CN111151303A - Application of novel MIL-53(Fe) -based catalyst in removal of antibiotics in water - Google Patents
Application of novel MIL-53(Fe) -based catalyst in removal of antibiotics in water Download PDFInfo
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- 239000013206 MIL-53 Substances 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
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- 239000003242 anti bacterial agent Substances 0.000 title abstract description 10
- 229940088710 antibiotic agent Drugs 0.000 title abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 238000000034 method Methods 0.000 claims abstract description 23
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- 239000000463 material Substances 0.000 claims abstract description 10
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- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical group C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 30
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- 230000001699 photocatalysis Effects 0.000 claims description 17
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/39—
-
- 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
- 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
Abstract
The invention discloses an MIL-53(Fe) -based catalyst which is designed and prepared and is applied to removing antibiotics in a water body. The catalyst is synthesized by an in-situ pyrolysis method and a hydrothermal method, realizes high-efficiency degradation of antibiotics, and is characterized in that: magnetic gamma Fe2O3Ultrafine particles are uniformly distributed in an MIL-53(Fe) octahedral pore structure to form a micro heterojunction, then layered Graphene Oxide (GO) with high conductivity enables MIL-53(Fe) with high crystallinity to be dispersed on the surface, and finally gamma Fe is synthesized2O3-MIL-53(Fe) -GO composite photocatalyst. Then at a certain timeThe composite catalyst gamma Fe is used for degrading antibiotics in water body under the condition2O3Compared with other MIL-53(Fe) -based composite catalysts, the MIL-53(Fe) -GO has the advantages that: high antibiotic degradation efficiency in water, large photoresponse range, low cost, short degradation period and high material reusability. Therefore, the composite material prepared by the method can be widely applied to removing antibiotics in water bodies, and has high application value and industrial prospect.
Description
Technical Field
The invention relates to the field of metal organic framework materials, in particular to a novel MIL-53(Fe) -based photocatalyst gamma Fe2O3Application of MIL-53(Fe) -GO in photocatalytic degradation of antibiotics in water.
Background
Norfloxacin, a family of fluoroquinolone antibiotics, has been used in the treatment of a variety of diseases in the human and veterinary fields due to its broad antibacterial activity and low side effects. However, due to the abuse of drugs and their low biodegradability, more than 75% of antibiotics accumulate in the environment, constituting a significant threat to the health of aquatic and terrestrial organisms, including humans. Norfloxacin levels in hong kong sewage are reported to reach milligram per liter levels; the values for wastewater from a Queensland-Australian wastewater treatment plant and surface water were 0.25 and 1.15mg/L, respectively. From the ecological and environmental point of view, the removal of norfloxacin prior to discharge is urgently required. In recent years, photocatalytic oxidation has been considered a cost-effective "green" pollution control technology because it is capable of degrading organic pollutants into biodegradable compounds or completely mineralizing into CO2And H2And O. The design and construction of photocatalysts remains central in photocatalytic research.
Metal Organic Frameworks (MOFs) are a class of microporous microcrystalline hybrid materials assembled from metal ions (or clusters) and organic linking groups. In the past decade MOFs have become promising photocatalysts due to large specific surface area, adjustable surface properties, unsaturated metal sites and an inherent porous structure. In particular, MIL-53(Fe) is a widely studied photocatalyst, not only because Fe (iii) oxide can be rapidly excited under visible light irradiation, but also Fe is cheap, non-toxic and environmentally friendly compared to other metals. MIL-53(Fe) has good photocatalytic reactivity in the aspects of Cr (VI) reduction, dye decoloration, tetracycline degradation, photoelectrochemical water oxidation and the like. However, it is not limited toIts photocatalytic performance is still hindered by the rapid recombination of photogenerated carriers. To overcome this drawback, constructing MIL-53(Fe) -based heterojunctions is an effective method to reduce electron/hole pair recombination while maintaining its properties. However, conventional surface loading causes such as gamma phase iron sesquioxide (gamma Fe)2O3) Such semiconductors are only in contact with the active sites on the MIL-53(Fe) surface, most of the internal active sites are not affected and therefore most of the charge carriers are not efficiently separated. Smaller gamma Fe can be pyrolyzed using a process known as in situ ethylenediamine pyrolysis2O3The integration of particles into MIL-53(Fe) crystals to form micro-heterojunctions is a desirable strategy to maximize the quantum yield of the composite. In this way, ethylenediamine first reacts with gamma Fe2O3Then the iron source is highly dispersed inside the MIL-53(Fe) particles by utilizing weak intermolecular force generated between the ethylenediamine and the acidic linker, and finally the precursor is complexed in the gamma Fe2O3Many micro-heterojunctions are formed between the nanoparticles and the MIL-53(Fe) units. The graphene is represented by sp2A two-dimensional material composed of carbon atoms in a hybrid orbital. Due to unique surface properties, excellent electrical conductivity and high surface area, graphene (Gr) and its derivatives, such as Graphene Oxide (GO), have been used to build various nanocomposites. More importantly, graphene treated with strong oxidants contains a large number of functional groups. The functionalized graphene oxide can be used as a template for MIL-53(Fe) unit growth by providing compact nucleation sites, and the high nuclear density can cause the increase of steric hindrance, so that the MIL-53(Fe) morphology and structure are changed. Thus, gamma Fe for production is designed2O3The MIL-53(Fe) pore structure is filled and loaded on the surface of graphene, so that a new breakthrough is found for the development of high-efficiency green photocatalyst at present, and the method has important significance in the technical field of photocatalytic oxidation.
Disclosure of Invention
Aiming at the problems existing at present, the invention designs and prepares a composite catalyst gamma Fe with a filling hole type structure and taking graphene oxide as a carrier2O3MIL-53(Fe) -GO, having a beta-cyclodextrin derivativeHigh photocatalytic performance and stability, low cost, simple operation, and gamma-Fe2O3The ferromagnetism of the composite photocatalyst improves the repeated utilization rate of the composite photocatalyst. By controlling experimental conditions and investigating the photocatalytic performance of materials, the method explores the gamma Fe2O3The optimal doping proportion of the three substances of MIL-53(Fe) and GO can quickly and efficiently degrade norfloxacin in water.
In order to achieve the aim, the invention provides a composite photocatalyst gamma Fe2O3-MIL-53(Fe) -GO, characterized in that:
the method comprises the following steps: preparing graphene by adopting an improved Hummesr method, in the process of cleaning the graphene to be neutral at the final stage of preparation, performing centrifugation and ultrasonic substitution on deionized water in a graphene suspension by using N, N-Dimethylformamide (DMF) solution to form a uniform N, N-dimethylformamide suspension containing graphene oxide, and storing at the temperature of 2-8 ℃.
Step two: FeCl, a suspension of graphene oxide-containing N, N-dimethylformamide obtained in step one3·6H2And (2) slowly dissolving O in the N, N-dimethylformamide solution while stirring, magnetically stirring for 30min to form a clear and transparent solution, dropwise adding the clear and transparent solution into the N, N-dimethylformamide suspension containing graphene oxide obtained in the step one, wherein the final content of the graphene oxide in the compound can be adjusted by changing the volume of the suspension, and then carrying out ultrasonic treatment on the mixture at room temperature for 2 h.
Step three: and (4) according to the mixture obtained in the second step, dropwise adding an N, N-dimethylformamide solution of terephthalic acid, and then carrying out ultrasonic treatment for 2 hours.
Step four: taking a certain amount of FeCl from the mixture obtained in the third step3·6H2Dissolving O and ethylenediamine in a certain volume of N, N-dimethylformamide, and performing ultrasonic treatment until the mixture is uniform. Finally, the mixed solution is added dropwise to the mixture obtained in the third step and is subjected to ultrasonic treatment for 30 min.
Step five: transferring the mixture obtained in the fourth step into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the mixture in a temperature programming box for 15-24 h at the temperature of 150-160 ℃, cooling to room temperature, centrifuging at the speed of 8000r/min for 5min, respectively washing with N, N-dimethylformamide and methanol for three times, vacuum-drying in a vacuum drying oven at the temperature of 80 ℃ for 12h, grinding with an agate mortar, and finally obtaining the magnetic solid powder.
Preferably, the concentration of the graphene oxide-containing N, N-dimethylformamide suspension in the first step is 8 mg/L-10 mg/L.
Preferably, FeCl is used in the second step3·6H2The mass ratio of O to N, N-dimethylformamide is 1: 140
Preferably, the content of the graphene oxide in the second step is adjusted by changing the volume of the taken graphene oxide-containing N, N-dimethylformamide suspension, and the addition amount of the graphene oxide is 20-80% of the mass of MIL-53 (Fe).
Preferably, the mass ratio of the terephthalic acid to the N, N-dimethylformamide in the step three is 1: 140 volume of solution and FeCl in step two3·6H2The volume of the N, N-dimethylformamide solution of O is the same.
Preferably, gamma Fe in step four2O3Precursor FeCl of3·6H2The mass ratio of O to ethylenediamine was 1: 3, gamma Fe2O3Precursor FeCl of3·6H2The concentration of O in the solution is 1.2 mM-200 mM, the concentration in N, N-dimethylformamide is 1.2 mM-200 mM and 3.6 mM-600 mM respectively, and the ratio of the mass of N, N-dimethylformamide to the mass of N, N-dimethylformamide in step three is 1: 5-1: 5.6.
gamma Fe prepared by the preparation method2O3Application of-MIL-53 (Fe) -GO photocatalyst in degradation of norfloxacin. The main process is as follows:
adding a certain amount of catalyst into the antibiotic solution, carrying out dark adsorption for 30min, then irradiating for 90min under visible light, and measuring the concentration of the antibiotic in the reaction solution every 15 min.
Preferably, the concentration of the catalyst in the antibiotic solution is 0.1g/L to 0.3 g/L.
Preferably, the antibiotic in the antibiotic wastewater is norfloxacin, and the concentration of the norfloxacin solution is 5 mg/L-20 mg/L.
Compared with the prior art, the invention has the advantages that: the invention provides a method for synthesizing a composite catalyst with MIL-53(Fe) as a main body, which is used for removing antibiotics in a water body. Simple operation, low cost, high repeated utilization rate and degradation efficiency, and high application value. Wherein, gamma Fe2O3Ultrafine particles are uniformly distributed in the MIL-53(Fe) pore structure and fill the pores, so that the light absorption performance and structural stability of the material are improved, and meanwhile, gamma Fe2O3The micro-heterojunction with the MIL-53(Fe) unit greatly improves the mobility of the photogenerated carriers. The functionalized graphene oxide disperses MIL-53(Fe) with high crystallinity on the surface thereof, prevents aggregation of MIL-53(Fe) units, and the good electrical conductivity and large specific surface area thereof provide an effective electron transport path and more active sites for photocatalytic reactions. In addition, gamma-Fe2O3The magnetic property of the nano particles improves the recovery rate and recoverability of the composite material, and reduces the loss of the material and the production cost.
Gamma Fe prepared by the invention2O3the-MIL-53 (Fe) -GO has improved norfloxacin degradation efficiency in water, the degradation efficiency is improved by 40% in 90min under visible light compared with that of pure MIL-53(Fe), and through 5-time cycle tests, the norfloxacin degradation efficiency is stable and still has 89.8% of degradation efficiency, so that the composite catalyst prepared by the method has good photocatalytic performance and stability.
Drawings
FIG. 1 shows graphene oxide and gamma-Fe2O3X-ray powder diffraction (XRD) patterns of comparative example 5 prepared by hydrothermal method, and example 2 prepared by in situ pyrolysis and hydrothermal method;
FIG. 2 is a graph of Fourier Infrared Spectroscopy (FTIR) comparison of graphene oxide, comparative example 3, comparative example 5 prepared using a hydrothermal method, and example 2 prepared by an in situ pyrolysis method and a hydrothermal method;
FIG. 3 is a scanning electron micrograph of comparative example 5, comparative example 3 and example 2, and an elemental analysis chart of example 2
FIG. 4 is a graph showing the photocatalytic degradation profiles of norfloxacin under visible light in comparative examples 1, 2, 3, 4 and 5
FIG. 5 is a graph showing the photocatalytic degradation profiles of norfloxacin under visible light in example 1, example 2, example 3, comparative example 3 and comparative example 5
FIG. 6 is a graph showing the photocatalytic degradation of norfloxacin by 5 cycles of photocatalytic process in example 2
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, and it should be noted that the present invention is not limited to the following examples.
Example 1
2.5mmol of FeCl3·6H2Dropwise adding 25ml of N, N-dimethylformamide solution of O into 4ml of N, N-dimethylformamide suspension containing graphene oxide with the concentration of 10mg/L, wherein the mass of the graphene oxide accounts for 20% of the mass of MIL-53(Fe) in the composite material, after ultrasonic treatment, dropwise adding 25ml of N, N-dimethylformamide solution containing 100mM terephthalic acid into the mixture, further ultrasonic treatment is carried out for 2h, and then 0.6mmol of FeCl is added3·6H2O and 250 μ l ethylene diamine in a ratio of 3: 1 in 5ml of N, N-dimethylformamide, and finally, the mixed solution was added dropwise to the previous mixture and sonicated to a uniform mixture. Transferring the obtained mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the temperature at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, respectively washing with N, N-dimethylformamide and methanol for three times, vacuum drying at 80 ℃ for 12h, grinding with an agate mortar to finally obtain gamma Fe2O3-MIL-53(Fe)-20％GO。
Example 2
2.5mmol of FeCl3·6H2Adding dropwise 25ml of N, N-dimethylformamide solution of O into 10ml of graphene oxide-containing N, N-dimethylformamide suspension with the concentration of 10mg/L, wherein the mass of GO accounts for 50% of the mass of MIL-53(Fe) in the composite material, and after ultrasonic treatment, adding dropwise 25ml of N, N-dimethylformamide solution containing 100mM terephthalic acid into the mixed materialThe mixture was sonicated for 2h and 0.6mmol of FeCl was added3·6H2O and 250 μ l ethylene diamine in a ratio of 3: 1 in 5ml of N, N-dimethylformamide, and finally, the mixed solution was added dropwise to the previous mixture and sonicated to a uniform mixture. Transferring the obtained mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the temperature at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, washing with N-dimethylformamide and methanol three times respectively, vacuum drying at 80 ℃ for 12h, grinding with an agate mortar to obtain the gamma Fe2O3-MIL-53(Fe)-50％GO。
Example 3
2.5mmol of FeCl3·6H2Adding dropwise 25ml of N, N-dimethylformamide solution of O into 16ml of graphene oxide-containing N, N-dimethylformamide suspension with the concentration of 10mg/L, wherein the mass of GO accounts for 50% of the mass of MIL-53(Fe) in the composite material, after ultrasonic treatment, adding dropwise 25ml of N, N-dimethylformamide solution containing 100mM terephthalic acid into the mixture, performing ultrasonic treatment for 2h, and then adding 0.6mmol of FeCl3·6H2O and 250 μ l ethylene diamine in a ratio of 3: 1 in 5ml of N, N-dimethylformamide, and finally, the mixed solution was added dropwise to the previous mixture and sonicated to a uniform mixture. Transferring the obtained mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the temperature at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, washing with N-dimethylformamide and methanol three times respectively, vacuum drying at 80 ℃ for 12h, grinding with an agate mortar to obtain the gamma Fe2O3-MIL-53(Fe)-80％GO。
Comparative example 1
25ml of a solution of 100mM terephthalic acid in N, N-dimethylformamide was added dropwise to a solution containing 2.5mmol FeCl3·6H2O in 25ml N, N-dimethylformamide for 30min, and then 0.006mmol FeCl3·6H2O and 2.5 μ l ethylene diamine in a ratio of 3: 1 in 5ml of N, N-dimethylformamide, sonicated to homogeneity, and finally the mixed solution was added dropwise to the previous mixture, sonicated to homogeneity. Transferring the obtained mixture to polytetrafluoroethyleneMaintaining the temperature in a high-pressure reaction kettle with an inner lining at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, respectively cleaning with N, N-dimethylformamide and methanol for three times, vacuum drying at 80 ℃ for 12h, grinding with agate mortar to obtain 0.006 gamma Fe2O3-MIL-53(Fe)。
Comparative example 2
25ml of a solution of 100mM terephthalic acid in N, N-dimethylformamide was added dropwise to a solution containing 2.5mmol FeCl3·6H2O in 25ml N, N-dimethylformamide for 30min, and then 0.06mmol FeCl3·6H2O and 25 μ l ethylene diamine in a ratio of 3: 1 in 5ml of N, N-dimethylformamide, sonicated to homogeneity, and finally the mixed solution was added dropwise to the previous mixture, sonicated to homogeneity. Transferring the obtained mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the temperature at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, respectively washing with N, N-dimethylformamide and methanol for three times, vacuum drying at 80 ℃ for 12h, grinding with an agate mortar to obtain 0.06 gamma Fe2O3-MIL-53(Fe)。
Comparative example 3
25ml of a solution of 100mM terephthalic acid in N, N-dimethylformamide was added dropwise to a solution containing 2.5mmol FeCl3·6H2O in 25ml N, N-dimethylformamide for 30min, and then 0.6mmol FeCl3·6H2O and 250 μ l ethylene diamine in a ratio of 3: 1 in 5ml of N, N-dimethylformamide, sonicated to homogeneity, and finally the mixed solution was added dropwise to the previous mixture, sonicated to homogeneity. Transferring the obtained mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the temperature at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, respectively washing with N, N-dimethylformamide and methanol for three times, vacuum drying at 80 ℃ for 12h, grinding with an agate mortar to obtain 0.6 gamma Fe2O3-MIL-53(Fe)。
Comparative example 4
25ml of a solution of 100mM terephthalic acid in N, N-dimethylformamide was added dropwise to a solution containing 2.5mmol FeCl3·6H2O in 25ml N, N-dimethylformamide for 30min, and then 1mmol FeCl3·6H2O and 400 μ l ethylene diamine in a ratio of 3: 1 in 5ml of N, N-dimethylformamide, sonicated to homogeneity, and finally the mixed solution was added dropwise to the previous mixture, sonicated to homogeneity. Transferring the obtained mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the temperature at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, respectively washing with N, N-dimethylformamide and methanol for three times, vacuum drying at 80 ℃ for 12h, grinding with an agate mortar to finally obtain 1 gamma Fe2O3-MIL-53(Fe)。
Comparative example 5
25ml of a solution of 100mM terephthalic acid in N, N-dimethylformamide was added dropwise to a solution containing 2.5mmol FeCl3·6H2And magnetically stirring the O solution in 25ml of N, N-dimethylformamide for 30min, transferring the obtained mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the temperature at 150 ℃ for 15h, cooling to room temperature, centrifuging at 8000r/min for 5min, respectively washing with N, N-dimethylformamide and methanol for three times, vacuum-drying at 80 ℃ for 12h, and grinding by using an agate mortar to finally obtain pure MIL-53 (Fe).
Using a 500W xenon lamp as a light source, wherein the wavelength of the light source is more than 420nm, and the illumination intensity is 100mW/cm2Is tested. In a typical photocatalytic process, 20mg of each of the catalysts prepared in examples 1, 2, 3 and comparative examples 1, 2, 3, 4, 5 was added to 100ml of norfloxacin solution having a concentration of 10mg/L, and then left for 30 minutes in the dark while magnetically stirring to establish an adsorption-desorption equilibrium between the catalyst and the contaminants. During the photoreaction, 2ml of the solution was taken out every 15 minutes, filtered through a microporous membrane (pore size of 0.45 μm), and then analyzed for norfloxacin concentration using High Performance Liquid Chromatography (HPLC), and the results are shown in fig. 4 and 5.
Gamma Fe obtained in comparative example 12O3The degradation efficiency of-MIL-53 (Fe) -20% GO on norfloxacin was 88%.
Gamma Fe obtained in comparative example 22O3-MIL-53(Fe)-50％The degradation efficiency of GO to norfloxacin is 93%.
Gamma Fe obtained in comparative example 32O3-MIL-53(Fe) -80% GO has a 90% degradation efficiency on norfloxacin.
0.006 gamma Fe obtained in comparative example 12O3The norfloxacin degradation efficiency of MIL-53(Fe) is 60%.
0.06. gamma. Fe obtained in comparative example 22O3The norfloxacin degradation efficiency of MIL-53(Fe) was 64%.
0.6. gamma. Fe obtained in comparative example 32O3The norfloxacin degradation efficiency of MIL-53(Fe) is 82%.
1 gamma Fe obtained in comparative example 42O3The norfloxacin degradation efficiency of MIL-53(Fe) is 79%.
The degradation efficiency of MIL-53(Fe) on norfloxacin prepared in comparative example 5 was 55%.
FIG. 1 shows X-ray powder diffraction patterns of example 2, comparative example 3 and comparative example 5 of the present invention, which demonstrate that a material having the same structure as that expected is successfully synthesized.
Fig. 2 is a fourier infrared spectrum of example 2, comparative example 3, comparative example 5 and graphene oxide in the present invention, which demonstrates that a material having the same structure as that expected is successfully synthesized. In the graphene oxide graph, the obvious peaks are located at wave numbers of 3341, 1740, 1635 and 1100cm-1And 1100cm-1Respectively due to O-H stretching vibration, C ═ O stretching vibration, from unoxidized sp2C ═ C for the C-C bond and the characteristic band for the C-O-C vibration, indicating that a regular graphene oxide phase is obtained. For MIL-53(Fe), at 749cm-1Peaks at positions corresponding to C-H bending vibrations of the benzene ring, 1542 and 1388cm-1The double peak band at (a) is assigned to the symmetrical vibration and the asymmetrical vibration of the carboxyl group. 543cm-1The peak at (A) indicates Fe3+And the carboxyl of the terephthalate forms a metal oxo cluster. And gamma Fe2O3After bonding, gamma Fe2O3MIL-53(Fe) at gamma Fe due to Fe-O2O3And MIL-53(Fe), and thus exhibits a wider Fe-O band area. In gamma Fe2O3In the ternary-MIL-53 (Fe) -GO composite material diagram, in addition to the existence of a wider Fe-O peak, stronger C-O-C vibration, COO, is observed-Asymmetric and symmetric tensile vibrations, thus verifying close association between MIL-53(Fe) and Fe-O and functionalized graphene oxide.
FIG. 3 is a graph showing the appearance and microstructure of comparative example 3, comparative example 5 and example 2 observed by a scanning electron microscope, and the elemental analysis of example 2
FIG. 4 shows the catalyst gamma Fe obtained in comparative examples 1, 2, 3, 4 and 52O3Comparison of the photocatalytic degradation efficiency of MIL-53(Fe) on norfloxacin. Ordinate Ct/C0Represents the ratio of norfloxacin concentration to initial norfloxacin concentration at the current time.
Fig. 5 is a comparison of the photocatalytic degradation efficiency of norfloxacin by the catalysts prepared in comparative example 1, example 2, example 3, comparative example 3 and comparative example 5.
FIG. 6 is a graph of example 2 for reusability and stability during photocatalysis, after each photocatalysis, the powder was collected by applying a magnetic field, then washed with ethanol at 60 deg.C, and finally dried in air. As shown in fig. 6, the degradation rate of norfloxacin was as high as 89.8% even after five cycles, indicating that γ Fe2O3the-MIL-53 (Fe) -GO composite catalyst has very high photocatalytic stability.
As can be seen from fig. 4 and 5, comparative example 3 has the best photocatalytic performance, but the gamma Fe prepared in examples 1, 2 and 3 has the best photocatalytic performance2O3The photocatalytic performance of the-MIL-53 (Fe) -GO composite catalyst is obviously higher than that of gamma Fe in comparative examples 3 and 52O3MIL-53(Fe) and MIL-53(Fe), and catalyst gamma Fe prepared in example 22O3MIL-53(Fe) -20% GO has the best photocatalytic degradation efficiency on norfloxacin.
The embodiments described above are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions or substitutions similar to those made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A novel MIL-53(Fe) -based catalyst design preparation is characterized in that: the method is characterized in that a porous regular octahedral crystal material MIL-53(Fe) is taken as a main body, and an in-situ pyrolysis method is adopted to grow magnetic gamma Fe2O3 ultrafine nanoparticles in an MIL-53(Fe) pore structure so as to form a micro heterojunction and obtain a more stable structure, so that the utilization efficiency of light is increased. And then loading the graphene oxide on layered graphene oxide by a one-step hydrothermal method, so that the separation efficiency of a photon-generated carrier is increased, the photocatalytic activity of the catalyst is improved, the steric hindrance is increased due to the high nuclear density of the surface of the graphene, the shape and the structure of MIL-53(Fe) are changed to form a spherical structure, and the expression of the prepared catalyst is gamma Fe2O3-MIL-53(Fe) -GO.
2. The preparation method of the composite photocatalyst gamma Fe2O3-MIL-53(Fe) -GO according to claim 1, which is characterized by comprising the following steps:
the method comprises the following steps: preparing graphene oxide by an improved Hummers method, and in the final cleaning stage of preparing graphene oxide, performing centrifugation and ultrasonic substitution on deionized water in a graphene suspension by using N, N-dimethylformamide to form a uniform N, N-dimethylformamide suspension containing graphene oxide, and storing at 2-8 ℃.
Step two: firstly, FeCl3 & 6H2O is slowly dissolved in an N, N-dimethylformamide solution while stirring, after magnetic stirring is carried out for 30min, a clear and transparent solution is formed, and then the clear and transparent solution is dropwise added into the N, N-dimethylformamide suspension containing graphene oxide obtained in the step one, the content of the graphene oxide in the compound can be adjusted by changing the volume of the taken N, N-dimethylformamide suspension containing graphene oxide, and then the mixture is ultrasonically dispersed for 2H at room temperature.
Step three: the N, N-dimethylformamide solution containing terephthalic acid was added dropwise to the above mixture and sonicated for 2 h.
Step four: and dissolving a certain amount of FeCl 3.6H2O and ethylenediamine in N, N-dimethylformamide, dropwise adding the mixed solution into the previous mixture, and performing ultrasonic treatment for 30 min.
Step five: transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, keeping the mixture in a temperature programming box for 15-24 h at 150-160 ℃, cooling to room temperature, centrifuging for 5min at 8000r/min, respectively centrifuging and cleaning for three times by using N, N-dimethylformamide and methanol, drying in a vacuum drying oven for 12h under vacuum at 80 ℃, grinding by using an agate mortar, and finally obtaining the magnetic solid powder.
3. The method of preparing the photocatalyst γ Fe2O3-MIL-53(Fe) -GO of claim 2, wherein: the concentration of the suspension of the N, N-dimethylformamide containing the graphene oxide in the step one is 8 mg/L-10 mg/L.
4. The method of preparing the photocatalyst γ Fe2O3-MIL-53(Fe) -GO of claim 2, wherein: in the second step, the mass ratio of FeCl 3.6H2O to N, N-dimethylformamide is 1: 140, regulating the content of the graphene oxide by changing the volume of the taken N, N-dimethylformamide suspension containing the graphene oxide, wherein the mass of the final graphene oxide is 20-80% of the mass of pure MIL-53(Fe) which does not contain the gamma Fe2O3 and the graphene oxide and is prepared under the same condition.
5. The method of preparing the photocatalyst γ Fe2O3-MIL-53(Fe) -GO of claim 2, wherein: in the third step, the mass ratio of the terephthalic acid to the N, N-dimethylformamide is 1: 140, the volume of the solution is the same as that of the N, N-dimethylformamide solution of FeCl3 & 6H2O in the second step.
6. The method of preparing the photocatalyst γ Fe2O3-MIL-53(Fe) -GO of claim 2, wherein: in the fourth step, the mass ratio of the precursors FeCl 3.6H 2O of the gamma-Fe 2O3 to the ethylenediamine is 1: 3, in N, N-dimethylformamide in a concentration of 1.2mM to 200mM and 3.6mM to 600mM, respectively, the ratio of the amount of the substance N, N-dimethylformamide to the amount of the substance N, N-dimethylformamide in step three being 1: 5-1: 5.6.
7. use of gamma Fe2O3-MIL-53(Fe) -GO prepared according to claim 2 for degrading antibiotic wastewater, characterized in that: adding a certain amount of catalyst into the antibiotic solution, continuously stirring, carrying out dark adsorption for 30min, irradiating under visible light, and measuring the concentration of the antibiotic in the reaction solution every 15 min.
8. The use according to claim 7 for degrading antibiotic wastewater, wherein: the concentration of the catalyst in the antibiotic solution is 0.1 g/L-0.3 g/L.
9. The use according to claim 7 for degrading antibiotic wastewater, wherein: the antibiotic in the antibiotic wastewater is norfloxacin, and the concentration of norfloxacin solution is 5 mg/L-20 mg/L.
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