CN115770559A - 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
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- 239000000696 magnetic material Substances 0.000 title claims abstract description 73
- 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
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 150000000703 Cerium Chemical class 0.000 claims abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 40
- 239000011574 phosphorus Substances 0.000 claims description 40
- 229910052698 phosphorus Inorganic materials 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 9
- 239000001632 sodium acetate Substances 0.000 claims description 9
- 235000017281 sodium acetate Nutrition 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 7
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- 239000001509 sodium citrate Substances 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 238000001179 sorption measurement Methods 0.000 abstract description 34
- 239000000463 material Substances 0.000 abstract description 11
- 239000011148 porous material Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- 229910019142 PO4 Inorganic materials 0.000 description 20
- 235000021317 phosphate Nutrition 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 17
- 239000010452 phosphate Substances 0.000 description 16
- -1 phosphate radicals Chemical class 0.000 description 15
- 239000008055 phosphate buffer solution Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
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- 239000012295 chemical reaction liquid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
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- 235000011176 polyphosphates Nutrition 0.000 description 2
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- 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
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000004480 active ingredient Substances 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 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
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 238000007885 magnetic separation Methods 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 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
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- 239000002101 nanobubble Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000008363 phosphate buffer 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
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
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- 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 1
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Abstract
The invention relates to the technical field of adsorption materials, in particular to CeMOFs @ Fe 3 O 4 Magnetic material and its preparation method and application. The invention uses soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and carrying out hydrothermal reaction to obtain CeMOFs @ Fe 3 O 4 A precursor; subjecting 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 net structure and a rich pore structure through one-step hydrothermal reaction, and simultaneously uses water-soluble Fe 3 O 4 The particles are loaded on the surface of CeMOFs, and activation treatment is carried out to finally obtain CeMOFs @ Fe with stable structure and large specific surface area 3 O 4 A magnetic material. The preparation method provided by the invention is simple to operate, easy to implement and free of harsh conditions.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to CeMOFs @ Fe 3 O 4 Magnetic material and its preparation method and application.
Background
Excessive phosphorus in the water ecosystem can cause the mass propagation of algae, cause the eutrophication of water bodies, cause the mass death of aquatic organisms and destroy the water quality of the water bodies. The phosphorus in the water body comprises orthophosphate, organic phosphorus and polyphosphate, and the organic phosphorus is finally converted into inorganic phosphate through the action of microorganisms, and the polyphosphate is also partially converted into orthophosphate through hydrolysis, so that the removal of the excessive phosphorus element in the water body is mainly to remove the 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 adds calcium, aluminum, iron and other ions into the phosphorus-containing wastewater to form insoluble substances with phosphate for dephosphorization, but a large amount of sludge is easily generated in the using process; the biological method adopts the ecological floating bed, the composite technology of micro-nano bubbles and an immersed resin floating bed, the addition of efficient composite bacteria and other methods to treat the phosphorus-containing wastewater, but the treatment period is longer and the reaction process is more complex; the adsorption method has the advantages of simple operation, no generation of a large amount of sludge and the like, and is a method with application significance. At present, metal organic framework Materials (MOFs) and cerium rare earth elements are combined to prepare CeMOFs, but the CeMOFs has small particle size and is difficult to separate from water after adsorption, so that the practical application of the CeMOFs in engineering is limited.
Disclosure of Invention
In view of the above problems, the present invention is to provide CeMOFs @ Fe 3 O 4 Magnetic material, preparation method and application thereof, and CeMOFs @ Fe obtained by the preparation method provided by the invention 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 CeMOFs @ Fe 3 O 4 The preparation method of the magnetic material comprises the following steps:
(1) Mixing soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and carrying out hydrothermal reaction to obtain CeMOFs @ Fe 3 O 4 A precursor;
(2) Subjecting 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 the water-soluble Fe 3 O 4 The mol ratio of the particles is 2-10; the terephthalic acid and water-soluble Fe 3 O 4 The molar ratio of the particles is 1-5.
Preferably, the soluble cerium salt comprises Ce (NO) 3 ) 3 、CeCl 3 And Ce 2 (SO 4 ) 3 One of (1); the water-soluble Fe 3 O 4 The particles are water-soluble nano Fe 3 O 4 And (3) granules.
Preferably, the water-soluble nano Fe 3 O 4 The preparation method of the particles comprises the following steps:
mixing sodium citrate and FeCl 3 Mixing sodium acetate and glycol for reaction to obtain water-soluble nano Fe 3 O 4 And (3) granules.
Preferably, the mixing is carried out by mixing soluble cerium salt and water-soluble Fe 3 O 4 The particles are in dimethylformamideCarrying out first ultrasonic mixing in amine to obtain a first mixed solution; 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 activation time is 16-24 h.
The invention also comprises CeMOFs @ Fe in the technical scheme 3 O 4 A magnetic material.
The invention also comprises CeMOFs @ Fe in the technical scheme 3 O 4 The magnetic material is applied as a phosphorus removal adsorbent.
Preferably, said 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 CeMOFs @ Fe 3 O 4 The preparation method of the magnetic material comprises the following steps:
(1) Mixing soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and carrying out 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 net 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 CeMOFs, and activation treatment is carried out to finally obtain CeMOFs @ Fe with stable structure and large specific surface area 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 CeMOFs @ Fe in the technical scheme 3 O 4 Magnetic material, the invention uses CeMOFs @ Fe 3 O 4 The magnetic material has a mutually cross-linked net structure and rich pore structures, so that active ingredients in the material are fully contacted with phosphate radicals in water, the phosphate can be effectively adsorbed, and the problem of the traditional method is solvedThe phosphorus removal material has the defects of low efficiency of removing low-concentration phosphorus in the practical application process and the like.
The invention utilizes CeMOFs @ Fe 3 O 4 Fe supported on magnetic material 3 O 4 The particles have stronger magnetism, can promote the stable structure of the material, and can be directly separated and recovered from the solution medium by adopting a magnetic separation mode.
The invention produces the Fe and CeMOFs through the coupling effect 3 O 4 The new phosphorus removal material CeMOFs @ Fe 3 O 4 The material has larger specific surface area, ceMOFs or Fe 3 O 4 Compared with the prior art, the phosphorus removal adsorbent has excellent adsorption performance on phosphate in water, higher adsorption saturation amount and higher adsorption rate, and has obvious phosphorus removal effect.
Drawings
FIG. 1 shows CeMOFs @ Fe obtained in example 1 of the present invention 3 O 4 FE-SEM images of the magnetic material;
FIG. 2 shows CeMOFs @ Fe obtained in example 1 of the present invention 3 O 4 XRD pattern of magnetic material;
FIG. 3 shows CeMOFs @ Fe obtained in example 1 of the present invention 3 O 4 A VSM plot of magnetic strength of a magnetic material;
FIG. 4 is CeMOFs @ Fe in application example 1 of the present invention 3 O 4 A time-dependent change curve chart of the adsorption quantity of the magnetic material to the phosphorus in the water body in different adding amounts;
FIG. 5 shows CeMOFs @ Fe obtained in example 1 of the present invention 3 O 4 FTIR patterns before and after magnetic material adsorption;
FIG. 6 shows the temperature of different environments vs. CeMOFs @ Fe in application example 2 of the present invention 3 O 4 Influence graph of magnetic material adsorption capacity;
FIG. 7 is the initial pH vs. CeMOFs @ Fe in application example 3 of the present invention 3 O 4 The influence of the magnetic material on adsorbing phosphate and the change of the pH value of the solution before and after adsorption are shown;
FIG. 8 shows the coexisting ion pair CeMOFs @ Fe in application example 4 of the present invention 3 O 4 Influence graph of phosphate adsorption of magnetic material;
FIG. 9 shows CeMOFs and Fe in comparative example 1 of the present invention 3 O 4 And CeMOFs @ Fe 3 O 4 The phosphorus removal rate in water is plotted against time.
