CN108905976B - Manganese ion doped metal organic framework material and preparation method and application thereof - Google Patents
Manganese ion doped metal organic framework material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 125
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 124
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 31
- 230000003115 biocidal effect Effects 0.000 claims abstract description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000004729 solvothermal method Methods 0.000 claims abstract description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 52
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- 239000011572 manganese Substances 0.000 claims description 51
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical group [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 49
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- 239000003242 anti bacterial agent Substances 0.000 claims description 15
- 229940088710 antibiotic agent Drugs 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
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- 238000005406 washing Methods 0.000 claims description 7
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- 238000006243 chemical reaction Methods 0.000 claims description 5
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- 239000007795 chemical reaction product Substances 0.000 claims description 3
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- 230000003534 oscillatory effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 26
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
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- 239000013078 crystal Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
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- 239000000243 solution Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
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- 229910000406 trisodium phosphate Inorganic materials 0.000 description 5
- 239000004098 Tetracycline Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
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- 229930101283 tetracycline Natural products 0.000 description 4
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- 150000003522 tetracyclines Chemical class 0.000 description 4
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
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- 239000000356 contaminant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 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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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
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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
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention discloses a manganese ion doped metal organic framework material, a preparation method and application thereof, wherein the material comprises UiO-66 (Zr) doped with manganese ions. The preparation method comprises the following steps: zirconium chloride, terephthalic acid, manganese chloride tetrahydrate and N, N-dimethylformamide are mixed for solvothermal reaction to obtain the manganese ion doped metal organic framework material. The manganese ion doped metal organic framework material has the advantages of large adsorption capacity, good adsorption performance, good stability and the like, is simple to synthesize, can be widely adopted, can efficiently adsorb and remove pollutants in water, is a novel adsorbent, and has the advantages of simple operation, convenient preparation, few raw material types, high yield, low cost and the like. The material can be widely used for treating antibiotic wastewater and/or heavy metal wastewater, has the advantages of convenient operation, simple equipment, low treatment cost, high treatment efficiency and good removal effect, and has good application value and application prospect.
Description
Technical Field
The invention belongs to the field of composite materials, and relates to a manganese ion doped metal organic framework material, and a preparation method and application thereof.
Background
Antibiotics are widely used in human and veterinary therapy, in animal husbandry and in aquaculture. For example, tetracycline is a broad spectrum antibiotic with annual yields of thousands of tons. However, tetracycline is rarely biodegraded and metabolized, with the majority (about 30% -90%) excreted to the environment through feces or raw urine. Tetracycline residues were detected in soil, sediment, surface water, ground water and even drinking water. Besides antibiotic pollution, heavy metal pollution also harms the environment. For example, chromium in the hexavalent form in aqueous environments is considered to be a toxic and carcinogenic substance in most cases. Therefore, effective removal of antibiotics and heavy metals from water environments is imminent.
At present, various technologies are used for removing antibiotics and heavy metals in aquatic environment, such as biodegradation, membrane separation, photocatalytic degradation and electrochemistry, but the method has certain defects and cannot be widely applied to removal of tetracycline and hexavalent chromium. The adsorption method has low cost, simple operation and no secondary pollution, and is considered to be a very competitive method, so that the development and preparation of efficient adsorbents are particularly important. Recently, Metal Organic Frameworks (MOFs), which are porous functional materials mainly formed by binding central metal ions and organic ligands through chemical bonds, have been the focus of research due to their ultra-high porosity, large specific surface area, adjustable pore size and shape, and easy functionalization. However, metal organic framework materials lack functional groups and adsorption sites, resulting in poor adsorption performance for contaminants in water. Therefore, how to comprehensively improve the performance of the existing metal organic framework material, obtain the metal organic framework material with good stability and adsorption performance and obtain the preparation method of the metal organic framework material with simple operation, few raw material types and low cost has important significance for efficiently and low-cost adsorption of antibiotics and heavy metals in water.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a manganese ion doped metal organic framework material with good stability and adsorption performance, and also provides a preparation method of the manganese ion doped metal organic framework material with simple treatment process, few raw material types and low cost and application of the manganese ion doped metal organic framework material in removing antibiotics and/or heavy metals in a water body.
In order to solve the technical problems, the invention adopts the following technical scheme:
a manganese ion doped metal organic framework material, comprising UiO-66 (Zr); the UiO-66 (Zr) is doped with manganese ions.
In the manganese ion doped metal organic framework material, the molar ratio of the manganese ions to the UiO-66 (Zr) is 1: 1.
