CN113842887B - Co-MIL-53(Fe)-NH 2 /UIO-66-NH 2 Composite material, preparation and application thereof - Google Patents
Co-MIL-53(Fe)-NH 2 /UIO-66-NH 2 Composite material, preparation and application thereof Download PDFInfo
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- 239000013206 MIL-53 Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004098 Tetracycline Substances 0.000 claims abstract description 17
- 229960002180 tetracycline Drugs 0.000 claims abstract description 17
- 229930101283 tetracycline Natural products 0.000 claims abstract description 17
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
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- 238000000034 method Methods 0.000 claims abstract description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
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- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001782 photodegradation Methods 0.000 claims description 3
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- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000243 solution Substances 0.000 description 5
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
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- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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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
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
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- 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
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Abstract
The invention belongs to the technical field of preparation of a nano composite material and an environmental material and degradation of environmental pollutants, and relates to Co-MIL-53 (Fe) -NH 2 /UIO‑66‑NH 2 Composite materials and their preparation and use. Octahedron UiO-66-NH is processed by an in-situ method 2 And Co-MIL-53 (Fe) -NH 2 Combined to successfully prepare Co-MIL-53 (Fe) -NH 2 /UIO‑66‑NH 2 The composite material is used for adsorbing and degrading antibiotic tetracycline under visible light (lambda is more than or equal to 420 nm), and Co-MIL-53 (Fe) -NH in the composite material 2 With UiO-66-NH 2 The mass ratio is 7:3 (Co-MIL-53 (Fe) -NH) with most efficient adsorption and photocatalytic synergistic degradation capability 2 45% of UiO-66-NH 2 53%).
Description
The technical field is as follows:
the invention belongs to the technical field of preparation of a nano composite material and an environmental material and degradation of environmental pollutants, and relates to Co-MIL-53 (Fe) -NH 2 /UIO-66-NH 2 Composite materials, their preparation and use.
Background art:
in recent years, the wide application of antibiotics causes the rapid increase of antibiotics in environmental water bodies, and poses great threat to human health. However, TC with different concentrations can be detected in a plurality of water bodies due to good water solubility and great degradation difficulty. The continuous accumulation of TC in the environmental water not only pollutes the environment, but also can enter a food chain and finally endanger the health of human beings. Therefore, there is an urgent need to develop possible methods for degrading TC.
Metal Organic Frameworks (MOFs) are a series of novel three-dimensional porous materials with high surface area and well-ordered pore size. They have good potential in adsorption, catalysis and gas storage applications. Of interest are some particular MOFs classes (e.g., fe-MOF, ti (IV) -MOF, zr-MOF, zn-MOF). They have good catalytic properties under light, due to their preparation for excited electron transfer. However, the low efficiency of MOFs in generating excited electrons and separating charges results in low efficiency of photocatalytic reaction. Therefore, it may be a feasible method to improve quantum efficiency by introducing transition metals into MOFs. For example, sun Dengrong has synthesized NH 2 UIO-66 (Zr/Ti), proving that the construction of bimetallic-based MOFs by metal substitution in MOFs is an effective way to improve the photocatalytic performance.
The invention content is as follows:
the invention aims to provide Co-MIL-53 (Fe) -NH 2 /UIO-66-NH 2 The composite material, the preparation and the application thereof are characterized in that Co-MIL-53 (Fe) -NH is prepared by doping transition metal cobalt 2 /UIO-66-NH 2 Dual MOFs materials of which UIO-66-NH 2 As a typical Zr-based MOFs material, the material can effectively promote the separation and transfer of photoelectric carriers. And the Co-doped Fe-based MOFs are introduced through Fe due to the element Co 3+ /Fe 2+ And Co 3+ /Co 2+ The redox process further facilitates charge transfer. Thus, by Co-MIL-53 (Fe) -NH 2 With UIO-66-NH 2 And the direct Z-shaped heterojunction is constructed by combination, so that the photocatalytic capacity and the adsorption capacity of the catalyst are improved. The prepared photocatalyst is beneficial to the transmission process of photon-generated carriers, has good visible light photocatalytic activity and also has large specific surface area.
In order to realize the purpose of the invention, the following technical scheme is adopted:
Co-MIL-53(Fe)-NH 2 /UIO-66-NH 2 the preparation method of the composite material comprises the following steps:
(1) Adding a set amount of Fe (NO) to DMF 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O and H 2 ATA, and carrying out ultrasonic treatment until the ATA is completely dissolved to obtain a mixed solution;
(2) Adding a set amount of UiO-66-NH into the mixed solution in the step (1) 2 Heating the stainless steel reaction kettle lined with polytetrafluoroethylene to 140 +/-10 ℃ and keeping the temperature for at least 6 hours;
(4) After cooling, the solid was collected by centrifugation and washed with methanol and deionized water, co-MIL-53 (Fe) -NH 2 /UIO-66-NH 2 A composite material.
Preferably, the vacuum drying temperature is 85 ℃.
Preferably, the reaction temperature in a stainless steel reaction kettle lined with polytetrafluoroethylene is controlled to be 140 +/-10 ℃, and the reaction duration is controlled to be 6 hours. If the temperature is too low, co-MIL-53 (Fe) -NH results 2 Incomplete crystallization and low yield. If the time is too short, the composite material is incompletely compounded and the yield is low.
Preferably, co-MIL-53 (Fe) -NH 2 With UIO-66-NH 2 Has a mass ratio of 1:1-7:3. Co-MIL-53 (Fe) -NH in composite material 2 With UiO-66-NH 2 The mass ratio is 7:3 has the most efficient adsorption and photocatalysis synergistic degradation capability.
Compared with the prior art, the application has the following beneficial effects: the Co-MIL-53 (Fe) -NH2/UIO-66-NH2 composite material is prepared by a simple in-situ method, the appearance is a wrapping structure, and the material has the advantages of high adsorption and photocatalysis performance, good stability and the like. The invention has simple process, cheap and easily obtained raw materials and low cost, and meets the environment-friendly requirement. The method does not need pretreatment such as high temperature and calcination, thereby reducing energy consumption and reaction cost and facilitating batch production.
Description of the drawings:
FIG. 1 shows UiO-66-NH in an embodiment of the present invention 2 ，Co-MIL-53(Fe)-NH 2 And Co-MIL-53 (Fe) -NH 2 /X％UIO-66-NH 2 XRD patterns and three-dimensional fluorescence (PL) patterns of the composite.
FIG. 2 shows UiO-66-NH in an embodiment of the present invention 2 ，Co-MIL-53(Fe)-NH 2 And Co-MIL-53 (Fe) -NH 2 /X％UIO-66-NH 2 FT-IR spectrum of the composite.
FIG. 3 shows UiO-66-NH in an embodiment of the present invention 2 And Co-MIL-53 (Fe) -NH 2 /X％UIO-66-NH 2 SEM image of (d).
FIG. 4 shows Co-MIL-53 (Fe) -NH in an example of the present invention 2 /X％UIO-66-NH 2 XPS spectra of (a).
FIG. 5 shows the adsorption degradation of tetracycline (0.02 g catalyst; 10mg PMS; 50mL 25mg/L TC) in the examples of the present invention.
FIG. 6 shows Co-MIL-53 (Fe) -NH in an example of the present invention 2 /X％UIO-66-NH 2 A TEM map of (a).
The specific implementation mode is as follows:
the present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Example (b):
UIO-66-NH 2 by conventional solvothermal synthesis. The method comprises the following steps:
A. to 40ml of DMF was added 0.81g H 2 ATA (2-Aminoterephthalic acid) and 1.05g ZrCl 4 Ultrasonic dissolving, adding 17ml acetic acid, stirring for 30 minutes until dissolving completely;
B. transferring the mixed solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, transferring the mixed solution into an oven, and reacting for 24 hours at 120 ℃;
C. cooling to room temperature, washing with ethanol and water, centrifuging and collecting a product;
D. finally, the product is dried in a vacuum oven at 80 ℃ to obtain UIO-66-NH 2 A composite material.
Co-MIL-53(Fe)-NH 2 /X％UIO-66-NH 2 Also synthesized by solvothermal method. The method comprises the following steps:
A. first, 40.4mg of Fe (NO) was added 3 ) 3 ·9H 2 O,87.3mg of Co (NO) 3 ) 2 ·6H 2 O and 18.1mg of H 2 Slowly adding ATA into 10ml DMF solution, and performing ultrasonic treatment until completely dissolving;
B. different amounts of UiO-66-NH were added to the solution of step A 2 ；
C. Transferring the mixed solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, transferring the mixed solution into an oven, and keeping the temperature of 140 +/-10 ℃ for reaction for 6 hours;
D. cooling to room temperature, washing with methanol and water, centrifuging and collecting a product;
E. finally, the product is dried in a vacuum oven at 80 ℃ to obtain Co-MIL-53 (Fe) -NH 2 / X％UIO-66-NH 2 A composite material.
Co-MIL-53 (Fe) -NH of the invention 2 /UIO-66-NH 2 Successful composite preparation is evidenced by X-ray diffraction (XRD), three-dimensional fluorescence (PL), fourier infrared (FT-IR), scanning Electron Microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and Transmission Electron Microscopy (TEM). The diffraction peak intensity of the composite material in the XRD pattern is increased at 2 theta =10-20 degrees, which shows that UIO-66-NH 2 Upper Co-MIL-53 (Fe) -NH 2 The content is increased, and the successful synthesis of the composite material is proved. UIO-66-NH in FT-IR chart 2 ，Co-MIL-53(Fe)-NH 2 With Co-MIL-53 (Fe) -NH 2 /UIO-66-NH 2 Peak energy of the composite material corresponds, and Co-MIL-53 (Fe) -NH 2 /UIO-66-NH 2 The peak values of Fe-O, co-O and Zr-O appear in the composite material, and the successful preparation of the composite material is proved. SEM and TEM images confirmed the binding of the composite. Co-MIL-53 (Fe) -NH 2 Has a particle diameter of about 5 to 12nm, uiO-66-NH 2 The particle size of (A) is 120-180 nm. EDS and XPS spectra confirm the presence of C, O, N, fe, co and Zr in the composite material, indicating the successful synthesis of the composite material.
The invention also provides the application of the composite material in the fields of adsorption and photodegradation, and the composite material is used for the adsorption and photodegradation of tetracycline in water.
Adsorption and photocatalytic activity evaluation: the reaction was carried out in a model GHX-2 photochemical reactor (available from science and technology limited, university of Yangzhou). 20mg of catalyst, 10mg of PMS and 50mL of a Tetracycline (TC) (25 mg/L) aqueous solution were mixed in a 50mL colorimetric tube and charged into a reactor of a photocatalytic instrument. The mixed solution was magnetically stirred in the dark for 40 minutes to reach adsorption equilibrium, and then the catalytic reaction was carried out by illumination with a xenon lamp for 30 minutes. 3mL of tetracycline solution was taken every 4 minutes, and the catalyst in the 3mL of tetracycline solution was immediately separated by centrifugation. The change in the concentration of tetracycline was detected by measuring the absorbance using an ultraviolet-visible spectrophotometer (UV-3600, shimadzu) at a measurement wavelength of 357nm. And (5) carrying out absorbance measurement on tetracycline solutions with different concentrations, and drawing a standard curve. Calculating the concentration of tetracycline according to the detected absorbance, and recording as C t . The initial concentration of 25mg/L is recorded as C 0 。
Co-MIL-53 (Fe) -NH prepared by the invention 2 /UIO-66-NH 2 Composite material, in particular Co-MIL-53 (Fe) -NH 2 /30％UIO-66-NH 2 The degradation rate of tetracycline can reach 88% after dark adsorption for 40 min and when xenon lamp is used for illumination for 8 min. The experimental results show that Co-MIL-53 (Fe) -NH is physically mixed 2 /30％UIO-66-NH 2 After dark reaction for 40 minutes, the degradation rate of tetracycline is up to 70 percent when the xenon lamp illuminates for 8 minutes, which is far lower than that of the composite material Co-MIL-53 (Fe) -NH 2 /30％UIO-66-NH 2 。
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any obvious modifications, substitutions or variations can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (5)
1. ACo-MIL-53 (Fe) -NH 2 /UIO-66-NH 2 The preparation method of the composite material is characterized by comprising the following steps: the method comprises the following steps:
(1) A set amount of Fe (NO) was added to DMF 3 ) 3 ·9H 2 O、Co(NO 3 ) 2 ·6H 2 O and H 2 ATA, and carrying out ultrasonic treatment until the ATA is completely dissolved to obtain a mixed solution;
(2) Adding a set amount of UiO-66-NH into the mixed solution in the step (1) 2 Ultrasonically dispersing the powder, placing the powder in a stainless steel reaction kettle lined with polytetrafluoroethylene, heating to 140 +/-10 ℃ and keeping the temperature for at least 6 hours; co-MIL-53 (Fe) -NH in step (2) 2 With UIO-66-NH 2 The mass ratio of 1:1-7: 3;
(3) After cooling, the solid was collected by centrifugation and washed with methanol and deionized water, and dried under vacuum to give the Co-MIL-53 (Fe) -NH 2 /UIO-66-NH 2 Composite material, UIO-66-NH in composite material 2 The particle size of (A) is 120-180 nm.
2. Co-MIL-53 (Fe) -NH according to claim 1 2 /UIO-66-NH 2 The preparation method of the composite material is characterized by comprising the following steps: the vacuum drying temperature in step (3) was 85 ℃.
3. Co-MIL-53 (Fe) -NH according to claim 1 2 /UIO-66-NH 2 The preparation method of the composite material is characterized by comprising the following steps: co-MIL-53 (Fe) -NH in composite material 2 The particle size of (A) is 5-20 nm.
4. Co-MIL-53 (Fe) -NH according to any of claims 1 to 2 2 /UIO-66-NH 2 Preparation method of Co-MIL-53 (Fe) -NH prepared by composite material 2 /UIO-66-NH 2 A composite material.
5. Co-MIL-53 (Fe) -NH as claimed in claim 4 2 /UIO-66-NH 2 The application of the composite material is characterized in that: used for the adsorption and photodegradation of tetracycline in water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111126110.9A CN113842887B (en) | 2021-09-26 | 2021-09-26 | Co-MIL-53(Fe)-NH 2 /UIO-66-NH 2 Composite material, preparation and application thereof |
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| CN113019454A (en) * | 2021-03-03 | 2021-06-25 | 兰州大学 | NH (hydrogen sulfide)2Preparation method and application of-MIL-101 (Fe) @ NiCoP composite nano photocatalyst |
| CN113318792A (en) * | 2021-06-22 | 2021-08-31 | 哈尔滨理工大学 | Flaky CeO2/UIO-66-NH2Composite photocatalytic material and preparation method thereof |
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| CN113318792A (en) * | 2021-06-22 | 2021-08-31 | 哈尔滨理工大学 | Flaky CeO2/UIO-66-NH2Composite photocatalytic material and preparation method thereof |
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| "Benzothiadiazole functionalized Co-doped MIL-53-NH2 with electron deficient units for enhanced photocatalytic degradation of bisphenol A and ofloxacin under visible light";Shi-Wen Lv et al.;《Journal of Hazardous Materials》;20200102;第387卷;第1-11页 * |
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