CN104128163A - Preparation method of microporous-mesoporous MIL-101 material and application thereof - Google Patents
Preparation method of microporous-mesoporous MIL-101 material and application thereof Download PDFInfo
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- CN104128163A CN104128163A CN201410382114.7A CN201410382114A CN104128163A CN 104128163 A CN104128163 A CN 104128163A CN 201410382114 A CN201410382114 A CN 201410382114A CN 104128163 A CN104128163 A CN 104128163A
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000013177 MIL-101 Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003115 biocidal effect Effects 0.000 claims abstract description 16
- 238000012546 transfer Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 14
- 239000003463 adsorbent Substances 0.000 abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 abstract description 7
- 229940088710 antibiotic agent Drugs 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000007385 chemical modification Methods 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 14
- 239000011148 porous material Substances 0.000 description 11
- 239000004098 Tetracycline Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 229960002180 tetracycline Drugs 0.000 description 9
- 229930101283 tetracycline Natural products 0.000 description 9
- 235000019364 tetracycline Nutrition 0.000 description 9
- 150000003522 tetracyclines Chemical class 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 229940063650 terramycin Drugs 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000012984 antibiotic solution Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention discloses a preparation method of a microporous-mesoporous MIL-101 material and an application thereof. The material disclosed by the invention is of a regular octahedron structure and has a multilevel hole structure, and the particle diameter is 100 to 300 nm. When the material is used for treating antibiotics in water, the antibiotics can be recycled and enriched, so as to suppress the transfer of the antibiotics in nature. Compared with an existing antibiotic adsorbent, chemical modification can be performed on the hole structure according to different kinds of adsorbed antibiotics, thereby realizing high selectivity and high adsorptivity to different kinds of antibiotics; the material has a high research value and an application prospect in the aspect of antibiotic adsorption.
Description
Technical field
The invention belongs to material and synthesize and water technology scope, relate generally to the application of antibiotics aspect in the metal-organic framework materials MIL-101 Adsorption water body that utilizes micropore-mesopore structure.
Background technology
China's antibiotic dosage is at the forefront in the world, and antibiotic output is very large, causes serious environmental pollution and unnecessary waste simultaneously.Many researchers have made a lot of work in Pharmaceutical Wastewater Treatment aspect antibiotic of physical treatment process, main adsorbent has active carbon, active mud, humic-acid kind, polymeric adsorbent, multi-walled carbon nano-tubes etc., but these adsorbents have feature separately, the selective bad and adsorption efficiency of active carbon and active mud is not high, and the preparation cost of resin and multi-walled carbon nano-tubes is higher, technique is more complicated.So the research and development of new antibiotic adsorbent become study hotspot.
Metal-organic framework materials (MOFs) is the method by Coordinative Chemistry, by organic ligand and metal ion self assembly and the class supermolecule porous material forming, because of its rule nano pore structure, high porosity, large specific area uniformly, all have broad application prospects in fields such as absorption, catalysis, biological medicine, electromagnetism.
The research that MOFs separates for Gas Phase Adsorption is more ripe, but because most of MOFs water stability is poor, less for the research of liquid phase separation.For the MOFs of water treatment, its stability in water is that material recycles, environmental protection, economy and prerequisite that can commercial Application.There are some researches show, the factor such as space structure of the stability of MOFs and the functional and material of metal center, cvdmetallorganiccvd ligand key power, organic ligand is relevant.Wherein the water stability relation of metallic atom arrowhead and MOFs is the closest, and the water stability order of the synthetic MOFs of conventional metallic atom arrowhead is Cr
3+>Cu
2+>Zn
2+.With Cr
3+for metal center, terephthalic acid (TPA) be the synthetic MIL-101 of part can be in water stable existence more than a year.This MOFs material application in liquid phase separation provides foundation.In recent years, have scholar to adopt MIL-101 to adsorb research to the large molecule of the medicines such as brufen, discovery up to 1.38g/g, also has good adsorption effect to some cancer therapy drugs to the adsorbance of brufen.But there is not yet up to now the report for patent of invention, the Research Literature etc. of antibiotic absorption by MOFs material.
Although MIL-101 contains heavy metal chromium, good water stability makes material structure in water treatment procedure keep stable, is difficult for caving in or decomposing, and makes Cr
3+can not be distributed in water, after adsorption process completes, MOFs can be separated from water to environmentally safe by means such as filtrations.In addition, it is emphasized that most of MOFs has microcellular structure, and this is disadvantageous for large molecules such as absorption antibiotic.Researchers are spared no effort to carry out modifying and decorating or are carried out load study to expect obtaining larger pore structure or hierarchical porous structure, widen the application of MOFs.Consult a large amount of documents and materials, there is not yet the report of preparing about micropore-mesopore structure MIL-101 material.
Summary of the invention
The object of the invention is to provide a kind of preparation method of micropore-mesopore MIL-101 material, and concrete operations are as follows:
(1) by Cr (NO
3)
39H
2o and H
2bDC(terephthalic acid (TPA)) in molar ratio 0.8:1-1.5:1 be dissolved in deionized water, slowly drip in the scope of HF to pH=2.5 ~ 3.0, after ultrasonic dispersion 15-30min, reactant transfer is reacted to 8 ~ 10h to hydrothermal reaction kettle at 200 ~ 250 DEG C;
(2) suction filtration product after cooling, and dry with vacuumizing at 60 DEG C after deionized water rinsing three times;
(3) solid is dissolved in to DMF(N, dinethylformamide) at 100 ~ 150 DEG C, activate 5h, suction filtration also rinses after three times with DMF, vacuumizes at 60 DEG C dry;
(4) solid is dissolved in to CH
2cl
2or CH
3cH
2in OH, at 100 ~ 150 DEG C, activate 16h, suction filtration, vacuumizes dry 24h at 160 DEG C, must have the MIL-101 material of micropore-mesopore structure.
Product of the present invention carries out structural characterization by following means: X-ray diffraction obtains under 200kV at Rigaku Rigaku D/Max-RB type high-resolution-ration transmission electric-lens; The cold field emission scanning electron microscope of S 4800 type that stereoscan photograph is produced in Japanese HITACHI company obtains under 3.0kV; The NOVA 4000 type surface area test instrument of producing by Kang Ta company of the U.S. are measured N
2absorption isotherm, the specific area of sample calculates by BET method; The heat stability testing of sample adopts Japanese Shimadzu DT-60 thermal analyzer, and temperature range is from room temperature to 500 DEG C, heating rate 10K/min, and carrier gas is N
2.
Preparation method's of the present invention main points are:
(1) by Cr (NO
3)
39H
2o and H
2bDC slowly drips left and right, HF to PH=2.5 ~ 3.0 after being dissolved in deionized water according to mol ratio 0.8:1-1.5:1, then by reactant transfer to ultrasonic dispersion 15-30min before hydrothermal reaction kettle;
(2) sample preparing is adopted to solvent C H
2cl
2or CH
3cH
2oH carries out activation processing 16h at 100 ~ 150 DEG C.
Another object of the present invention is that micropore-mesopore MIL-101 material is applied in and is processed in water body in antibiotic.
The material that above step makes is put into 1 ~ 5g/L in the aqueous solution that contains terramycin and tetracycline, stir at normal temperatures, mixing time is more than 30min, centrifugation precipitation under 3500r/min rotating speed, get supernatant liquor ultraviolet specrophotometer and measure absorbance and calculate its absorptivity, obtaining material absorptivity is 15% ~ 40%.
The present invention compared with prior art has the following advantages and effect:
(1) the micropore-mesopore MIL-101 that the present invention makes is compared with existing preparation MIL-101 technology, and the material making has hierarchical porous structure, and for antibiotic, macromolecular absorption is favourable for this.
(2) the present invention is mainly for the processing of residual antibiotic discharge in pharmacy waste water, and the adsorbent of hierarchical porous structure prepared by employing the present invention is processed the antibiotic in waste water, thereby plays the effect of protection of the environment.
(3) the present invention is compared with existing antibiotic adsorbent, and pore structure can be carried out chemical modification according to the difference of absorption Antibiotics, thereby realizes the antibiotic high selectivity of variety classes and high adsorption.
Brief description of the drawings
Fig. 1 is the XRD figure of micropore-mesopore MIL-101 material of the present invention;
Fig. 2 is the SEM figure of micropore-mesopore MIL-101 material of the present invention;
Fig. 3 is the TG figure of micropore-mesopore MIL-101 material of the present invention;
Fig. 4 is the N of micropore-mesopore MIL-101 material of the present invention
2adsorption-desorption thermoisopleth;
Fig. 5 is the graph of pore diameter distribution of micropore-mesopore MIL-101 material of the present invention;
Fig. 6 is micropore-mesopore MIL-101 material adsorptional earth mycin ultraviolet figure of the present invention;
Fig. 7 is micropore-mesopore MIL-101 material absorption tetracycline ultraviolet figure of the present invention.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but protection domain of the present invention is not limited to described content, chemical reagent used in embodiment is chemical pure.
Embodiment 1: this micropore-mesopore MIL-101 material, material particle size is 500nm, specific area is 2232m
2/ g, average pore size is 2.11nm, has micropore and mesoporous two kinds of pore structures simultaneously.
The preparation method of above-mentioned material is as follows:
(1) by Cr (NO
3)
39H
2o and H
2bDC in molar ratio 1.5:1 is dissolved in deionized water, slowly drips HF to pH and equals 2.5 left and right, after ultrasonic dispersion 15min, reactant transfer is reacted to 10h to hydrothermal reaction kettle under 200 DEG C of environment;
(2) suction filtration product, and dry with vacuumizing at 60 DEG C after deionized water rinsing three times;
(3) solid is dissolved in DMF and activates 5h at 150 DEG C, suction filtration also rinses after three times with DMF, vacuumizes at 60 DEG C dry;
(4) solid is dissolved in to CH
3cH
2in OH, at 150 DEG C, activate 16h, suction filtration, vacuumizes dry 24h at 160 DEG C, obtains micropore-mesopore MIL-101 material;
(5) material powder that weighing 0.025g step (4) makes joins respectively 25mL, concentration is in the antibiotic solution of 80mg/L terramycin and tetracycline, stir 30min, under 3500r/min rotating speed, centrifugation separates, get supernatant liquor ultraviolet specrophotometer and measure absorbance, then calculating terramycin adsorption rate is 32.3%, and tetracycline is that each characterization result of the material that makes of 35.2%(embodiment 1 is shown in Fig. 1-7).
Fig. 1 is known, and this crystal making is 2.9
o, 3.4
o, 5.3
o, 8.5
o, 9.1
othere is the principal character peak of MIL-101 in place, it is basically identical that this and its XRD that calculates by mono-crystalline structures data composes peak position.Fig. 2 represents the SEM figure of synthetic material under different amplification in this embodiment, and from figure, we can find out, this material has regular octahedron structure, and particle diameter is greatly between 100-300nm, and structure is more regular, and surface is more smooth.TG curve in Fig. 3 discloses the material making and has good heat endurance, can be before 300 DEG C stable existence, material has about 10% weightlessness between 30-100 DEG C, this is because the micromolecular loss such as some water, ethanol in duct cause; The weightlessness of second stage approximately occurs in 300 DEG C of left and right, and this is because caving in of skeleton caused.Nitrogen adsorption desorption isotherm by the MIL-101 of Fig. 4 can be found out the starting stage lower at relative pressure, i.e. P/P
0be less than at 0.2 o'clock, along with the increase of relative pressure, utmost point sharp increase adds nitrogen adsorption amount, and at P/P
0the 0.2 rear nitrogen adsorption amount that is greater than has again the trend a bit increasing with the increase of relative pressure, but the relatively mild and final absorption platform that forms of ascendant trend, and form a distant hysteresis loop.And this characterization result is except the specific area that obtains material is greatly about 2300m
2outside/g, same with the pore-size distribution of Fig. 5 what can obtain synthesizing be this important conclusion of micropore-mesopore MIL-101 material.Fig. 6 and Fig. 7 are respectively the ultraviolet adsorption curve figure of MIL-101 to terramycin and tetracycline, and from figure, we can find out that material all has good adsorption effect to two kinds of antibiotic intuitively.
Embodiment 2: this micropore-mesopore MIL-101 material, material particle size is 500nm, specific area is 2491m
2/ g, average pore size is 1.90nm, has micropore and mesoporous two kinds of pore structures simultaneously.
The preparation method of above-mentioned material is as follows:
(1) by Cr (NO
3)
39H
2o and H
2bDC in molar ratio 1.0:1 is dissolved in deionized water, slowly drips HF to pH and equals 2.5 left and right, after ultrasonic dispersion 20min, reactant transfer is reacted to 9h to hydrothermal reaction kettle under 220 DEG C of environment;
(2) suction filtration product, and dry with vacuumizing at 60 DEG C after deionized water rinsing three times;
(3) solid is dissolved in DMF and activates 5h at 120 DEG C, suction filtration also rinses after three times with DMF, vacuumizes at 60 DEG C dry;
(4) solid is dissolved in to CH
3cH
2in OH, at 100 DEG C, activate 24h, suction filtration, vacuumizes dry 24h at 160 DEG C, obtains micropore-mesopore MIL-101 material;
(5) weighing the material powder that makes of 0.025g step (4) joins respectively in the antibiotic solution that 25mL terramycin and tetracycline concentration are 80mg/L, stir 30min, under 3500r/min rotating speed, centrifugation separates, get supernatant liquor ultraviolet specrophotometer and measure absorbance, then calculating terramycin adsorption rate is 28.1%, and tetracycline is 24.6%.
Embodiment 3: this micropore-mesopore MIL-101 material, material particle size is 500nm, specific area is 2495m
2/ g, average pore size is 1.94nm, has micropore and mesoporous two kinds of pore structures simultaneously.
The preparation method of above-mentioned material is as follows:
(1) by Cr (NO
3)
39H
2o and H
2bDC in molar ratio 0.8:1 is dissolved in deionized water, slowly drips HF to pH and equals 3 left and right, after ultrasonic dispersion 30min, reactant transfer is reacted to 8h to hydrothermal reaction kettle under 250 DEG C of environment;
(2) suction filtration product, and dry with vacuumizing at 60 DEG C after deionized water rinsing three times;
(3) solid is dissolved in DMF and activates 5h at 100 DEG C, suction filtration also rinses after three times with DMF, vacuumizes at 60 DEG C dry;
(4) solid is dissolved in to CH
2cl
2in at 120 DEG C, activate 20h, suction filtration, vacuumizes dry 24h at 160 DEG C, prepares micropore-mesopore MIL-101 material;
(5) weighing the absorbent powder prepared of 0.025g joins respectively in the antibiotic solution that 25mL terramycin and tetracycline concentration are 80mg/L, stir 30min, under 3500r/min rotating speed, centrifugation separates, get supernatant liquor ultraviolet specrophotometer and measure absorbance, then calculating terramycin adsorption rate is 30.5%, and tetracycline is 22.9%.
Claims (2)
1. a preparation method for micropore-mesopore MIL-101 material, is characterized in that carrying out as follows:
(1) by Cr (NO
3)
39H
2o and H
2bDC in molar ratio 0.8:1-1.5:1 is dissolved in deionized water, slowly drips HF to pH=2.5 ~ 3.0, after ultrasonic dispersion 15-30min, reactant transfer is reacted to 8 ~ 10h to hydrothermal reaction kettle at 200 ~ 250 DEG C;
(2) suction filtration product, and dry with vacuumizing at 60 DEG C after deionized water rinsing three times;
(3) solid is dissolved in DMF and activates 5h at 100 ~ 150 DEG C, suction filtration also rinses after three times with DMF, vacuumizes at 60 DEG C dry;
(4) solid is dissolved in to CH
2cl
2or CH
3cH
2in OH, at 100 ~ 150 DEG C, activate 16 ~ 24h, suction filtration then vacuumizes dry 24h at 160 DEG C, obtains micropore-mesopore MIL-101 material.
2. the micropore-mesopore MIL-101 material that described in claim 1, the preparation method of micropore-mesopore MIL-101 material makes is the application in antibiotic in processing water body.
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Cited By (8)
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| CN104324696A (en) * | 2014-11-11 | 2015-02-04 | 天津工业大学 | Novel preparation and application method of water treatment thin film doped with mesoporous composite material |
| CN104923166A (en) * | 2015-06-17 | 2015-09-23 | 昆明理工大学 | Micropore Fe-N-MOF material and preparation method and application thereof |
| CN104992740A (en) * | 2015-05-25 | 2015-10-21 | 南京理工大学 | Application of micropore MIL-101 material for adsorbing trace iodine in water |
| CN105524112A (en) * | 2015-08-28 | 2016-04-27 | 浙江理工大学 | Preparation method of DMF-modified MIL-101 |
| CN105536710A (en) * | 2016-01-20 | 2016-05-04 | 昆明理工大学 | Mesoporous NH2-MIL-101(Cr) material as well as preparation method and application thereof |
| CN106622145A (en) * | 2016-10-12 | 2017-05-10 | 昆明理工大学 | Oxytetracycline adsorbent preparation method |
| CN107511134A (en) * | 2017-06-29 | 2017-12-26 | 湖南大学 | A kind of mesoporous Zr polymerization of olefin using catalyst polymer and its preparation and application |
| CN108911009A (en) * | 2018-07-24 | 2018-11-30 | 湖南大学 | Utilize the method for antibiotic in nickel doping metals organic framework material removal water body |
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| CN104324696A (en) * | 2014-11-11 | 2015-02-04 | 天津工业大学 | Novel preparation and application method of water treatment thin film doped with mesoporous composite material |
| CN104992740A (en) * | 2015-05-25 | 2015-10-21 | 南京理工大学 | Application of micropore MIL-101 material for adsorbing trace iodine in water |
| CN104923166A (en) * | 2015-06-17 | 2015-09-23 | 昆明理工大学 | Micropore Fe-N-MOF material and preparation method and application thereof |
| CN104923166B (en) * | 2015-06-17 | 2017-09-08 | 昆明理工大学 | A kind of micropore Fe N MOF materials and its preparation method and application |
| CN105524112A (en) * | 2015-08-28 | 2016-04-27 | 浙江理工大学 | Preparation method of DMF-modified MIL-101 |
| CN105536710A (en) * | 2016-01-20 | 2016-05-04 | 昆明理工大学 | Mesoporous NH2-MIL-101(Cr) material as well as preparation method and application thereof |
| CN106622145A (en) * | 2016-10-12 | 2017-05-10 | 昆明理工大学 | Oxytetracycline adsorbent preparation method |
| CN107511134A (en) * | 2017-06-29 | 2017-12-26 | 湖南大学 | A kind of mesoporous Zr polymerization of olefin using catalyst polymer and its preparation and application |
| CN108911009A (en) * | 2018-07-24 | 2018-11-30 | 湖南大学 | Utilize the method for antibiotic in nickel doping metals organic framework material removal water body |
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