CN105148853A - Magnetic MOFs solid phase extraction adsorbent as well as preparation method and application thereof - Google Patents
Magnetic MOFs solid phase extraction adsorbent as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnetic MOFs solid phase extraction adsorbent as well as a preparation method and application thereof. The preparation method of the adsorbent comprises the following steps: (1) preparing magnetic Fe3O4 nanospheres with the particle size of 10-20 nm by adopting a coprecipitation method; (2) preparing Fe3O4@SiO2 with a core-shell structure by adopting a Stober silica gel coupling method; (3) preparing Fe3O4@SiO2@MOF by adopting an in-situ growth method; (4) adjusting the ratio of organic ligands in the synthesis process of the step 3 to prepare the amino-functionalized magnetic MOFs solid phase extraction adsorbent with different ratios, wherein the prepared magnetic MOFs solid phase extraction adsorbent comprises a magnetic Fe3O4 core as well as an SiO2 layer and an MOF layer covering the Fe3O4 core from the inside to outside in sequence, and the MOF layer is MIL-53(NH2) or MIL-100. The preparation method is simple, novel, low in cost and environment-friendly; the prepared magnetic MOFs solid phase adsorbent has the advantages of being high in adsorption speed, large in adsorption capacity, high in removing efficiency and the like for removing organic dyestuff and metal ions in water body.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of preparation method and application of magnetic MOF adsorbent.
Background technology
Along with the fast development of industry now, a large amount of pollutants such as organic dyestuff and heavy metal ion etc. are constantly discharged in environment, and environmental pollution is on the rise, and has become the problem of the common concern in the whole world.The health of a large amount of discharges to environment and the mankind of organic dyestuff and heavy metal has very large harm, therefore develops that one is simply efficient carries out treatment technology to pollutant in water body and just seem very important.At present, water technology mainly contains precipitation, absorption, UF membrane etc., wherein absorption because of have simple to operate, be separated quick, cost is low, rate of recovery advantages of higher, is widely used in water treatment field.And for adsorption technology, most important have high selectivity, efficiently new adsorbent no more than developing to target contaminant.
Metal-organic framework materials (MOFs) is a class with metal ion or metal cluster for part center, with containing oxygen or nitrogenous organic ligand by forming the porous organic-inorganic hybrid material had compared with strong chemical bond effect.Compared with traditional mesoporous material, there is because of it advantages such as extra specific surface area, synthetic method are simple, wide variety, be widely used in gas absorption and be separated, catalysis, sensing, adsorb and be separated.The magnetic MOFs composite (magneticMOFscomposites prepared and MOFs combines with magnetic material, MFCs), the Dominant Facies such as specific area larger with MOFs for the advantage of magnetic material quick separating can be combined, prepared MFCs has a good application prospect in multiple field.But at present MFCs is mainly prepared by solvent heat and the method independently filled layer by layer, all there are some defects in it: solvent-thermal method often needs higher reaction temperature, longer reaction time and with an organic solvent as DMF (DMF); And although autonomous dress method is comparatively simple layer by layer, the required reaction time longer (general needs 25 times, at every turn for up to 45 minutes).On the other hand, these MFCs materials are mainly decorative material based on HKUST-1, and are not stablize especially when HKUST-1 contacts with water, and the Cu of high concentration
2+itself there is certain toxicity for biology, easily cause secondary pollution, therefore having some limitations when applying.Therefore develop a kind of environmental friendliness, MFCs with low cost, good stability has a good application prospect.
Summary of the invention
The object of the invention is the deficiency overcoming existing technology of preparing, a kind of preparation method and application of simple, economic, eco-friendly magnetic MOFs solid-phase adsorbent are provided.The adsorption rate of adsorbent prepared by the method is fast, and adsorption capacity is large, and the pH wide ranges be suitable for, is applicable in polluted-water and removes fast while dyestuff and metal ion.
Object of the present invention is achieved through the following technical solutions:
A kind of magnetic MOFs solid extracting agent, comprises magnetic Fe
3o
4core and Fe
3o
4the SiO that core wraps up from inside to outside successively
2layer and MOF layer, described MOF layer is MIL-53 (NH
2) or MIL-100.
Described magnetic Fe
3o
4the particle diameter of core is 10-20nm.
Prepare a method for above-mentioned magnetic MOFs solid extracting agent, comprise the steps:
(1) being coupling agent with tetraethoxysilane, take particle diameter as the magnetic Fe of 10-20nm
3o
4nanosphere is core, adopts
the preparation of silica gel coupling method has the Fe of nucleocapsid structure
3o
4siO
2;
(2) by Fe prepared by step (1)
3o
4siO
2ultrasonic disperse, in pure water, adds soluble metallic salt, and ultrasonic mixing, obtains solution I; Added water with organic ligand by NaOH and mix, ultrasonic disperse, obtains solution II; Described organic ligand is amino ligands or Carboxylic acid ligand;
(3) under agitation, be added dropwise in solution II by solution I prepared by step (2), form suspension, stir, washing, activation, namely obtains magnetic MOFs solid extracting agent.
Described particle diameter is the magnetic Fe of 10-20nm
3o
4nanosphere is prepared by coprecipitation.
Fe in described step (2)
3o
4siO
2be 1:5-7.5 with the mass ratio of soluble metallic salt; Described soluble metallic salt is AlCl
36H
2o, Al (NO
3)
3h
2o or FeCl
36H
2o.
Described organic ligand and the mol ratio of NaOH are 1:2-3.
Described organic ligand is one or more in terephthalic acid (TPA), the amino terephthalic acid (TPA) of 2-, trimesic acid.
Described step (3) is specially: under the stirring at room temperature condition of rotating speed 400-600 rev/min, is added dropwise in solution II by solution I prepared by step (2), forms suspension, continues to stir 6-24 hour; Then with high purity water washing, drying at room temperature; In the DMF solution of 150 DEG C, activate 5 hours again, finally wash with ethanol.
Above-mentioned magnetic MOFs solid extracting agent is containing the application in heavy metal and dye wastewater treatment.
Described heavy metal is As (V), and organic dyestuff is methylene blue (methyleneblue, MB).
The preparation method of magnetic MOFs solid extracting agent provided by the invention is (its synthetic route schematic diagram as shown in Figure 1): (1) adopts coprecipitation (Liu, X.; Ma, Z.; Xing, J.; Liu, H., " PreparationandCharacterizationofAmino – SilaneModifiedSuperparamagneticSilicaNanospheres ". [J] J.Magn.Magn.Mater.2004,270 (1), 1-6.) prepare the magnetic Fe that particle diameter is 10-20nm
3o
4nanosphere; (2) be coupling agent with tetraethoxysilane, pass through
silica gel coupling method has prepared the Fe with nucleocapsid structure
3o
4siO
2; (3) take soluble metallic salt as raw material, by the method for room temperature growth in situ in water, preparation magnetic MOFs adsorbent, by regulating slaine and Fe
3o
4siO
2ratio, effectively can regulate the thickness of shell; (4) the magnetic MOFs of gained in step (3) is activated, namely under 150 DEG C of DMF environment, activate 5h, to remove the organic ligand having neither part nor lot in coordination in MOF duct.
Preparation method provided by the invention, can by regulating slaine and Fe
3o
4siO
2mass ratio, effectively regulate the thickness of shell; By regulating the ratio of organic ligand, the functional group ratio in material can be regulated, realizing the optimization of material property.
At room temperature, take water as solvent, method environmental protection, with low cost, method is simple, and prepared novel nano MFCs material, by nanometer Fe
3o
4the advantage of the magnetic quick separating specific area larger with MOFs material, good absorption property combine, there is extraordinary application prospect.
Prepared MFCs solid-phase adsorbent contains the amino and carboxyl comparatively pretended with metal, dyestuff, and therefore adsorbable various heavy and organic dyestuff, has good application prospect in field of waste water treatment.
The present invention has the following advantages and beneficial effect relative to prior art tool:
(1) preparation method provided by the invention has reaction condition gentleness, energy consumption is low, synthetic method is simple, cost is low, environmental friendliness and can realize the advantages such as suitability for industrialized production.
(2) the MFCs solid-phase adsorbent prepared of the present invention is removing in the As (V) in aqueous systems and MB, shows the advantages such as adsorption rate is fast, adsorption capacity large, the pH value of solution scope of application is wide, removal efficiency is high, antijamming capability is strong.
Accompanying drawing explanation
Fig. 1 is the synthetic route schematic diagram of MFCs solid-phase adsorbent of the present invention;
The Fe of Fig. 2 prepared by embodiment 1
3o
4siO
2transmission electron microscope picture;
The transmission electron microscope picture of the MFC of Fig. 3 prepared by embodiment 3;
The scanning electron microscope (SEM) photograph of the MFC of Fig. 4 prepared by embodiment 3;
The FT-IR spectrogram of the MFC solid extracting agent of Fig. 5 prepared by embodiment 1-3;
The XRD spectra of the MFC of Fig. 6 prepared by embodiment 1-3;
The hysteresis curve of the MFC of Fig. 7 prepared by embodiment 3;
Fig. 8 is prepared MFC absorption property graph of a relation in MB, As (V) pH value of solution and embodiment 3;
The MFC solid-phase adsorbent of Fig. 9 prepared by embodiment 1-3 is to the graph of a relation of the absorption property of MB;
The MFC solid-phase adsorbent of Figure 10 prepared by embodiment 2 is to the graph of a relation of As (V) absorption property.
Detailed description of the invention
The invention provides a kind of preparation method of MFC solid-phase adsorbent, set forth the present invention further below in conjunction with the drawings and specific embodiments, but these embodiments are only limitted to the present invention is described, can not limit the scope of the invention.
EXAMPLE l
Coprecipitation prepares the magnetic Fe that particle diameter is 10-20nm
3o
4nanosphere: 11.68g iron chloride and 4.30g frerrous chloride are dissolved in 200mL high purity water, are heated with stirring to 85 DEG C under nitrogen protection.Then the NH of 20mL30% is added
3h
2o, the color of solution becomes black by crocus rapidly.After reacting half an hour, stop reaction, be cooled to room temperature, gained nano particle uses high purity water and 0.02molL successively
-1naCl washing to neutral, finally preserve with high purity water.
the preparation of silica gel coupling method has the Fe of nucleocapsid structure
3o
4siO
2: the Fe pipetting half
3o
4nano particle drops in the mixed solvent containing 160mL ethanol and 40mL high purity water, under agitation, drips the NH of 5mL30% in mixed liquor successively
3h
2o and 6mL tetraethoxysilane (TEOS), then at room temperature, mechanical agitation 12h.After reaction terminates, successively by high purity water and ethanol washing extremely neutrality, by the Fe of gained
3o
4siO
2nano particle is stored in high purity water with for subsequent use.Its TEM figure is shown in Fig. 2.
Adopt the method for room temperature growth in situ, preparation MFC-N-0: by 1.0gFe
3o
4siO
2add in 15mL high purity water, after ultrasonic disperse, add 7.5gAl (NO
3)
39H
2o, then ultrasonic mixing 20 minutes, obtains solution I; Add water 0.8gNaOH and 1.66g terephthalic acid (TPA) mixing, and ultrasonic disperse, obtains solution II.Under the stirring at room temperature condition of rotating speed 400 revs/min, solution I is added dropwise in solution II, forms suspension, continue stirring 24 hours; Then with high purity water washing, drying at room temperature; In the DMF solution of 150 DEG C, activate 5 hours again, finally with ethanol washing, obtain MFC-N-0 solid-phase adsorbent.
As shown in Figure 1, method provided by the invention has reaction condition gentleness to the synthetic route schematic diagram of magnetic Nano material adsorbent of the present invention, energy consumption is low, synthetic method is simple, cost is low, environmental friendliness and can realize the advantages such as suitability for industrialized production.
Embodiment 2
Difference from Example 1 is: synthesis MFC-N-50: by 1.0gFe
3o
4siO
2be added in 15mL high purity water, after ultrasonic disperse, add 5.0gAlCl
36H
2o, then ultrasonic mixing 20 minutes, obtains solution I; Add water 1.68gNaOH, 1.66g terephthalic acid (TPA) and the amino terephthalic acid (TPA) of 1.81g2-mixing, and ultrasonic disperse, obtains solution II.Under the stirring at room temperature condition of rotating speed 600 revs/min, solution I is added dropwise in solution II, forms suspension, continue stirring 15 hours; Then with high purity water washing, drying at room temperature; In the DMF solution of 150 DEG C, activate 5 hours again, finally with ethanol washing, obtain MFC-N-50 solid-phase adsorbent.
Embodiment 3
Difference from Example 1 is: synthesis MFC-N-100: by 1.0gFe
3o
4siO
2be added in 15mL high purity water, after ultrasonic disperse, add 5.0gAlCl
36H
2o, then ultrasonic mixing 20 minutes, obtains solution I; Add water amino for 1.76gNaOH and 3.62g2-terephthalic acid (TPA) mixing, and ultrasonic disperse, obtains solution II.Under the stirring at room temperature condition of rotating speed 500 revs/min, solution I is added dropwise in solution II, forms suspension, continue stirring 6 hours; Then with high purity water washing, drying at room temperature; In the DMF solution of 150 DEG C, activate 5 hours again, finally with ethanol washing, obtain MFC-N-100 solid-phase adsorbent.Its TEM is shown in Fig. 3, and SEM is shown in Fig. 4, and FT-IR is shown in Fig. 5, and XRD is shown in Fig. 6, and magnetic property is shown in Fig. 7.
Performance test
(1) MFC-N-100 adsorbent is tested the absorption property of As (V)
Select As (V) as the representative of common heavy metal, the absorption property of the MFC-N-50 adsorbent of preparation in embodiment 2 is tested.The operating procedure of test is as follows:
1) the MFC solid-phase adsorbent getting oven dry is scattered in (10gL in water
-1), form MFC solid-phase adsorbent suspension;
2) method of stepwise dilution is adopted, As (V) solution of preparation 10ppm: As (V) the storing solution 1.5mL getting 1.0mg/mL is diluted to 15mL, get 4mL again and be diluted to 40mL, the concentration repeating to be diluted to As (V) is 10ppm, uses HNO
3solution or ammonia spirit regulate its pH to be respectively 2,3,4,5,6,7,8 and 9;
3) 10mL10ppmAs (V) solution is pipetted in 10mL centrifuge tube, add 100 μ LMFC solid-phase adsorbent suspension, shaking table shakes Magneto separate after 6h, get supernatant and be introduced into the concentration measuring in plasma atomic emission spectrometer (ICP-OES) and remain target analytes in solution, the clearance all reaching pollutant reached for more than 99.9% (as Figure 10 shows).
Determine the removal effect of MFC-N-50 solid-phase adsorbent to As (V) solution of variable concentrations according to the method described above, see Figure 10, experimental result display MFC condition maximum adsorption capacity when pH7 is 62mgg
-1.
(2) MFC-N-100 adsorbent is tested the absorption property of organic dyestuff MB
Select MB as the representative of common organic dyes, the absorption property of the MFC-N-100 adsorbent of preparation in embodiment 3 is tested.The operating procedure of test is as follows:
1) the MFC solid-phase adsorbent getting oven dry is scattered in (10gL in water
-1), form MFC solid-phase adsorbent suspension;
2) method of stepwise dilution is adopted, the MB solution of preparation 100ppm: the MB storing solution 40mL getting 1.0mg/mL is diluted to 400mL, uses HNO
3solution or ammonia spirit regulate its pH to be respectively 2,3,4,5,6,7,8 and 9;
3) pipette 10mL100ppmMB solution in 10mL centrifuge tube, add 100 μ LMFC solid-phase adsorbent suspension, shaking table shakes Magneto separate after 6h, and get supernatant ultraviolet specrophotometer and measure the concentration remaining target analytes in solution, result such as Fig. 8 shows.
Determine the removal effect of MFC solid-phase adsorbent to the MB solution of variable concentrations according to the method described above, see Fig. 9, experimental result display MFC is 358mgg at room temperature condition maximum adsorption capacity
-1.
The adsorption capacity of prepared MFC solid phase vapor is large, and can realize mother liquor quick separating fast, and adsorption effect reappearance is good, and result is satisfactory.
Claims (10)
1. a magnetic MOFs solid extracting agent, is characterized in that: comprise magnetic Fe
3o
4core and Fe
3o
4the SiO that core wraps up from inside to outside successively
2layer and MOF layer, described MOF layer is MIL-53 (NH
2) or MIL-100.
2. magnetic MOFs solid extracting agent according to claim 1, is characterized in that: described magnetic Fe
3o
4the particle diameter of core is 10-20nm.
3. prepare a method for the magnetic MOFs solid extracting agent described in claim 1 or 2, it is characterized in that, comprise the steps:
(1) being coupling agent with tetraethoxysilane, take particle diameter as the magnetic Fe of 10-20nm
3o
4nanosphere is core, adopts
the preparation of silica gel coupling method has the Fe of nucleocapsid structure
3o
4siO
2;
(2) by Fe prepared by step (1)
3o
4siO
2ultrasonic disperse, in pure water, adds soluble metallic salt, and ultrasonic mixing, obtains solution I; Added water with organic ligand by NaOH and mix, ultrasonic disperse, obtains solution II; Described organic ligand is amino ligands or Carboxylic acid ligand;
(3) under agitation, be added dropwise in solution II by solution I prepared by step (2), form suspension, stir, washing, activation, namely obtains magnetic MOFs solid extracting agent.
4. the method preparing magnetic MOFs solid extracting agent according to claim 3, is characterized in that: described particle diameter is the magnetic Fe of 10-20nm
3o
4nanosphere is prepared by coprecipitation.
5. the method preparing magnetic MOFs solid extracting agent according to claim 3, is characterized in that: Fe in described step (2)
3o
4siO
2be 1:5-7.5 with the mass ratio of soluble metallic salt; Described soluble metallic salt is AlCl
36H
2o, Al (NO
3)
3h
2o or FeCl
36H
2o.
6. the method preparing magnetic MOFs solid extracting agent according to claim 3, is characterized in that: described organic ligand and the mol ratio of NaOH are 1:2-3.
7. the method preparing magnetic MOFs solid extracting agent according to claim 3, is characterized in that: described organic ligand is one or more in terephthalic acid (TPA), the amino terephthalic acid (TPA) of 2-, trimesic acid.
8. the method preparing magnetic MOFs solid extracting agent according to claim 3, it is characterized in that: described step (3) is specially: under the stirring at room temperature condition of rotating speed 400-600 rev/min, solution I prepared by step (2) is added dropwise in solution II, form suspension, continue to stir 6-24 hour; Then with high purity water washing, drying at room temperature; In the DMF solution of 150 DEG C, activate 5 hours again, finally wash with ethanol.
9. the magnetic MOFs solid extracting agent described in claim 1 or 2 is containing the application in heavy metal and dye wastewater treatment.
10. magnetic MOFs solid extracting agent, containing the application in heavy metal and dye wastewater treatment, is characterized in that: described heavy metal is As (V), and described dyestuff is methylene blue according to claim 9.
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