CN115301294A - Indium-zinc sulfide modified iron-based metal organic framework, preparation method thereof and application thereof in adsorption-photocatalyst - Google Patents
Indium-zinc sulfide modified iron-based metal organic framework, preparation method thereof and application thereof in adsorption-photocatalyst Download PDFInfo
- Publication number
- CN115301294A CN115301294A CN202210959180.0A CN202210959180A CN115301294A CN 115301294 A CN115301294 A CN 115301294A CN 202210959180 A CN202210959180 A CN 202210959180A CN 115301294 A CN115301294 A CN 115301294A
- Authority
- CN
- China
- Prior art keywords
- mil
- stirring
- znin
- adsorption
- indium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 18
- -1 Indium-zinc sulfide modified iron Chemical class 0.000 title claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 title abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000013206 MIL-53 Substances 0.000 claims abstract description 60
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 9
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- UKCIUOYPDVLQFW-UHFFFAOYSA-K indium(3+);trichloride;tetrahydrate Chemical compound O.O.O.O.Cl[In](Cl)Cl UKCIUOYPDVLQFW-UHFFFAOYSA-K 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000001179 sorption measurement Methods 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 230000031700 light absorption Effects 0.000 abstract description 8
- 239000000969 carrier Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007704 transition Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical group [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides an indium-zinc sulfide modified iron-based metal organic framework based on MIL-53 (Fe) and ZnIn, a preparation method thereof and application thereof in an adsorption-photocatalyst 2 S 4 The structure advantage, good adsorption and photocatalysis characteristics of the ZnIn are constructed 2 S 4 the/MIL-53 (Fe) heterojunction composite material forms an interface with close contact, photogenerated charges and photogenerated carriers are effectively separated, and meanwhile, the adsorption-photocatalysis high-efficiency removal of ciprofloxacin in water is realized by fully utilizing the adsorption characteristic of MIL-53 (Fe). By constructing a heterojunction composite structure, znIn can be improved 2 S 4 The electron transition behavior promotes the effective separation of the photo-generated electron-hole pairs, can obviously improve the light absorption capacity, and realizes better photocatalysis performance.
Description
Technical Field
The invention relates to the fields of photocatalysis technology and environmental remediation, in particular to an indium-zinc sulfide modified iron-based metal organic framework, a preparation method thereof and application thereof in an adsorption-photocatalyst.
Background
In the past decades, the synthesis of highly efficient and stable semiconductor photocatalysts has been an important direction for improving photocatalytic efficiency. In recent years, novel semiconductor photocatalysts such as MOFs, COFs and the like are proved to have good photocatalytic response to visible light, and the application of a photocatalytic technology in environmental remediation is further promoted. The iron-based metal organic framework materials (Fe-MOFs) are typical highly ordered porous materials formed by coordination of organic ligands and inorganic metal ions or metal clusters. The good crystallinity, the high surface area and the abundant adsorption sites of the composite material enable the composite material to be applied to the field of environmental remediation by more and more people, especially to the aspect of adsorbing and removing organic pollution and heavy metals in water. Meanwhile, MIL-53 (Fe) is proved to have rich active sites and proper band gaps, can absorb visible light of 300nm-600nm, and has good photocatalytic application prospects. However, pure MIL-53 (Fe) has the disadvantage of fast annihilation of photon-generated carriers, and thus the photocatalytic performance of the Fe needs to be improved.
ZnIn having a layered structure 2 S 4 Has good visible light absorption capacity, high specific surface area and proper conduction band position, and is considered as one type of visible light absorptionA compound having good photocatalytic performance under irradiation of light. But as a single catalyst, znIn 2 S 4 The separation efficiency and the migration capability of the photocatalyst are poor, the effective separation of photoexcited carriers (electrons and holes) is hindered, and the photocatalyst has serious photo-corrosivity in the photocatalytic degradation process, so that the application of the photocatalyst in the aspect of photocatalysis is limited.
Therefore, it is necessary to provide a composition having both MIL-53 (Fe) and ZnIn 2 S 4 A composite material with the advantages of photocatalysis.
Disclosure of Invention
The invention provides an indium-zinc sulfide modified iron-based metal organic framework, a preparation method thereof and application thereof in an adsorption-photocatalyst, and aims to solve the problems in the background art.
In order to achieve the above purpose, embodiments of the present invention provide an indium zinc sulfide modified iron-based metal organic framework, a preparation method thereof, and an application thereof in an adsorption-photocatalyst.
The embodiment of the invention provides a preparation method of an indium zinc sulfide modified iron-based metal organic framework, which comprises the following steps:
s1: mixing ferric chloride hexahydrate and terephthalic acid (H) 2 BDC) and N, N-Dimethylformamide (DMF) are mixed and stirred to obtain a uniform and transparent mixed solution, then the mixed solution is heated for reaction, precipitates are centrifugally separated, and MIL-53 (Fe) is obtained after drying;
s2: dissolving indium chloride tetrahydrate and zinc acetate in a DMF solution, ultrasonically stirring, adding 0-100 mg of MIL-53 (Fe), stirring into a uniform solution, stirring in an oil bath to obtain a dark yellow precipitate, and drying to obtain ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction composite material is an indium zinc sulfide modified iron-based metal organic framework.
Preferably, in the step S1, ferric chloride hexahydrate and terephthalic acid (H) 2 BDC), N-Dimethylformamide (DMF) were used in an amount of 230mg,370mg, and 60mL.
Preferably, in the step S1, the particle size of ferric chloride hexahydrate is greater than 50 μm.
Preferably, in the step S1, the stirring is magnetic stirring, the heating temperature is 150 ℃, the reaction time is 4-6 hours, and the drying condition is as follows: vacuum drying at 60 deg.c for 8-12 hr.
Preferably, the step S1 further comprises washing the precipitate by centrifugation at 20-30 ℃ for more than three times, and washing with ethanol for 3min each time at 8000-10000rpm.
Preferably, in the step S2, the dosage of the indium chloride tetrahydrate, the zinc acetate and the DMF solution is 108.4mg,26.2mg and 30mL.
Preferably, in the step S2, the stirring time in the ultrasonic stirring is 120min, and the ultrasonic stirring is performed for 30min; stirring into uniform solution for 60min; the oil bath temperature is 120 ℃, and the stirring time of the oil bath is 10 hours.
Preferably, the step S2 further comprises washing the dark yellow precipitate product with ethanol by centrifugation three times or more; drying conditions are as follows: drying in a vacuum oven for 12h at 50 ℃.
Based on one general inventive concept, the present invention also provides an indium zinc sulfide modified iron-based metal organic framework, namely ZnIn, obtained by the above preparation method 2 S 4 the/MIL-53 (Fe) heterojunction composite material.
ZnIn obtained by the preparation method 2 S 4 the/MIL-53 (Fe) heterojunction composite material is applied to adsorption-photocatalytic degradation of ciprofloxacin.
The scheme of the invention has the following beneficial effects:
the invention fully utilizes the adsorbability of the MIL-53 (Fe) structure and ZnIn 2 S 4 The visible light absorption capacity and the characteristics of proper conduction band position are adopted to construct ZnIn 2 S 4 MIL-53 (Fe) heterojunction system. ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction composite material has a close contact interface, and can effectively separate photogenerated charges from photogenerated carriers; can also improve ZnIn 2 S 4 The electron transition behavior promotes the effective separation of photo-generated electron-hole pairs, obviously improves the light absorption capacity and realizes better photocatalytic performance; thereby realizing the high-efficiency adsorption-photocatalysis removal of the ciprofloxacin antibiotic in the water. Transient fluorescence test results also indicate electron-hole recombinationThe reduction, the increase in lifetime of the photo-generated charge carriers.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows pure MIL-53 (Fe) and pure ZnIn of the present invention 2 S 4 And XRD pattern (a), nitrogen adsorption-desorption isotherm (b), and pore size distribution pattern (c) of MIL-53 (Fe)/ZIS-2 composite;
FIG. 2 is ZnIn of the present invention 2 S 4 SEM picture (a) of the/MIL-53 (Fe) composite structure and TEM picture (b) of the MIL-53 (Fe)/ZIS-2 composite structure;
FIG. 3 is a graph (a) of the relationship between different catalysts and adsorption, a graph (b) of reaction rate k, a graph (c) of adsorption time and adsorption performance, a quasi-first order kinetics fitted curve (d), and a quasi-second order kinetics fitted curve (e) according to the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
MIL-53 (Fe) is proved to have rich active sites and proper band gaps, can absorb visible light of 300nm-600nm, and has good photocatalytic application prospects. However, pure MIL-53 (Fe) has the disadvantage of fast annihilation of photogenerated carriers, and is photocatalyticCan be improved. ZnIn having a layered structure 2 S 4 Having good visible light absorption ability, high specific surface area and suitable conduction band position, is considered to be a compound having good photocatalytic performance under visible light irradiation. But as a single catalyst, znIn 2 S 4 The separation efficiency and the migration capability of the photocatalyst are low, the effective separation of photoexcited carriers (electrons and holes) is hindered, and the photocatalyst has serious photo-corrosivity in the photocatalytic degradation process, so that the application of the photocatalyst in the aspect of photocatalysis is limited.
Aiming at the existing problems, the invention provides a preparation method of an indium-zinc sulfide modified iron-based metal organic framework and application thereof in an adsorption-photocatalyst.
The invention provides a preparation method of an indium-zinc sulfide modified iron-based metal organic framework, which comprises the following steps:
s1: mixing ferric chloride hexahydrate and terephthalic acid (H) 2 BDC) and N, N-Dimethylformamide (DMF) are mixed and stirred to be uniform and transparent mixed solution, then the mixed solution is heated for reaction, precipitate is centrifugally separated out, and MIL-53 (Fe) is obtained after drying;
s2: dissolving indium chloride tetrahydrate and zinc acetate in a DMF solution, ultrasonically stirring, adding 0-100 mg of MIL-53 (Fe), stirring into a uniform solution, stirring in an oil bath to obtain a dark yellow precipitate, and drying to obtain ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction composite material is an indium zinc sulfide modified iron-based metal organic framework.
Preferably, in the step S1, ferric chloride hexahydrate and terephthalic acid (H) 2 BDC), N-Dimethylformamide (DMF) was used in an amount of 230mg,370mg, and 60mL.
Preferably, in the step S1, the particle size of ferric chloride hexahydrate is greater than 50 μm.
Preferably, in the step S1, the stirring is magnetic stirring, the heating temperature is 150 ℃, the reaction time is 4-6 hours, and the drying condition is as follows: vacuum drying at 60 deg.c for 8-12 hr.
Preferably, the step S1 further comprises washing the precipitate by centrifugation at 20-30 ℃ for more than three times, and washing with ethanol for 3min each time at 8000-10000rpm.
Preferably, in the step S2, the dosage of the indium chloride tetrahydrate, the zinc acetate and the DMF solution is 108.4mg,26.2mg and 30mL.
Preferably, in the step S2, the stirring time in the ultrasonic stirring is 120min, and the ultrasonic stirring is performed for 30min; stirring into uniform solution for 60min; the oil bath temperature is 120 ℃, and the stirring time of the oil bath is 10 hours.
Preferably, the step S2 further comprises washing the dark yellow precipitate product with ethanol by centrifugation three times or more; drying conditions are as follows: drying in a vacuum oven for 12h at 50 ℃.
Based on one general inventive concept, the present invention also provides an indium zinc sulfide modified iron-based metal organic framework, namely ZnIn, obtained by the above preparation method 2 S 4 the/MIL-53 (Fe) heterojunction composite material.
ZnIn obtained by the preparation method 2 S 4 the/MIL-53 (Fe) heterojunction composite material is applied to adsorption-photocatalytic degradation of ciprofloxacin.
Preparation of MIL-53 (Fe)
230mg of FeCl 3 ·6H 2 O、370mg H 2 BDC and 60ml DMF were mixed and subsequently stirred for 60min until a homogeneous and transparent solution was formed. Subsequently, the mixed and homogeneous clear solution was transferred to a teflon-lined stainless steel and then heated to 150 ℃. After a reaction time of 6 hours had elapsed, the suspension was centrifuged at 8000r/min for 5min to separate the precipitate. After washing with ethylene glycol 3 times, the resulting orange-yellow precipitate was dried under vacuum at 60 ℃ for 12 hours to give MIL-53 (Fe).
Preparation of ZnIn 2 S 4 MIL-53 (Fe) heterojunction system
108.4mg of InCl 3 ·4H 2 O and 26.2mg Zn (AC) 2 Dissolving in N, N-Dimethylformamide (DMF) solution 30mL, and ultrasonically treating for 30min to obtain uniform solution, and stirring at room temperature for 120min. Then, a certain amount (0 mg,10mg,50mg and 100 mg) of the synthesized MIL-53 (Fe) was added thereto, and the stirring was continued for 60min to obtain a uniform solution. Then stirring for 10h in an oil bath at 120 ℃ to obtain deep yellowPrecipitating the product, centrifugally washing the obtained product with ethanol for more than three times, drying in a vacuum oven for 12 hours at 50 ℃, and collecting the obtained final product with a sample bottle to obtain ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction system.
ZnIn 2 S 4 Application of MIL-53 (Fe) heterojunction system in adsorption-photocatalysis
Weighing 30mg of ciprofloxacin to dissolve in 1L of deionized water to prepare a ciprofloxacin aqueous solution of 30mg/L, weighing 100mL of ciprofloxacin aqueous solution to place in a beaker, weighing 5mg of prepared material to disperse in the ciprofloxacin aqueous solution, and stirring the suspension for 1h under a shading condition to ensure that a reaction system reaches saturated adsorption balance. The beaker was then placed under light for a total of 60min, samples were taken at 15min intervals and filtered using a 0.22 μm frit to remove solid material. The residual concentration of ciprofloxacin was then measured.
Comparative example 1
MIL-53 (Fe) was modified with bismuth sulfide, a semiconductor with a narrow band gap (1.3 eV-1.7 eV). 4.85g of bismuth nitrate pentahydrate was dissolved in 25mL of ultrapure water with continuous stirring, and after 30 minutes, thiourea (1.35 g) was added to the solution, and then the resulting mixture was transferred to a hydrothermal reactor and heated at 140 ℃ for 10 hours, and finally the solid product was recovered by filtration, washed 3 times with ultrapure water and absolute ethanol, and dried at 60 ℃. The obtained bismuth sulfide modified MIL-53 (Fe) has very limited increase of ciprofloxacin removal efficiency, which is only 1.2 times and 1.7 times of that of MIL-53 (Fe) and bismuth sulfide, and almost negligible improvement of adsorption effect.
Comparative example 2
Using wide band gap C 3 N 4 MIL-53 (Fe) was modified (about 2.7 eV). Calcining melamine for 4h at 550 ℃, wherein the heating rate is 4 ℃/min, and obtaining blocky C 3 N 4 . Adding a certain amount of C in the MIL-53 (Fe) synthesis process 3 N 4 The analysis of different addition ratios shows that the degradation efficiency of the ciprofloxacin is improved by a very limited way compared with that of C 3 N 4 And MIL-53 (Fe), the degradation rate of the composite structure is improved by 1.6 times and 1.3 times.
The invention prepares spindle-shaped MIL-53 (Fe) and layered ZnIn by a hot solvent method 2 S 4 And a series of MIL-53 (Fe)/ZIS composite materials, which make full use of ZnIn 2 S 4 The characteristics of good visible light absorption capacity, high specific surface area and proper conduction band position; the composite material is characterized by SEM/TEM, XRD, XPS and the like. In a series of MIL-53 (Fe)/ZIS composite materials prepared, MIL-53 (Fe)/ZIS-2 has the best adsorption-photocatalysis efficiency. Wherein, the MIL-53 (Fe)/ZIS-2 has the best adsorption removal efficiency which can reach 44.7%. Meanwhile, the fitting result shows that the adsorption process of ciprofloxacin on the surfaces of the monomer and the composite material relates to a chemical adsorption process by performing quasi-second-order kinetic fitting on the adsorption data. Under the illumination condition, through 45min illumination, the removal rate of ciprofloxacin in an MIL-53 (Fe)/ZIS-2 composite structure system reaches more than 99 percent, and is obviously higher than that of pure MIL-53 (Fe) (75.7 percent) and pure ZnIn 2 S 4 (51.2%) degradation efficiency in the system. By calculating the reaction constant k, the reaction constant of MIL-53 (Fe)/ZIS-2 is about 0.0544, which is pure MIL-53 (Fe) and pure ZnIn, respectively 2 S 4 5.8 and 3.8 times the photocatalytic system.
FIG. 1 shows pure MIL-53 (Fe) and pure ZnIn of the present invention 2 S 4 And XRD pattern (a) of the MIL-53 (Fe)/ZIS-2 composite; pure MIL-53 (Fe), pure ZnIn 2 S 4 And a nitrogen adsorption-desorption isotherm (b) and pore size profile (c) for the MIL-53 (Fe)/ZIS-2 composite;
FIG. 2 is ZnIn of the present invention 2 S 4 SEM picture (a) of the/MIL-53 (Fe) composite structure and TEM picture (b) of the MIL-53 (Fe)/ZIS-2 composite structure;
FIG. 3 is a graph (a) of the relationship between different catalysts and adsorption, a graph (b) of reaction rate k, a graph (c) of adsorption time and adsorption performance, a quasi-first order kinetics fitted curve (d), and a quasi-second order kinetics fitted curve (e) according to the present invention.
The invention fully utilizes the adsorbability of the MIL-53 (Fe) structure and ZnIn 2 S 4 Visible light absorption capacity and proper conduction band position,to construct ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction system. ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction composite material has a close contact interface, and can effectively separate photogenerated charges from photogenerated carriers; can also improve ZnIn 2 S 4 The electron transition behavior promotes the effective separation of photo-generated electron-hole pairs, obviously improves the light absorption capacity and realizes better photocatalytic performance; thereby realizing the high-efficiency adsorption-photocatalysis removal of the ciprofloxacin antibiotic in the water. Transient fluorescence test results also indicate a reduction in electron-hole recombination and an increase in the lifetime of the photogenerated charge carriers.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of an indium-zinc sulfide modified iron-based metal organic framework is characterized by comprising the following steps:
s1: mixing ferric chloride hexahydrate and terephthalic acid (H) 2 BDC) and N, N-Dimethylformamide (DMF) are mixed and stirred to obtain a uniform and transparent mixed solution, then the mixed solution is heated for reaction, precipitates are centrifugally separated, and MIL-53 (Fe) is obtained after drying;
s2: dissolving indium chloride tetrahydrate and zinc acetate in a DMF solution, ultrasonically stirring, adding 0-100 mg of MIL-53 (Fe), stirring into a uniform solution, stirring in an oil bath to obtain a dark yellow precipitate, and drying to obtain ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction composite material is an indium zinc sulfide modified iron-based metal organic framework.
2. The method according to claim 1, wherein in step S1, ferric chloride hexahydrate and terephthalic acid (H) are mixed together 2 BDC), N-Dimethylformamide (DMF) were used in an amount of 230mg,370mg, and 60mL.
3. The method according to claim 1, wherein in step S1, the particle size of ferric chloride hexahydrate is greater than 50 μm.
4. The preparation method according to claim 1, wherein in the step S1, the stirring is magnetic stirring, the heating temperature is 150 ℃, the reaction time is 4-6 h, and the drying conditions are as follows: vacuum drying at 60 deg.c for 8-12 hr.
5. The method according to claim 1, wherein the step S1 further comprises washing the precipitate by centrifugation at 20-30 ℃ for more than three times, washing with ethanol for 3min each time, and rotating at 8000-10000rpm.
6. The method according to claim 1, wherein the amount of indium chloride tetrahydrate, zinc acetate, and DMF solution used in step S2 is 108.4mg,26.2mg, and 30mL.
7. The preparation method according to claim 1, wherein in the step S2, the stirring time in the ultrasonic stirring is 120min, and the ultrasonic stirring is performed for 30min; stirring into uniform solution for 60min; the oil bath temperature is 120 ℃, and the stirring time of the oil bath is 10 hours.
8. The method according to claim 1, wherein the step S2 further comprises washing the dark yellow precipitate product with ethanol by centrifugation three or more times; drying conditions are as follows: drying in a vacuum oven for 12h at 50 ℃.
9. An indium zinc sulfide modified iron-based metal organic framework obtained by the method of any one of claims 1 to 8, namely ZnIn 2 S 4 the/MIL-53 (Fe) heterojunction composite material.
10. ZnIn obtained by the preparation method according to claim 1 to 8 2 S 4 Application of/MIL-53 (Fe) heterojunction composite material in adsorption-photocatalysisDegrading the ciprofloxacin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210959180.0A CN115301294A (en) | 2022-08-10 | 2022-08-10 | Indium-zinc sulfide modified iron-based metal organic framework, preparation method thereof and application thereof in adsorption-photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210959180.0A CN115301294A (en) | 2022-08-10 | 2022-08-10 | Indium-zinc sulfide modified iron-based metal organic framework, preparation method thereof and application thereof in adsorption-photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115301294A true CN115301294A (en) | 2022-11-08 |
Family
ID=83861525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210959180.0A Pending CN115301294A (en) | 2022-08-10 | 2022-08-10 | Indium-zinc sulfide modified iron-based metal organic framework, preparation method thereof and application thereof in adsorption-photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115301294A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116422373A (en) * | 2023-04-12 | 2023-07-14 | 西安交通大学 | Ni-BDC/ZnIn for preparing hydrogen by visible light photocatalytic water splitting 2 S 4 Material, preparation method and application thereof |
| CN117643900A (en) * | 2023-11-20 | 2024-03-05 | 吉林农业大学 | Preparation method and application of S-type heterojunction copper ferrite/zinc indium sulfide visible light catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964305A (en) * | 2016-05-14 | 2016-09-28 | 上海大学 | ZnIn2S4/NH2-MIL-125(Ti) composite visible-light catalyst and preparation method thereof |
| CN106513050A (en) * | 2016-09-24 | 2017-03-22 | 上海大学 | Method for preparing CdS/MIL-53(Fe) visible-light-induced photocatalyst |
| CN111437834A (en) * | 2020-05-19 | 2020-07-24 | 福州大学 | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application |
| CN111617804A (en) * | 2020-05-19 | 2020-09-04 | 南京大学 | Preparation method and application of layered visible light composite catalyst |
| CN113996323A (en) * | 2021-11-24 | 2022-02-01 | 新乡学院 | Indium-zinc sulfide composite visible light catalyst and preparation method and application thereof |
| KR20220028808A (en) * | 2020-08-31 | 2022-03-08 | 연세대학교 산학협력단 | Hexagonal Ternary Sulfide Having Novel Structure And Photocatalysts Comprising The Same |
| CN114345418A (en) * | 2021-12-27 | 2022-04-15 | 东北大学 | Hollow tubular MIL-68(In)/In2S3/ZnIn2S4Preparation method and application of photocatalyst |
-
2022
- 2022-08-10 CN CN202210959180.0A patent/CN115301294A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105964305A (en) * | 2016-05-14 | 2016-09-28 | 上海大学 | ZnIn2S4/NH2-MIL-125(Ti) composite visible-light catalyst and preparation method thereof |
| CN106513050A (en) * | 2016-09-24 | 2017-03-22 | 上海大学 | Method for preparing CdS/MIL-53(Fe) visible-light-induced photocatalyst |
| CN111437834A (en) * | 2020-05-19 | 2020-07-24 | 福州大学 | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application |
| CN111617804A (en) * | 2020-05-19 | 2020-09-04 | 南京大学 | Preparation method and application of layered visible light composite catalyst |
| KR20220028808A (en) * | 2020-08-31 | 2022-03-08 | 연세대학교 산학협력단 | Hexagonal Ternary Sulfide Having Novel Structure And Photocatalysts Comprising The Same |
| CN113996323A (en) * | 2021-11-24 | 2022-02-01 | 新乡学院 | Indium-zinc sulfide composite visible light catalyst and preparation method and application thereof |
| CN114345418A (en) * | 2021-12-27 | 2022-04-15 | 东北大学 | Hollow tubular MIL-68(In)/In2S3/ZnIn2S4Preparation method and application of photocatalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116422373A (en) * | 2023-04-12 | 2023-07-14 | 西安交通大学 | Ni-BDC/ZnIn for preparing hydrogen by visible light photocatalytic water splitting 2 S 4 Material, preparation method and application thereof |
| CN117643900A (en) * | 2023-11-20 | 2024-03-05 | 吉林农业大学 | Preparation method and application of S-type heterojunction copper ferrite/zinc indium sulfide visible light catalyst |
| CN117643900B (en) * | 2023-11-20 | 2024-04-30 | 吉林农业大学 | Preparation method and application of S-type heterojunction copper ferrite/zinc indium sulfide visible light catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhong et al. | In-situ growth of COF on BiOBr 2D material with excellent visible-light-responsive activity for U (VI) photocatalytic reduction | |
| Zhou et al. | Enhanced photocatalytic CO2-reduction activity to form CO and CH4 on S-scheme heterostructured ZnFe2O4/Bi2MoO6 photocatalyst | |
| CN107308990B (en) | TiO22Preparation method of porphyrin/MOFs ultrathin heteroplasmon | |
| CN108786812B (en) | Porous carbon/nano bimetal oxide composite photocatalytic material with adsorption and catalysis functions and preparation method thereof | |
| He et al. | Construction of Schottky-type Ag-loaded fiber-like carbon nitride photocatalysts for tetracycline elimination and hydrogen evolution | |
| Vo et al. | Facile synthesis of magnetic framework composite MgFe2O4@ UiO-66 (Zr) and its applications in the adsorption–photocatalytic degradation of tetracycline | |
| CN115301294A (en) | Indium-zinc sulfide modified iron-based metal organic framework, preparation method thereof and application thereof in adsorption-photocatalyst | |
| CN112563515B (en) | Iron-nitrogen co-doped carbon and MXene compound and preparation method and application thereof | |
| CN112844484B (en) | Boron nitride quantum dot/porous metal organic framework composite photocatalytic material and preparation method and application thereof | |
| CN105148964B (en) | A kind of three-dimensional redox graphene Mn3O4/MnCO3Nano composite material and preparation method thereof | |
| Wang et al. | Biomass encapsulated ZIF-8-derived ZnO carbon aerogels for efficient uranium extraction by synergistic adsorption-photoreduction | |
| Cheng et al. | Lollipop-shaped Co9S8/CdS nanocomposite derived from zeolitic imidazolate framework-67 for the photocatalytic hydrogen production | |
| CN112090448A (en) | Preparation method of ZIF-8@ g-C3N4 catalyst with zeolite structure | |
| CN110302826B (en) | Basic bismuth nitrate and bismuth oxyiodide composite photocatalyst and preparation method and application thereof | |
| CN113976147B (en) | Bi/Bi 4 O 5 Br 2 Photocatalyst, preparation method and application thereof | |
| CN111569944A (en) | Manganese ion doped metal organic framework material and preparation method thereof | |
| CN112569950B (en) | Preparation of magnetic ferroferric oxide-zinc oxide composite photocatalyst with octahedral structure, product and application thereof | |
| CN113976148A (en) | Z-shaped C60/Bi/BiOBr composite photocatalyst and preparation method and application thereof | |
| CN113351231A (en) | Preparation method and catalytic application of high-performance bismuth oxyhalide/graphene nanocomposite | |
| Fan et al. | Rational design of Z-scheme CoS@ NC/CdS heterojunction with N doped carbon (NC) as an electron mediator for enhanced photocatalytic H2 evolution | |
| CN115518690B (en) | Cu (copper) alloy 7 S 4 -MOF composite material and preparation method and application thereof | |
| CN110629245A (en) | Nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photoelectric reduction of CO2Method of producing a composite material | |
| CN111330627A (en) | Processing technology of semiconductor photocatalyst material | |
| CN111359633B (en) | Z-type magnetic composite visible light catalyst and preparation and application thereof | |
| CN114768871B (en) | PANI/NH 2 MIL-101 (Fe) composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |