CN115770559B - Cerium metal organic framework magnetic material and preparation method and application thereof - Google Patents
Cerium metal organic framework magnetic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115770559B CN115770559B CN202211585350.XA CN202211585350A CN115770559B CN 115770559 B CN115770559 B CN 115770559B CN 202211585350 A CN202211585350 A CN 202211585350A CN 115770559 B CN115770559 B CN 115770559B
- Authority
- CN
- China
- Prior art keywords
- cemofs
- magnetic material
- soluble
- water
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000696 magnetic material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 title description 4
- 229910052684 Cerium Inorganic materials 0.000 title description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title description 3
- 239000002245 particle Substances 0.000 claims abstract description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 42
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 150000000703 Cerium Chemical class 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 25
- 239000011574 phosphorus Substances 0.000 claims description 25
- 229910052698 phosphorus Inorganic materials 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 22
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 239000010452 phosphate Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 239000008055 phosphate buffer solution Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000002101 nanobubble Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Abstract
The invention relates to the technical field of adsorption materials, in particular to a CeMOFs@Fe 3 O 4 Magnetic material, and its preparation method and application are provided. The invention uses soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and performing hydrothermal reaction to obtain CeMOFs@Fe 3 O 4 A precursor; the CeMOFs@Fe 3 O 4 Activating the precursor to obtain CeMOFs@Fe 3 O 4 A magnetic material. The invention obtains CeMOFs with a reticular structure and a rich pore structure through one-step hydrothermal reaction, and simultaneously, the water-soluble Fe is added 3 O 4 The particles are loaded on the surface of the CeMOFs, and then the CeMOFs@Fe with stable structure and large specific surface area is finally obtained through activation treatment 3 O 4 A magnetic material. The preparation provided by the inventionThe method is simple to operate and easy to implement, and does not need harsh conditions.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a CeMOFs@Fe 3 O 4 Magnetic material, and its preparation method and application are provided.
Background
Excessive phosphorus in the water ecological system can cause algae mass propagation, cause water eutrophication, cause massive death of water organisms and destroy water quality. Phosphorus in a water body comprises orthophosphate, organic phosphorus and polyphosphate, and since organic phosphorus is finally converted into inorganic phosphate through the action of microorganisms, the polyphosphate is also partially converted into orthophosphate through hydrolysis, so that the removal of excessive phosphorus elements in the water body is mainly to remove excessive orthophosphate.
Common methods for treating the phosphorus-containing wastewater include a chemical precipitation method, a biological method, a membrane separation method and an adsorption method, wherein the chemical precipitation method is used for removing phosphorus by adding calcium, aluminum, iron and other ions into the phosphorus-containing wastewater to form indissolvable substances with phosphate, but a large amount of sludge is easy to produce in the use process; the biological method adopts the methods of ecological floating bed, micro-nano bubble and immersed resin floating bed composite technology, high-efficiency composite bacteria addition and the like to treat the phosphorus-containing wastewater, but the treatment period is longer, and the reaction process is more complex; the adsorption method is a method with application significance because of the advantages of simple operation, no generation of a large amount of sludge and the like. At present, metal organic framework Materials (MOFs) are combined with cerium rare earth elements to prepare the CeMOFs, but the CeMOFs are difficult to separate from water after adsorption due to small particle size, so that practical application of the CeMOFs in engineering is limited.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a CeMOFs@Fe 3 O 4 Magnetic material, preparation method and application thereof, and CeMOFs@Fe obtained by the preparation method 3 O 4 The magnetic material has excellent adsorption performance on phosphate in water, obvious dephosphorization effect, easy separation and simple preparation method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a CeMOFs@Fe 3 O 4 The preparation method of the magnetic material comprises the following steps:
(1) Dissolving soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and performing hydrothermal reaction to obtain CeMOFs@Fe 3 O 4 A precursor;
(2) The CeMOFs@Fe 3 O 4 Activating the precursor to obtain CeMOFs@Fe 3 O 4 A magnetic material.
Preferably, the soluble cerium salt and water-soluble Fe 3 O 4 The molar ratio of the particles is 2-10:1; the terephthalic acid and water-soluble Fe 3 O 4 The molar ratio of the particles is 1-5:1.
Preferably, the soluble cerium salt comprises Ce (NO 3 ) 3 、CeCl 3 And Ce (Ce) 2 (SO 4 ) 3 One of the following; the water-soluble Fe 3 O 4 The particles are water-soluble nano Fe 3 O 4 And (3) particles.
Preferably, the water-soluble nano Fe 3 O 4 The preparation method of the particles comprises the following steps:
sodium citrate, feCl 3 Mixing sodium acetate and glycol, and reacting to obtain water-soluble nano Fe 3 O 4 And (3) particles.
Preferably, the mixing is to mix a soluble cerium salt and water-soluble Fe 3 O 4 The particles are subjected to first ultrasonic mixing in dimethylformamide to obtain a first mixed solutionThe method comprises the steps of carrying out a first treatment on the surface of the And carrying out second ultrasonic mixing on the terephthalic acid and the first mixed solution.
Preferably, the temperature of the hydrothermal reaction is 110-170 ℃ and the time is 16-24 h.
Preferably, the activation temperature is 140-170 ℃ and the time is 16-24 h.
The invention also comprises the CeMOFs@Fe according to the technical scheme 3 O 4 A magnetic material.
The invention also comprises the CeMOFs@Fe according to the technical scheme 3 O 4 The application of the magnetic material as the dephosphorization adsorbent.
Preferably, the CeMOFs@Fe 3 O 4 The adding amount of the magnetic material in the phosphorus-containing water body is 0.04-0.10 g/L; the initial pH value of the phosphorus-containing water body is 3-12.
The invention provides a CeMOFs@Fe 3 O 4 The preparation method of the magnetic material comprises the following steps:
(1) Dissolving soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and performing hydrothermal reaction to obtain CeMOFs@Fe 3 O 4 A precursor; (2) The CeMOFs@Fe 3 O 4 Activating the precursor to obtain CeMOFs@Fe 3 O 4 A magnetic material. The invention obtains CeMOFs with a reticular structure and a rich pore structure through one-step hydrothermal reaction, and simultaneously, the water-soluble Fe is added 3 O 4 The particles are loaded on the surface of the CeMOFs, and then the CeMOFs@Fe with stable structure and large specific surface area is finally obtained through activation treatment 3 O 4 A magnetic material. The preparation method provided by the invention is simple to operate, easy to implement and free from harsh conditions.
The invention also provides the CeMOFs@Fe adopting the technical scheme 3 O 4 The invention uses CeMOFs@Fe as the magnetic material 3 O 4 The magnetic material has a cross-linked network structure and rich pore structures, so that active components in the material are fully contacted with phosphate radical in water, phosphate can be effectively adsorbed, and the problem that the traditional dephosphorization material removes low-concentration phosphorus in the practical application process is solvedLow removal efficiency, etc.
The invention utilizes CeMOFs@Fe 3 O 4 Loading Fe on magnetic material 3 O 4 The particles have stronger magnetism, can promote the structural stability of materials, and can be directly separated and recovered from a solution medium by adopting a magnetic separation mode.
The invention generates a product different from CeMOFs and Fe through coupling effect 3 O 4 CeMOFs@Fe serving as new dephosphorization material 3 O 4 The material has larger specific surface area, and can be used for preparing CeMOFs or Fe 3 O 4 Compared with the method, the method has excellent adsorption performance on phosphate in water, higher adsorption saturation capacity and faster adsorption rate, and has remarkable dephosphorization effect.
Drawings
FIG. 1 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 FE-SEM images of magnetic materials;
FIG. 2 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 XRD pattern of the magnetic material;
FIG. 3 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 VSM plot of magnetic material magnetic strength;
FIG. 4 shows CeMOFs@Fe in application example 1 of the present invention 3 O 4 A curve graph of the adsorption quantity of the different addition quantities of the magnetic materials to the phosphorus in the water body along with time;
FIG. 5 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 FTIR plot before and after magnetic material adsorption;
FIG. 6 shows the temperature of CeMOFs@Fe at different temperatures in application example 2 of the present invention 3 O 4 An influence diagram of the adsorption capacity of the magnetic material;
FIG. 7 shows initial pH vs. CeMOFs@Fe in application example 3 of the present invention 3 O 4 A change chart of pH of the solution before and after adsorption, wherein the influence of adsorption of phosphate by the magnetic material;
FIG. 8 shows the coexisting ion pair CeMOFs@Fe in application example 4 of the present invention 3 O 4 An influence diagram of adsorption of phosphate by the magnetic material;
FIG. 9 shows CeMOFs, fe in comparative example 1 of the present invention 3 O 4 And CeMOFs@Fe 3 O 4 Graph of phosphorus removal rate over time in water.
Detailed Description
The invention provides a CeMOFs@Fe 3 O 4 The preparation method of the magnetic material comprises the following steps:
(1) Dissolving soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and performing a hydrothermal reaction (denoted as first hydrothermal reaction) to obtain CeMOFs@Fe 3 O 4 A precursor;
(2) The CeMOFs@Fe 3 O 4 Activating the precursor to obtain CeMOFs@Fe 3 O 4 A magnetic material.
In the present invention, each of the substances is commercially available as known to those skilled in the art unless otherwise specified.
The invention uses soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and performing a hydrothermal reaction (denoted as first hydrothermal reaction) to obtain CeMOFs@Fe 3 O 4 A precursor. In the present invention, the soluble cerium salt and water-soluble Fe 3 O 4 The molar ratio of the particles is preferably 2 to 10:1, more preferably 4:1; the terephthalic acid and water-soluble Fe 3 O 4 The molar ratio of the particles is preferably 1 to 5:1, more preferably 1:1; the soluble cerium salt preferably comprises Ce (NO 3 ) 3 、CeCl 3 And Ce (Ce) 2 (SO 4 ) 3 One of them is more preferably Ce (NO 3 ) 3 ·6H 2 O; the mixing is preferably performed by mixing a soluble cerium salt and water-soluble Fe 3 O 4 Carrying out first ultrasonic mixing on the particles in dimethylformamide to obtain a first mixed solution; performing second ultrasonic mixing on terephthalic acid and the first mixed solution; the time of the first mixing is preferably 20-60 min; the second mixing time is preferably 10 to 60 minutes. Due to water-solubility of Fe 3 O 4 The particles are easy to agglomerate and difficult to load on the surface of CeMOFs, the invention adopts ultrasonic waves, and controls the ultrasonic time to lead the water-soluble Fe 3 O 4 The particles are uniformly dispersed in the mixed solution. The invention strictly controls the soluble cerium salt and the water-soluble Fe 3 O 4 Molar ratio of the particles, ensures water-solubility Fe 3 O 4 The particles are better supported on the surface of the CeMOFs. The invention adopts terephthalic acid as an organic ligand to obtain MIL-101 CeMOFs@Fe 3 O 4 The magnetic material has the characteristics of high porosity, large specific surface area and good water stability, is favorable for adsorbing phosphate and improves the dephosphorization effect.
In the present invention, the temperature of the first hydrothermal reaction is preferably 110 to 170 ℃, more preferably 140 ℃, and the time is preferably 16 to 24 hours, more preferably 20 hours; the first hydrothermal reaction equipment is preferably a polytetrafluoroethylene reaction kettle, and in the specific embodiment of the invention, the reaction raw materials are preferably placed in the polytetrafluoroethylene reaction kettle, and then the polytetrafluoroethylene reaction kettle is placed in an oven for reaction.
After the first hydrothermal reaction is completed, the reaction liquid is naturally cooled to room temperature, and then CeMOFs@Fe is cooled by using a magnet 3 O 4 The precursor is separated from the reaction liquid, and then CeMOFs@Fe is treated 3 O 4 Washing and drying the precursor; the washing solvent is preferably dimethylformamide; the number of times of washing is preferably 3; the drying mode is preferably drying; the drying temperature is preferably 50-70 ℃ and the drying time is preferably 10-14 h.
In the present invention, the water-soluble Fe 3 O 4 The particles are preferably water-soluble nano Fe 3 O 4 And (3) particles. In a specific embodiment of the invention, the water-soluble nano Fe 3 O 4 The preparation method of the particles is preferably as follows: sodium citrate, feCl 3 Mixing sodium acetate and glycol, and performing hydrothermal reaction (denoted as second hydrothermal reaction) to obtain water-soluble nano Fe 3 O 4 And (3) particles. In the present invention, the sodium citrate is preferably sodium citrate dihydrate; the FeCl 3 Preferably anhydrous FeCl 3 The method comprises the steps of carrying out a first treatment on the surface of the The mixing is preferably to mix sodium citrate dihydrate and anhydrous FeCl 3 In ethylene glycolThirdly, mixing to obtain a third mixed solution; fourth mixing sodium acetate with the third mixed solution; the third mixing is preferably performed under stirring conditions, and the stirring time is preferably 30-60 min; the sodium citrate and FeCl 3 Preferably 1:5.9; the fourth mixing is preferably to uniformly add sodium acetate into the third mixed solution for 10-12 times, and continuously stir for 30-60 min after the addition is finished; the molar ratio of the sodium citrate to the sodium acetate is preferably 1:21.5; the temperature of the second hydrothermal reaction is preferably 160-240 ℃, more preferably 200 ℃, and the time is preferably 10-15 h, more preferably 12h; the second hydrothermal reaction equipment is preferably a polytetrafluoroethylene reaction kettle, and in the specific embodiment of the invention, the reaction raw materials are preferably placed in the polytetrafluoroethylene reaction kettle, and then the polytetrafluoroethylene reaction kettle is placed in an oven for reaction.
After the second hydrothermal reaction is completed, the reaction liquid is naturally cooled to room temperature, and then the magnet is used for naturally cooling the water-soluble nano Fe 3 O 4 The particles are separated from the reaction liquid, and then the water-soluble nano Fe is treated 3 O 4 Washing, drying and grinding the particles; the washing solvent is preferably ethanol; the number of times of washing is preferably 3; the drying mode is preferably vacuum drying; the drying temperature is preferably 50-70 ℃, preferably 60 ℃, and the drying time is preferably 20-28 h, more preferably 24h; the method of grinding is not particularly limited, and the method well known to those skilled in the art can be selected. The invention grinds the obtained water-soluble nano Fe 3 O 4 The particles are uniformly dispersed.
Obtaining CeMOFs@Fe 3 O 4 After the precursor, the invention leads the CeMOFs@Fe to be 3 O 4 Activating the precursor to obtain CeMOFs@Fe 3 O 4 A magnetic material. In the present invention, the activation is preferably performed by CeMOFs@Fe 3 O 4 Mixing the precursor with methanol, and placing the mixture in an oven for activation; the CeMOFs@Fe 3 O 4 The volume ratio of the mass of the precursor to the methanol is 2g: 10-20 mL; the activation temperature is preferably 140 to 170 ℃, more preferably 150 DEG CThe time is preferably 16 to 24 hours, more preferably 20 hours. The invention can effectively remove substances and partial impurities which do not completely react in the pores through activation, enlarge the specific surface area and improve CeMOFs@Fe 3 O 4 Dephosphorization performance of the magnetic material.
The invention also provides CeMOFs@Fe prepared by the preparation method 3 O 4 Magnetic material comprising CeMOFs and Fe supported on the surface of the CeMOFs 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The CeMOFs@Fe 3 O 4 The particle size of the magnetic material is preferably 10 to 30 μm; with CeMOFs and Fe 3 O 4 In contrast, ceMOFs@Fe 3 O 4 The diffraction angles 2θ=51.99, 54.94 and 60.73 of the magnetic material have new peaks, indicating that cemofs@fe 3 O 4 The magnetic material is a new substance, ceMOFs@Fe 3 O 4 The magnetic material has excellent adsorption performance on phosphate in water body, and is matched with CeMOFs or Fe 3 O 4 Compared with the prior art, the method has higher adsorption saturation amount and faster adsorption rate, and has remarkable dephosphorization effect.
The invention also provides the CeMOFs@Fe adopting the technical scheme 3 O 4 The application of the magnetic material as the dephosphorization adsorbent. In the present invention, the CeMOFs@Fe 3 O 4 The adding amount of the magnetic material in the phosphorus-containing water body is preferably 0.04-0.10 g/L; the initial pH value of the phosphorus-containing water body is preferably 3-12, more preferably 4-10; the CeMOFs@Fe 3 O 4 The use temperature of the magnetic material is preferably 15-35 ℃; the adsorption time is preferably 1 to 24 hours, more preferably 1 to 6 hours.
To further illustrate the present invention, the present invention provides a CeMOFs@Fe composition as described in the following examples 3 O 4 Magnetic materials, and methods of making and using the same, are described in detail and are not to be construed as limiting the scope of the invention.
Example 1
(1) Will be 0.4gC 6 H 5 Na 3 O 7 ·2H 2 O and 1.3g anhydrous FeCl 3 Placing in 40mL of ethylene glycol, and fully stirring for 60min by using a magnetic stirrer to fully dissolve the ethylene glycol;
(2) Adding 2.4g of sodium acetate (NaAc) into the solution for continuous stirring for 60min for 12 times, and transferring the obtained solution into a 100mL polytetrafluoroethylene reaction kettle after the NaAc is completely dissolved;
(3) Placing a polytetrafluoroethylene reaction kettle in a baking oven, and reacting for 12 hours in the baking oven at 200 ℃ to obtain water-soluble nano Fe 3 O 4 The reaction liquid of the particles is naturally cooled to room temperature;
(4) The obtained water-soluble nano Fe is treated by using a black magnet 3 O 4 Separating the particles from the reaction solution, washing with ethanol for 3 times, collecting the obtained wet water-soluble nanometer Fe 3 O 4 Drying the particles in a vacuum drying oven at 60 ℃ for 24 hours, and then grinding uniformly;
(5) To 30mL of dimethylformamide was added 4 mmole Ce (NO 3 ) 3 ·6H 2 O and 1mmol of ground water-soluble nano Fe 3 O 4 Performing ultrasonic treatment on the granules for 20min to obtain a uniform mixed solution;
(6) 1mmol of terephthalic acid is added into the mixed solution, ultrasonic treatment is carried out for 10min, and then the obtained mixed solution is filled into a 50mL polytetrafluoroethylene reaction kettle;
(7) 50mL of polytetrafluoroethylene reaction kettle is placed in a 140 ℃ oven for reaction for 20 hours, and the catalyst containing CeMOFs@Fe is obtained 3 O 4 The reaction liquid of the precursor is cooled to room temperature, and CeMOFs@Fe in the reaction liquid is collected by a black magnet 3 O 4 The precursor was then rinsed with dimethylformamide, and the rinsing repeated 3 times, wet CeMOFs@Fe 3 O 4 Drying the precursor in a 60 ℃ oven for 12 hours;
(8) Drying 2g CeMOFs@Fe 3 O 4 Mixing the precursor with 10mL of methanol, and activating for 20h in a baking oven at 150 ℃ to obtain CeMOFs@Fe 3 O 4 A magnetic material.
FIG. 1 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 As can be seen from FIG. 1, the FE-SEM image of the magnetic material shows rods as CeMOFs and spherical particles as water-soluble nano Fe 3 O 4 Granule, water-soluble nano Fe 3 O 4 The particles are loaded on the surface of CeMOFs, and the particles and the CeMOFs are tightly combined.
FIG. 2 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 As can be seen from FIG. 2, the XRD patterns of the magnetic materials are CeMOFs@Fe 3 O 4 The position of the peak of the magnetic material and CeMOFs and Fe 3 O 4 All have partial coincidence, which indicates that the CeMOFs are successfully loaded with Fe 3 O 4 Particles, with CeMOFs and Fe 3 O 4 Compared with the peak position of CeMOFs@Fe 3 O 4 The magnetic material showed obvious new peaks at diffraction angles 2θ=51.99, 54.94 and 60.73, indicating that CeMOFs and Fe 3 O 4 The binding creates new chemical bonds, proving the creation of new species.
FIG. 3 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 From the VSM diagram of the magnetic strength of the magnetic material, it can be seen from FIG. 3 that CeMOFs@Fe 3 O 4 Has better magnetism.
In the application example of the invention, phosphate buffer solution is adopted to simulate a phosphorus-containing water body, and the preparation method of the phosphate buffer solution comprises the following steps:
solution A (0.2 mol/L sodium dihydrogen phosphate aqueous solution): naH (NaH) 2 PO 4 ·H 2 27.6g of O is dissolved in distilled water and diluted to 1000ml;
liquid B (0.2 mol/L disodium hydrogen phosphate aqueous solution): na (Na) 2 HPO 4 ·7H 2 53.6g of O is dissolved in distilled water and diluted to 1000ml;
31mL of A solution and 69 of mlB solution are mixed to obtain 0.2mol/L (6.2 g/L) of phosphate buffer solution, 80.6mL of 6.2g/L of phosphate buffer solution is diluted to 1000mL to obtain 0.5g/L of phosphate buffer solution, and 10mL of 0.5g/L of phosphate buffer solution is diluted to 1000mL to obtain 5mg/L of phosphate buffer solution.
Application example 1
0.008g, 0.010g, 0.012g, 0.014g, 0.016g, 0.018g and 0.020g of CeMOFs@Fe prepared in example 1 were respectively used 3 O 4 The magnetic material is put into 200mL phosphate buffer solution containing 5.0mg/L phosphorus (calculated by the mass of P element) and adsorbed at 25 ℃ and 150rpm6h；
The adsorbed solutions were sampled and analyzed for phosphate concentration by molybdate spectrophotometry, and FIG. 4 shows CeMOFs@Fe in application example 1 3 O 4 As can be seen from FIG. 4, ceMOFs@Fe 3 O 4 When the adding amount of the magnetic material is 0.050g/L, the dephosphorization effect is optimal, and the removal rate is 98.0%.
FIG. 5 shows CeMOFs@Fe obtained in example 1 of the present invention 3 O 4 FTIR of magnetic material before and after adsorption, wherein CeMOFs@Fe after adsorption 3 O 4 As can be seen from FIG. 5, the magnetic material was 624cm in the spectrum before and after adsorption under the conditions of 0.010g of the magnetic material corresponding to application example 1 -1 Characteristic peaks appear at the positions, but do not appear in the CeMOFs spectrogram, and the stretching vibration of Fe-O is positioned at 613cm -1 Here, it is shown that the CeMOFs successfully loaded Fe 3 O 4 And (3) particles. It can be seen in the infrared spectrum after adsorption that the infrared spectrum is 1046cm -1 With obvious PO4 3- The antisymmetric and telescopic characteristic peak of (2) shows that the phosphate radical is reacted by CeMOFs@Fe 3 O 4 Adsorbed by the magnetic material.
Application example 2
18 parts by mass of CeMOFs@Fe prepared in example 1 were mixed together to give a mixture of 0.010g 3 O 4 The magnetic material is respectively put into 3 parts of phosphate buffer solution containing 2.5mg/L, 5mg/L, 10mg/L, 20mg/L, 30mg/L or 50mg/L (calculated by the mass of P element) of the same volume, wherein each part of phosphate buffer solution is 200mL, and each three parts of phosphate buffer solution containing the same phosphorus concentration are respectively adsorbed for 24 hours at 15 ℃, 25 ℃ and 35 ℃.
Samples were taken from each of the adsorbed solutions, and the concentration of phosphate was analyzed by molybdate spectrophotometry, and FIG. 6 shows the difference in ambient temperature versus CeMOFs@Fe in application example 2 3 O 4 As can be seen from FIG. 6, the adsorption capacity of the magnetic material is fitted by using a Freundlich isothermal model, and CeMOFs@Fe is calculated at 25 DEG C 3 O 4 The theoretical saturated adsorption quantity of the magnetic material to phosphate is 132.92 mg.g -1 Is substantially in accordance with the actual measured data (the measured adsorption amount is 119.79 mg.g) -1 ) And relative to CeMOFs98.79 mg.g -1 The saturated adsorption capacity of the catalyst is greatly improved. From this, it can be seen that CeMOFs@Fe is higher in the external environment temperature 3 O 4 The larger the adsorption amount of the magnetic material to the phosphate is, the adsorption reaction of the material is an endothermic reaction.
Application example 3
200ml of phosphate buffer solution having a phosphorus content of 5.0mg/L (calculated as the mass of P element) was adjusted to pH=3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 with 0.1mol/L NaOH and HCl, respectively, and 0.010g of CeMOFs@Fe prepared in example 1 was added 3 O 4 The magnetic materials were put into the respective cases and adsorbed at 25℃and 150rpm for 24 hours.
Samples were taken from the above adsorbed solutions, and phosphate concentration analysis was performed by molybdate spectrophotometry, and FIG. 7 shows the initial pH vs. CeMOFs@Fe in application example 3 3 O 4 As can be seen from FIG. 7, ceMOFs@Fe, the effect of adsorption of phosphate by the magnetic material and the pH change of the solution before and after adsorption 3 O 4 The magnetic material can adapt to a wide pH, and the initial pH is in the range of 3-12.
Application example 4
4 parts by mass of CeMOFs@Fe prepared in example 1 were mixed together to give a mixture of 0.010g 3 O 4 Magnetic materials respectively added with SO 4 2- 、Cl - 、NO 3 - 、CO 3 2- In a phosphate buffer solution containing 5.0mg/L (calculated as the mass of P element) of phosphorus at 25 ℃ and 150rpm for 24 hours, wherein SO 4 2- 、Cl - 、NO 3 - 、CO 3 2- With PO (PO) 4 2- The molar ratio of (2) is 40: 1. 20:1, 10: 1. 5:1, a step of;
the above-mentioned adsorbed solutions were sampled and analyzed for phosphate concentration by molybdate spectrophotometry, and FIG. 8 shows the coexisting ion pair CeMOFs@Fe in application example 4 3 O 4 As can be seen from FIG. 8, ceMOFs@Fe prepared in example 1 3 O 4 Magnetic materialMaterial at S0 4 2- 、Cl - 、NO 3 - The dephosphorization efficiency is not affected in the presence, the phosphate ion removal rate is more than 90 percent, and the phosphate ion removal rate is equal to or higher than CO 3 2- In the presence of the ion, the removal of phosphate ions is affected.
Comparative example 1
20mg of CeMOFs@Fe prepared in example 1 were reacted 3 O 4 Magnetic material, 20mg CeMOFs and 20mg water-soluble nano Fe after grinding in step (4) of example 1 3 O 4 The granules are respectively put into 200mL phosphate buffer solution containing 5.0mg/L phosphorus (calculated by the mass of P element) and adsorbed for 60min at 25 ℃ and 150 rpm;
the preparation method of the CeMOFs comprises the following steps:
to 30mL of dimethylformamide was added 4 mmole Ce (NO 3 ) 3 ·6H 2 O, carrying out ultrasonic treatment for 20min to obtain a uniform mixed solution;
1mmol of terephthalic acid is added into the mixed solution, ultrasonic treatment is carried out for 10min, and then the obtained mixed solution is filled into a 50mL polytetrafluoroethylene reaction kettle;
placing 50mL of polytetrafluoroethylene reaction kettle in a 140 ℃ oven for reaction for 20 hours to obtain a reaction solution containing a CeMOFs precursor, then performing centrifugal separation on the reaction solution containing the CeMOFs precursor to obtain a solid part, then washing the solid part with dimethylformamide, repeating the washing for 3 times to obtain a wet CeMOFs precursor, and placing the wet CeMOFs precursor in the 60 ℃ oven for drying for 12 hours;
the dried 2g CeMOFs precursor was mixed with 10mL methanol and activated in an oven at 150℃for 20h to give CeMOFs material.
The above adsorbed solutions were sampled and analyzed for phosphate concentration by molybdate spectrophotometry, and FIG. 9 shows CeMOFs, fe 3 O 4 And CeMOFs@Fe 3 O 4 As can be seen from FIG. 9, ceMOFs@Fe 3 O 4 The dephosphorization efficiency of the catalyst is greatly improved compared with that of CeMOFs, mainly because of CeMOFs@Fe 3 O 4 The magnetic material being present with a new substance, the substance beingHelps to improve CeMOFs@Fe 3 O 4 Is used for the phosphorus removal performance of the steel.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (9)
1. CeMOFs@Fe 3 O 4 The preparation method of the magnetic material is characterized by comprising the following steps:
(1) Dissolving soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and performing hydrothermal reaction to obtain CeMOFs@Fe 3 O 4 A precursor;
(2) The CeMOFs@Fe 3 O 4 Activating the precursor to obtain CeMOFs@Fe 3 O 4 A magnetic material;
the soluble cerium salt and water-soluble Fe 3 O 4 The molar ratio of the particles is 2-10:1; the terephthalic acid and water-soluble Fe 3 O 4 The molar ratio of the particles is 1-5:1.
2. The method of claim 1, wherein the soluble cerium salt comprises Ce (NO 3 ) 3 、CeCl 3 And Ce (Ce) 2 (SO 4 ) 3 One of the following; the water-soluble Fe 3 O 4 The particles are water-soluble nano Fe 3 O 4 And (3) particles.
3. The method of claim 2, wherein the water-soluble nano Fe 3 O 4 The preparation method of the particles comprises the following steps:
sodium citrate, feCl 3 Mixing sodium acetate and glycol, and performing hydrothermal reaction to obtain water-soluble nano Fe 3 O 4 And (3) particles.
4. A production method according to any one of claims 1 to 3, wherein the mixing is performed by mixing a soluble cerium salt and water-soluble Fe 3 O 4 Carrying out first ultrasonic mixing on the particles in dimethylformamide to obtain a first mixed solution; and carrying out second ultrasonic mixing on the terephthalic acid and the first mixed solution.
5. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 110 to 170 ℃ for a time of 16 to 24 hours.
6. The method according to claim 1, wherein the activation temperature is 140 to 170 ℃ for 16 to 24 hours.
7. CeMOFs@Fe obtained by the preparation method as claimed in any one of claims 1 to 6 3 O 4 A magnetic material.
8. The cemofs@fe of claim 7 3 O 4 The application of the magnetic material as the dephosphorization adsorbent.
9. The use according to claim 8, wherein the cemofs@fe 3 O 4 The adding amount of the magnetic material in the phosphorus-containing water body is 0.04-0.10 g/L; the initial pH value of the phosphorus-containing water body is 3-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211585350.XA CN115770559B (en) | 2022-12-09 | 2022-12-09 | Cerium metal organic framework magnetic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211585350.XA CN115770559B (en) | 2022-12-09 | 2022-12-09 | Cerium metal organic framework magnetic material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115770559A CN115770559A (en) | 2023-03-10 |
| CN115770559B true CN115770559B (en) | 2024-03-15 |
Family
ID=85391886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211585350.XA Active CN115770559B (en) | 2022-12-09 | 2022-12-09 | Cerium metal organic framework magnetic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115770559B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112316906A (en) * | 2020-09-21 | 2021-02-05 | 中国建筑第二工程局有限公司 | Preparation method of ferromagnetic amino-modified lanthanide metal organic framework material and application of material in adsorption and dephosphorization |
| CN112604660A (en) * | 2020-11-27 | 2021-04-06 | 华侨大学 | Preparation method and application of Ce-MOFs phosphorus removal adsorbent |
| CN113702538A (en) * | 2021-09-02 | 2021-11-26 | 中国烟草总公司郑州烟草研究院 | Magnetic porous carbon-based QuEChERS purification material and application thereof in sample pretreatment and tobacco pesticide residue detection |
| CN115254071A (en) * | 2022-08-04 | 2022-11-01 | 华侨大学 | Magnetic metal organic framework composite material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11345615B2 (en) * | 2019-11-13 | 2022-05-31 | King Fahd University Of Petroleum And Minerals | Activated carbon-iron/cerium oxide nanocomposite suitable for dye removal |
-
2022
- 2022-12-09 CN CN202211585350.XA patent/CN115770559B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112316906A (en) * | 2020-09-21 | 2021-02-05 | 中国建筑第二工程局有限公司 | Preparation method of ferromagnetic amino-modified lanthanide metal organic framework material and application of material in adsorption and dephosphorization |
| CN112604660A (en) * | 2020-11-27 | 2021-04-06 | 华侨大学 | Preparation method and application of Ce-MOFs phosphorus removal adsorbent |
| CN113702538A (en) * | 2021-09-02 | 2021-11-26 | 中国烟草总公司郑州烟草研究院 | Magnetic porous carbon-based QuEChERS purification material and application thereof in sample pretreatment and tobacco pesticide residue detection |
| CN115254071A (en) * | 2022-08-04 | 2022-11-01 | 华侨大学 | Magnetic metal organic framework composite material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Fabrication of magnetic cerium-organic framework-activated carbon composite for charged dye removal from aqueous solutions;Roxana Paz et al.;《Journal of Molecular Liquids》;20210526;第337卷;116578（1-13） * |
| La‑MOFs in situ loaded Al2O3 particles for effective removal of phosphate in water: characterization, application potential analysis, and mechanism;Huiying Ai et al.;《Environmental Science and Pollution Research》;20231005;第30卷;110901–110912 * |
| 磁性金属有机骨架材料Fe_3O_4@NH_2-MIL-53(Al)的制备及对铅的吸附研究;赵方彪;宋乃忠;宁维坤;贾琼;;光谱学与光谱分析;20150915(09);全文 * |
| 磁性金属有机骨架材料吸附分离靛蓝二磺酸钠;吴晨;刘涛;陈立钢;丁杰;;环境科学与技术;20171015(10);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115770559A (en) | 2023-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Applications of water-stable metal-organic frameworks in the removal of water pollutants: A review | |
| Jia et al. | Adsorption removal and reuse of phosphate from wastewater using a novel adsorbent of lanthanum-modified platanus biochar | |
| Qiu et al. | Preferable phosphate sequestration by nano-La (III)(hydr) oxides modified wheat straw with excellent properties in regeneration | |
| Liu et al. | Efficient recovery of phosphate from simulated urine by Mg/Fe bimetallic oxide modified biochar as a potential resource | |
| Asadollahzadeh et al. | Extraction and separation of rare earth elements by adsorption approaches: current status and future trends | |
| Pan et al. | HKUST-1 derived carbon adsorbents for tetracycline removal with excellent adsorption performance | |
| Xu et al. | 2D water-stable zinc-benzimidazole framework nanosheets for ultrafast and selective removal of heavy metals | |
| CN103657596B (en) | Synthesis method of magnetic metal organic framework composite material | |
| US20220219142A1 (en) | Polymeric lanthanum nanocomposite, and preparation method and application thereof | |
| Ren et al. | Defective SO3H-MIL-101 (Cr) for capturing different cationic metal ions: Performances and mechanisms | |
| CN110237820B (en) | Preparation method and application of microwave-assisted magnetic hollow Zn/Co zeolite imidazole nanocage material | |
| Yang et al. | Synthesis of ZIF-8@ GO-COOH and its adsorption for Cu (II) and Pb (II) from water: Capability and mechanism | |
| CN102063988A (en) | Magnetic clay material and preparation method thereof | |
| CN101574641A (en) | Environment-friendly carbon nanotube/sodium alginate heavy metal ion sorbing material and preparation method thereof | |
| CN112316906A (en) | Preparation method of ferromagnetic amino-modified lanthanide metal organic framework material and application of material in adsorption and dephosphorization | |
| JP5352853B1 (en) | Method of treating radioactive Cs contaminated water | |
| Mola ali abasiyan et al. | Polyvinyl alcohol-based nanocomposite hydrogels containing magnetic laponite RD to remove cadmium | |
| CN112521617A (en) | Polyacid-based metal organic framework material for adsorbing antibiotics and preparation method and application thereof | |
| JP5744940B2 (en) | Method for treating radioactive Cs-contaminated water, radioactive Cs adsorbent and method for producing the same | |
| Xia et al. | Phosphorus hyperaccumulation in nano-MgO using a circular recovery process based on multiple phase transitions from periclase to brucite | |
| Liu et al. | Three-dimensional porous aerogel-bead absorbent with high dispersibility of lanthanum active sites to boost phosphorus scavenging | |
| CN110026169A (en) | A kind of polymer-based nano lanthanum carbonate material, preparation method, application and regeneration method | |
| CN113318740B (en) | Cu 2 O/MgFe 2 O 4 Catalyst, preparation method and application thereof | |
| Li et al. | Green water-etching synthesized La-MIL-101 (Fe)-NH2@ SiO2 yolk-shell nanocomposites with superior pH stability for efficient and selective phosphorus recovery | |
| CN115770559B (en) | Cerium metal organic framework magnetic material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |