CN114849650A - Preparation method and application of double-surface-characteristic magnetically-modified zirconium MOFs adsorbent - Google Patents
Preparation method and application of double-surface-characteristic magnetically-modified zirconium MOFs adsorbent Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 46
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 27
- 150000003754 zirconium Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 34
- 229940064958 chromium citrate Drugs 0.000 claims abstract description 31
- SWXXYWDHQDTFSU-UHFFFAOYSA-K chromium(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cr+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SWXXYWDHQDTFSU-UHFFFAOYSA-K 0.000 claims abstract description 31
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 12
- 230000007547 defect Effects 0.000 claims abstract description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 239000004005 microsphere Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 5
- -1 chromium hydroxyethylidene diphosphonate Chemical compound 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- BBMHARZCALWXSL-UHFFFAOYSA-M sodium dihydrogenphosphate monohydrate Chemical compound O.[Na+].OP(O)([O-])=O BBMHARZCALWXSL-UHFFFAOYSA-M 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 claims description 4
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BLSQUKMVYMBIIK-UHFFFAOYSA-H chromium(3+);2,3-dihydroxybutanedioate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O BLSQUKMVYMBIIK-UHFFFAOYSA-H 0.000 claims description 4
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 claims description 4
- 230000002950 deficient Effects 0.000 claims description 4
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims description 4
- 229940049920 malate Drugs 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 230000002860 competitive effect Effects 0.000 claims description 3
- 238000011067 equilibration Methods 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000013096 zirconium-based metal-organic framework Substances 0.000 claims 1
- 239000013207 UiO-66 Substances 0.000 abstract description 14
- 239000011258 core-shell material Substances 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
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- 238000001291 vacuum drying Methods 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]
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to the technical field of heavy metal wastewater treatment, and particularly relates to a preparation method of a double-surface-characteristic magnetically-modified zirconium MOFs adsorbent 3 O 4 -C @ UIO-deX-PEI, said adsorbent introducing a defect structure on the basis of the existing PEI-UIO-66 backbone to increase the adsorption sites for chromium citrate; and the UIO-deX-PEI and the magnetic core form a semi-core-shell structure in a semi-wrapping mode, and the UIO-deX-PEI has good performanceThe magnetic core has good adsorption performance, and the magnetic force of the magnetic core cannot be influenced by the core-shell structure, so that the recovery rate is extremely high under an external magnetic field; later experimental data show that the adsorbent can be stably used within the pH value range of 3-10, and the removal rate of low-concentration chromium citrate reaches 99%, so that the adsorbent has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of heavy metal wastewater treatment, and particularly relates to a preparation method of a double-surface-characteristic magnetically-modified zirconium MOFs adsorbent.
Background
The common chromium in the water body is divided into Cr (VI) and Cr (III), and the traditional treatment method is suitable for reducing the accumulation of high-toxicity Cr (VI), but is not suitable for the complex treatment of Cr (III) and organic matters.
Compared with other processes, the adsorption method removes the chromium complex as a whole, does not need to add chemical reagents, has no secondary pollution, low cost and high efficiency, is suitable for a water treatment system with large treatment capacity and low pollutant concentration, and can realize the recovery of heavy metals if the adsorbent with saturated adsorption is properly treated.
Literature Reactive&Functional Polymers,156(2020), Wang et al magnetic carbon functionalized with diethylene diamine (Fe) 3 O 4 @ C @ DETA) removes Cr-EDTA in the water body by adsorption, but the saturated adsorption capacity under the condition of pH 3 is only 22.24 mg/g.
Kauspedicine et al in Journal of Hazardous Materials,179(2010)933-939 explored the rule of removing chromium dye complex under different experimental conditions of activated carbon, and the result shows that the chromium dye complex pollutant and the activated carbon mainly interact through electrostatic attraction, are nonselective, and the adsorption effect is inhibited under the coexistence of competitive ions.
In order to solve the above problems, there are researchers (document UiO-66-NH) 2 And the modified material thereof on the adsorption of Cr (VI) in water) to note that: the organic substance Polyethyleneimine (PEI) modified zirconium series metal organic framework (UIO-66) has the characteristics of large specific surface area, high stability and strong adsorbability, so that the organic substance Polyethyleneimine (PEI) modified zirconium series metal organic framework can be used for removing U (VI) in water.
Inspired by the above, the invention tries to introduce a defect structure into the original skeleton to increase adsorption sites on the basis of the prepared PEI-UIO-66; and the adsorbent (UIO-deX-PEI) with a defect structure and the magnetic core form a half core-shell structure by adopting a half wrapping mode, so that the prepared magnetically-modified zirconium MOFs adsorbent containing the magnetic particle core and having asymmetric surface characteristics and shapes is prepared, and the problems that the pH condition and the complex water environment inhibit the performance of the adsorbent and the magnetic core magnetic force is weakened by the core-shell structure to cause the recovery rate of the adsorbent to be low in the prior art are solved.
Disclosure of Invention
In order to achieve the purpose, the invention provides a dual-surface-characteristic magnetically-modified zirconium MOFs adsorbent, which has good environmental pH value adaptability, high salt resistance and high recovery rate, and the specific scheme is as follows:
preparation method of magnetically modified zirconium MOFs adsorbent with one or two surface characteristics
S1 preparation of defective zirconium metal organic framework
S1-1, preparing a mixed solution composed of N, N-dimethylformamide and acetic acid, weighing zirconium chloride, 2-amino terephthalic acid and amino terephthalic acid, adding into the mixed solution, and performing ultrasonic dispersion uniformly;
s1-2, transferring the mixed solution prepared in the step S1-1 into a tetrafluoroethylene autoclave for heating, cooling to room temperature after the reaction is finished, and obtaining light yellow solid powder after centrifugation, washing and drying: UIO-66-deX;
s1-3, adding the UIO-66-deX prepared in the step S1-2 into a PEI solution, uniformly mixing, dropwise adding glutaraldehyde, continuously stirring at room temperature for reaction, and after the reaction is finished, centrifuging and washing to obtain the defect zirconium metal organic framework: UIO-deX-PEI;
s2 preparation of hollow magnetic microspheres
S2-1, adding polystyrene microspheres into pure water, performing ultrasonic treatment until the polystyrene microspheres are fully dispersed, and then adding dopamine hydrochloride and FeCl 3 Obtaining mixed solution;
s2-2, adding a dihydrogen phosphate-sodium hydroxide buffer solution into the mixed solution prepared in the step S1-1, continuously stirring until the mixed solution becomes dark brown, and centrifuging, washing and freeze-drying to obtain solid powder;
s2-3, annealing the solid powder prepared in the step S1-2 at high temperature to obtain the hollow magnetic microsphere: fe 3 O 4 -C;
S3 preparation of magnetically modified zirconium MOFs adsorbent with double surface characteristics
S3-1, preparation of Fe by step S2-3 3 O 4 Adding the-C into pure water for uniform dispersion, adding oleic acid, stirring at constant temperature of 87 ℃, washing and drying after stirring to obtain black solid powder;
s3-2, uniformly dispersing the black solid powder prepared in the step S3-1 in chloroform to obtain a solution, uniformly dispersing the solution on the liquid level of pure water, starting a sliding barrier pressing film after the solvent is evaporated, vertically lifting by using a negative plate and drying in the air;
s3-3, placing the negative film prepared in the step S3-2 at the bottom of a solution tank filled with ethanol, and applying a magnetic field outside the solution tank, wherein the direction of the magnetic field points to the negative film from the liquid level; dropwise adding thioglycollic acid into the solution tank, uniformly oscillating by ultrasonic waves, standing for reaction, emptying the solution tank after the reaction is finished, closing the external magnetic field, and repeatedly washing the bottom sheet by using DMF (dimethyl formamide) solution to obtain Fe modified by thioglycollic acid 3 O 4 -C;
s3-4, adding the UIO-deX-PEI prepared in the step S1-3 into the mixed liquid prepared in the step S3-3, uniformly mixing, transferring to a tetrafluoroethylene autoclave, sealing, heating and reacting, and after the reaction is finished, performing magnetic separation, washing and drying to obtain the double-surface-characteristic magnetically-modified zirconium MOFs adsorbent: fe 3 O 4 -C@UIO-deX-PEI。
Further, in the step S1:
in step S1-1, the molar ratio of zirconium chloride to mixed ligand is 1: 1;
in step S1-3, in UIO-deX-PEI, X represents the proportion of 2-amino terephthalic acid in the mixed ligand, and is respectively 0.6, 0.7, 08 and 0.9;
in the step S1-3, in the UIO-deX-PEI, PEI is polyethyleneimine with the molecular weight of 1800, and the mass percentage of PEI to UIO-deX is 3: 1.
further, in the step S2:
in step S2-1, polystyrene microspheres, dopamine hydrochloride, FeCl 3 The mass ratio of (1) to (2): 6: 7;
in step S2-2, the pH value of the dihydrogen phosphate-sodium hydroxide buffer solution is 8.5;
in step S2-3, the parameters of the high temperature annealing are: annealing at 800 deg.C for 3h at 1.5 deg.C/min under protective atmosphere.
Further, in the step S3:
in step S3-1, Fe in ethanol 3 O 4 The concentration of C is 1.2 kg/L;
in the step S3-2, the concentration of oleic acid is 3.186mol/L, the film pressure during slide barrier film pressing is 30mN/m, and the film pulling speed is 2.5 mm/min;
in the step S3-3, the concentration of thioglycolic acid is 1.74 mmol/L;
in the mixed solution of the step S3-4, Fe modified by thioglycolic acid is contained 3 O 4 The mass ratio of-C to UIO-deX-PEI is 3: 1.
secondly, the application of the magnetically modified zirconium MOFs adsorbent with double surface characteristics,
the adsorbent Fe prepared as described above 3 O 4 -C @ UIO-deX-PEI exhibits excellent adsorption of chromium citrate, the experimental procedure is as follows:
SA1, taking Fe at a dose of 0.5g/L 3 O 4 Adding the-C @ UIO-deX-PEI into a chromium citrate solution, stirring at a constant speed, sampling at different time intervals, measuring the removal rate of chromium by using an inductively coupled plasma mass spectrometry, and determining the adsorption equilibrium time;
SA2, influence factor examination: investigating the removal effect of the chromium citrate under different pH values; simulating a real water body, adding various anions into the chromium citrate solution, and inspecting the removal effect of the chromium citrate;
SA3, universality: the adsorption removal effect on various heavy metal complexes is examined.
Further, in the step SA1, 0.5g/L Fe is taken 3 O 4 -C @ UIO-deX-PEI was charged into an erlenmeyer flask and 300mL of chromium citrate solution was added to determine the equilibration time to within 3 h.
Further, in the step SA2, hydrochloric acid and sodium hydroxide are used for adjusting the pH value to 3-10; when simulating a real water body, adding 50mM Cl into a chromium citrate solution - 、NO 3 - 、SO 4 2- And simulating the competitive environment in the actual wastewater.
Further, in SA3, the heavy metal complexes include nickel citrate, copper citrate, chromium hydroxyethylidene diphosphonate, chromium malate, chromium tartrate and chromium oxalate. .
The invention has the beneficial effects that:
(1) more binding sites are added on the surface of the adsorbent in a defect mode, so that the adsorption quantity of the chromium citrate is improved.
(2) The removal rate of the adsorbent to low-concentration chromium citrate (<20mg/L) reaches 99 percent, which is far higher than that of the existing adsorbent.
(3) The time for the adsorbent to reach adsorption equilibrium is only 3-4 h, and the efficiency is higher compared with the equilibrium time of more than 10h such as an ion exchange method, a membrane separation method and the like.
(4) The adsorbent can be stably used within the range of pH value of 3-10, and has good environmental pH value adaptability.
(5) The adsorbent shows excellent removal effect on various heavy metal complexes and has good high-salt resistance.
(6) The adsorbent adopts a half-wrapping mode, so that the adsorbent with a defect structure and the magnetic core form a half-core-shell structure, and the prepared adsorbent has good adsorption performance and cannot influence the magnetic force of the magnetic core due to the core-shell structure, so that the recovery rate is extremely high under an applied magnetic field.
Drawings
FIG. 1 is an EPR spectrum of a defective UIO-66-deX prepared with different ligand ratios;
FIG. 2 is an X-ray diffraction pattern of UIO-66-deX before and after PEI modification;
FIG. 3 is a graph of the adsorption thermodynamics of UIO-deX-PEI and the initial UIO-66 against chromium citrate;
FIG. 4 is a plot of the adsorption kinetics of UIO-de0.7-PEI and the initial UIO-66 on chromium citrate;
FIG. 5 shows SO concentrations 4 2- Under the condition of ion coexistence, UIO-de0.7-PEI and initial UIO-66 are used for absorbing chromium citrate with the initial concentration of 20 mg/L;
FIG. 6 is a graph showing the removal rate of chromium citrate by UIO-de0.7-PEI at an initial concentration of 10mg/L at an initial pH of 3-10;
FIG. 7 is a graph showing the adsorption of UIO-de0.7-PEI to a heavy metal complex such as nickel citrate, copper citrate, chromium hydroxyethylidene diphosphonate, chromium malate, chromium tartrate, chromium oxalate, etc., at a concentration of 40 mg/L.
Detailed Description
To further illustrate the manner in which the present invention is made and the effects achieved, the following description of the present invention will be made in detail and completely with reference to the accompanying drawings.
Example 1
The main objective of example 1 is to illustrate the preparation of UIO-66-deX as follows:
preparing a defect zirconium metal organic framework material UIO-66-deX by using a mixed ligand of terephthalic acid and 2-amino terephthalic acid:
weighing zirconium chloride, 2-amino terephthalic acid (NH) 2 -BDC) and amino terephthalic acid (H) 2 BDC) was dispersed in a mixed solution of N, N-dimethylformamide (DMF, 50mL), 99% acetic acid (10mL), wherein the molar ratio of zirconium chloride to mixed ligand was 1: 1;
adding the mixed solution into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and heating and reacting for 24 hours at 120 ℃; after the reaction is finished and cooled to room temperature, obtaining light yellow solid through centrifugation, then alternately cleaning the light yellow solid with DMF and ethanol for three times, transferring the obtained viscous solid to a ceramic crucible, and then putting the ceramic crucible into a vacuum drying oven to be dried to obtain UIO-66-deX, wherein X is the proportion of amino ligand in the mixed ligand and is respectively 0.6, 0.7, 0.8 and 0.9.
Referring to FIG. 1, it can be seen that by varying the ligand ratio, defects to UIO-66-deX defects are achieved, with increasing oxygen vacancy concentration as the amino ligand content decreases.
Example 2
Example 2 the main objective is to illustrate the preparation of UIO-deX-PEI as follows:
a certain amount of PEI was dissolved in 50mL of deionized water and then UIO-66-deX (1g) prepared in example 1 was added; stirring for 0.5h, uniformly mixing, dropwise adding glutaraldehyde (1mL), reacting for 12h under the condition of stirring at room temperature, washing with ethanol for three times, and centrifuging to obtain UIO-deX-PEI, wherein the mass ratio of PEI to UIO-66-deX is 3: 1.
example 3
The main purpose of example 3 is to illustrate the preparation of UIO-de0.7-PEI at a specific formulation as follows:
UIO-66-de 0.7-UIO-de 0.7-PEI with a polyethyleneimine-modified amino ligand ratio of 0.7 was prepared by the protocol described in examples 1 and 2:
a certain amount of PEI was dissolved in 50mL of deionized water, and then the above UIO-66-de0.7(1g) was added; stirring for 0.5h, uniformly mixing, dropwise adding glutaraldehyde (1mL), reacting for 12h under the condition of stirring at room temperature, washing with ethanol for three times, and centrifuging to obtain UIO-de0.7-PEI, wherein the mass ratio of PEI to UIO-66-de0.7 is 3: 1.
referring to FIG. 2, it can be seen that the characteristic reflection of UIO-de0.7-PEI is completely absent compared to the original UIO-66, and all diffraction corresponds to square t-ZrO 2 (t-ZrO 2 PDF #50-1089), the broad peak at 30.27 ° belongs to t-ZrO 2 Is reflected due to the PEI modification causing lattice distortion.
Example 4
Example 4 the main objective was to demonstrate hollow magnetic microspheres-Fe 3 O 4 The preparation method of the-C comprises the following steps:
adding polystyrene microspheres (1.5g) into pure water (150mL) for ultrasonic treatment until the polystyrene microspheres are fully dispersed, and then adding dopamine hydrochloride (0.6g) and FeCl 3 (0.7g) to obtain a mixed solution;
adding dihydrogen phosphate-sodium hydroxide buffer solution with pH of 8.5 into the above mixed solution, stirring until the mixed solution turns dark brown, centrifuging, washing, and lyophilizing to obtain solid powder;
annealing the prepared solid powder at 800 ℃ for 3h at the speed of 1.5 ℃/min to obtain the hollow magnetic microspheres: fe 3 O 4 -C;
Example 5
Example 5 the main objective was to demonstrate the dual surface properties of the magnetically modified zirconium MOFs adsorbent-Fe 3 O 4 -C @ UIO-deX-PEI, comprising the following contents:
fe prepared in example 4 3 O 4 Adding the-C into pure water, uniformly dispersing (the concentration is 1.2g/mL), adding oleic acid (3.186mol/L), stirring at the constant temperature of 87 ℃, washing and drying after stirring to obtain black solid powder;
uniformly dispersing the prepared black solid powder in trichloromethane to obtain a solution, uniformly dispersing the solution on the liquid level of pure water, starting a sliding barrier pressing film (the film pressure is 30mN/m) after the solvent is evaporated, vertically lifting by using a negative plate (the lifting speed is 2.5mm/min), and drying;
placing the prepared negative film at the bottom of a solution tank filled with ethanol, and applying a magnetic field outside the solution tank, wherein the direction of the magnetic field points to the negative film from the liquid level; dropwise adding thioglycollic acid (1.74mmol/L) into the solution tank, uniformly oscillating by ultrasonic waves, standing for reaction, emptying the solution tank after the reaction is finished, closing the external magnetic field, and repeatedly washing the bottom plate by using DMF (dimethyl formamide) solution to obtain Fe modified by thioglycollic acid 3 O 4 -C;
the UIO-de0.7-PEI prepared in example 4 and Fe modified with thioglycolic acid were added to the above-obtained mixture 3 O 4 The mass ratio of-C to UIO-deX-PEI is 3: 1, uniformly mixing, transferring to a tetrafluoroethylene high-pressure kettle, sealing, heating and reacting, and after the reaction is finished, performing magnetic separation, washing and drying to obtain the double-surface-characteristic magnetically-modified zirconium MOFs adsorbent: fe 3 O 4 [email protected]。
Application example 1
50mL of a chromium citrate solution having a concentration of 2, 5, 10, 20, 26, 40mg/L was measured and placed in an Erlenmeyer flask, 0.025g of UIO-deX-PEI prepared in example 2 was added while stirring with a mechanical stirrer using unmodified UIO-66 as a contrast, and after 6 hours, the supernatant was taken, the adsorbent was filtered off with a 0.22 μm filter membrane, and the residual chromium ion concentration was measured with ICPs.
The measurement result is shown in FIG. 3, and it can be seen from FIG. 3 that the adsorption amount of chromium citrate is greatly improved by modification of PEI. Meanwhile, the defect degree of zirconium MOFs also influences the modification, and when the ratio of the amino ligand in the mixed ligand is 0.7, the adsorption capacity is the highest and reaches 63.14mg/g, which is 4 times of the original UIO-66.
Application example 2
300mL of a solution with a chromium citrate concentration of 20mg/L is measured and placed in an erlenmeyer flask, 0.15g of the adsorbent UIO-de0.7-PEI prepared in example 3 is added at 25 ℃, meanwhile, unmodified UIO-66 is used as comparison, mechanical stirring slurry is used for stirring, supernatant is taken at regular intervals, the adsorbent is filtered out by a 0.22 mu m filter membrane, the concentration of residual chromium ions is measured by ICPs, the measurement result is shown in figure 4, as can be seen from figure 4, the modification of PEI advances the equilibrium time by nearly 8 hours (shortens to 3 hours), and the pollutant removal rate is greatly improved.
Application example 3
300mL of a solution having a chromium citrate concentration of 20mg/L was measured and placed in an Erlenmeyer flask, and 0.15g of the adsorbent Fe prepared in example 5 was added thereto at 25 ℃ 3 O 4 -C @ UIO-de0.7-PEI, with unmodified UIO-66 as a comparison, with mechanical stirring, with recovery of the adsorbent (yield 99%) by means of an external magnetic field, and measurement of the residual chromium ion concentration using ICPs, the determination showing that Fe is present compared to the initial UIO-66 3 O 4 The adsorption equilibration time was reduced to 3.5h by-C @ UIO-de 0.7-PEI.
See FIG. 5 for SO at different concentrations 4 2- Under the condition of ion coexistence, the PEI modified defective zirconium MOFsUIO-de0.7-PEI and the initial UIO-66 have the adsorption condition on chromium citrate with the initial concentration of 20mg/L, and the result shows that the UIO-de0.7-PEI still maintains the adsorption performance on the chromium citrate under the high-salt condition, when SO 4 2- When the concentration was increased to 400mM, the adsorption capacity decreased only 14.0% to 18.22mg/g and the UIO-66 decreased 70.0% to 4.41 mg/g.
By comparison, the addition of the magnetic core in the adsorbent causes the adsorption performance of the adsorbent to be reduced, which is caused by Fe in unit mass 3 O 4 The content of the component having an adsorption effect in C @ UIO-de0.7-PEI is diluted, resulting in impaired adsorption; and the same as thisOf (i) Fe 3 O 4 The hollow porous carbon spheres in the C provide more active sites for the adsorption of chromium citrate; under the combined action of the two phenomena, Fe is enabled 3 O 4 The adsorption performance of-C @ UIO-de0.7-PEI decreases, but not so much.
In Fe 3 O 4 Fe on the premise that the adsorption performance of-C @ UIO-de0.7-PEI reaches the standard 3 O 4 the-C @ UIO-de0.7-PEI can be recycled by adopting magnetic force, so that the recycling can reach 99%. Thus, Fe 3 O 4 The combination of-C @ UIO-de0.7-PEI has significant advantages.
Application example 4
50mL of a solution containing 10mg/L of chromium citrate is weighed and placed in a conical flask, the pH of the solution is adjusted to about 3, 4, 5, 6, 7, 8, 9 and 10 at 25 ℃, and 0.025g of the Fe adsorbent prepared in example 5 is added 3 O 4 -C @ UIO-de0.7-PEI, stirred with a mechanical stirrer, reacted for 6h, then the adsorbent was recovered using an applied magnetic field and its residual cadmium ion concentration was measured using ICPs, the results of which are shown in FIG. 6. FIG. 6 Total results show Fe prepared 3 O 4 the-C @ UIO-de0.7-PEI can greatly improve the adsorbability of the adsorbent to chromium citrate, the removal rate is 86.6-98.5%, and the change of the pH value in the solution before and after adsorption is small, which indicates that the material is stable in a water body and does not disintegrate to release a terephthalic acid ligand.
Application example 5
50mL of different heavy metal complex solutions with the concentration of 40mg/L are measured and placed in a conical flask, the heavy metal complexes respectively comprise nickel citrate, copper citrate, chromium hydroxyethylidene diphosphonate, chromium malate, chromium tartrate and chromium oxalate, and 0.025g of the adsorbent Fe prepared in example 5 is added at 25 DEG C 3 O 4 -C @ UIO-de0.7-PEI, stirred with a mechanical stirrer, reacted for 6h, then the adsorbent was recovered using an external magnetic field and its residual cadmium ion concentration was measured using ICPs. The results are shown in FIG. 7, Fe 3 O 4 the-C @ UIO-de0.7-PEI shows excellent removal effect on various heavy metal complexes, and has a wide application prospect.
Claims (8)
1. A preparation method of a dual-surface-characteristic magnetically-modified zirconium MOFs adsorbent is characterized by comprising the following steps:
s1 preparation of defective zirconium metal organic framework
S1-1, preparing a mixed solution composed of N, N-dimethylformamide and acetic acid, weighing zirconium chloride, 2-amino terephthalic acid and amino terephthalic acid, adding into the mixed solution, and performing ultrasonic dispersion uniformly;
s1-2, transferring the mixed solution prepared in the step S1-1 into a tetrafluoroethylene autoclave for heating, cooling to room temperature after the reaction is finished, and obtaining light yellow solid powder after centrifugation, washing and drying: UIO-66-deX;
s1-3, adding the UIO-66-deX prepared in the step S1-2 into a PEI solution, uniformly mixing, dropwise adding glutaraldehyde, continuously stirring at room temperature for reaction, and after the reaction is finished, centrifuging and washing to obtain the defect zirconium metal organic framework: UIO-deX-PEI;
s2 preparation of hollow magnetic microspheres
S2-1, adding polystyrene microspheres into pure water, performing ultrasonic treatment until the polystyrene microspheres are fully dispersed, and then adding dopamine hydrochloride and FeCl 3 Obtaining mixed liquid;
s2-2, adding a dihydrogen phosphate-sodium hydroxide buffer solution into the mixed solution prepared in the step S1-1, continuously stirring until the mixed solution becomes dark brown, and centrifuging, washing and freeze-drying to obtain solid powder;
s2-3, annealing the solid powder prepared in the step S1-2 at high temperature to obtain the hollow magnetic microsphere: fe 3 O 4 -C;
S3 preparation of magnetically modified zirconium MOFs adsorbent with double surface characteristics
S3-1, preparation of Fe by step S2-3 3 O 4 Adding the-C into pure water for uniform dispersion, adding oleic acid, stirring at constant temperature of 87 ℃, washing and drying after stirring to obtain black solid powder;
s3-2, uniformly dispersing the black solid powder prepared in the step S3-1 in chloroform to obtain a solution, uniformly dispersing the solution on the liquid level of pure water, starting a sliding barrier pressing film after the solvent is evaporated, vertically lifting by using a negative plate and drying in the air;
s3-3, placing the negative film prepared in the step S3-2 at the bottom of a solution tank filled with ethanol, and applying a magnetic field outside the solution tank, wherein the direction of the magnetic field points to the negative film from the liquid level; dropwise adding thioglycollic acid into the solution tank, uniformly oscillating by ultrasonic waves, standing for reaction, emptying the solution tank after the reaction is finished, closing the external magnetic field, and repeatedly washing the bottom sheet by using DMF (dimethyl formamide) solution to obtain Fe modified by thioglycollic acid 3 O 4 -C;
s3-4, adding the UIO-deX-PEI prepared in the step S1-3 into the mixed liquid prepared in the step S3-3, uniformly mixing, transferring to a tetrafluoroethylene autoclave, sealing, heating and reacting, and after the reaction is finished, performing magnetic separation, washing and drying to obtain the double-surface-characteristic magnetically-modified zirconium MOFs adsorbent: fe 3 O 4 -C@UIO-deX-PEI。
2. The method of claim 1, wherein in step S1:
in step S1-1, the molar ratio of zirconium chloride to mixed ligand is 1: 1;
in step S1-3, in UIO-deX-PEI, X represents the proportion of 2-amino terephthalic acid in the mixed ligand, and is respectively 0.6, 0.7, 08 and 0.9;
in the step S1-3, in the UIO-deX-PEI, PEI is polyethyleneimine with the molecular weight of 1800, and the mass percentage of PEI to UIO-deX is 3: 1.
3. the method of claim 1, wherein in step S2:
in step S2-1, polystyrene microspheres, dopamine hydrochloride, FeCl 3 The mass ratio of (1) to (2): 6: 7;
in step S2-2, the pH value of the dihydrogen phosphate-sodium hydroxide buffer solution is 8.5;
in step S2-3, the parameters of the high temperature annealing are: annealing at 800 deg.C for 3h at 1.5 deg.C/min under protective atmosphere.
4. The method for preparing dual-surface-characteristic magnetically modified zirconium MOFs adsorbent according to claim 1, wherein in said step S3:
in step S3-1, Fe in ethanol 3 O 4 The concentration of C is 1.2 kg/L;
in the step S3-2, the concentration of oleic acid is 3.186mol/L, the film pressure during slide barrier film pressing is 30mN/m, and the film pulling speed is 2.5 mm/min;
in the step S3-3, the concentration of thioglycolic acid is 1.74 mmol/L;
in the mixed solution of the step S3-4, Fe modified by thioglycolic acid is contained 3 O 4 The mass ratio of-C to UIO-deX-PEI is 3: 1.
5. use of the dual-surface-property magnetically modified zirconium MOFs adsorbent according to claim 1, wherein Fe is 3 O 4 -C @ UIO-deX-PEI exhibits excellent adsorption of chromium citrate, the experimental procedure is as follows:
SA1, taking Fe at a dose of 0.5g/L 3 O 4 Adding the-C @ UIO-deX-PEI into a chromium citrate solution, stirring at a constant speed, sampling at different time intervals, measuring the removal rate of chromium by using an inductively coupled plasma mass spectrometry, and determining the adsorption equilibrium time;
SA2, influence factor examination: investigating the removal effect of the chromium citrate under different pH values; simulating a real water body, adding various anions into the chromium citrate solution, and inspecting the removal effect of the chromium citrate;
SA3, universality: the adsorption removal effect on various heavy metal complexes is examined.
6. The use of the dual-surface-property magnetically modified zirconium MOFs adsorbent according to claim 5, wherein in said step SA1, 0.5g/L Fe is taken 3 O 4 -C @ UIO-deX-PEI was charged into an erlenmeyer flask and 300mL of chromium citrate solution was added to determine the equilibration time to within 3 h.
7. The method of claim 5 for preparing the dual-surface-property magnetically modified zirconium MOFs adsorbentThe method is characterized in that in the step SA2, hydrochloric acid and sodium hydroxide are used for adjusting the pH value to 3-10; when simulating a real water body, adding 50mM Cl into a chromium citrate solution - 、NO 3 - 、SO 4 2- And simulating the competitive environment in the actual wastewater.
8. The use of modified zirconium-based MOFs according to claim 5, wherein said heavy metal complexes in SA3 comprise nickel citrate, copper citrate, chromium hydroxyethylidene diphosphonate, chromium malate, chromium tartrate and chromium oxalate.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115505130A (en) * | 2022-09-19 | 2022-12-23 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
CN115722203A (en) * | 2022-11-08 | 2023-03-03 | 中国科学院上海高等研究院 | Yttrium-europium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
CN115722213A (en) * | 2022-11-29 | 2023-03-03 | 浙江工业大学 | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103894161A (en) * | 2014-04-09 | 2014-07-02 | 复旦大学 | Synthesis method of magnetic metal organic framework composite material and application of material |
CN105233799A (en) * | 2015-06-03 | 2016-01-13 | 西北师范大学 | Magnetic metal-organic framework material with core-shell structure and preparation method therefor |
US20190127252A1 (en) * | 2017-10-26 | 2019-05-02 | Soochow University | Magnetic nanoparticle microbial composite with core-shell structure, preparation method thereof, and its application in the treatment of azo dyes |
CN110508163A (en) * | 2019-09-06 | 2019-11-29 | 南京大学 | A kind of MOF film of crosslinked polyethylenimine and preparation method thereof |
CN111103719A (en) * | 2020-01-07 | 2020-05-05 | 哈尔滨工业大学 | Method for preparing flexible trans-polymer dispersed liquid crystal film by utilizing LB (Langmuir-Blodgett) film technology |
CN112604661A (en) * | 2020-12-29 | 2021-04-06 | 复旦大学 | Hydrophilic magnetic zirconium-based-organic metal carbon framework material and preparation method and application thereof |
-
2022
- 2022-05-09 CN CN202210502750.3A patent/CN114849650B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103894161A (en) * | 2014-04-09 | 2014-07-02 | 复旦大学 | Synthesis method of magnetic metal organic framework composite material and application of material |
CN105233799A (en) * | 2015-06-03 | 2016-01-13 | 西北师范大学 | Magnetic metal-organic framework material with core-shell structure and preparation method therefor |
US20190127252A1 (en) * | 2017-10-26 | 2019-05-02 | Soochow University | Magnetic nanoparticle microbial composite with core-shell structure, preparation method thereof, and its application in the treatment of azo dyes |
CN110508163A (en) * | 2019-09-06 | 2019-11-29 | 南京大学 | A kind of MOF film of crosslinked polyethylenimine and preparation method thereof |
CN111103719A (en) * | 2020-01-07 | 2020-05-05 | 哈尔滨工业大学 | Method for preparing flexible trans-polymer dispersed liquid crystal film by utilizing LB (Langmuir-Blodgett) film technology |
CN112604661A (en) * | 2020-12-29 | 2021-04-06 | 复旦大学 | Hydrophilic magnetic zirconium-based-organic metal carbon framework material and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
TINGTING ZHOU ET AL.: "Enhanced removal of toxic hexavalent chromium from aqueous solution by magnetic Zr-MOF@polypyrrole: performance and mechanism", 《ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115505130A (en) * | 2022-09-19 | 2022-12-23 | 中国林业科学研究院林产化学工业研究所 | Lignin-based metal organic complex and preparation method and application thereof |
CN115722203A (en) * | 2022-11-08 | 2023-03-03 | 中国科学院上海高等研究院 | Yttrium-europium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
CN115722203B (en) * | 2022-11-08 | 2024-03-29 | 中国科学院上海高等研究院 | Yttrium-europium-zirconium-terephthalic acid-based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof |
CN115722213A (en) * | 2022-11-29 | 2023-03-03 | 浙江工业大学 | Amino-functionalized MOFs material, preparation method thereof and application thereof in deep removal of organic phosphorus in sewage and wastewater |
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