Detailed Description
The invention provides CeMOFs @ Fe 3 O 4 The preparation method of the magnetic material comprises the following steps:
(1) Mixing soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and carrying out hydrothermal reaction (denoted as a first hydrothermal reaction) to obtain CeMOFs @ Fe 3 O 4 A precursor;
(2) Subjecting the CeMOFs @ Fe 3 O 4 Activating the precursor to obtain CeMOFs @ Fe 3 O 4 A magnetic material.
In the present invention, unless otherwise specified, each of the substances is a commercially available product well known to those skilled in the art.
The invention uses soluble cerium salt and water-soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and carrying out hydrothermal reaction (denoted as first hydrothermal reaction) to obtain CeMOFs @ Fe 3 O 4 And (3) precursor. In the present invention, the soluble cerium salt and the water-soluble Fe 3 O 4 The molar ratio of the particles is preferably 2 to 10, more preferably 4; the terephthalic acid and water-soluble Fe 3 O 4 The molar ratio of the particles is preferably 1 to 5, more preferably 1; the soluble cerium salt preferably comprises Ce (NO) 3 ) 3 、CeCl 3 And Ce 2 (SO 4 ) 3 More preferably Ce (NO) 3 ) 3 ·6H 2 O; the mixing is preferably carried out by mixing a soluble cerium salt and a water soluble Fe 3 O 4 Carrying out first ultrasonic mixing on the particles in dimethylformamide to obtain a first mixed solution; carrying out second ultrasonic mixing on the terephthalic acid and the first mixed solution; the time of the first mixing is preferably 20 to 60min; the time of the second mixing is preferably 10 to 60min. Due to water-soluble Fe 3 O 4 The particles are easy to agglomerate and are difficult to load on the surface of CeMOFs, and the invention adopts ultrasoundAnd controlling the ultrasonic time to make 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 The mol ratio of the particles ensures the water solubility of Fe 3 O 4 The particles are better loaded on the surface of CeMOFs. The invention adopts terephthalic acid as an organic ligand to obtain MIL-101 type 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 device is preferably a polytetrafluoroethylene reaction kettle, and in a specific embodiment of the present 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 solution is preferably naturally cooled to room temperature, and then CeMOFs @ Fe is processed by using a magnet 3 O 4 Separating the precursor from the reaction solution, and then subjecting to CeMOFs @ Fe 3 O 4 Washing and drying the precursor; the washing solvent is preferably dimethylformamide; the number 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) granules. In a specific embodiment of the present invention, the water-soluble nano-Fe 3 O 4 The preparation method of the particles is preferably as follows: mixing sodium citrate and FeCl 3 Mixing sodium acetate and ethylene glycol, and then carrying out hydrothermal reaction (marked 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 (ii) a The mixing is preferably performed by mixing citric acid dihydrateSodium and anhydrous FeCl 3 Performing third mixing in ethylene glycol to obtain a third mixed solution; performing fourth mixing on sodium acetate and the third mixed solution; the third mixing is preferably carried out under stirring conditions, and the stirring time is preferably 30-60 min; the sodium citrate and FeCl 3 Preferably 1; the fourth mixing is preferably to divide the sodium acetate equally for 10 to 12 times and add the sodium acetate to the third mixed solution, and the sodium acetate is continuously stirred for 30 to 60min after the addition; the molar ratio of sodium citrate to sodium acetate is preferably 1; 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 device is preferably a polytetrafluoroethylene reaction kettle, and in a specific embodiment of the present 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 finished, the invention preferably naturally cools the obtained reaction liquid to room temperature, and then uses a magnet to dissolve the water-soluble nano Fe 3 O 4 Separating the particles from the reaction solution, and then adding water-soluble nano Fe 3 O 4 Washing, drying and grinding the particles; the washing solvent is preferably ethanol; the number of washing is preferably 3; the drying mode is preferably vacuum drying; the drying temperature is preferably 50-70 ℃, preferably 60 ℃, and the time is preferably 20-28 h, and more preferably 24h; the mode of grinding is not particularly required in the present invention, and a mode 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 uses CeMOFs @ Fe 3 O 4 Activating the precursor to obtain CeMOFs @ Fe 3 O 4 A magnetic material. In the present invention, the activation is preferably CeMOFs @ Fe 3 O 4 Mixing the precursor with methanol, and then placing the mixture in an oven for activation; the CeMOFs @ Fe 3 O 4 The mass of the precursor to the volume ratio of methanol is 2g: 10-20 mL; said activationThe temperature of (A) is preferably 140 to 170 ℃, more preferably 150 ℃, and the time is preferably 16 to 24 hours, more preferably 20 hours. The invention can effectively remove incompletely reacted substances and partial impurities in pores through activation, enlarge the specific surface area, and improve CeMOFs @ Fe 3 O 4 And the phosphorus removal performance of the magnetic material.
The invention also provides CeMOFs @ Fe prepared by the preparation method of the technical scheme 3 O 4 Magnetic material comprising CeMOFs and Fe loaded on the surface of the CeMOFs 3 O 4 (ii) a 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 magnetic material has new peaks at diffraction angles 2 θ =51.99, 54.94 and 60.73, illustrating 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 and is CeMOFs or Fe 3 O 4 Compared with the prior art, the phosphorus removal catalyst has higher adsorption saturation amount and higher adsorption rate, and has obvious phosphorus removal effect.
The invention also provides CeMOFs @ Fe in the technical scheme 3 O 4 The magnetic material is applied as a phosphorus removal adsorbent. In the present invention, said 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, and 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.
In order to further illustrate the invention, the following examples are combined to provide a CeMOFs @ Fe 3 O 4 The magnetic materials and their preparation and use are described in detail but they are not to be construed as limiting the scope of the invention.
Example 1
(1) 0.4gC 6 H 5 Na 3 O 7 ·2H 2 O and 1.3g of anhydrous FeCl 3 Placing in 40mL of ethylene glycol, and filling with a magnetic stirrerStirring for 60min to dissolve completely;
(2) Adding 2.4g of sodium acetate (NaAc) into the solution evenly for 12 times, continuously stirring for 60min, and after NaAc is completely dissolved, transferring the obtained solution into a 100mL polytetrafluoroethylene reaction kettle;
(3) Placing the polytetrafluoroethylene reaction kettle in an oven, and reacting for 12h in the oven at 200 ℃ to obtain water-soluble nano Fe 3 O 4 The reaction solution 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, and collecting the wet water-soluble nano Fe 3 O 4 Drying the granules in a vacuum drying oven at 60 ℃ for 24 hours, and then uniformly grinding;
(5) To 30mL of dimethylformamide was added 4mmol of Ce (NO) 3 ) 3 ·6H 2 O and 1mmol of ground water-soluble nano Fe 3 O 4 Carrying out ultrasonic treatment on the particles for 20min to obtain a uniform mixed solution;
(6) Adding 1mmol of terephthalic acid into the mixed solution, performing ultrasonic treatment for 10min, and then putting the obtained mixed solution into a 50mL polytetrafluoroethylene reaction kettle;
(7) Placing a 50mL polytetrafluoroethylene reaction kettle in an oven at 140 ℃ for reaction for 20h to obtain a product containing CeMOFs @ Fe 3 O 4 Cooling the reaction kettle to room temperature, and collecting CeMOFs @ Fe in the reaction solution by using a black magnet 3 O 4 Precursor, then cleaning with dimethylformamide, cleaning repeatedly for 3 times, wet CeMOFs @ Fe 3 O 4 Drying the precursor in an oven at 60 ℃ for 12h;
(8) Drying 2gCeMOFs @ Fe 3 O 4 Mixing the precursor with 10mL of methanol, and activating in a 150 ℃ oven for 20h 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 shown in FIG. 1, the magnetic material has an FE-SEM image in which the rod-like objects are CeMOFs and the spherical particles are water-soluble nano Fe 3 O 4 Granular, water-soluble nano-Fe 3 O 4 The particles are loaded on the surface of CeMOFs, and the CeMOFs are tightly combined.
FIG. 2 shows CeMOFs @ Fe obtained in example 1 of the present invention 3 O 4 XRD pattern of magnetic material, from FIG. 2, ceMOFs @ Fe 3 O 4 Magnetic material peak position and CeMOFs and Fe 3 O 4 All have partial coincidence, which shows that Fe is successfully loaded on CeMOFs 3 O 4 Particles of CeMOFs and Fe 3 O 4 Compared with the peak position of CeMOFs @ Fe 3 O 4 The magnetic material has obvious new peaks at diffraction angles 2 theta =51.99, 54.94 and 60.73, which shows that CeMOFs and Fe 3 O 4 The binding produced a new chemical bond, demonstrating the production of a new species.
FIG. 3 shows CeMOFs @ Fe obtained in example 1 of the present invention 3 O 4 VSM graph of magnetic strength of magnetic material, as can be seen from FIG. 3, ceMOFs @ Fe 3 O 4 Has better magnetism.
In the application example of the invention, a 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 (sodium hydroxide) 2 PO 4 ·H 2 O27.6g is dissolved in distilled water and diluted to 1000ml;
solution B (0.2 mol/L aqueous disodium hydrogenphosphate solution): na (Na) 2 HPO 4 ·7H 2 O53.6g is dissolved in distilled water and diluted to 1000ml;
mixing 31mL of A solution and 69mL of B solution to obtain 0.2mol/L (6.2 g/L) of phosphate buffer solution, diluting 80.6mL of 6.2g/L of phosphate buffer solution to 1000mL to obtain 0.5g/L of phosphate buffer solution, and diluting 10mL of 0.5g/L of phosphate buffer solution 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, 0.020g CeMOFs @ Fe prepared in example 1 were added 3 O 4 The magnetic material was charged into 200mL of phosphate buffer containing 5.0mg/L of phosphorus (calculated as the mass of P element)Adsorbing in the solution at 25 deg.C and 150rpm for 6 hr;
the adsorbed solutions were sampled, and the concentration of phosphate was analyzed by molybdate spectrophotometry, and FIG. 4 shows CeMOFs @ Fe in application example 1 3 O 4 The change curve of the adsorption amount of the magnetic material to phosphorus in the water body with time according to different adding amounts of the magnetic material can be known from FIG. 4, ceMOFs @ Fe 3 O 4 When the adding amount of the magnetic material is 0.050g/L, the phosphorus removal 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 patterns before and after adsorption of magnetic materials, wherein CeMOFs @ Fe after adsorption 3 O 4 The magnetic material was 624cm in the spectrum before and after the adsorption as can be seen from FIG. 5 under the condition of 0.010g of the magnetic material corresponding to application example 1 -1 The characteristic peak appears, but does not appear in the CeMOFs spectrogram, and the stretching vibration of Fe-O is positioned at 613cm -1 Here, it shows that Fe is successfully loaded on CeMOFs 3 O 4 And (3) granules. Can be seen in the infrared spectrogram after adsorption at 1046cm -1 Has obvious PO4 3- The antisymmetric expansion characteristic peak of (A) indicates that the phosphate radical is CeMOFs @ Fe after the reaction 3 O 4 The magnetic material is adsorbed.
Application example 2
18 parts by mass of 0.010g of CeMOFs @ Fe obtained in example 1 3 O 4 The magnetic materials are 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 weight of P element) with the same volume, wherein each part of phosphate buffer solution is 200mL, and each three parts of phosphate buffer solution with the same phosphorus concentration are respectively adsorbed for 24h at 15 ℃, 25 ℃ and 35 ℃.
Samples were taken from each solution after adsorption, and the concentration of phosphate was analyzed by molybdate spectrophotometry, and FIG. 6 is a graph of the application of CeMOFs @ Fe at different ambient temperatures in example 2 3 O 4 FIG. 6 shows an influence graph of the adsorption capacity of the magnetic material, which is obtained by fitting a Freundlich isothermal model and calculating CeMOFs @ Fe at 25 ℃ 3 O 4 Magnetic material for phosphateHas a theoretical saturated adsorption capacity of 132.92mg g -1 The adsorption quantity is basically consistent with the actually measured data (the actually measured adsorption quantity is 119.79mg g) -1 ) Relative to CeMOFs98.79mg g -1 The saturated adsorption capacity of the adsorbent is greatly improved. From this, it is understood that CeMOFs @ Fe is higher in the temperature of the external environment 3 O 4 The larger the adsorption amount of the magnetic material to the phosphate is, the more endothermic the adsorption reaction of the material is.
Application example 3
200ml of a phosphate buffer solution with a phosphorus content of 5.0mg/L (calculated as the mass of the P element) were 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 obtained in example 1 was added 3 O 4 The magnetic materials were separately charged therein and adsorbed at 25 ℃ for 24 hours at 150 rpm.
Samples were taken from the adsorbed solutions, and the concentrations of phosphates were analyzed by molybdate spectrophotometry, and FIG. 7 shows the initial pH vs. CeMOFs @ Fe in application example 3 3 O 4 The influence of the magnetic material on the adsorption of phosphate and the pH change of the solution before and after adsorption are shown in FIG. 7, in which CeMOFs @ Fe 3 O 4 The magnetic material can adapt to a wide pH range, and the initial pH range is 3-12.
Application example 4
4 parts by mass of 0.010g of CeMOFs @ Fe prepared in example 1 3 O 4 Magnetic materials, each of which is charged with a solution containing SO 4 2- 、Cl - 、NO 3 - 、CO 3 2- Is adsorbed at 150rpm for 24h at 25 ℃ in a phosphate buffer solution containing 5.0mg/L (calculated by the mass of the P element) of phosphorus, wherein the SO is 4 2- 、Cl - 、NO 3 - 、CO 3 2- And PO 4 2- All molar ratios of (A) to (B) are 40: 1. 20: 1. 5:1;
samples were taken from the adsorbed solutions, and the concentrations of phosphates were analyzed by molybdate spectrophotometry, and FIG. 8 shows the coexisting ion pair CeMOFs @ Fe in application example 4 3 O 4 FIG. 8 shows the effect of phosphate adsorption of the magnetic material, and the magnetic material obtained in example 1 was usedCeMOFs @ Fe of 3 O 4 Magnetic material in S0 4 2- 、Cl - 、NO 3 - The phosphorus removal efficiency is not affected under the existing conditions, the removal rate of phosphate radical ions is more than 90 percent, and the removal rate is in CO 3 2- The presence of the acid has an effect on the removal of phosphate ions.
Comparative example 1
20mg of CeMOFs @ Fe obtained in example 1 were added 3 O 4 Magnetic Material, 20mgCeMOFs and 20mg Water-soluble Nano Fe ground in step (4) of example 1 3 O 4 The particles are respectively put into 200mL phosphate buffer solution containing 5.0mg/L of phosphorus (calculated by the mass of P element), and are adsorbed for 60min under the conditions of 25 ℃ and 150 rpm;
the preparation method of the CeMOFs comprises the following steps:
to 30mL of dimethylformamide was added 4mmol of Ce (NO) 3 ) 3 ·6H 2 O, performing ultrasonic treatment for 20min to obtain a uniform mixed solution;
adding 1mmol of terephthalic acid into the mixed solution, performing ultrasonic treatment for 10min, and then putting the obtained mixed solution into a 50mL polytetrafluoroethylene reaction kettle;
placing a 50mL polytetrafluoroethylene reaction kettle in an oven at 140 ℃ for reacting for 20h to obtain reaction liquid containing a CeMOFs precursor, then carrying out centrifugal separation on the reaction liquid containing the CeMOFs precursor to obtain a solid part, then cleaning the solid part with dimethylformamide, repeating the cleaning for 3 times to obtain a wet CeMOFs precursor, and placing the wet CeMOFs precursor in the oven at 60 ℃ for drying for 12h;
and mixing the dried 2g of CeMOFs precursor with 10mL of methanol, and activating in an oven at 150 ℃ for 20h to obtain the CeMOFs material.
Samples were taken from the adsorbed solutions, and the concentrations of phosphates were analyzed by molybdate spectrophotometry, and CeMOFs and Fe are shown in FIG. 9 3 O 4 And CeMOFs @ Fe 3 O 4 As shown in FIG. 9, the removal rate of phosphorus in water was plotted with time by using CeMOFs @ Fe 3 O 4 The phosphorus removal efficiency of the phosphorus removal catalyst is greatly improved compared with that of CeMOFs, mainly because of CeMOFs @ Fe 3 O 4 The magnetic material has new substances which are helpful for improving CeMOFs @ Fe 3 O 4 The phosphorus removal performance of the material is improved.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that modifications and adaptations can be made by those skilled in the art without departing from the principle of the present invention, and should be considered as within the scope of the present invention.
Claims (10)
1. CeMOFs @ Fe 3 O 4 The preparation method of the magnetic material is characterized by comprising the following steps of:
(1) Mixing soluble cerium salt and water soluble Fe 3 O 4 Mixing the particles, terephthalic acid and dimethylformamide, and carrying out hydrothermal reaction to obtain CeMOFs @ Fe 3 O 4 A precursor;
(2) Subjecting the CeMOFs @ Fe 3 O 4 Activating the precursor to obtain CeMOFs @ Fe 3 O 4 A magnetic material.
2. The method of claim 1, wherein the soluble cerium salt and the water soluble Fe are present in the form of cerium salts and Fe salts 3 O 4 The mol ratio of the particles is 2-10; the terephthalic acid and water-soluble Fe 3 O 4 The molar ratio of the particles is 1-5.
3. The method of claim 1 or 2, wherein the soluble cerium salt comprises Ce (NO) 3 ) 3 、CeCl 3 And Ce 2 (SO 4 ) 3 One of (1); the water-soluble Fe 3 O 4 The particles are water-soluble nano Fe 3 O 4 And (3) granules.
4. The method according to claim 3, wherein the water-soluble nano Fe 3 O 4 The preparation method of the particles comprises the following steps:
mixing sodium citrate and FeCl 3 Mixing sodium acetate and ethylene glycol, and carrying out hydrothermal reaction to obtain water-soluble nano Fe 3 O 4 And (3) granules.
5. The method according to any one of claims 1 to 3, wherein the mixing is performed by mixing a soluble cerium salt and a 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.
6. The preparation method according to claim 1 or 2, characterized in that the temperature of the hydrothermal reaction is 110-170 ℃ and the time is 16-24 h.
7. The method according to claim 1, wherein the activation temperature is 140-170 ℃ and the activation time is 16-24 h.
8. CeMOFs @ Fe obtained by the production method according to any one of claims 1 to 7 3 O 4 A magnetic material.
9. CeMOFs @ Fe of claim 8 3 O 4 The magnetic material is applied as a phosphorus removal adsorbent.
10. Use according to claim 9, characterized in that said 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.
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