CN114405480A - Iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics and preparation method thereof - Google Patents
Iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics and preparation method thereof Download PDFInfo
- Publication number
- CN114405480A CN114405480A CN202210080920.3A CN202210080920A CN114405480A CN 114405480 A CN114405480 A CN 114405480A CN 202210080920 A CN202210080920 A CN 202210080920A CN 114405480 A CN114405480 A CN 114405480A
- Authority
- CN
- China
- Prior art keywords
- mil
- composite material
- solution
- rifampicin
- adsorption
- 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.)
- Granted
Links
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
- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/38—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/003—Wastewater from hospitals, laboratories and the like, heavily contaminated by pathogenic microorganisms
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics and a preparation method thereof. The iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics is MIL-53(Fe) @ TA-Co. The method has the advantages of simple synthesis method and mild reaction conditions, and is an economic and effective method. The MIL-53(Fe) @ TA-Co can be directly used as a novel composite material for treating rifampicin. The present invention solves the problem of few materials and methods for removing rifampicin molecules, and the novel composite adsorbent material provided by the present invention has good adsorption performance. MIL-53(Fe) @ TA-Co has great potential application value as a rifampicin molecule removal material.
Description
The technical field is as follows:
the invention belongs to the technical field of rifampicin antibiotic adsorption materials, and particularly relates to an iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics and a preparation method thereof.
Background art:
in recent years, with the increasing reports of organic pollution in water environments, the pharmaceutical industry has received great attention as a drug product classified as a new type of pollutant, including rifampicin in the rifamycin broad-spectrum antibiotic family, which is a semi-synthetic antibiotic with a complex structure, commonly used in combination with other antitubercular drugs to exert a synergistic effect, and widely used in the treatment of meningitis, staphylococcus aureus infections, and tuberculosis, which is the second largest infectious disease in the world. The antibiotic has poor bioavailability, water solubility and environmental stability, so that the medicament for treating the diseases has high dosage and long use duration, and a large amount of rifampicin molecules which are not digested in organisms are discharged into natural water. However, most sewage treatment plants are not designed to construct process facilities for eliminating low concentration organic pollutants, and even rifampicin molecules in a low concentration state are harmful to human and biological health through biological amplification effect due to their chronic toxicity, which makes it necessary to find other effective methods for removing residual low concentration organic pollutants with high efficiency. Although the removal methods for novel micro-pollutants are more and more, the adsorption method is still one of the most applied and most promising methods at present, has the advantages of high removal efficiency, simple design and operation method, low energy consumption and operation cost, low requirements on environment and equipment and the like, and is suitable for the increasingly complex treatment of organic polluted wastewater. The key of using an adsorption method to treat Organic polluted wastewater is that the fields of adsorbents and Metal Organic Frameworks (MOFs) are rapidly developed in the last twenty years, and the adsorption method has great potential in various application aspects such as adsorption, sensing, catalysis and storage due to the advantages of ultra-large specific surface area, adjustable pore structure and property, unsaturated Metal coordination centers and the like. Therefore, it is necessary to prepare MOFs materials having excellent adsorption effect and solve the defect that the pore structure of the materials is difficult to control. Tannic acid belonging to a typical glucose galloyl compound has a plurality of ortho-phenolic hydroxyl structures, can be used as a multi-base ligand to perform a complex reaction with metal ions, so that additional adsorption sites on the surface of a composite material are added, the aggregation tendency of the material can be effectively inhibited, the structure is uniform, a foundation is provided for good adsorption performance, even a free hydrogen ion is released, the free hydrogen ion penetrates into MOFs and destroys the etching effect of the internal framework of the MOFs, and the exposed surface of the MOFs is blocked, so that the mutual synergistic effect of the protection effect of preventing the exterior of the MOFs from being further etched and preventing the shell from collapsing is achieved, and finally, a hollow MOFs material is obtained, and the layered porous structure and the internal generated gap of the hollow MOFs provide an additional preferential flow path for water molecules. Therefore, the MIL-53(Fe) @ TA-Co composite material is prepared by a method with simple operation and mild reaction conditions, and the composite material is used as a novel adsorbent of rifampicin antibiotic molecules and shows good adsorption performance.
The invention content is as follows:
the invention aims to provide an iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics and a preparation method thereof, aiming at the current situation that the rifampicin antibiotics are few in removal method, exerting the synergistic effect of a metal organic framework and a metal polyphenol network, further improving the specific surface area of the material and increasing the contact area and adsorption sites with rifampicin antibiotics. The obtained spindle-shaped iron-cobalt polyphenol supramolecular modified organic framework composite material MIL-53(Fe) @ TA-Co for efficiently treating the medical wastewater containing the rifampicin antibiotic is taken as a novel RFP removing material, and the novel RFP supramolecular modified organic framework composite material has good adsorption performance and capability of resisting common ions of the medical wastewater.
In order to realize the purpose, the invention is realized by the following technical scheme:
a preparation method of a ferrum-cobalt-polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics comprises the following steps:
(1) preparing MIL-53(Fe) @ TA-Co material precursor: adding the central metal salt and the organic ligand into a solvent, stirring for several hours, uniformly mixing, and clarifying the solution to obtain a central metal salt/organic ligand solution; transferring the central metal salt/organic ligand solution into a polytetrafluoroethylene high-pressure hydrothermal reaction kettle, putting the kettle into an oven for high-temperature reaction for a plurality of hours, and washing, centrifuging and drying the kettle when the kettle is cooled to room temperature to obtain an MIL-53(Fe) @ TA-Co material precursor;
(2) preparing MIL-53(Fe) @ TA-Co composite material: preparing MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2O solution and tannic acid solution, and mixing MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2Mixing and stirring the O solution and the tannic acid solution for a plurality of hours, washing, centrifuging and drying to obtain the MIL-53(Fe) @ TA-Co composite material, grinding to a certain mesh number and reserving for later use.
In the preparation method, the central metal salt in the step (1) is selected from one or more of ferric chloride, ferric sulfate and ferric nitrate; the organic ligand is selected from one or more of terephthalic acid and trimesic acid; the solvent is one or more of ultrapure water, methanol, ethanol and N, N-dimethylformamide.
In the above production method, the central metal salt in the step (1): organic ligand: the molar ratio of the solvent is as follows: 1:1: 290.
in the preparation method, the stirring time in the step (1) is 1 hour; the high-temperature reaction temperature is 170 ℃, and the reaction time is 10 hours; the washing is sequentially and respectively washing by using N, N-dimethylformamide, methanol and ultrapure water; the centrifugation is carried out at the rotating speed of 10000 rpm for 2 minutes; the drying is vacuum drying at 100 ℃ for 12 hours; the grinding mesh number of the composite material precursor is 100 meshes.
In the above-described production method, the MIL-53(Fe) @ TA-Co material precursor solution, and Co (NO) in the step (2)3）2·6H2O solution and tannic acid solutionRespectively at a concentration of 10 mg. multidot.mL-1(ii) a MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2The volume ratio of the O solution to the tannic acid solution is 1:1:1 and mixing.
The stirring time in the step (2) is 0.75 hour, and the washing is performed by using H2Washing with water; the drying is carried out for 12 hours at the temperature of 60 ℃ under normal pressure.
The MIL-53(Fe) @ TA-Co composite material prepared by the method. The MIL-53(Fe) @ TA-Co composite material is composed of spindle-shaped particles with the length of 3-5 mu m and uniform size.
The MIL-53(Fe) @ TA-Co composite material is applied as a rifampicin antibiotic adsorbent.
The invention has the beneficial effects that:
the invention provides an iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics and a preparation method thereof. The MIL-53(Fe) @ TA-Co composite material is composed of spindle-shaped particles with the length of 3-5 mu m and uniform size, the synthetic process is simple, the reaction condition is mild, and the method is economical and effective; the obtained MIL-53(Fe) @ TA-Co composite material is used as a novel material, and has good adsorption performance and capability of resisting the influence of common ions of medical wastewater.
Description of the drawings:
FIG. 1 is a SEM image of a sample of MIL-53(Fe) @ TA-Co composite material obtained in example 1 of the present invention. and a-f are SEM images under different scales.
FIG. 2 is a TEM image of a transmission electron microscope of a sample of MIL-53(Fe) @ TA-Co composite material obtained in example 1 of the present invention. and a-f are TEM images of the transmission electron microscope under different scales.
FIG. 3 is an XRD pattern before and after adsorption of an MIL-53(Fe) @ TA-Co composite material sample obtained in example 1 of the present invention.
FIG. 4 is a FT-IR chart before and after adsorption of a sample of MIL-53(Fe) @ TA-Co composite material obtained in example 1 of the present invention.
FIG. 5 is a graph of adsorption performance for different loading amounts of MIL-53(Fe) @ TA-Co composite samples obtained in example 2 of the present invention.
FIG. 6 is a graph of the adsorption performance of MIL-53(Fe) @ TA-Co composite material samples obtained in example 2 of the present invention with time under different pH value factors. (a) The method comprises the following steps The adsorption removal rate of the MIL-53(Fe) @ TA-Co composite material to rifampicin under different pH conditions; (b) the change of the adsorption removal rate of the rifamycin sodium is delayed along with time when the pH value of the composite material is 1, 2.5 and 4 by MIL-53(Fe) @ TA-Co.
FIG. 7 is a graph of adsorption performance over time for MIL-53(Fe) @ TA-Co composite samples obtained in example 2 of the present invention under different adsorbent dosage factors.
FIG. 8 is a graph of the adsorption performance of the MIL-53(Fe) @ TA-Co composite material sample obtained in example 2 of the present invention with time under different antibiotic concentration factors.
FIG. 9 is a graph of the adsorption performance of MIL-53(Fe) @ TA-Co composite material samples obtained in example 2 of the present invention with time under different temperature factors.
FIG. 10 is a graph of the adsorption performance of MIL-53(Fe) @ TA-Co composite material samples obtained in example 2 of the present invention with time under different ion interference conditions.
FIG. 11 is a graph of adsorption kinetics under different temperature factors for MIL-53(Fe) @ TA-Co composite material samples obtained in example 2 of the present invention. (a) Is a pseudo-first-stage adsorption kinetic model diagram, (b) is a pseudo-second-stage adsorption kinetic model diagram, (c) is a particle internal diffusion model diagram, and (d) is a liquid film diffusion model diagram.
The specific implementation mode is as follows:
the invention provides a spindle-shaped iron-cobalt polyphenol supramolecular modified organic framework hybrid composite adsorbent for efficiently treating rifampicin-containing antibiotic medical wastewater, which is an MIL-53(Fe) @ TA-Co composite material, is composed of spindle-shaped particles with the length of 3-5 mu m and uniform size, and is used as a material for removing RFP molecules.
The invention is further illustrated by the following figures and examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adjustments to the present invention based on the above disclosure and still fall within the scope of the present invention.
Example 1:
a preparation method of a ferrum-cobalt-polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics comprises the following steps:
(1) FeCl is added3·6H2O, terephthalic acid (H)2BDC), N-Dimethylformamide (DMF) in a molar ratio of 1.00: 1.00: 290.00, stirring uniformly by a magnetic machine for 1 hour, clarifying the solution, transferring the solution into a polytetrafluoroethylene high-pressure hydrothermal reaction kettle, putting the kettle into an oven for high-temperature reaction at 170 ℃ for 10 hours, washing the product by DMF, methanol and water sequentially when the product is cooled to room temperature, centrifuging the product at 10000 rpm for 2 min and drying the product at 100 ℃ in vacuum for 12 hours to obtain an MIL-53(Fe) @ TA-Co material precursor;
(2) MIL-53(Fe) @ TA-Co material precursor and Co (NO) obtained in the step (1)3）2·6H2O, tannic acid and H2O is 1: 100 was prepared in a concentration of 10 mg/mL-1The solution of (1); MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2Mixing O solution and tannic acid solution at a volume ratio of 1:1:1, stirring for 0.75 hr, and adding H2Washing with O, centrifuging at 10000 rpm for 2 min, drying at 60 deg.C under normal pressure for 12 hr to obtain MIL-53(Fe) @ TA-Co composite material, grinding to 100 mesh, and reserving.
A series of characterizations were performed on the MIL-53(Fe) @ TA-Co composite material obtained in this example by a scanning electron microscope, a transmission electron microscope, X-ray powder diffraction, Fourier transform infrared spectroscopy, and the like.
FIG. 1 is a SEM image of a sample of MIL-53(Fe) @ TA-Co composite material obtained in example 1 of the present invention. As can be seen from the graphs in FIG. 1 (a-f), the MIL-53(Fe) @ TA-Co composite material has a spindle-like structural morphology, and the sizes of the samples are different, and the range is 3-5 μm. Part of the particles, which are gathered and attached on the surface of the material, can be broken or incompletely formed MIL-53(Fe) material in the preparation process.
FIG. 2 is a TEM image of a transmission electron microscope of a sample of MIL-53(Fe) @ TA-Co composite material obtained in example 1 of the present invention, as can be seen from FIGS. 2 (a-c). The shape of the outer layer of the material can be partially damaged in the preparation process, but the whole material still presents a spindle-like structure, which is probably caused by the etching effect of the introduced tannic acid when the metal polyphenol network is loaded. In the graph (d-f), the MIL-53(Fe) @ TA-Co composite material has a large number of pore structures, effective reaction sites with pollutants can be increased, and the removal performance of the rifampicin is improved to a certain extent.
Example 2
A preparation method of a ferrum-cobalt-polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics comprises the following steps:
(1) mixing iron sulfate and terephthalic acid (H)2BDC), N-Dimethylformamide (DMF) in a molar ratio of 1.00: 1.00: 290.00, stirring uniformly by a magnetic machine for 1 hour, clarifying the solution, transferring the solution into a polytetrafluoroethylene high-pressure hydrothermal reaction kettle, putting the kettle into an oven for high-temperature reaction at 170 ℃ for 10 hours, washing the product by DMF, methanol and water sequentially when the product is cooled to room temperature, centrifuging the product at 10000 rpm for 2 min and drying the product at 100 ℃ in vacuum for 12 hours to obtain an MIL-53(Fe) @ TA-Co material precursor;
(2) MIL-53(Fe) @ TA-Co material precursor and Co (NO) obtained in the step (1)3）2·6H2O, tannic acid and H2O is 1: 100 was prepared in a concentration of 10 mg/mL-1The solution of (1); MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2Mixing O solution and tannic acid solution at a volume ratio of 1:1:1, stirring for 0.75 hr, and adding H2Washing with O, centrifuging at 10000 rpm for 2 min, drying at 60 deg.C under normal pressure for 12 hr to obtain MIL-53(Fe) @ TA-Co composite material, grinding to 100 mesh, and reserving.
Example 3
A preparation method of a ferrum-cobalt-polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics comprises the following steps:
(1) mixing ferric nitrate, trimesic acid and N, N-Dimethylformamide (DMF) according to a molar ratio of 1.00: 1.00: 290.00, stirring uniformly by a magnetic machine for 1 hour, clarifying the solution, transferring the solution into a polytetrafluoroethylene high-pressure hydrothermal reaction kettle, putting the kettle into an oven for high-temperature reaction at 170 ℃ for 10 hours, washing the product by DMF, methanol and water sequentially when the product is cooled to room temperature, centrifuging the product at 10000 rpm for 2 min and drying the product at 100 ℃ in vacuum for 12 hours to obtain an MIL-53(Fe) @ TA-Co material precursor;
(2) MIL-53(Fe) @ TA-Co material precursor and Co (NO) obtained in the step (1)3）2·6H2O, tannic acid and H2O is 1: 100 was prepared in a concentration of 10 mg/mL-1The solution of (1); MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2Mixing O solution and tannic acid solution at a volume ratio of 1:1:1, stirring for 0.75 hr, and adding H2Washing with O, centrifuging at 10000 rpm for 2 min, drying at 60 deg.C under normal pressure for 12 hr to obtain MIL-53(Fe) @ TA-Co composite material, grinding to 100 mesh, and reserving.
Example 2: an application of supermolecule modified organic frame heterozygote adsorbent for treating rifampicin antibiotics.
The MIL-53(Fe) @ TA-Co composite material prepared in the embodiment 1 of the invention is applied to removal of rifampicin antibiotics: the method comprises the steps of taking an MIL-53(Fe) @ TA-Co composite material as a feeding agent, feeding a certain mass into a centrifugal tube containing a Rifampicin (RFP) solution with a certain concentration, adjusting the pH value and the ion concentration, placing the centrifugal tube into a constant-temperature oscillator with a specific temperature, oscillating the centrifugal tube for a plurality of hours, taking out the centrifugal tube, centrifuging the centrifugal tube, passing through a membrane, and testing the centrifugal tube at a specific wavelength by using an ultraviolet spectrophotometer. Wherein the volume of the centrifugal tube is 50 ml, the pH value is 2.0-10.0, the adding amount of the adsorbent is 0.125-0.875 g/L, the concentration of rifampicin antibiotic is 5-50 ppm, the ion concentration is 0.01-0.15 mol/L, the temperature is 293-323K, the shaking speed is 250 rpm, and the shaking time is 10-300 min; the centrifugal speed is 10000 rpm, the centrifugal time is 5 minutes, the diameter and the aperture of the needle cylinder type filter membrane are respectively 25 mm and 45 μm, and the wavelength of the ultraviolet spectrophotometer is 474 nm. The pH value of the solution is adjusted by using a strong acid solution or a strong alkali solution respectively, wherein the common solvent of the strong acid solution is ultrapure water, and the common solute is hydrochloric acid, nitric acid and sulfuric acid; the solvent of the strong alkaline solution is ultrapure water, and the solute is sodium hydroxide or potassium hydroxide. Wherein the concentration of the strong acid solution or the strong alkali solution is 0.01-1 mol/L.
FIG. 3 is an XRD pattern before and after adsorption of rifampicin antibiotics by MIL-53(Fe) @ TA-Co composite material samples prepared in example 1. Diffraction peaks before the reaction of the material and rifampicin respectively appear at 9.21 degrees, 10.42 degrees, 17.34 degrees, 18.81 degrees, 21.05 degrees, 25.21 degrees and 27.88 degrees, and are consistent with diffraction peaks of MIL-53(Fe), which indicates that the TA-Co loaded metal polyphenol network does not greatly damage the basic structure of the MIL-53(Fe) carrier material, and the composite material is successfully prepared. Meanwhile, the MIL-53(Fe) @ TA-Co composite material has weaker diffraction peak intensity, probably because the higher synthesis temperature and shorter synthesis time reduce the crystallinity of the material. The diffraction peak of the material at 10.42 ° indicates that the MIL-53(Fe) material obtained by this synthesis method has a change in the crystal growth direction, and the material generates a portion of the structural defects. In contrast to the main diffraction peak of MIL-53(Fe) @ TA-Co composite material for removing organic substances from aqueous solution, it was observed that the intensity of the diffraction peak of the material was reduced after the reaction, probably due to the adsorption of rifampicin molecules on the surface of the material. In addition, the diffraction peak position of the material after adsorbing the organic matters has no obvious deviation, which shows that the structure of the MIL-53(Fe) @ TA-Co composite material is not damaged in the removal process, and the material has excellent chemical stability under the reaction condition and can reserve more active sites for effectively adsorbing RFP molecules.
FIG. 4 is FT-IR chart before and after adsorption of MIL-53(Fe) @ TA-Co composite sample obtained in example 1. The composite material was first analyzed at 526 cm before removing RFP molecules (20 ppm) from the aqueous solution-1And 1509 cm-1Vibration peak due to stretching vibration of Fe-O bond and H2C = C skeleton vibration of BDC, pair of-COO-bonds on organic linking groupThe vibration peak is 1388 cm-1And the asymmetric vibration peak is from 1543 cm-1Shift to 1579 cm-1The reason is that the MIL-53(Fe) @ TA-Co composite material generates structural defects in the preparation process, so that 1543 cm is obtained-1The peak of vibration is reduced and is 1579 cm-1New peak is generated, which indicates that inorganic metal Fe3+And the formation of Fe-oxo clusters between the carboxyl functional groups of the organic ligands. Meanwhile, the out-of-plane and in-plane bending vibration peaks of the terephthalic acid C-H bond surface are respectively 746 cm-1、822 cm-1、880 cm-1At a distance of 1022 cm-1、1087 cm-1、1199 cm-1To (3). By comparing with MIL-53(Fe) @ TA-Co composite material after removing RFP in aqueous solution, 1087 cm can be found-1And 1199 cm-1The characteristic peak of (A) is shifted to 1117 cm-1And 1161 cm-1Here, it is shown that the group plays a role in adsorbing organic substances. In addition, the main characteristic peak position of the material was not changed much after the reaction, indicating that each type of functional group was not destroyed, and 746 cm-1And 1291 cm-1The increase of the intensity of the vibration peak represents that the rifampicin molecule is adsorbed on the MIL-53(Fe) @ TA-Co composite material.
FIG. 5 shows MIL-53(Fe) @ TA-Co composite material of example 2 in different Co2+Graph of the effect of loading on RFS (20 ppm) adsorption performance. Observation enabled the adsorption efficiency of the material to RIF molecules to be maximized at MIL53(Fe) @ TA: Co = 1: 1. Meanwhile, along with the increase of the loading amount of the Co metal ions, the removal effect of the material on pollutants also shows a trend of increasing firstly and then decreasing, which is probably because the thickness of the metal polyphenol network is gradually reduced as the coating structure is more compact along with the increase of the concentration of the Co metal ions or the decrease of the TA concentration. In addition, phenolic hydroxyl groups in TA interact with more Co metal ions, resulting in a continuous decrease in residual hydrophilic groups, resulting in a gradual increase in the surface roughness and contact angle of the metal polyphenol network. Therefore, in the initial stage of increasing the content of Co metal ions, the thickness of the metal polyphenol network plays a main role, the contact resistance between the MIL-53(Fe) @ TA-Co composite material and rifampicin is reduced, and when the content of Co metal ions is further increasedWhen the content of Co metal ions is increased, the inhibiting effect of the reduction of the hydrophilicity of the metal polyphenol network exceeds the promoting effect of the coating thickness on the removal of organic matters, so that the RIF removal effect of the MIL-53(Fe) @ TA-Co composite material shows a process of increasing firstly and then decreasing with the increase of the content of the Co metal ions.
FIG. 6 is a graph of the adsorption performance of the MIL-53(Fe) @ TA-Co composite material of example 2 at different pH values (pH 1, 2.5, 4, 5, 6, 7, 8, 9, 10, 11, 12) over time. As can be seen from the graph (a), the amount of the additive was constant (0.5 g. L)-1) Under the removal conditions of pollutant concentration (20 ppm), solution temperature (303K) and the like, when the pH influence range is 1.0-9.0, the adsorption rate of the MIL-53(Fe) @ TA-Co composite material on RFP is integrally maintained to be more than 75%, and when the influence range is changed to be 10.0-12.0, the removal performance is greatly reduced, probably because effective active sites on the material are damaged in a strong alkaline environment. Meanwhile, MIL-53(Fe) @ TA-Co composite was found to be able to react with more contaminants at pH =2.5, indicating that the adsorption process is strongly dependent on the initial pH. The influence of pH =1.0, pH =2.5 and pH =4.0 on the adsorption performance at different time points is studied to obtain a graph (b), and it is known from the graph that the composite material has similar removal tendency at different pH values (pH 1, 2.5 and 4), the adsorption efficiency for rifampicin antibiotic is faster in the first 60 min, and the adsorption rate at 120 min does not change any more, which indicates that the adsorption rate decreases and approaches to the adsorption equilibrium state as the adsorption reaction continues to proceed. When the pH values are 1.0 and 4.0, the removal rate and adsorption capacity of rifampicin are 78.31% and 31.32 mg g respectively at 300 min-1And 83.28% with 33.31 mg g-1Under the condition of the optimal initial pH of 2.5, the removal rate and the adsorption capacity at 120 min reach 89.13 percent and 35.65 mg-g-1It is explained that the time required for removing the same amount of contaminants can be greatly shortened by selecting an appropriate initial pH as the reaction conditions of the MIL-53(Fe) @ TA-Co composite material.
FIG. 7 is a graph showing the adsorption performance of MIL-53(Fe) @ TA-Co composite material samples obtained in example 2 of the present invention at different adsorbent dosages (0.25 g/L, 0.50g/L, 0.75 g/L) with time. In thatAs can be seen from the course of the adsorption rate as a function of time, changing the amount of MIL-53(Fe) @ TA-Co composite added did not affect the tendency to remove contaminants, although more (0.75 g. L.) was added at a shorter adsorption time (30 min) and a fixed contaminant concentration (20 ppm)-1) The removal of organic substances was accelerated, but the adsorption time was increased to 0.50 g.L-1The amount of the added material can achieve the same adsorption rate as the former. When the amount of the additive is further reduced to 0.25 g.L-1During the process, the removal of the rifampicin by the composite material can be found to be balanced in the rapid adsorption stage, the removal capacity of the rifampicin is not changed greatly in the subsequent slow adsorption process, the selection of a more appropriate dosage is illustrated, the effective reaction sites carried by the composite material can be utilized to the maximum extent while certain adsorption performance is ensured, and the adsorption capacity of the rifampicin on RFP is improved.
FIG. 8 is a graph showing adsorption performance of MIL-53(Fe) @ TA-Co composite samples obtained in example 2 at different antibiotic concentrations (10 ppm, 20ppm, 40 ppm) with time. The adsorption effect and the adsorption capacity of the composite material to rifampicin molecules are in negative correlation and positive correlation to a certain extent, the adsorption rates are 92.20% (10 ppm), 91.78% (20 ppm) and 86.93% (40 ppm), respectively, it can be obviously seen that the adsorption rate is limited when the pollutant concentration is 10ppm, which indicates that the composite material may generate competitive adsorption to rifampicin molecules when the concentration is lower, and the removal rate is only slightly reduced when the rifampicin concentration is increased from 10ppm to 20ppm, which indicates that the adsorption sites of the composite material are effectively utilized, so that the adsorption capacity is greatly improved while the removal rate is approximately unchanged, but the adsorption rate begins to obviously change when the concentration is further increased to 40ppm, and some reasons are that certain repulsive force static electricity is generated among more rifampicin molecules in the solution, so that free rifampicin molecules are difficult to contact the composite material, the other reason is that under the condition of fixed dosage of the adsorbent, the provided adsorption sites are fixed differently, the active sites on the adsorbent gradually approach saturation, and the adsorption capacity gradually approaches equilibrium. As can be seen from the adsorption rate and adsorption capacity of the composite material for rifampicin with different concentrations, 20ppm is the optimum concentration of rifampicin solution, which not only can effectively remove rifampicin, but also can greatly utilize the adsorption sites of the composite material.
FIG. 9 is a graph showing the adsorption performance of MIL-53(Fe) @ TA-Co composite material samples obtained in example 2 of the present invention at different temperatures (293K, 303K, 313K) with time. The initial pH (2.5) and the amount (0.5 g.L) added were measured-1) And contaminant concentration (20 ppm) were kept constant, the reaction proceeded with the same trend as before as the solution temperature was gradually increased from 293K, indicating that the time points of the fast and slow adsorption stages did not change with temperature. Meanwhile, the adsorption performance of the material shows a phenomenon of strengthening and weakening, the optimal adsorption rate of 91.78% is reached at 303K, which shows that the temperature has certain influence on the removal of the rifampicin solution by the composite material, because the balance approaches towards the heat absorption direction by raising the temperature under the fixed environment condition, the adsorption capacity is obviously improved along with the temperature increase from 293K to 303K, which shows that the movement rate of rifampicin molecules can be increased by raising the temperature, the possibility of collision among rifampicin molecules can be increased, and the adsorption rate of the composite material on the rifampicin molecules is improved. As the temperature further increases from 303K to 323K, the adsorption capacity decreases, and the kinetic energy of the rifampicin molecules is likely to be greater than the interaction force between the composite material and rifampicin molecules, resulting in a decrease in adsorption rate. Therefore, it is very important to select an appropriate ambient temperature for the adsorption reaction.
FIG. 10 shows the initial pH (2.5) and the amount (0.5 g. L) of the MIL-53(Fe) @ TA-Co composite material sample obtained in example 2 of the present invention-1) Na, contaminant concentration (20 ppm), solution temperature (303K), and the like+、K+、Mg2+、Cl-And SO4 2-And (3) an adsorption performance graph which changes along with time under the interference of different ions and the like. The adsorption tendency of the material under the interference of ions with the same concentration is approximately the same, a large amount of pollutants can be removed in a short time, but the adsorption tendency is different in the subsequent slow reaction stage, namely NaCl, KCl and MgCl2The degree of influence of (A) is similar, while Na2SO4The effect of (A) is stronger than that of NaCl, due to SO4 2-Cl having a charge of the amount-Twice, stronger interference effect is caused under the same concentration, and the MIL-53(Fe) @ TA-Co (1.0) composite material is also shown to be more susceptible to anions in the process of removing rifampicin.
FIG. 11 is a graph showing adsorption kinetics at different temperatures (293K, 303K, 313K) for MIL-53(Fe) @ TA-Co composite samples obtained in example 2 of the present invention. From the graphs (a-b), it can be seen that the fitting coefficients of pseudo-first-order adsorption kinetics are 0.90677 and 0.99999 at 293K, 0.84103 and 0.99990 at 303K, and 0.85054 and 0.99976 at 313K, respectively, and the latter is far higher than the former at different temperatures, and the calculated saturated adsorption capacity of the latter is closer to the experimental adsorption capacity, which indicates that the reaction process between the composite material and the RFP molecules belongs to chemical adsorption, and is more suitable for analysis by a pseudo-second-order adsorption kinetics model. As can be seen from the graph (c), the process of adsorbing pollutants by the MIL-53(Fe) @ TA-Co composite material can be divided into three stages, except for the rapid adsorption stage, the fit line of the second stage and the third stage does not pass through the origin of the coordinate axis, which indicates that the rate-limiting step of the process is not controlled by the intra-particle diffusion alone. Therefore, further analysis in conjunction with plot (d) revealed that the linear model of liquid film diffusion also did not pass through the origin of the coordinate axes, indicating that the process of MIL-53(Fe) @ TA-Co composite material for removing RFP is coordinated by intra-particle diffusion and liquid film diffusion.
The embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above embodiments, and any modification, equivalent replacement, or improvement made by those skilled in the art within the spirit and principle of the present invention should be within the protection scope of the present invention.
Claims (8)
1. A preparation method of a ferrum-cobalt-polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics is characterized by comprising the following steps:
(1) preparing MIL-53(Fe) @ TA-Co material precursor: adding the central metal salt and the organic ligand into a solvent, stirring for several hours, uniformly mixing, and clarifying the solution to obtain a central metal salt/organic ligand solution; transferring the central metal salt/organic ligand solution into a polytetrafluoroethylene high-pressure hydrothermal reaction kettle, putting the kettle into an oven for high-temperature reaction for a plurality of hours, and washing, centrifuging and drying the kettle when the kettle is cooled to room temperature to obtain an MIL-53(Fe) @ TA-Co material precursor;
(2) preparing MIL-53(Fe) @ TA-Co composite material: preparing MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2O solution and tannic acid solution, and mixing MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2Mixing and stirring the O solution and the tannic acid solution for a plurality of hours, washing, centrifuging and drying to obtain the MIL-53(Fe) @ TA-Co composite material, grinding to a certain mesh number, and reserving for later use.
2. The method of claim 1, wherein: the central metal salt in the step (1) is selected from one or more of ferric chloride, ferric sulfate and ferric nitrate; the organic ligand is selected from one or more of terephthalic acid and trimesic acid; the medium solvent is one or more of ultrapure water, methanol, ethanol and N, N-dimethylformamide.
3. The method of claim 1, wherein: the central metal salt in the step (1): organic ligand: the mixing molar ratio of the solvents is as follows: 1:1: 290.
4. the method of claim 1, wherein: the stirring time in the step (1) is 1 hour; the high-temperature reaction temperature is 170 ℃, and the reaction time is 10 hours; the drying is vacuum drying for 12 hours at 100 ℃.
5. The method of claim 1, wherein: MIL-53(Fe) @ TA-Co material precursor solution and Co (NO) in step (2)3）2·6H2The concentrations of the O solution and the tannic acid solution were 10 mg/mL, respectively-1(ii) a The MIL-53(Fe) @ TA-Co material precursor solution and Co (NO)3）2·6H2The volume ratio of the O solution to the tannic acid solution is 1:1:1 and mixing.
6. The method of claim 1, wherein: the stirring time in the step (2) is 0.75 hour; the drying is carried out for 12 hours at the temperature of 60 ℃ under normal pressure.
7. MIL-53(Fe) @ TA-Co composite material obtainable by a process according to any one of claims 1 to 6.
8. The use of MIL-53(Fe) @ TA-Co composite material of claim 7 as an adsorbent for rifampicin antibiotics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210080920.3A CN114405480B (en) | 2022-01-24 | 2022-01-24 | Iron-cobalt polyphenol supermolecule modified organic framework composite material for treating rifampicin antibiotics and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210080920.3A CN114405480B (en) | 2022-01-24 | 2022-01-24 | Iron-cobalt polyphenol supermolecule modified organic framework composite material for treating rifampicin antibiotics and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114405480A true CN114405480A (en) | 2022-04-29 |
| CN114405480B CN114405480B (en) | 2023-06-13 |
Family
ID=81276988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210080920.3A Active CN114405480B (en) | 2022-01-24 | 2022-01-24 | Iron-cobalt polyphenol supermolecule modified organic framework composite material for treating rifampicin antibiotics and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114405480B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646465A (en) * | 2022-11-08 | 2023-01-31 | 中国农业科学院蔬菜花卉研究所 | Porous composite material, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533237A (en) * | 2020-05-12 | 2020-08-14 | 湖南鑫恒环境科技有限公司 | Method for treating antibiotic wastewater by using manganese ion doped metal organic framework material |
| CN112968185A (en) * | 2021-03-05 | 2021-06-15 | 福州大学 | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure |
| CN113512735A (en) * | 2021-03-16 | 2021-10-19 | 吉林大学 | Hollow metal organic framework-tannic acid-polypyrrole composite material and preparation method and application thereof |
| CN113813938A (en) * | 2021-10-22 | 2021-12-21 | 福州大学 | Rod-shaped modified iron-nickel organic framework composite adsorbent |
| CN113877521A (en) * | 2021-10-22 | 2022-01-04 | 南京大学 | Preparation method and application of clay/tannin/metal ion composite material for efficiently adsorbing antibiotics |
-
2022
- 2022-01-24 CN CN202210080920.3A patent/CN114405480B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111533237A (en) * | 2020-05-12 | 2020-08-14 | 湖南鑫恒环境科技有限公司 | Method for treating antibiotic wastewater by using manganese ion doped metal organic framework material |
| CN112968185A (en) * | 2021-03-05 | 2021-06-15 | 福州大学 | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure |
| CN113512735A (en) * | 2021-03-16 | 2021-10-19 | 吉林大学 | Hollow metal organic framework-tannic acid-polypyrrole composite material and preparation method and application thereof |
| CN113813938A (en) * | 2021-10-22 | 2021-12-21 | 福州大学 | Rod-shaped modified iron-nickel organic framework composite adsorbent |
| CN113877521A (en) * | 2021-10-22 | 2022-01-04 | 南京大学 | Preparation method and application of clay/tannin/metal ion composite material for efficiently adsorbing antibiotics |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115646465A (en) * | 2022-11-08 | 2023-01-31 | 中国农业科学院蔬菜花卉研究所 | Porous composite material, preparation method and application thereof |
| CN115646465B (en) * | 2022-11-08 | 2024-04-30 | 中国农业科学院蔬菜花卉研究所 | Porous composite material, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114405480B (en) | 2023-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Efficient removal of tetracycline by a hierarchically porous ZIF-8 metal organic framework | |
| Guo et al. | Green and facile synthesis of cobalt-based metal–organic frameworks for the efficient removal of Congo red from aqueous solution | |
| Peng et al. | Advanced MOFs@ aerogel composites: construction and application towards environmental remediation | |
| Jiang et al. | In-situ growth of bimetallic FeCo-MOF on magnetic biochar for enhanced clearance of tetracycline and fruit preservation | |
| CN109569725B (en) | Method for preparing magnetic Cu (I) microsphere catalyst by one-step method | |
| Maru et al. | Dye contaminated wastewater treatment through metal–organic framework (MOF) based materials | |
| Denizli et al. | Removal of heavy metal ions from aquatic solutions by membrane chromatography | |
| CN113813938A (en) | Rod-shaped modified iron-nickel organic framework composite adsorbent | |
| Wang et al. | A water resistance magnetic graphene-anchored zeolitic imidazolate framework for efficient adsorption and removal of residual tetracyclines in wastewater | |
| Nguyen et al. | Synergistic biosorption between phenol and nickel (II) from Binary mixtures on chemically and biologically modified chitosan beads | |
| CN110252267B (en) | Preparation and application of nano hybrid material | |
| Li et al. | Hollow C, N-TiO2@ C surface molecularly imprinted microspheres with visible light photocatalytic regeneration availability for targeted degradation of sulfadiazine | |
| Zhang et al. | Fabrication of an efficient ZIF-8 alginate composite hydrogel material and its application to enhanced copper (ii) adsorption from aqueous solutions | |
| CN114405480A (en) | Iron-cobalt polyphenol supramolecular modified organic framework composite material for treating rifampicin antibiotics and preparation method thereof | |
| Huang et al. | In situ decoration of La (OH) 3 on polyethyleneimine-linked dendritic mesoporous silica nanospheres targeting at efficient and simultaneous removal of phosphate and Congo red | |
| Li et al. | Adsorption of heavy metals and antibacterial activity of silicon-doped chitosan composite microspheres loaded with ZIF-8 | |
| WO2021042599A1 (en) | Method for preparing water-purifying charcoal composite material with low loading amount of nano zero-valent iron and nano silver | |
| Liu et al. | Rational design of three-dimensional graphene/graphene oxide-based architectures for the efficient adsorption of contaminants from aqueous solutions | |
| Zhang et al. | Synchronous, efficient and fast removal of phosphate and organic matter by carbon-coated lanthanum nanorods | |
| Guo et al. | Preparation of Mg@ MIL-101 (Fe)/NH2-MIL-125 (Ti) bis-MIL composites and their sorption performance towards Pb (II) from aqueous solution | |
| Zha et al. | Quasi-reverse-emulsion-templated approach for a facile and sustainable environmental remediation for cadmium | |
| CN114405481A (en) | Preparation method of copper-based-covalent organic framework composite core-shell adsorbent for adsorbing rifamycin sodium | |
| CN105536710A (en) | Mesoporous NH2-MIL-101(Cr) material as well as preparation method and application thereof | |
| Vinayagam et al. | Equilibrium and kinetics of adsorption of cationic dyes by STISHOVITE clay-TiO2 nanocomposite | |
| Deng et al. | Photo-degradation of methyl orange by polysaccharides/LaFe0. 8Cu0. 2O3 composite films |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |