CN105148852A - Thiohydroxy-modified magnetic MOFs adsorbent and preparation method and application thereof - Google Patents
Thiohydroxy-modified magnetic MOFs adsorbent and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a thiohydroxy-modified magnetic MOFs adsorbent and a preparation method and application thereof. The preparation method 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 silicone coupling method; (3) preparing Fe3O4@SiO2@MOF through a solvothermal in-situ growth method; (4) carrying out thiol-functionalization on Fe3O4@SiO2@MOF synthesized in the step (3) in a solvent auxiliary ligand exchange manner, and preparing the thiol-functionalized magnetic MOFs adsorbent with different proportions through adjusting the proportion of mercaptoacetic acid to Fe3O4@SiO2@MOF. According to the invention, the preparation method is mild in reaction conditions, low in cost, and simple and convenient to operate; the prepared magnetic MOFs adsorbent has the advantages of being high in adsorption speed, large in adsorption capacity and good in selectivity when removing the metal ions in water.
Description
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind of sulfhydryl modified magnetic MOFs adsorbent and its preparation method and application.
Background technology
Along with the fast development of modernization industry, a large amount of heavy metals is discharged in environment, and current heavy metal pollution has become one of several large harm of threat human health.By traditional method as precipitation waits the heavy metal ion removed in the aqueous solution, not only cost is high, complicated operation, and often produces a large amount of poisonous discarded objects, forms secondary pollution.A large amount of work has been done in environmentalist and the Heavy Metal Pollution Control such as researcher is low in development cost, simple to operate.
Mercury, as a kind of heavy metal element of severe toxicity, the mercury especially in water environment, can by directly take in or biological concentration, biomagnification mode enter human body, and then cause various harm, as eyesight and Hearing, the growth that affects people even distort, nervous system injury etc.Therefore develop a kind of simple efficiently mercury tool that technology is removed in water body to be of great significance.At present, the method for carrying out removing for the mercury in water body mainly contains precipitation, absorption, UF membrane etc., wherein adsorb because of simple to operate, be separated fast, cost is low, rate of recovery advantages of higher, be widely used.Although at present existing multiple material is applied to the removal of Mercury in Water Body as adsorbent, as clay, active carbon, Graphene etc., the relatively poor selective and lower adsorption capacity of these materials, to be separated comparatively difficulty heavy, limits its extensive use.Therefore, develop to target contaminant mercury have high selectivity, high-adsorption-capacity be easy to be separated new adsorbent be of great practical significance.
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, because of its there is extra specific surface area, synthetic method is simple, aperture is adjustable, be easy to the advantages such as Post functionalization modification, be widely applied with separation field in absorption.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 MFCs prepared at present often lacks certain functional unit, weak with the interaction of mercury, poor selectivity not, therefore needs to carry out further Post functionalization to MFC, thus improves its selective and adsorption capacity.On the other hand, current most of MFCs material is mainly decorative material based on HKUST-1, and is 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 selective good, stability is strong, adsorption capacity is high sulfhydryl modified magnetic Zr-MOF solid-phase adsorbent and its preparation method and application is 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 to the quick removal of heavy metal ion in polluted-water.
Object of the present invention is achieved through the following technical solutions:
A kind of sulfhydryl modified magnetic MOFs adsorbent, 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 UIO-66 or UIO-66-NH
2, described UIO-66 is through mercaptoalkyl carboxylic acid functional.
Described magnetic Fe
3o
4the particle diameter of core is 10-20nm.
Prepare a method for above-mentioned sulfhydryl modified magnetic MOFs adsorbent, 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 St ber silica gel coupling method to have the Fe of nucleocapsid structure
3o
4siO
2;
(2) by Fe prepared by step (1)
3o
4siO
2ultrasonic disperse, in DMF, adds soluble metallic salt, and ultrasonic mixing, obtains solution
; Organic ligand is added in DMF and dissolves, ultrasonic disperse, obtain solution
;
(3) under agitation, by solution
add solution
in, form suspension, stir, heating, washing, activation, dry, obtain magnetic MOFs material MFC-O;
(4) mercaptoalkyl carboxylic acid is scattered in water, adds KOH and regulate pH, then add MFC-O, leave standstill, heating, washing, dry, obtain sulfhydryl modified magnetic MOFs adsorbent.
Described particle diameter is the magnetic Fe of 10-20nm
3o
4nanosphere is prepared by coprecipitation; Fe in described step (2)
3o
4siO
2be 1:1-3 with the mass ratio of soluble metallic salt; Described soluble metallic salt is ZrCl
4; Described organic ligand is carboxyl ligand.
Described carboxyl ligand is the amino terephthalic acid (TPA) of terephthalic acid (TPA) or 2-, is 1:1 with the mol ratio of slaine.
Described step (3) is specially: room temperature, under the stirring condition of rotating speed 400-600 rev/min, by solution
add solution
in, form suspension, continue to stir 12-24 hour, 110-150
oc heats, and uses DMF and methanol wash successively; In methyl alcohol, activate 24 hours under room temperature, repetition of activation 3 times, drying at room temperature, obtains magnetic MOFs material MFC-O.
Mercaptoalkyl carboxylic acid described in step (4) is TGA, mercaptopropionic acid or DMSA, and in mercaptoalkyl carboxylic acid and step (4), contained by MFC-O, the mol ratio of UIO-66 is 1-3:1.
Described step (4) is specially: be scattered in water by mercaptoalkyl carboxylic acid, adds KOH and regulates pH to be 7; Then add MFC-O, leave standstill, under Ar gas shielded, be heated to 25-60
oc, keeps 3-72 hour; Then use water and methanol wash successively, drying at room temperature, obtain sulfhydryl modified magnetic MOFs adsorbent.
Above-mentioned sulfhydryl modified magnetic MOFs adsorbent is containing the application in heavy metal containing wastewater treatment.
Described heavy metal is Hg
2+.
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) take tetraethoxysilane as coupling agent, prepared the Fe with nucleocapsid structure by St ber silica gel coupling method
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) exchanged by solvent assistant ligand Post functionalization is carried out to the magnetic MOFs of gained in step (3), be i.e. sulfydryl in modification on MOF.
In 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 mercaptoalkyl carboxylic acid and MFC-O, the functional group sulfydryl ratio in material can be regulated, realizing the optimization of material property.
Under mild conditions, take water as solvent, the novel nano MFCs material prepared by the mode exchanged by solvent assistant ligand, by nanometer Fe
3o
4the advantage of magnetic quick separating combine with MOFs material high selectivity, larger adsorption capacity, fast absorption property, method is simple to operate, with low cost, has extraordinary application prospect.
Prepared magnetic MOFs solid-phase adsorbent water stability is good, containing the sulfydryl strong with heavy metal affinity, therefore can remove the various heavy in water body, have 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, easily realize the advantages such as suitability for industrialized production.
(2) the magnetic Zr-MOFs solid-phase adsorbent that prepared by the present invention is removing the Hg in aqueous systems
2+aspect, show that adsorption rate is fast, adsorption capacity be large, the pH value of solution scope of application wide, selective good, antijamming capability strong and the advantage such as can to reuse.
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-S-3 of Fig. 3 prepared by embodiment 3;
The scanning electron microscope (SEM) photograph of the MFC-S-3 of Fig. 4 prepared by embodiment 3;
The FT-IR spectrogram of the MFC-S-X solid extracting agent of Fig. 5 prepared by embodiment 1-3;
The XRD spectra of the MFC-S-X of Fig. 6 prepared by embodiment 1-3;
The hysteresis curve of the MFC-S-3 of Fig. 7 prepared by embodiment 3;
Fig. 8 is Hg
2+prepared MFC-S-3 absorption property graph of a relation in pH value of solution and embodiment 3;
The MFC-S-3 solid-phase adsorbent of Fig. 9 prepared by embodiment 3 is to Hg
2+the graph of a relation of absorption property.
Detailed description of the invention
The invention provides a kind of preparation method of magnetic Zr-MOFs 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 St ber 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 solvent heat growth in situ, preparation MFC-O: by 1.0gFe
3o
4siO
2be added in 150mLDMF, after ultrasonic disperse, add 1.16gZrCl
4, by ultrasonic for mixed liquor mixing 20 minutes, obtain solution I; 0.83g terephthalic acid (TPA) is added in 50mLDMF, ultrasonic disperse, obtain solution II.Room temperature, under the stirring condition of rotating speed 400 revs/min, by solution
add solution
in, form suspension, continue to stir 12-24 hour, 110-150
oc heats, and uses DMF and methanol wash successively; In methyl alcohol, activate 24 hours under room temperature, repetition of activation 3 times, drying at room temperature, obtains magnetic MOFs material MFC-O.
1mmol sulfydryl second carboxylic acid is scattered in water, add KOH regulate pH to 7, after add 400mg activation magnetic MOFs, leave standstill, be heated to 60 under Ar gas shielded
oc, keeps 3 hours; Then use water and methanol wash successively, drying at room temperature, obtain sulfhydryl modified magnetic MOFs adsorbent MFC-S-1.
As shown in Figure 1, method provided by the invention has reaction condition gentleness to the synthesis 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-S-2: 2mmol sulfydryl second carboxylic acid is scattered in water, add KOH regulate pH to 7, after add 400mg activation MFC-O, leave standstill, be heated to 40 under Ar gas shielded
oc, keeps 40 hours; Then use water and methanol wash successively, drying at room temperature, obtain sulfhydryl modified magnetic MOFs adsorbent MFC-S-2.
Embodiment 3
Difference from Example 1 is: synthesis MFC-S-3: 3mmol sulfydryl second carboxylic acid is scattered in water, add KOH regulate pH to 7, after add 400mg activation MFC-O, leave standstill, be heated to 25 under Ar gas shielded
oc, keeps 72 hours; Then use water and methanol wash successively, drying at room temperature, obtain sulfhydryl modified magnetic MOFs adsorbent MFC-S-3.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: MFC-S-3 adsorbent is to Hg
2+absorption property test
Select Hg
2+as the representative of common heavy metal, the absorption property of the MFC-S-3 adsorbent of preparation in embodiment 3 is tested.The operating procedure of test is as follows:
1) the MFC-S-3 solid-phase adsorbent getting oven dry is scattered in (10gL in water
-1), form MFC-S-3 solid-phase adsorbent suspension;
2) method of stepwise dilution is adopted, the Hg of preparation 10ppm
2+solution: the Hg getting 1.0mg/mL
2+storing solution 1.5mL is diluted to 15mL, then gets 4mL and be diluted to 40mL, repeats to be diluted to Hg
2+concentration be 10ppm, use HNO
3solution or ammonia spirit regulate its pH to be respectively 2,3,4,5,6,7 and 8;
3) 10ppmHg of 10mL is got
2+solution is in 10mL centrifuge tube, add 100 μ LMFC-S-3 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, removal effect good (as Fig. 8 shows).
Determine the Hg of MFC solid-phase adsorbent to variable concentrations according to the method described above
2+the removal effect of solution, is shown in Fig. 9, and experimental result display MFC-S-3 condition maximum adsorption capacity when pH3 is 282mgg
-1.
The adsorption capacity of prepared MFC-S-3 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 sulfhydryl modified magnetic MOFs adsorbent, 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 UIO-66 or UIO-66-NH
2, described UIO-66 is through mercaptoalkyl carboxylic acid functional.
2. sulfhydryl modified magnetic MOFs adsorbent 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 sulfhydryl modified magnetic MOFs adsorbent 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 St ber silica gel coupling method to have the Fe of nucleocapsid structure
3o
4siO
2;
(2) by Fe prepared by step (1)
3o
4siO
2ultrasonic disperse, in DMF, adds soluble metallic salt, and ultrasonic mixing, obtains solution
; Organic ligand is added in DMF and dissolves, ultrasonic disperse, obtain solution
;
(3) under agitation, by solution
add solution
in, form suspension, stir, heating, washing, activation, dry, obtain magnetic MOFs material MFC-O;
(4) mercaptoalkyl carboxylic acid is scattered in water, adds KOH and regulate pH, then add MFC-O, leave standstill, heating, washing, dry, obtain sulfhydryl modified magnetic MOFs adsorbent.
4. the method for the sulfhydryl modified magnetic MOFs adsorbent of preparation according to claim 3, is characterized in that: described particle diameter is the magnetic Fe of 10-20nm
3o
4nanosphere is prepared by coprecipitation; Fe in described step (2)
3o
4siO
2be 1:1-3 with the mass ratio of soluble metallic salt; Described soluble metallic salt is ZrCl
4; Described organic ligand is carboxyl ligand.
5. the method for the sulfhydryl modified magnetic MOFs adsorbent of preparation according to claim 4, is characterized in that: described carboxyl ligand is the amino terephthalic acid (TPA) of terephthalic acid (TPA) or 2-, is 1:1 with the mol ratio of slaine.
6. the method for the sulfhydryl modified magnetic MOFs adsorbent of preparation according to claim 3, is characterized in that: described step (3) is specially: room temperature, under the stirring condition of rotating speed 400-600 rev/min, by solution
add solution
in, form suspension, continue to stir 12-24 hour, 110-150
oc heats, and uses DMF and methanol wash successively; In methyl alcohol, activate 24 hours under room temperature, repetition of activation 3 times, drying at room temperature, obtains magnetic MOFs material MFC-O.
7. the method for the sulfhydryl modified magnetic MOFs adsorbent of preparation according to claim 3, it is characterized in that: the mercaptoalkyl carboxylic acid described in step (4) is TGA, mercaptopropionic acid or 2,3-dimercaptosuccinic acid, in mercaptoalkyl carboxylic acid and step (4), contained by MFC-O, the mol ratio of UIO-66 is 1-3:1.
8. the method for the sulfhydryl modified magnetic MOFs adsorbent of preparation according to claim 3, is characterized in that: described step (4) is specially: be scattered in water by mercaptoalkyl carboxylic acid, adds KOH and regulates pH to be 7; Then add MFC-O, leave standstill, under Ar gas shielded, be heated to 25-60
oc, keeps 3-72 hour; Then use water and methanol wash successively, drying at room temperature, obtain sulfhydryl modified magnetic MOFs adsorbent.
9. the sulfhydryl modified magnetic MOFs adsorbent described in claim 1 or 2 is containing the application in heavy metal containing wastewater treatment.
10. sulfhydryl modified magnetic MOFs adsorbent according to claim 9 is containing the application in heavy metal containing wastewater treatment, it is characterized in that: described heavy metal is Hg
2+.
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