CN110064372A - A kind of metal organic framework magnetic composite and its preparation method and application - Google Patents
A kind of metal organic framework magnetic composite and its preparation method and application Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
- B01J20/28009—Magnetic properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to Materials Science and Engineering field, a kind of metal organic framework magnetic composite and its preparation method and application is disclosed, comprising the following steps: (1) by Fe3O4Particle is carboxy-functionalized, then will be carboxy-functionalized after Fe3O4Particle is washed and is activated；(2) Fe after will be carboxy-functionalized3O4Particle is added in reaction dissolvent and ultrasonic disperse is uniform, obtains mixed liquor A；Organic ligand is added in reaction dissolvent, stirring makes it completely dissolved, then mixed liquor A is added, it is uniformly mixed, add aluminum soluble salt and adjuvant, mixed liquid B is formed after being uniformly mixed, then temperature reaction, obtain metal organic framework magnetic composite head product after reaction；(3) head product is washed, then heat-activated obtains composite material.The composite material is compared to individual MOF material and Fe3O4Particle, adsorption capacity is higher, and adsorption time greatly shortens.
Description
Technical field
The invention belongs to Materials Science and Engineering field, in particular to a kind of system of metal organic framework magnetic composite
Preparation Method and application.
Background technique
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) are by organic bridge ligand and nothing
The ordered network structure that the coordination of the metal ion of machine is constituted.MOFs material has the specific surface area of superelevation, and lower crystal is close
The advantages that degree and pore size and function adjustability, adsorbs the fields such as antibiotic removal in aqueous solution and shows good application
Prospect.But since MOFs material is generally powder, applying in water process will receive limitation, it is difficult to industrial applications, therefore
It can be generally prepared into composite material, for example make it have magnetism, overcome by Magnetic solid phases extraction or weakened
This deficiency, to improve the practical application of MOFs class material.
In recent years, Magnetic solid phases extraction (MSPE) has proved to be a kind of simple, efficiently, inexpensive and environmental-friendly side
Method, for extracting target analytes from complex matrices.Fe3O4A kind of magnetic microsphere, Magnetic solid phases extraction in often by
The material used, metal organic framework and magnetic particle, which carry out compound method, common are four kinds of methods: implantation, layer by layer certainly
Construction from part, envelope and mixing method.Metal-organic framework materials and magnetic nano-particle, which combine, has the advantage that (1) gram
Simple magnetic nano-particle has been taken to be easy to reunite, lack the deficiencies of selectivity.By magnetic particle and metal-organic framework materials
The features such as combining, can use Large ratio surface, porous structure, the surface functional group abundant of metal-organic framework materials, mentions
The application efficiency of high magnetic Nano material；(2) Objective for increasing metal-organic framework materials application, due to the organic bone of metal
The controlledly synthesis of frame material can obtain particular needs by adjusting the approach such as synthesis condition, synthetic method according to specific object
The metal-organic framework materials (such as environmental sample adsorbing separation, certain drug release etc.) wanted.(3) simplify operation
Step saves analysis time.Such as in environmental contaminants context of detection, when metal-organic framework materials are used to be enriched with object,
It usually requires to can be only achieved the recycling of lesser degree by other means (such as collosol and gel, film protection etc.).And magnetic metal
Organic framework material only need to can be separated from sample substrate, be saved significantly under externally-applied magnetic field after being enriched with to object
Analysis time is saved.(4) reusability of metal-organic framework materials improves.Used metal-organic framework materials are passed through
Certain subsequent processing can be recycled for multiple times, and show that the material of synthesis has excellent stability, and repeat recycling and use,
Experimental cost is saved.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that provide a kind of metal organic
The preparation method of skeleton magnetic composite.
Another object of the present invention is to provide the metal organic framework magnetic composite of above method preparation.
Still a further object of the present invention is to provide above-mentioned metal organic framework magnetic composite in terms of adsorbing antibiotic
Using.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of metal organic framework magnetic composite, comprising the following steps:
(1) by Fe3O4Particle is carboxy-functionalized, then will be carboxy-functionalized after Fe3O4Particle is washed and is activated；
(2) Fe by step (1) after carboxy-functionalized3O4Particle is added in reaction dissolvent and ultrasonic disperse is uniform, is mixed
Close liquid A；Organic ligand is added in reaction dissolvent, stirring makes it completely dissolved, and mixed liquor A is then added, and is stirred
It is even, aluminum soluble salt and adjuvant are added, forms mixed liquid B after being uniformly mixed, then temperature reaction, after reaction
Obtain metal organic framework magnetic composite head product；
(3) head product that step (2) obtains is washed, then heat-activated obtains metal organic framework magnetic coupling
Material.
Preferably, reagent carboxy-functionalized described in step (1) is at least one of thioacetic acid or citric acid；Institute
The carboxy-functionalized solvent stated is ethyl alcohol.
Preferably, organic ligand described in step (2) is terephthalic acid (TPA)；The reaction dissolvent is N, N '-diformazan
Base formamide, N, at least one of N '-diethylformamide, dimethyl sulfoxide or n,N-dimethylacetamide.
Preferably, aluminum soluble salt described in step (2) be in ANN aluminium nitrate nonahydrate or Aluminium chloride hexahydrate at least
It is a kind of；The adjuvant is at least one of calcium carboxylate or sulfasalazine, and adjuvant can guide crystallization and coordination anti-
It answers.
Preferably, organic ligand in mixed liquid B described in step (2), aluminum soluble salt, adjuvant, it is carboxy-functionalized after
Fe3O4The mass ratio of particle is 5~25:4.88~24.4:3.3~16.5:0.5~3；Organic ligand in the mixed liquid B
Mass concentration is 10~20g/L.
Preferably, temperature reaction described in step (2), which refers to, is warming up to 100~150 DEG C of 7~20h of reaction；It is preferred that
130 DEG C of reaction 18h.
Preferably, washing described in step (3) refers to first cleaned with DMF after, again with methanol cleaning, have to wash away metal
Impurity in machine skeleton magnetic composite surface and duct；The heat-activated refers under 80~100 DEG C of vacuum conditions
Keep 10h or more.
Preferably, activation described in step (1), which refers to, activates 4h under the conditions of 50 DEG C；The washing is to use deionization
Water and ethanol washing；The Fe3O4Particle is that a kind of diameter is the≤magnetic microsphere of 20nm；It is described it is carboxy-functionalized be room temperature
Under be stirred to react for 24 hours.
Preferably, the condition of step (2) ultrasonic disperse is that ultrasonic time is 10~15min at room temperature；After mixed liquor A is added
The condition of stirring be at room temperature mixing time be 2~4h.
Application of the above-mentioned metal organic framework magnetic composite in terms of adsorbing antibiotic, especially at absorption Fourth Ring
Application in terms of plain class antibiotics minocycline.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) composite material prepared by the present invention can not only overcome MOFs material defect itself, while can promote MOFs
Absorption property, greatly shorten adsorption time.
(2) present invention utilizes Fe3O4The magnetism that particle has can be inhaled in aqueous solution by compound with MOFs material
It is easily isolated and recycled after attached antibiotic.
(3) the metal organic framework magnetic composite that the present invention obtains is compared to individual MOF material for water-soluble
There is faster adsorption rate and bigger adsorption capacity with antibiotic existing for ionic forms in liquid.
(4) the obtained metal organic framework magnetic composite of the present invention has pore structure more abundant, and independent
MOFs and Fe3O4It compares, metal organic framework magnetic composite improves the adsorption effect to antibiotic.
(5) preparation method of the invention is simple and easy to operate, and preparation process carries out under normal pressure, easy large-scale production.
Detailed description of the invention
Fig. 1 is the sample and raw material Fe prepared in Examples 1 to 43O4Powder xrd pattern.
Fig. 2 is the BET figure of the sample prepared in Examples 1 to 4.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.Fe used in embodiment3O4Particle
It is purchased from Shanghai Aladdin biochemical technology limited liability company.
Embodiment 1
0.99g Aluminium chloride hexahydrate and 1.00g terephthalic acid (TPA) are dissolved in 60mLN, in N '-dimethylformamide, uniformly
Stirring makes it completely dissolved, and is stirred to react 18h, cooled to room temperature under 130 DEG C of constant temperatures.Filtered product first uses N,
N '-dimethylformamide rinses 3 times, and methanol cleans 3 times, then activates 12h under 100 DEG C of vacuum conditions, obtains sample and mark
Remember that this sample is MIL-68 (Al).
Embodiment 2:
By 0.50gFe3O4Particle and 0.30g citric acid monohydrate close object and are added in 50mL ethanol solution, ultrasonic disperse
Then 30min is stirred at room temperature for 24 hours.Filtered product is first washed three times with ethyl alcohol, then is washed with deionized water three times, in 50
Dry activation 4h, obtains carboxy-functionalized Fe under DEG C vacuum condition3O4Particle.1.00g terephthalic acid (TPA) is weighed in 50mLDMF
Middle stirring, after completely dissolution, addition be dissolved in the 0.05g in 10mLDMF and after 15min ultrasonic disperse it is carboxy-functionalized after
Fe3O4Particle continues to be stirred to react 2h at room temperature, 0.99g Aluminium chloride hexahydrate and 0.50g calcium carboxylate is added, after completely dissolution,
15h, cooled to room temperature are stirred to react under 130 DEG C of constant temperatures.Filtered product first uses N, N '-dimethylformamide
It rinses 3 times, is cleaned 3 times with methanol, activate 12h under 100 DEG C of vacuum conditions, marking this sample is Fe3O4@MIL-68(Al)-
1。
Embodiment 3:
By 0.50gFe3O4Particle and 0.30g citric acid monohydrate close object and are added in 50mL ethanol solution, ultrasonic disperse
Then 30min is stirred at room temperature for 24 hours.Filtered product is first washed three times with ethyl alcohol, then is washed with deionized water three times, in 50
Dry activation 4h, obtains carboxy-functionalized Fe under DEG C vacuum condition3O4Particle.1.00g terephthalic acid (TPA) is weighed in 50mLDMF
Middle stirring, after completely dissolution, addition be dissolved in the 0.10g in 10mLDMF and after 15min ultrasonic disperse it is carboxy-functionalized after
Fe3O4Particle continues to be stirred to react 2h at room temperature, 0.99g Aluminium chloride hexahydrate and 0.50g calcium carboxylate is added, after completely dissolution,
18h, cooled to room temperature are stirred to react under 130 DEG C of constant temperatures.Filtered product first uses N, N '-dimethylformamide
It rinses 3 times, is cleaned 3 times with methanol, activate 12h under 100 DEG C of vacuum conditions, marking this sample is Fe3O4@MIL-68(Al)-
2。
Embodiment 4:
By 0.50gFe3O4Particle and 0.30g citric acid monohydrate close object and are added in 50mL ethanol solution, ultrasonic disperse
Then 30min is stirred at room temperature for 24 hours.Filtered product is first washed three times with ethyl alcohol, then is washed with deionized water three times, in 50
Dry activation 4h, obtains carboxy-functionalized Fe under DEG C vacuum condition3O4Particle.1.00g terephthalic acid (TPA) is weighed in 50mLDMF
Middle stirring, after completely dissolution, addition be dissolved in the 0.20g in 10mLDMF and after 15min ultrasonic disperse it is carboxy-functionalized after
Fe3O4Particle continues to be stirred to react 2h at room temperature, 0.99g Aluminium chloride hexahydrate and 0.50g calcium carboxylate is added, after completely dissolution,
10h, cooled to room temperature are stirred to react under 150 DEG C of constant temperatures.Filtered product first uses N, N '-dimethylformamide
It rinses 3 times, is cleaned 3 times with methanol, activate 12h under 100 DEG C of vacuum conditions, marking this sample is Fe3O4@MIL-68(Al)-
3。
Interpretation of result:
(1) XRD characterization
The sharp shadow X-ray diffractometer of Empyrean produced using Dutch Panaco company is made to the embodiment of the present invention 1~4
Standby obtained material and raw material Fe3O4Particle is characterized, wherein operating condition are as follows: copper target, 40KV, 40mA, step-length 0.0131
Degree, 9.664 seconds/step of scanning speed.The preparation-obtained material of Examples 1 to 4 and Fe3O4The XRD diagram of particle is as shown in Figure 1.
Fe3O4Particle diffraction maximum corresponds to (220), (311), (400) respectively at 30.4 °, 35.5 °, 43 °, 56.7 °, 62.7 °,
(511), (440) plane is attributable to Fe3O4Crystal structure, this is consistent with report.MIL-68 (Al) diffraction maximum exists respectively
4.8 °, 8.8 °, 9.7 °, 14.5 °, 17.5 °, 19.5 °, correspond to (110), (130), (040), (060), (170) and (061),
Consistent with report document, the successful preparation of display MIL-68 (Al) is made.
The Fe of embodiment 13O4@MIL-68 (Al) -1 is due to Fe3O4Content is low, does not observe apparent Fe3O4Diffraction maximum.
And in the Fe of embodiment 23O4The Fe of@MIL-68 (Al) -2 and embodiment 33O4@MIL-68 (Al) -3 can observe its spy well
Levy diffraction maximum.Compound Fe3O4@MIL-68 (Al) is similar with the crystal structure of MIL-68 (AL).Illustrate Fe3O4Addition, do not have
Destroy original crystal structure, MIL-68 (Al) and Fe3O4It is coexisted in magnetic composite well.
(2) BET is characterized
The sample and original using ASAP2020 specific surface area and distribution of pores structural test machines prepared by Examples 1 to 4
Expect Fe3O4The pore structure of particle is characterized, as shown in Figure 2.Design parameter is as shown in table 1.
1 porous material structural parameters of table
| Sample | BET specific surface (cm2/g) | Vmeso/Vtotal(cm3.g-1) |
| MIL-68(Al) | 1666.25 | 0.16 |
| Fe3O4@MIL-68(Al)-1 | 1278.37 | 0.39 |
| Fe3O4@MIL-68(Al)-2 | 1260.23 | 0.31 |
| Fe3O4@MIL-68(Al)-3 | 1209.72 | 0.28 |
Illustrated by 1 data of table, Fe prepared by embodiment 2~43O4The specific surface area phase of@MIL-68 (Al) magnetic composite
Than reducing in individual MIL-68 (Al), but aperture produces variation, generate it is new mesoporous, composite material
Vmeso/VtotalRatio is higher than monomer MIL-68 (Al).
(3) absorption property of tetracycline antibiotics minocycline is measured
Concentration before and after adsorbing minocycline is measured using ultraviolet specrophotometer to judge absorption property.As a result such as table 2
It is shown.
Adsorption capacity and equilibration time of 2 composite material of table to minocycline
Table 2 is shown, Fe is used in embodiment 2, embodiment 3 and embodiment 43O4@MIL-68(Al)-1、Fe3O4@MIL-68
(Al) -2 and Fe3O4- 3 magnetic composite of@MIL-68 (Al) is above individual Fe to the adsorbance of minocycline3O4Particle
With MIL-68 (Al), illustrates to generate new crystal form in the composite, generates new duct, produce new suction-operated,
And the magnetic response of composite materials accelerates the removal to minocycline, time of equilibrium adsorption greatly improves, this wants absorption
It is significantly for asking.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of metal organic framework magnetic composite, which comprises the following steps:
(1) by Fe3O4Particle is carboxy-functionalized, then will be carboxy-functionalized after Fe3O4Particle is washed and is activated；
(2) Fe by step (1) after carboxy-functionalized3O4Particle is added in reaction dissolvent and ultrasonic disperse is uniform, obtains mixed liquor
A；Organic ligand is added in reaction dissolvent, stirring makes it completely dissolved, and mixed liquor A is then added, it is uniformly mixed, then
Aluminum soluble salt and adjuvant is added, forms mixed liquid B after being uniformly mixed, then temperature reaction, obtains after reaction
Metal organic framework magnetic composite head product；
(3) head product that step (2) obtains is washed, then heat-activated obtains metal organic framework magnetic coupling material
Material.
2. preparation method according to claim 1, which is characterized in that carboxy-functionalized reagent described in step (1) is
At least one of thioacetic acid or citric acid；The carboxy-functionalized solvent is ethyl alcohol.
3. preparation method according to claim 1, which is characterized in that organic ligand described in step (2) is to benzene two
Formic acid；The reaction dissolvent is N, N '-dimethylformamide, N, N '-diethylformamide, dimethyl sulfoxide or N, N- diformazan
At least one of yl acetamide.
4. preparation method according to claim 1, which is characterized in that aluminum soluble salt described in step (2) is nine water
Close at least one of aluminum nitrate or Aluminium chloride hexahydrate；The adjuvant is at least one in calcium carboxylate or sulfasalazine
Kind.
5. preparation method according to claim 1, which is characterized in that organic ligand in mixed liquid B described in step (2),
Aluminum soluble salt, adjuvant, it is carboxy-functionalized after Fe3O4The mass ratio of particle is 5~25:4.88~24.4:3.3~16.5:
0.5~3；The mass concentration of organic ligand is 10~20g/L in the mixed liquid B.
6. preparation method according to claim 1, which is characterized in that temperature reaction described in step (2) refers to heating
To 100~150 DEG C of 7~20h of reaction；It is preferred that in 130 DEG C of reaction 18h.
7. preparation method according to claim 1, which is characterized in that washing described in step (3) refers to first clear with DMF
After washing, again with methanol cleaning；The heat-activated refers to the holding 10h or more under 80~100 DEG C of vacuum conditions.
8. preparation method described in any one according to claim 1~4, which is characterized in that activation described in step (1) is
Finger activates 4h under the conditions of 50 DEG C；The washing is with deionized water and ethanol washing；The Fe3O4Particle is a kind of straight
Diameter is the≤magnetic microsphere of 20nm；It is described it is carboxy-functionalized be to be stirred to react at room temperature for 24 hours；
The time of step (2) ultrasonic disperse is 10~15min；Mixing time is 2~4h after mixed liquor A is added.
9. the metal organic framework magnetic composite of described in any item method preparations according to claim 1~8.
10. application of the metal organic framework magnetic composite as claimed in claim 9 in absorption antibiotic, is especially inhaling
Application in attached tetracycline antibiotics, the especially application in absorption minocycline.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586052A (en) * | 2019-09-25 | 2019-12-20 | 南开大学 | Preparation and application of magnetic composite porous network adsorption material |
| CN110702647A (en) * | 2019-09-02 | 2020-01-17 | 湘潭大学 | Construction and application of novel fluorescent imprinting sensor based on magnetic Metal Organic Framework (MOF) |
| CN111298842A (en) * | 2020-02-13 | 2020-06-19 | 河北科技大学 | Magnetic metal organic framework composite material and preparation method and application thereof |
| CN111569836A (en) * | 2020-05-25 | 2020-08-25 | 华工同创(深圳)新材料有限公司 | Metal organic framework composite granules and preparation method and application thereof |
| CN114409913A (en) * | 2022-01-11 | 2022-04-29 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Magnetic metal organic framework material and preparation method and application thereof |
| CN115715978A (en) * | 2022-11-24 | 2023-02-28 | 中国原子能科学研究院 | Ferroferric oxide-loaded MOF composite material adsorbent and preparation method and application thereof |
| CN117089082A (en) * | 2023-08-15 | 2023-11-21 | 北京建筑大学 | Preparation method of iron-based metal organic framework material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143331A (en) * | 2013-03-12 | 2013-06-12 | 复旦大学 | Synthetic method for magnetic metal organic framework composite material coated by [Cu3(btc)2] on surfaces of ferroferric oxide microspheres and application of composite material |
| US8648002B2 (en) * | 2007-04-24 | 2014-02-11 | Basf Se | Process for making and using metal organic frameworks based on aluminum, iron and chromium |
| CN104226262A (en) * | 2014-09-29 | 2014-12-24 | 天津工业大学 | Preparing method and application thereof of functional magnetic MOFs (Metal-Organic Frameworks) material |
| CN106512948A (en) * | 2016-10-21 | 2017-03-22 | 华南理工大学 | Metal-organic framework material MIL-68 (Al), and preparation method and application thereof |
| CN108940211A (en) * | 2018-07-06 | 2018-12-07 | 华南协同创新研究院 | A kind of metal-organic framework materials and its forming method and application |
-
2019
- 2019-05-08 CN CN201910378085.XA patent/CN110064372A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8648002B2 (en) * | 2007-04-24 | 2014-02-11 | Basf Se | Process for making and using metal organic frameworks based on aluminum, iron and chromium |
| CN103143331A (en) * | 2013-03-12 | 2013-06-12 | 复旦大学 | Synthetic method for magnetic metal organic framework composite material coated by [Cu3(btc)2] on surfaces of ferroferric oxide microspheres and application of composite material |
| CN104226262A (en) * | 2014-09-29 | 2014-12-24 | 天津工业大学 | Preparing method and application thereof of functional magnetic MOFs (Metal-Organic Frameworks) material |
| CN106512948A (en) * | 2016-10-21 | 2017-03-22 | 华南理工大学 | Metal-organic framework material MIL-68 (Al), and preparation method and application thereof |
| CN108940211A (en) * | 2018-07-06 | 2018-12-07 | 华南协同创新研究院 | A kind of metal-organic framework materials and its forming method and application |
Non-Patent Citations (2)
| Title |
|---|
| NING TIAN等: "Highly efficient capture of rubidium ion by a novel HS-Fe3O4@MIL-53(Al) composite material", 《POLYHEDRON》 * |
| YONGLEI WU等: "Core-shell structured magnetic metal-organic framework composites for T highly selective enrichment of endogenous N-linked glycopeptides and phosphopeptides", 《TALANTA》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110702647A (en) * | 2019-09-02 | 2020-01-17 | 湘潭大学 | Construction and application of novel fluorescent imprinting sensor based on magnetic Metal Organic Framework (MOF) |
| CN110586052A (en) * | 2019-09-25 | 2019-12-20 | 南开大学 | Preparation and application of magnetic composite porous network adsorption material |
| CN111298842A (en) * | 2020-02-13 | 2020-06-19 | 河北科技大学 | Magnetic metal organic framework composite material and preparation method and application thereof |
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| CN114409913A (en) * | 2022-01-11 | 2022-04-29 | 军事科学院军事医学研究院环境医学与作业医学研究所 | Magnetic metal organic framework material and preparation method and application thereof |
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| CN115715978B (en) * | 2022-11-24 | 2024-02-20 | 中国原子能科学研究院 | MOF composite material adsorbent loaded with ferroferric oxide and preparation method and application thereof |
| CN117089082A (en) * | 2023-08-15 | 2023-11-21 | 北京建筑大学 | Preparation method of iron-based metal organic framework material |
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Application publication date: 20190730 |