88B (Fe) @ TpCp-COFs core-shell efficient composite light Fenton catalyst has the advantages of simple process and relatively mild reaction conditions, and the prepared product has high catalytic activity under visible light, thereby having obvious reference significance for solving the problem of antibiotic pollution in water by utilizing solar energy.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst and a preparation method thereof.
Background
With the development of cities and the increase of population, the wide use of industrial organic dyes and agricultural chemicals makes environmental pollution, particularly water pollution, increasingly prominent, and has directly or indirectly influenced the health of people, thus becoming a hot problem of social attention. Among the water pollutant treating technologies, the photo-Fenton catalytic oxidation technology is concerned because of mild reaction conditions and relatively thorough degradation. The method generates a series of free radicals with high reaction activity through the interaction of a catalyst, hydrogen peroxide and light, thereby achieving the purpose of degrading organic pollutants in water and being the object of research of many scholars at present. For example: the liquid catalyst carrier is prepared by using MIL-101 type covalent organic framework Materials (MOFs), a surfactant and a complexing agent, and iron ions are complexed in the liquid catalyst carrier to obtain a liquid Fenton reaction composite catalyst, so that the treatment efficiency of organic pollutants can be effectively improved (CN 111825201A); in Return et al, mixed metal salt of ferric salt and ferrous salt is added into an organic ligand solution, and on the basis, a ferrous-doped Fe-MOFs Fenton catalyst is obtained, so that the efficiency of mineralizing organic pollutants in water can be obviously improved (CN 112206828A); ferric acetylacetonate, zinc nitrate hexahydrate and dimethylimidazole are dissolved in methanol by Kothereto et al, an MOFs supported iron-based material precursor is prepared by solvothermal reaction, and a dodecahedral monatomic iron catalyst with large specific surface area is obtained by high-temperature calcination in argon atmosphere, so that the high-efficiency degradation of sulfonamide antibiotics is realized (CN 113070090)A) (ii) a The Ourman and others adopt an ultrasonic assembly-solvent evaporation method to remove nano TiO2After being compounded with UiO-66, the composite not only improves the adsorption capacity of the material, but also greatly improves the degradation effect on organic dye rhodamine B (CN 113058659A). Many research results show that the MOFs material is used for effectively degrading organic pollutants in water through a photo-Fenton reaction, and two appropriate materials are found to be capable of promoting carrier separation and transfer at the interface of the composite material through constructing a built-in electric field, so that the synergistic advantage is played, and the photocatalytic activity of the composite material is further improved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst and preparation method thereof, and Fe-MOFs material [ NH ] suitable for photo-Fenton reaction is selected2-MIL-88B(Fe)]And on the basis of the above-mentioned reaction solution an NH is constructed2The MIL-88B (Fe) @ TpCp-COFs core-shell efficient composite light Fenton catalyst has the advantages of simple process and relatively mild reaction conditions, and the prepared product has high catalytic activity under visible light, thereby having obvious reference significance for solving the problem of antibiotic pollution in water by utilizing solar energy.
The technical scheme adopted by the invention is as follows: NH (hydrogen sulfide)2The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst comprises the following steps:
s1: reacting NH2Dispersing MIL-88B (Fe) nanorods and trialdehyde phloroglucinol into tetrahydrofuran, and stirring for 10-30 minutes to obtain a solution A; NH (NH)2MIL-88B (Fe) at a concentration of 1-1.5 g/L; the concentration of the trialdehyde phloroglucinol is 0.5-2.5 mmol/L;
fully dispersing p-phenylenediamine in tetrahydrofuran, and stirring for 10-30 minutes to obtain a solution B; the concentration of p-phenylenediamine is 0.7-3.5 mmol/L;
slowly adding the solution B into the solution A, and continuously stirring for 10-30 minutes to obtain a mixed solution;
s2: placing the mixed solution in a polytetrafluoroethylene-lined hydrothermal reaction kettle, and then placing the kettle in a forced air drying oven to keep the temperature at 40-55 ℃ for 22-27 hours;
s3: putting the hydrothermal reaction kettle in an ovenTaking out and naturally cooling to room temperature, fully washing the product in the hydrothermal reaction kettle with tetrahydrofuran, filtering, and drying in a vacuum oven at 40-60 ℃ to constant weight to obtain NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst.
Specifically, in step S3, the average thickness of the TpCp-COFs shell layer is 4.7-23 nm.
Further, in step S3, the average thickness of the TpCp-COFs shell layer is 14 nm.
Specifically, in step S1, the NH is performed2The MIL-88B (Fe) nanorods are hexagonal three-dimensional rod-shaped structures, the average diameter is 100nm, and the average length is 600 nm.
Further, in step S1, FeCl is taken3·6H2Fully dissolving O, poloxamer, glacial acetic acid and 2-aminoterephthalic acid in 65mL deionized water, and then placing the deionized water in a polytetrafluoroethylene-lined hydrothermal reaction kettle; wherein the concentration of iron ions is 45 mmol/L; the concentration of poloxamer is 10.7 g/L; the concentration of the glacial acetic acid is 21 g/L; the concentration of the 2-amino terephthalic acid is 21.7 mmol/L; placing the hydrothermal reaction kettle in a forced air drying oven, keeping the temperature at 100 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, naturally cooling to room temperature, fully washing the product with N, N-dimethylformamide, filtering, placing in a vacuum oven at 60 ℃ and drying to constant weight to obtain NH2-MIL-88b (fe) nanorods.
The technical scheme adopted by the invention is as follows: NH (hydrogen sulfide)2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst, NH2MIL-88B (Fe) as core, TpCp-COFs as shell, average shell thickness 4.7-23 nm.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is realized by constructing NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst capable of exerting NH2The material-MIL-88B (Fe) and TpCp-COFs have synergistic advantages, a strong electric field is effectively constructed at an interface, the separation efficiency of a photon-generated carrier front is remarkably improved, and the excellent catalytic degradation effect on antibiotics under visible light is realized.
2. The thickness of the TpCp-COFs shell layer precursor can be changed by controlling the adding amount of the TpCp-COFs shell layer precursor, so that the regulation and control of the photo-Fenton catalytic activity of the product are realized.
3. The invention has the advantages of simple process, mild reaction conditions and high catalytic activity of the prepared product under visible light.
Drawings
FIG. 1 is a transmission electron microscope image of a product in example 3 of the present invention, (a): NH (NH)2-MIL-88B(Fe)；(b)：NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst; (c) the method comprises the following steps NH (NH)2-MIL-88B (Fe) @ TpCp-COFs shell layer thickness of the core-shell composite photo-Fenton catalyst;
FIG. 2 is an X-ray diffraction pattern of the product of example 3 of the present invention;
FIG. 3 is a graph of the UV-diffuse reflectance spectrum of the product of example 3 of the present invention;
FIG. 4 is a diagram showing the effect of the product of example 3 of the present invention on the catalytic degradation of tetracycline hydrochloride, (a): drawing by dark suction; (b) the method comprises the following steps Degradation efficiency under visible light.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
The embodiment of the invention provides NH2The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst comprises the following steps:
s1: taking FeCl3·6H2O (national medicine group chemical reagent Co., Ltd., the same below), poloxamer (Aradin Biotechnology Co., Ltd., the same below), glacial acetic acid (Aradin Biotechnology Co., Ltd., the same below), and 2-aminoterephthalic acid (Bailingwei science Co., Ltd., the same below) were sufficiently dissolved in 65mL of deionized water, and then placed in a hydrothermal reaction vessel lined with polytetrafluoroethylene. Wherein the concentration of iron ions is 45 mmol/L; the concentration of poloxamer is 10.7 g/L; the concentration of the glacial acetic acid is 21 g/L; the concentration of 2-aminoterephthalic acid was 21.7 mmol/L. Placing the hydrothermal reaction kettle in a forced air drying oven at 100 DEG CHeating for 20 hours, taking out the hydrothermal reaction kettle after the reaction is finished, naturally cooling to room temperature, fully washing the product with N, N-dimethylformamide, filtering, and drying in a vacuum oven at 60 ℃ to constant weight to obtain NH2-MIL-88b (fe) nanorods.
Collecting 2mg of trialdehyde phloroglucinol (Michelin Biochemical technology Co., Ltd., the same below) and NH obtained by the above process2MIL-88B (Fe) nanorods were well dispersed in 16mL tetrahydrofuran and stirred for 10 minutes to obtain solution A. 1.5mg of p-phenylenediamine (Aladdin Biotechnology Ltd., the same applies hereinafter) was dispersed in 4mL of tetrahydrofuran and stirred for 10 minutes to obtain a solution B. And slowly adding the solution B into the solution A, and continuously stirring for 10 minutes to obtain a mixed solution. Wherein NH2MIL-88B (Fe) at a concentration of 1 g/L; the concentration of the trialdehyde phloroglucinol is 0.5 mmol/L; the concentration of p-phenylenediamine is 0.7 mmol/L.
S2: and (3) placing the prepared mixed solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and placing the kettle in a blast oven at 40 ℃ for heat preservation for 22 hours.
S3: taking the hydrothermal reaction kettle in the S2 out of the oven, naturally cooling to room temperature, fully washing the product in the hydrothermal reaction kettle with tetrahydrofuran, filtering, and drying in a vacuum oven at 40 ℃ to constant weight to obtain NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst.
NH in the composite product2The MIL-88B (Fe) core is a hexagonal three-dimensional rod-like structure with an average diameter of about 100nm, an average length of about 600nm, and an average thickness of the TpCp-COFs shell layer of about 4.7 nm.
25mg of NH were taken2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is placed in 50mL tetracycline hydrochloride (national drug group chemical reagent Co., Ltd., the same below) solution (the concentration is 200mg/L, the same below), a 300W xenon lamp is used as a simulated light source (Beijing Zhongjinyuan science and technology Co., Ltd., model CEL-HXF300, provided with a filter with lambda > 420nm, the same below), and 100 mu L hydrogen peroxide is added to test the catalytic activity of the catalyst. The experimental result shows that the degradation efficiency of the product to tetracycline hydrochloride solution in 27 minutes is 78.9%.
Example 2
The embodiment of the invention provides NH2The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst comprises the following steps:
s1: taking FeCl3·6H2O, poloxamer, glacial acetic acid and 2-aminoterephthalic acid are fully dissolved in 65mL deionized water and are placed in a hydrothermal reaction kettle lined with polytetrafluoroethylene. Wherein the concentration of iron ions is 45 mmol/L; the concentration of poloxamer is 10.7 g/L; the concentration of the glacial acetic acid is 21 g/L; the concentration of 2-aminoterephthalic acid was 21.7 mmol/L. Placing the hydrothermal reaction kettle in a forced air drying oven, preserving heat for 22 hours at 100 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, naturally cooling to room temperature, fully washing the product with N, N-dimethylformamide, filtering, placing in a vacuum oven at 60 ℃ and drying to constant weight to obtain NH2-MIL-88b (fe) nanorods.
Taking 4.4mg of trialdehyde phloroglucinol and NH obtained in the process2MIL-88B (Fe) nanorods were well dispersed in 16.2mL tetrahydrofuran and stirred for 15 minutes to obtain solution A. 3.3mg of p-phenylenediamine was dispersed thoroughly in 4.4mL of tetrahydrofuran and stirred for 15 minutes to obtain solution B. And slowly adding the solution B into the solution A, and continuously stirring for 20 minutes to obtain a mixed solution. Wherein NH2MIL-88B (Fe) at a concentration of 1.1 g/L; the concentration of the trialdehyde phloroglucinol is 1 mmol/L; the concentration of p-phenylenediamine is 1.4 mmol/L.
S2: and (3) placing the prepared mixed solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and placing the kettle in a 45 ℃ blast oven for heat preservation for 23 hours.
S3: taking the hydrothermal reaction kettle in the S2 out of the oven, naturally cooling to room temperature, fully washing the product in the hydrothermal reaction kettle with tetrahydrofuran, filtering, and drying in a vacuum oven at 45 ℃ to constant weight to obtain NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst.
NH in the composite product2The MIL-88B (Fe) core is a hexagonal three-dimensional rod-like structure with an average diameter of about 100nm, an average length of about 600nm, and an average thickness of the TpCp-COFs shell layer of about 9.3 nm.
25mg of NH were taken2the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is placed in 50mL tetracycline hydrochloride solution, a 300W xenon lamp is used as a simulated light source, and 100 mu L hydrogen peroxide is added to test the catalytic activity of the catalyst. The experimental result shows that the degradation efficiency of the product to tetracycline solution in 27 minutes is 89.9%.
Example 3
The embodiment of the invention provides NH2The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst comprises the following steps:
s1: taking FeCl3·6H2O, poloxamer, glacial acetic acid and 2-aminoterephthalic acid are fully dissolved in 65mL deionized water and are placed in a hydrothermal reaction kettle lined with polytetrafluoroethylene. Wherein the concentration of iron ions is 45 mmol/L; the concentration of poloxamer is 10.7 g/L; the concentration of the glacial acetic acid is 21 g/L; the concentration of 2-aminoterephthalic acid was 21.7 mmol/L. Placing the hydrothermal reaction kettle in a forced air drying oven, preserving heat for 23 hours at 100 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, naturally cooling to room temperature, fully washing the product with N, N-dimethylformamide, filtering, placing in a vacuum oven at 60 ℃ and drying to constant weight to obtain NH2-MIL-88b (fe) nanorods.
Taking 7.2mg of trialdehyde phloroglucinol and NH obtained in the process2MIL-88B (Fe) nanorods were well dispersed in 19.2mL tetrahydrofuran and stirred for 20 minutes to obtain solution A. 5.4mg of p-phenylenediamine was dispersed thoroughly in 4.8mL of tetrahydrofuran and stirred for 20 minutes to obtain solution B. And slowly adding the solution B into the solution A, and continuously stirring for 20 minutes to obtain a mixed solution. Wherein NH2MIL-88B (Fe) at a concentration of 1.2 g/L; the concentration of the trialdehyde phloroglucinol is 1.5 mmol/L; the concentration of p-phenylenediamine is 2.1 mmol/L.
S2: and (3) placing the prepared mixed solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and placing the kettle in a blowing oven at 50 ℃ for heat preservation for 24 hours.
S3: taking the hydrothermal reaction kettle in the S2 out of the oven, naturally cooling to room temperature, fully washing the product in the hydrothermal reaction kettle with tetrahydrofuran, filtering, and drying in a vacuum oven at 50 ℃ to constant weight to obtain the productTo NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst.
NH in the composite product2The MIL-88B (Fe) core is a hexagonal three-dimensional rod-like structure with an average diameter of about 100nm, an average length of about 600nm, and an average thickness of the TpCp-COFs shell layer of about 14 nm.
25mg of NH were taken2the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is placed in 50mL tetracycline hydrochloride solution, a 300W xenon lamp is used as a simulated light source, and 100 mu L hydrogen peroxide is added to test the catalytic activity of the catalyst. The experimental result shows that the degradation efficiency of the product to tetracycline hydrochloride solution in 27 minutes is 93.2%.
FIG. 1 depicts NH2MIL-88B (Fe) and NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst morphology figure 1(a) shows that the prepared NH2The MIL-88B (Fe) sample is in a hexagonal three-dimensional rod-shaped structure, is regular in shape, has an average diameter of about 100nm and an average length of 600 nm; as can be seen from FIG. 1(b), TpCp-COFs are loaded more uniformly on NH2-MIL-88b (fe) surface; for NH in FIG. 1(c)2The results of linear scanning of carbon element and iron element of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite Fenton catalyst show that the shell thickness of the composite sample is about 14 nm.
FIG. 2 depicts NH2MIL-88B (Fe), TpCp-COFs and NH2X-ray diffraction pattern of-MIL-88B (Fe) @ TpCp-COFs core-shell composite Fenton catalyst, from which it is clear that NH was obtained2MIL-88B (Fe) is consistent with XRD diffraction peaks simulated by data (CCDC)647646 in a crystallography database of Cambridge university, and impurity peaks do not appear in the product, which indicates that the purity of the obtained product is higher.
FIG. 3 depicts NH2MIL-88B (Fe), TpCp-COFs and NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst ultraviolet-diffuse reflectance spectrogram. As can be seen from the figure, the light absorption edge of TpCp-COFs is about 610nm, and the composite material has an obvious red shift phenomenon and no obvious absorption edge in the range of 300-600nm compared with the pure sample, which shows that the composite material obtained by the technology has good performance under visible light or even infrared lightThe light response is realized, and the light absorption effect is good.
FIG. 4 depicts NH2-MIL-88B(Fe)、NH2A graph of dark adsorption of MIL-88B (Fe) @ TpCp-COFs photo-Fenton catalyst and the photo-catalytic degradation efficiency of tetracycline hydrochloride solution, and as can be seen from the dark adsorption graph in FIG. 4(a), the two photo-Fenton catalysts reach adsorption-desorption equilibrium within 45 minutes; as can be seen from the degradation efficiency graph in visible light in FIG. 4(b), NH2The core-shell composite photo-Fenton catalyst of-MIL-88B (Fe) @ TpCp-COFs degrades 93.2% tetracycline hydrochloride solution in 27 minutes under visible light, compared with NH2An increase of 11.5% in the degradation efficiency of 81.7% for MIL-88B (Fe).
Example 4
The embodiment of the invention provides NH2The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst comprises the following steps:
s1: taking FeCl3·6H2O, poloxamer, glacial acetic acid and 2-aminoterephthalic acid are fully dissolved in 65mL deionized water and are placed in a hydrothermal reaction kettle lined with polytetrafluoroethylene. Wherein the concentration of iron ions is 45 mmol/L; the concentration of poloxamer is 10.7 g/L; the concentration of the glacial acetic acid is 21 g/L; the concentration of 2-aminoterephthalic acid was 21.7 mmol/L. Placing the hydrothermal reaction kettle in a forced air drying oven, preserving heat for 24 hours at 100 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, naturally cooling to room temperature, fully washing the product with N, N-dimethylformamide, filtering, placing in a vacuum oven at 60 ℃ and drying to constant weight to obtain NH2-MIL-88b (fe) nanorods.
Taking 11.2mg of trialdehyde phloroglucinol and NH obtained in the process2MIL-88B (Fe) nanorods were well dispersed in 22.4mL tetrahydrofuran and stirred for 25 minutes to obtain solution A. 8.4mg of p-phenylenediamine was dispersed thoroughly in 5.6mL of tetrahydrofuran and stirred for 25 minutes to give solution B. And slowly adding the solution B into the solution A, and continuously stirring for 25 minutes to obtain a mixed solution. Wherein NH2MIL-88B (Fe) at a concentration of 1.4 g/L; the concentration of the trialdehyde phloroglucinol is 2 mmol/L; the concentration of p-phenylenediamine is 2.8 mmol/L.
S2: and (3) placing the prepared mixed solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and placing the kettle in a blast oven at 55 ℃ for heat preservation for 26 hours.
S3: taking the hydrothermal reaction kettle in the step S2 out of the oven, naturally cooling to room temperature, fully washing the product in the hydrothermal reaction kettle with tetrahydrofuran, filtering, and drying in a vacuum oven at 55 ℃ to constant weight to obtain NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst.
NH in the composite product2The MIL-88B (Fe) core is a hexagonal three-dimensional rod-like structure with an average diameter of about 100nm, an average length of about 600nm, and an average thickness of the TpCp-COFs shell layer of about 18.6 nm.
25mg of NH were taken2the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is placed in 50mL tetracycline hydrochloride solution, a 300W xenon lamp is used as a simulated light source, and 100 mu L hydrogen peroxide is added to test the catalytic activity of the catalyst. The experimental result shows that the degradation efficiency of the product to tetracycline solution in 27 minutes is 88.6%.
Example 5
The embodiment of the invention provides NH2The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst comprises the following steps:
s1: taking FeCl3·6H2O, poloxamer, glacial acetic acid and 2-aminoterephthalic acid are fully dissolved in 65mL deionized water and are placed in a hydrothermal reaction kettle lined with polytetrafluoroethylene. Wherein the concentration of iron ions is 45 mmol/L; the concentration of poloxamer is 10.7 g/L; the concentration of the glacial acetic acid is 21 g/L; the concentration of 2-aminoterephthalic acid was 21.7 mmol/L. Placing the hydrothermal reaction kettle in a forced air drying oven, keeping the temperature at 100 ℃ for 25 hours, taking out the hydrothermal reaction kettle after the reaction is finished, naturally cooling to room temperature, fully washing the product with N, N-dimethylformamide, filtering, placing in a vacuum oven at 60 ℃ and drying to constant weight to obtain NH2-MIL-88b (fe) nanorods.
Taking 15mg of trialdehyde phloroglucinol and NH obtained in the process2MIL-88B (Fe) nanorods were well dispersed in 24mL tetrahydrofuran and stirred for 30 minutes to obtain solution A. 11.3mg of p-phenylenediamine was dispersed thoroughly in 6mL of tetraStirring in tetrahydrofuran for 30 minutes to obtain solution B. And slowly adding the solution B into the solution A, and continuously stirring for 30 minutes to obtain a mixed solution. Wherein NH2MIL-88B (Fe) at a concentration of 1.5 g/L; the concentration of the trialdehyde phloroglucinol is 2.5 mmol/L; the concentration of p-phenylenediamine is 3.5 mmol/L.
S2: and (3) placing the prepared mixed solution into a polytetrafluoroethylene-lined hydrothermal reaction kettle, and placing the kettle in a 55-DEG C air blast oven for heat preservation for 27 hours.
S3: taking the hydrothermal reaction kettle in the step S2 out of the oven, naturally cooling to room temperature, fully washing the product in the hydrothermal reaction kettle with tetrahydrofuran, filtering, and drying in a vacuum oven at 60 ℃ to constant weight to obtain NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst.
NH in the composite product2The MIL-88B (Fe) core is a hexagonal three-dimensional rod-like structure with an average diameter of about 100nm, an average length of about 600nm, and an average thickness of the TpCp-COFs shell layer of about 23 nm.
25mg of NH were taken2the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is placed in 50mL tetracycline hydrochloride solution, a 300W xenon lamp is used as a simulated light source, and 100 mu L hydrogen peroxide is added to test the catalytic activity of the catalyst. The experimental result shows that the degradation efficiency of the product to tetracycline solution in 27 minutes is 83.6%.
As can be seen from the photocatalytic degradation efficiencies of the products in examples 1 to 5, the degradation efficiencies of the products obtained in examples 1 to 5 exhibited a tendency to increase and then decrease, and the degradation efficiency of the product in example 3 was the most excellent. The thickness of the TpCp-COFs shell layer precursor can be changed by controlling the adding amount of the TpCp-COFs shell layer precursor, so that the photo-Fenton catalytic activity of the product is regulated and controlled.
The present invention has been described in detail with reference to the embodiments, but the description is only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The scope of the invention is defined by the claims. The technical solutions of the present invention or those skilled in the art, based on the teaching of the technical solutions of the present invention, should be considered to be within the scope of the present invention, and all equivalent changes and modifications made within the scope of the present invention or equivalent technical solutions designed to achieve the above technical effects are also within the scope of the present invention.
Claims (6)
1. NH (hydrogen sulfide)2The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1: reacting NH2Dispersing MIL-88B (Fe) nanorods and trialdehyde phloroglucinol into tetrahydrofuran, and stirring for 10-30 minutes to obtain a solution A; NH (NH)2MIL-88B (Fe) at a concentration of 1-1.5 g/L; the concentration of the trialdehyde phloroglucinol is 0.5-2.5 mmol/L;
fully dispersing p-phenylenediamine in tetrahydrofuran, and stirring for 10-30 minutes to obtain a solution B; the concentration of p-phenylenediamine is 0.7-3.5 mmol/L;
slowly adding the solution B into the solution A, and continuously stirring for 10-30 minutes to obtain a mixed solution;
s2: placing the mixed solution in a polytetrafluoroethylene-lined hydrothermal reaction kettle, and then placing the kettle in a forced air drying oven to keep the temperature at 40-55 ℃ for 22-27 hours;
s3: taking the hydrothermal reaction kettle out of the oven and naturally cooling to room temperature, fully washing the product in the hydrothermal reaction kettle with tetrahydrofuran, filtering, and drying in a vacuum oven at 40-60 ℃ to constant weight to obtain NH2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst.
2. The NH of claim 12The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is characterized by comprising the following steps: in step S3, the average thickness of TpCp-COFs shell layers is 4.7-23 nm.
3. The NH of claim 22The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is characterized by comprising the following steps: the average thickness of the TpCp-COFs shell layer is 14 nm.
4. The NH of claim 12-MIL-88B(Fe) The preparation method of the @ TpCp-COFs core-shell composite photo-Fenton catalyst is characterized by comprising the following steps of: in step S1, the NH2The MIL-88B (Fe) nanorods are hexagonal three-dimensional rod-shaped structures, the average diameter is 100nm, and the average length is 600 nm.
5. The NH of claim 42The preparation method of the-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst is characterized by comprising the following steps: in step S1, FeCl is taken3·6H2Fully dissolving O, poloxamer, glacial acetic acid and 2-aminoterephthalic acid in 65mL deionized water, and then placing the deionized water in a polytetrafluoroethylene-lined hydrothermal reaction kettle; wherein the concentration of iron ions is 45 mmol/L; the concentration of poloxamer is 10.7 g/L; the concentration of the glacial acetic acid is 21 g/L; the concentration of the 2-amino terephthalic acid is 21.7 mmol/L; placing the hydrothermal reaction kettle in a forced air drying oven, keeping the temperature at 100 ℃, taking out the hydrothermal reaction kettle after the reaction is finished, naturally cooling to room temperature, fully washing the product with N, N-dimethylformamide, filtering, placing in a vacuum oven at 60 ℃ and drying to constant weight to obtain NH2-MIL-88b (fe) nanorods.
6. NH (hydrogen sulfide)2-MIL-88B (Fe) @ TpCp-COFs core-shell composite photo-Fenton catalyst, which is characterized in that: NH (NH)2MIL-88B (Fe) as core, TpCp-COFs as shell, average shell thickness 4.7-23 nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409914A (en) * | 2022-01-12 | 2022-04-29 | 中山大学肿瘤防治中心（中山大学附属肿瘤医院、中山大学肿瘤研究所） | Preparation method of iron-based metal organic framework composite material with MOF-On-MOF framework, obtained product and application |
| CN114471730A (en) * | 2022-02-25 | 2022-05-13 | 武汉工程大学 | NH2-MIL-101(Fe) @ SNW-1 composite catalyst and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170186A (en) * | 2015-09-09 | 2015-12-23 | 济南大学 | Preparation method of core-shell structure BiOX@MTL(Fe) photocatalyst |
| CN108393097A (en) * | 2018-05-15 | 2018-08-14 | 济南大学 | A kind of ferrous metals containing redox mediators-organic framework material type Fenton catalyst preparation method |
| CN110102349A (en) * | 2019-05-27 | 2019-08-09 | 哈尔滨理工大学 | A kind of α-Fe2O3The preparation of/TpPa-2 composite material and photolysis water hydrogen |
| CN110437458A (en) * | 2019-07-25 | 2019-11-12 | 北京化工大学 | A kind of class fenton catalyst [NH that can be reused2- MIL-101 (Fe)] preparation and application method |
| CN110694691A (en) * | 2019-11-04 | 2020-01-17 | 湘潭大学 | photo-Fenton catalyst, preparation method and application method |
| CN111957354A (en) * | 2020-08-28 | 2020-11-20 | 哈尔滨理工大学 | Preparation method of oxygen-deficient titanium dioxide/TpPa-1-COF heterojunction photocatalyst |
| CN112604715A (en) * | 2020-11-27 | 2021-04-06 | 嘉兴哲夫埃特环保科技有限公司 | Ion exchange type COF @ MOF/M composite material and preparation method thereof |
| CN112642482A (en) * | 2020-12-16 | 2021-04-13 | 福州大学 | Metal-anchored hollow covalent organic framework material and preparation method and catalytic application thereof |
| CN113318788A (en) * | 2021-06-25 | 2021-08-31 | 哈尔滨理工大学 | Cu-NH2Preparation of-MIL-125/TpPa-2 composite material and hydrogen production by photolysis of water |
| CN113426488A (en) * | 2021-06-29 | 2021-09-24 | 赵晓丽 | MOFs/COFs heterojunction composite photocatalyst and preparation method and application thereof |
-
2021
- 2021-10-11 CN CN202111184653.6A patent/CN113842953A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170186A (en) * | 2015-09-09 | 2015-12-23 | 济南大学 | Preparation method of core-shell structure BiOX@MTL(Fe) photocatalyst |
| CN108393097A (en) * | 2018-05-15 | 2018-08-14 | 济南大学 | A kind of ferrous metals containing redox mediators-organic framework material type Fenton catalyst preparation method |
| CN110102349A (en) * | 2019-05-27 | 2019-08-09 | 哈尔滨理工大学 | A kind of α-Fe2O3The preparation of/TpPa-2 composite material and photolysis water hydrogen |
| CN110437458A (en) * | 2019-07-25 | 2019-11-12 | 北京化工大学 | A kind of class fenton catalyst [NH that can be reused2- MIL-101 (Fe)] preparation and application method |
| CN110694691A (en) * | 2019-11-04 | 2020-01-17 | 湘潭大学 | photo-Fenton catalyst, preparation method and application method |
| CN111957354A (en) * | 2020-08-28 | 2020-11-20 | 哈尔滨理工大学 | Preparation method of oxygen-deficient titanium dioxide/TpPa-1-COF heterojunction photocatalyst |
| CN112604715A (en) * | 2020-11-27 | 2021-04-06 | 嘉兴哲夫埃特环保科技有限公司 | Ion exchange type COF @ MOF/M composite material and preparation method thereof |
| CN112642482A (en) * | 2020-12-16 | 2021-04-13 | 福州大学 | Metal-anchored hollow covalent organic framework material and preparation method and catalytic application thereof |
| CN113318788A (en) * | 2021-06-25 | 2021-08-31 | 哈尔滨理工大学 | Cu-NH2Preparation of-MIL-125/TpPa-2 composite material and hydrogen production by photolysis of water |
| CN113426488A (en) * | 2021-06-29 | 2021-09-24 | 赵晓丽 | MOFs/COFs heterojunction composite photocatalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| GUILONG LU等: "Covalently integrated core-shell MOF@COF hybrids as efficient visible-light-driven photocatalysts for selective oxidation of alcohols", 《JOURNAL OF ENERGY CHEMISTRY》, vol. 43, pages 8 - 15, XP085926302, DOI: 10.1016/j.jechem.2019.07.014 * |
| 孙苗;徐文清;王黎;庞月红;: "基于共价有机骨架修饰电极的苯并芘电化学发光传感器", 分析测试学报, no. 05, pages 29 - 34 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409914A (en) * | 2022-01-12 | 2022-04-29 | 中山大学肿瘤防治中心（中山大学附属肿瘤医院、中山大学肿瘤研究所） | Preparation method of iron-based metal organic framework composite material with MOF-On-MOF framework, obtained product and application |
| CN114471730A (en) * | 2022-02-25 | 2022-05-13 | 武汉工程大学 | NH2-MIL-101(Fe) @ SNW-1 composite catalyst and preparation method and application thereof |
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