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
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- 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
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- 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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]
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- 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
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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.
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| 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 |
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