In the manganese ion-doped metal organic framework material, the manganese ion-doped metal organic framework material is further improved and prepared by taking zirconium chloride, terephthalic acid, tetrahydrate manganese chloride and N, N-dimethylformamide as raw materials through a solvothermal reaction.
As a general technical concept, the invention also provides a preparation method of the manganese ion doped metal organic framework material, which comprises the following steps: zirconium chloride, terephthalic acid, manganese chloride tetrahydrate and N, N-dimethylformamide are mixed for solvothermal reaction to obtain the manganese ion doped metal organic framework material.
In a further improvement of the above preparation method, the molar ratio of the manganese chloride tetrahydrate, the zirconium chloride, the terephthalic acid and the N, N-dimethylformamide is 1: 162.
In the preparation method, the mixing is carried out under stirring; the stirring speed is 300 r/min-500 r/min; the stirring time is 1-3 h; the solvent thermal reaction is carried out at the temperature of 120-150 ℃; the solvothermal reaction time is 24-36 h.
The preparation method is further improved, and further comprises the following steps: centrifuging, washing and drying a reaction product obtained after the solvothermal reaction is finished; the rotating speed of the centrifugation is 5000 r/min-6000 r/min; the washing adopts N, N dimethylformamide and ethanol, and the washing is carried out for 3 to 5 times respectively; the drying treatment is drying under a vacuum condition; the drying temperature is 60-80 ℃; the drying time is 8-12 h.
As a general technical concept, the invention also provides an application of the manganese ion doped metal organic framework material or the manganese ion doped metal organic framework material prepared by the preparation method in removing antibiotics and/or heavy metals in water.
The application is further improved, and comprises the following steps: mixing a manganese ion doped metal organic framework material, antibiotic wastewater and/or heavy metal wastewater to carry out oscillation adsorption, and finishing the treatment of the antibiotic and/or heavy metal in the water body; the ratio of the manganese ion doped metal organic framework material to the antibiotic wastewater and/or the heavy metal wastewater is 0.3-0.5 g: 1L.
In the above application, it is further improved that the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotics in the antibiotic wastewater is 5 mg/L-70 mg/L; the pH value of the antibiotic wastewater is 2-12; heavy metals in the heavy metal wastewater are Cr (VI); the concentration of heavy metal in the heavy metal wastewater is 1 mg/L-30 mg/L; the pH value of the heavy metal wastewater is 2-12.
The application is further improved, and the oscillation adsorption is carried out at the rotating speed of 150 r/min-300 r/min; the time of the oscillation adsorption is 12-24 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a manganese ion doped metal organic framework material, which comprises UiO-66 (Zr) and manganese ion doped UiO-66 (Zr). In the invention, the doping of manganese ions can affect the UiO-66 (Zr) crystal structure, so that the specific surface area and the pore structure of the UiO-66 (Zr) crystal are changed, wherein the specific surface area and the pore diameter of the UiO-66 (Zr) crystal doped with the manganese ions are 797.18m respectively2g-1And 1.68 nm, which exhibits a large specific surface area and a large pore size, which are advantageous for improving the adsorption capacity of the UiO-66 (Zr) crystal, and the specific surface area and the pore size of the UiO-66 (Zr) crystal are 582.34 m, respectively2g-1And 1.35 nm. Meanwhile, manganese ions doped into the crystal lattice of the UiO-66 (Zr) crystal contribute valence band electrons and generate more adsorption sites. Compared with other metal organic framework materials, the manganese ion doped metal organic framework material has the advantages of large adsorption capacity, good adsorption performance, good stability and the like, is simple to synthesize, can be widely adopted, can efficiently adsorb and remove pollutants in water, and is a novel adsorbent.
(2) The invention provides a preparation method of a manganese ion doped metal organic framework material, which is characterized in that zirconium chloride, terephthalic acid, manganese chloride tetrahydrate and N, N-dimethylformamide are taken as raw materials, and the manganese ion doped metal organic framework material with good stability and good adsorption performance is synthesized for the first time through solvothermal reaction.
(3) The invention provides application of a manganese ion doped metal organic framework material in removal of antibiotics and/or heavy metals in a water body. The method utilizes the manganese ion doped metal organic framework material to remove antibiotics and/or heavy metals in the water body, has the advantages of convenient operation, simple equipment, low treatment cost, high treatment efficiency and good removal effect, can be widely used for treating antibiotic wastewater and/or heavy metal wastewater, and has good application value and application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a scanning electron micrograph of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 of the present invention and a metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1, wherein (a) is UiO-66 (Zr) and (b) is MnUiO-66 (Zr).
FIG. 2 is XRD patterns of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) produced in example 1 of the present invention, a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr) + TC) produced in example 2, to which tetracycline hydrochloride is adsorbed, a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr) + Cr (VI)) produced in example 2, and a metal-organic framework material (UiO-66 (Zr)) produced in comparative example 1.
FIG. 3 is a Fourier infrared spectrum of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 of the present invention and a metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1.
FIG. 4 is thermogravimetric analysis graphs of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 of the present invention and a metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1.
FIG. 5 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride and Cr (VI) in example 2 of the present invention, wherein (a) is TC and (b) is Cr (VI).
FIG. 6 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride and Cr (VI) under different coexisting ion conditions in example 3 of the present invention, wherein (a) is TC and (b) is Cr (VI).
FIG. 7 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride wastewater and Cr (VI) -containing wastewater of different pH values and the corresponding zeta potential maps in example 4 of the present invention, wherein (a) is TC and (b) is Cr (VI).
FIG. 8 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride wastewater and Cr (VI) -containing wastewater of different concentrations in example 5 of the present invention, wherein (a) is TC and (b) is Cr (VI).
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
Example 1
A manganese ion doped metal organic framework material comprises UiO-66 (Zr), wherein the UiO-66 (Zr) is doped with manganese ions.
In this example, the molar ratio of manganese ions to UiO-66 (Zr) was 1: 1.
A method for preparing the manganese ion-doped metal organic framework material in the embodiment includes the following steps:
(1) weighing zirconium chloride, terephthalic acid and manganese chloride tetrahydrate, dispersing in N, N Dimethylformamide (DMF), and stirring at the rotation speed of 150r/min for 1h to obtain a mixed solution; wherein the molar ratio of the zirconium chloride to the manganese chloride tetrahydrate to the terephthalic acid to the N, N-dimethylformamide is 1: 162.
(2) And (2) placing the mixed solution prepared in the step (1) into a reaction kettle containing a polytetrafluoroethylene lining, and carrying out solvothermal reaction at the temperature of 120 ℃ for 24 hours.
(3) And (3) naturally cooling a reaction product obtained after the reaction in the step (2) is finished, centrifuging at the rotating speed of 5000 r/min, washing solids obtained by centrifuging respectively 3 times by adopting N, N-dimethylformamide and ethanol, and drying in vacuum at 60 ℃ for 12h to obtain the manganese ion doped metal organic framework material named as MnUiO-66 (Zr).
Comparative example 1
A method of producing a metal-organic framework material (UiO-66 (Zr)) substantially the same as in example 1, except that: manganese chloride tetrahydrate is not added in the step (1).
Example 2
An application of a manganese ion doped metal organic framework material in removing antibiotics or heavy metals in a water body, in particular to a method for removing tetracycline hydrochloride and Cr (VI) in the water body by adopting the manganese ion doped metal organic framework material in an adsorption manner, which comprises the following steps:
the manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 and the metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1 are weighed, 30mg of each material is respectively added into 100mL tetracycline hydrochloride wastewater with the concentration of 20mg/L, pH of 5.74, and oscillation adsorption is carried out at the rotating speed of 150r/min, so that the tetracycline hydrochloride in the water body is removed. During the course of the shaking adsorption, 4mL of samples were taken at intervals and centrifuged. And (3) measuring the absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the tetracycline hydrochloride after adsorption, thereby obtaining the adsorption effect of the manganese ion doped metal organic framework material on the tetracycline hydrochloride. And after the tetracycline hydrochloride is adsorbed, carrying out solid-liquid separation, wherein the obtained solid matter is a manganese ion doped metal organic framework material adsorbed with the tetracycline hydrochloride and is named as MnUiO-66 (Zr) + TC.
30mg of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) prepared in the example 1 and 30mg of the metal organic framework material (UiO-66 (Zr)) prepared in the comparative example 1 are respectively added into 100mL of Cr (VI) -containing wastewater with the concentration of 20mg/L, pH of 7.0, and oscillation adsorption is carried out at the rotating speed of 150r/min, so that the removal of Cr (VI) in the water body is completed. During the course of the shaking adsorption, 3mL of samples were taken at intervals and centrifuged. And (3) taking supernatant obtained by centrifugation, and determining the concentration of Cr (VI) after adsorption by a diphenylcarbonyldihydrazide spectrophotometry, thereby obtaining the adsorption effect of the manganese ion-doped metal organic framework material on the Cr (VI). And after the adsorption of the Cr (VI) is finished, carrying out solid-liquid separation, wherein the obtained solid matter is a manganese ion doped metal organic framework material adsorbed with the Cr (VI), and is named as MnUiO-66 (Zr) + Cr (VI).
FIG. 1 is a scanning electron micrograph of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 of the present invention and a metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1, wherein (a) is UiO-66 (Zr) and (b) is MnUiO-66 (Zr). As can be seen from FIG. 1, the metal organic framework material (UiO-66 (Zr)) exhibits an agglomerated morphology and a poor dispersibility, while the manganese ion doped metal organic framework material (MnUiO-66 (Zr)) of the present invention has a cubic morphology and is relatively dispersed.
XRD analyses were carried out on the manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) obtained in example 1, the manganese ion-doped metal-organic framework material (MnUiO-66 (Zr) + TC) with tetracycline hydrochloride adsorbed obtained in example 2, the manganese ion-doped metal-organic framework material (MnUiO-66 (Zr) + Cr (VI)) with Cr (VI) adsorbed obtained in example 2, and the metal-organic framework material (UiO-66 (Zr)) obtained in comparative example 1, and the results are shown in FIG. 2. FIG. 2 is XRD patterns of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) produced in example 1 of the present invention, a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr) + TC) produced in example 2, to which tetracycline hydrochloride is adsorbed, a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr) + Cr (VI)) produced in example 2, and a metal-organic framework material (UiO-66 (Zr)) produced in comparative example 1. As can be seen from FIG. 2, all samples have good crystallinity, and the XRD diffraction patterns of MnUiO-66 (Zr) doped with manganese ions are similar to that of pure UiO-66 (Zr), and no other impurity peaks appear, which indicates that the topological structure of UiO-66 (Zr) is not changed due to the doping of manganese ions. Meanwhile, the XRD diffraction pattern does not have a characteristic peak of manganese or manganese oxide, which indicates that the manganese element is doped into UiO-66 (Zr) crystal lattice in the form of manganese ions. The content of manganese ions doped in the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) is only 1.06 percent according to ICP-AES analysis. Since metal ions are hardly doped into the crystal lattice, manganese ions doped into the UiO-66 (Zr) crystal are low in content and highly dispersed, and thus a characteristic peak of manganese does not appear in the XRD pattern. Three main peaks of 7.3 degrees, 8.5 degrees and 25.8 degrees appear in the XRD pattern, which correspond to the (111), (200) and (442) crystal planes of UiO-66 (Zr), respectively. In addition, the peak shape of MnUiO-66 (Zr) is not changed after adsorbing tetracycline hydrochloride and Cr (VI), which shows that the peak shape cannot be damaged by the adsorption reaction.
The manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 and the metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1 were subjected to Fourier infrared analysis, and the results are shown in FIG. 3. FIG. 3 is a Fourier infrared spectrum of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in an example of the present invention and a metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1. As can be seen from FIG. 3, the peak profile of the metal-organic framework material (UiO-66 (Zr)) is almost unchanged, while the manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) of the present invention is 3450 cm after doping with manganese ions-1The peak shape becomes wider, the peak strength becomes stronger, which shows that the content of guest water molecules in the crystal pore channel is increased after the manganese ions are doped. Meanwhile, the doping of manganese ions may cause the pore diameter to be enlarged, so that more guest water molecules are concentrated in the pore channel.
The manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 and the metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1 were subjected to thermogravimetric analysis, and the results were as shown in FIG. 4Shown in the figure. FIG. 4 is thermogravimetric analysis graphs of a manganese ion-doped metal-organic framework material (MnUiO-66 (Zr)) prepared in example 1 of the present invention and a metal-organic framework material (UiO-66 (Zr)) prepared in comparative example 1. As can be seen from FIG. 4, the thermogravimetric loss is divided into two stages, the first stage is 25 ℃ to 400 ℃, and is the loss of guest water molecules, and the thermogravimetric losses of UiO-66 (Zr) and MnUiO-66 (Zr) at this stage are 29.69% and 41.42% respectively, which shows that the doping of manganese ions increases the content of guest water molecules in the crystal pore channels of UiO-66 (Zr). The second stage is 400-800 deg.C, and the collapse of skeleton structure to finally produce metal oxide (ZrO)2Or ZrO2And MnO), the thermogravimetric losses of uo-66 (Zr) and mnuo-66 (Zr) at this stage were 35.83% and 26.82%, respectively, with less residual content of mnuo-66 (Zr) indicating successful doping of manganese ions into the uo-66 (Zr) crystals. In addition, as can be seen from fig. 4, the manganese ion-doped UiO-66 (Zr) crystal has good thermal stability, and can maintain stable structure within a temperature range of 400 ℃.
FIG. 5 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride and Cr (VI) in example 2 of the present invention, wherein (a) is TC and (b) is Cr (VI). As can be seen from FIG. 5, the adsorption was performed rapidly 10min before the shaking adsorption and then slowly until the equilibrium was reached. At 60min, UiO-66 (Zr) and MnUiO-66 (Zr) reached adsorption equilibrium. At 1440 min, the adsorption capacity of UiO-66 (Zr) to TC and Cr (VI) is 12.2 mg/g and 8.1 mg/g respectively, and the adsorption capacity of MnUiO-6 (Zr) to TC and Cr (VI) is 72.5 mg/g and 25.1 mg/g respectively, which shows that the adsorption capacity of UiO-66 (Zr) is greatly improved by the doping of manganese ions.
Example 3
An application of a manganese ion doped metal organic framework material in removing antibiotics or heavy metals in a water body, in particular to a method for removing tetracycline hydrochloride and Cr (VI) in the water body by adopting the manganese ion doped metal organic framework material in an adsorption manner, which comprises the following steps:
9 parts of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) prepared in example 1 (30 mg each) was weighed, and added thereto9 parts of tetracycline hydrochloride waste water with the concentration of 20mg/L, pH of 5.74 are added with NaCl and Na respectively2SO4、Na3PO4And control NaCl and Na2SO4、Na3PO4The concentration of the solution is respectively 5 mmol/L, 10 mmol/L and 15 mmol/L, and the oscillating adsorption is carried out for 24 hours at the rotating speed of 150r/min, thus completing the removal of tetracycline hydrochloride in the water body. During the course of the shaking adsorption, 4mL of samples were taken at intervals and centrifuged. And (3) measuring the absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the tetracycline hydrochloride after adsorption, thereby obtaining the adsorption effect of the manganese ion doped metal organic framework material on the tetracycline hydrochloride.
9 parts of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) prepared in example 1, 30mg each, were weighed out and added to 9 parts of 100mL of Cr (VI) -containing wastewater having a concentration of 20mg/L, pH of 7.0, and NaCl and Na were added to the 9 parts of Cr (VI) -containing wastewater, respectively2SO4、Na3PO4And control NaCl and Na2SO4、Na3PO4The concentration of the solution is respectively 5 mmol/L, 10 mmol/L and 15 mmol/L, and the oscillating adsorption is carried out for 24 hours at the rotating speed of 150r/min, thus finishing the removal of Cr (VI) in the water body. During the course of the shaking adsorption, 3mL of samples were taken at intervals and centrifuged. And (3) taking supernatant obtained by centrifugation, and determining the concentration of Cr (VI) after adsorption by a diphenylcarbonyldihydrazide spectrophotometry, thereby obtaining the adsorption effect of the manganese ion doped metal organic framework material on the Cr (VI).
FIG. 6 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride and Cr (VI) under different coexisting ion conditions in example 3 of the present invention, wherein (a) is TC and (b) is Cr (VI). As can be seen from FIG. 6, the effect of different coexisting ions on the adsorption effect of MnUiO-66 (Zr) is different, e.g., the effect of adding NaCl on the adsorption effect of MnUiO-66 (Zr) is not so large, while adding Na2SO4、Na3PO4Can obviously reduce MnUiO-66 (Zr)The adsorption effect of (1). In addition, as the concentration of coexisting ions increases, the adsorption effect of MnUiO-66 (Zr) further decreases because too many coexisting anions compete with contaminant molecules for adsorption active sites, and thus the removal rate decreases. Meanwhile, the higher the valence state of the anion, the lower the removal rate of pollutants by MnUiO-66 (Zr) is.
Example 4
An application of a manganese ion doped metal organic framework material in removing antibiotics or heavy metals in a water body, in particular to a method for removing tetracycline hydrochloride and Cr (VI) in the water body by adopting the manganese ion doped metal organic framework material in an adsorption manner, which comprises the following steps:
6 parts of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) prepared in example 1, 30mg of each of the manganese ion-doped metal organic framework material, are respectively added into tetracycline hydrochloride wastewater with pH values of 2, 4, 6, 8, 10 and 12 (the volumes of the wastewater are all 100mL, the concentrations of the wastewater are all 20 mg/L), and oscillation adsorption is carried out for 24h at the rotating speed of 150r/min, so that the tetracycline hydrochloride in the water body is removed. During the course of the shaking adsorption, 4mL of samples were taken at intervals and centrifuged. And (3) measuring the absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of tetracycline hydrochloride after adsorption, thereby obtaining the adsorption effect of the manganese ion doped metal organic framework material on tetracycline hydrochloride wastewater with different pH values.
6 parts of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) prepared in the example 1 are weighed, 30mg of the manganese ion-doped metal organic framework material is respectively added into wastewater containing Cr (VI) with the pH values of 2, 4, 6, 8, 10 and 12 (the volume of the wastewater is 100mL, the concentration of the wastewater is 10 mg/L), and the wastewater is subjected to oscillation adsorption for 24 hours at the rotating speed of 150r/min to complete the removal of the Cr (VI) in the water body. During the course of the shaking adsorption, 3mL of samples were taken at intervals and centrifuged. And (3) taking supernatant obtained by centrifugation, and determining the concentration of Cr (VI) after adsorption by a diphenylcarbonyldihydrazide spectrophotometry, thereby obtaining the adsorption effect of the manganese ion doped metal organic framework material on the Cr (VI) containing wastewater with different pH values.
FIG. 7 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride wastewater and Cr (VI) -containing wastewater of different pH values and the corresponding zeta potential maps in example 4 of the present invention, wherein (a) is TC and (b) is Cr (VI). As can be seen from FIG. 7 (a), the adsorption capacity of MnUiO-66 (Zr) for tetracycline hydrochloride increased from 16.5 mg/g to 73.5 mg/g as the pH increased from 2 to 8. It is noted that the adsorption capacity of MnUiO-66 (Zr) to tetracycline hydrochloride is almost unchanged in the pH range of 4 to 12, which indicates that the adsorption of MnUiO-66 (Zr) to tetracycline hydrochloride is less affected by the pH value of the solution, and the adsorption is mainly affected by the pi-pi bond between tetracycline hydrochloride and the organic ligand in MnUiO-66 (Zr). The zeta potential isoelectric point of MnUiO-66 (Zr) in water is 9.85, the zeta potential isoelectric point of MnUiO-66 (Zr) in tetracycline hydrochloride solution is 11.15, and the increase of the zeta potential isoelectric point is probably because the benzene ring of tetracycline hydrochloride and the organic ligand in MnUiO-66 (Zr) generate hydrogen bonds. As can be seen from 7 (b), the adsorption of Cr (VI) by MnUiO-66 (Zr) is greatly influenced by pH, indicating that the adsorption of Cr (VI) by MnUiO-66 (Zr) is mainly influenced by electrostatic action. At a pH of 6, the maximum adsorption amount of MnUiO-66 (Zr) to Cr (VI) was 25.4 mg/g. The zeta potential isoelectric point of MnUiO-66 (Zr) in the Cr (VI) solution was 7.11, and was lowered compared with that of MnUiO-66 (Zr) in water (9.85), because of the aggregation of anions in the Cr (VI) solution.
Example 5
An application of a manganese ion doped metal organic framework material in removing antibiotics or heavy metals in a water body, in particular to a method for removing tetracycline hydrochloride and Cr (VI) in the water body by adopting the manganese ion doped metal organic framework material in an adsorption manner, which comprises the following steps:
5 parts of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) prepared in example 1, 30mg of each of the manganese ion-doped metal organic framework material, are respectively added into tetracycline hydrochloride wastewater with the concentrations of 5 mg/L, 10mg/L, 30 mg/L, 50 mg/L and 70 mg/L (the volume of the wastewater is 100mL, the pH value is 5.74), and oscillation adsorption is carried out for 24 hours at the rotating speed of 150r/min, so that the tetracycline hydrochloride in the water body is removed. During the course of the shaking adsorption, 4mL of samples were taken at intervals and centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the adsorbed antibiotic, thereby obtaining the adsorption effect of the manganese ion doped metal organic framework material on tetracycline hydrochloride wastewater with different concentrations.
5 parts of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) prepared in the example 1 are weighed, 30mg of the manganese ion-doped metal organic framework material is respectively added into Cr (VI) -containing wastewater with the concentration of 1 mg/L, 5 mg/L, 10mg/L, 20mg/L and 30 mg/L (the volume of the wastewater is 100mL, the pH value is 7.0), and the oscillating adsorption is carried out for 24 hours at the rotating speed of 150r/min, so that the removal of Cr (VI) in the water body is completed. During the course of the shaking adsorption, 3mL of samples were taken at intervals and centrifuged. And (3) taking supernatant obtained by centrifugation, and determining the concentration of Cr (VI) after adsorption by a diphenylcarbonyldihydrazide spectrophotometry, thereby obtaining the adsorption effect of the manganese ion-doped metal organic framework material on the Cr (VI).
FIG. 8 is a graph showing the adsorption effect of manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) on tetracycline hydrochloride wastewater and Cr (VI) -containing wastewater of different concentrations in example 5 of the present invention, wherein (a) is TC and (b) is Cr (VI). As can be seen from FIG. 8 (a), the concentration of the tetracycline hydrochloride waste water is increased from 5 mg/L to 70 mg/L, and the adsorption amount of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) to the tetracycline hydrochloride is increased from 19.39 mg/g to 184.49 mg/g, because the increase of the tetracycline hydrochloride concentration increases the driving force of the concentration gradient, thereby increasing the adsorption capacity. Meanwhile, as the concentration of tetracycline hydrochloride increases, the number of available adsorption sites on MnUiO-66 (Zr) is relatively small, and the removal rate decreases. As can be seen from FIG. 8 (b), the concentration of the wastewater containing Cr (VI) was increased from 1 mg/L to 30 mg/L, and the adsorption amount of the manganese ion-doped metal organic framework material (MnUiO-66 (Zr)) to Cr (VI) was increased from 3.32 mg/g to 32.77 mg/g, because the increase in the concentration of Cr (VI) increases the driving force of the concentration gradient, thereby increasing the adsorption capacity. Meanwhile, as the concentration of Cr (VI) increases, the number of available adsorption sites on MnUiO-66 (Zr) is relatively reduced, and the removal rate is reduced.
Therefore, the manganese ion doped metal organic framework material (MnUiO-66 (Zr)) has good adsorption effect on tetracycline hydrochloride and Cr (VI). Particularly, the manganese ion doped metal organic framework material (MnUiO-66 (Zr)) has better adsorption effect on low-concentration tetracycline hydrochloride antibiotic wastewater and wastewater containing Cr (VI). In actual wastewater, the content of tetracycline hydrochloride and Cr (VI) is often very low, and the manganese ion doped metal organic framework material (MnUiO-66 (Zr)) improves the removal rate of the tetracycline hydrochloride and the Cr (VI) in the low-concentration wastewater, so that the manganese ion doped metal organic framework material (MnUiO-66 (Zr)) has very high commercial value and application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. An application of a manganese ion doped metal organic framework material in removing antibiotics and/or heavy metals in a water body; the manganese ion doped metal organic framework material comprises UiO-66 (Zr); manganese ions are doped in the UiO-66 (Zr); the molar ratio of the manganese ions to the UiO-66 (Zr) is 1: 1.
2. Use according to claim 1, characterized in that it comprises the following steps: mixing a manganese ion doped metal organic framework material, antibiotic wastewater and/or heavy metal wastewater to carry out oscillation adsorption, and finishing the treatment of the antibiotic and/or heavy metal in the water body; the ratio of the manganese ion doped metal organic framework material to the antibiotic wastewater and/or the heavy metal wastewater is 0.3-0.5 g: 1L.
3. The use according to claim 2, wherein the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotics in the antibiotic wastewater is 5 mg/L-70 mg/L; the pH value of the antibiotic wastewater is 2-12; heavy metals in the heavy metal wastewater are Cr (VI); the concentration of heavy metal in the heavy metal wastewater is 1 mg/L-30 mg/L; the pH value of the heavy metal wastewater is 2-12.
4. The use according to claim 2 or 3, characterized in that the oscillatory sorption is carried out at a rotation speed of 150r/min to 300 r/min; the time of the oscillation adsorption is 12-24 h.
5. The use according to claim 1, wherein the preparation method of the manganese ion doped metal organic framework material comprises the following steps: zirconium chloride, terephthalic acid, manganese chloride tetrahydrate and N, N-dimethylformamide are mixed for solvothermal reaction to obtain the manganese ion doped metal organic framework material.
6. The use according to claim 5, wherein the manganese ion-doped metal-organic framework material is prepared by a method in which the molar ratio of manganese chloride tetrahydrate, zirconium chloride, terephthalic acid and N, N-dimethylformamide is 1: 162.
7. Use according to claim 5 or 6, wherein in the preparation method of the manganese ion doped metal organic framework material, the mixing is performed under stirring conditions; the stirring speed is 300 r/min-500 r/min; the stirring time is 1-3 h; the solvent thermal reaction is carried out at the temperature of 120-150 ℃; the solvothermal reaction time is 24-36 h.
8. The use according to claim 5 or 6, wherein the preparation method of the manganese ion doped metal organic framework material further comprises the following steps: centrifuging, washing and drying a reaction product obtained after the solvothermal reaction is finished; the rotating speed of the centrifugation is 5000 r/min-6000 r/min; the washing adopts N, N dimethylformamide and ethanol, and the washing is carried out for 3 to 5 times respectively; the drying treatment is drying under a vacuum condition; the drying temperature is 60-80 ℃; the drying time is 8-12 h.
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| CN111545245A (en) * | 2020-05-12 | 2020-08-18 | 湖南垚恒环境科技有限公司 | Iron ion doped metal organic framework material and preparation method thereof |
| 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 |
| CN111569944A (en) * | 2020-05-20 | 2020-08-25 | 湖南垚恒环境科技有限公司 | Manganese ion doped metal organic framework material and preparation method thereof |
| CN113663736A (en) * | 2021-09-27 | 2021-11-19 | 长春工业大学 | Preparation and application of Pd/UiO-66 by strong electrostatic adsorption method |
| CN114950410B (en) * | 2022-05-20 | 2023-09-01 | 福州大学 | Synthetic method of zirconium-manganese composite material |
| CN116173917A (en) * | 2022-11-11 | 2023-05-30 | 广西民族大学 | Preparation and application of arsenic and chromium bifunctional adsorbent lanthanum zirconium MOFs |
| CN116116397B (en) * | 2023-04-07 | 2024-01-02 | 江苏中丽新材料有限公司 | High-purity composite alumina powder for water treatment agent |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363416A (en) * | 2015-12-07 | 2016-03-02 | 中国科学院生态环境研究中心 | Manganese dioxide nanowire @ multidimensional mesoporous metal organic framework adsorbent and preparation method thereof |
| CN105642349A (en) * | 2016-02-17 | 2016-06-08 | 上海电力学院 | Preparation method of manganese-based MOF (metal-organic framework) magnetic material |
| CN106750470A (en) * | 2016-11-09 | 2017-05-31 | 中国科学院长春应用化学研究所 | A kind of metal organic frame composite, its preparation method and application |
| CN106824090A (en) * | 2016-12-01 | 2017-06-13 | 中国科学院城市环境研究所 | A kind of preparation method and applications of novel magnetic metal organic framework composite |
| CN107722285A (en) * | 2017-09-15 | 2018-02-23 | 广西大学 | A kind of hydrophobicity zirconium metal-organic framework materials and preparation method thereof |
| CN108084453A (en) * | 2018-01-10 | 2018-05-29 | 蚌埠学院 | The aperture expanding method of UiO-66 metal-organic framework materials and application |
| CN108160042A (en) * | 2018-01-30 | 2018-06-15 | 湖南大学 | Utilize the method for ZnO thin film metal-organic framework materials processing antibiotic waste water |
| CN108176414A (en) * | 2017-12-12 | 2018-06-19 | 上海大学 | Catalyst MnFe2O4- MIL-53 (Al) magnetic composite, preparation method and application |
| CN108295825A (en) * | 2018-01-31 | 2018-07-20 | 广东工业大学 | A kind of preparation method of adsorbent and its application in heavy metal adsorption |
-
2018
- 2018-07-24 CN CN201810820329.0A patent/CN108905976B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105363416A (en) * | 2015-12-07 | 2016-03-02 | 中国科学院生态环境研究中心 | Manganese dioxide nanowire @ multidimensional mesoporous metal organic framework adsorbent and preparation method thereof |
| CN105642349A (en) * | 2016-02-17 | 2016-06-08 | 上海电力学院 | Preparation method of manganese-based MOF (metal-organic framework) magnetic material |
| CN106750470A (en) * | 2016-11-09 | 2017-05-31 | 中国科学院长春应用化学研究所 | A kind of metal organic frame composite, its preparation method and application |
| CN106824090A (en) * | 2016-12-01 | 2017-06-13 | 中国科学院城市环境研究所 | A kind of preparation method and applications of novel magnetic metal organic framework composite |
| CN107722285A (en) * | 2017-09-15 | 2018-02-23 | 广西大学 | A kind of hydrophobicity zirconium metal-organic framework materials and preparation method thereof |
| CN108176414A (en) * | 2017-12-12 | 2018-06-19 | 上海大学 | Catalyst MnFe2O4- MIL-53 (Al) magnetic composite, preparation method and application |
| CN108084453A (en) * | 2018-01-10 | 2018-05-29 | 蚌埠学院 | The aperture expanding method of UiO-66 metal-organic framework materials and application |
| CN108160042A (en) * | 2018-01-30 | 2018-06-15 | 湖南大学 | Utilize the method for ZnO thin film metal-organic framework materials processing antibiotic waste water |
| CN108295825A (en) * | 2018-01-31 | 2018-07-20 | 广东工业大学 | A kind of preparation method of adsorbent and its application in heavy metal adsorption |
Non-Patent Citations (1)
| Title |
|---|
| Microwave-Activated Mn-Doped Zirconium Metal−Organic Framework Nanocubes for Highly Effective Combination of Microwave Dynamic and Thermal Therapies Against Cancer;Changhui Fu，等;《ACS Nano》;20171229;第12卷;第2201-2210页 * |
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