CN105148852B - A kind of sulfhydryl modified magnetic MOFs adsorbents and its preparation method and application - Google Patents
A kind of sulfhydryl modified magnetic MOFs adsorbents and its preparation method and application Download PDFInfo
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- CN105148852B CN105148852B CN201510659036.5A CN201510659036A CN105148852B CN 105148852 B CN105148852 B CN 105148852B CN 201510659036 A CN201510659036 A CN 201510659036A CN 105148852 B CN105148852 B CN 105148852B
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Abstract
The invention discloses a kind of sulfhydryl modified magnetic MOFs adsorbents and its methods and applications, its preparation method to comprise the following steps：（1）Coprecipitation is used to prepare magnetic Fe of the particle diameter for 10 20 nm3O4Nanosphere；（2）Fe with core shell structure is prepared using St ber silica gel coupling methods3O4@SiO2；（3）Fe is prepared by the method for solvent heat growth in situ3O4@SiO2@MOF；（4）To step by way of solvent assistant ligand exchanges（3）The Fe of synthesis3O4@SiO2@MOF progress is mercapto-functionalized, passes through and adjusts addition TGA and Fe3O4@SiO2@MOF ratio, prepare the mercapto-functionalized magnetic MOFs adsorbents of different proportion.Method reaction condition provided by the invention is gentle, and cost is cheap, easy to operate；The removal of magnetic MOFs adsorbents prepared by the present invention to metal ion in water body has the advantages such as adsorption rate is fast, adsorption capacity is big, selectivity is good.
Description
Technical field
The invention belongs to field of waste water treatment, and in particular to a kind of sulfhydryl modified magnetic MOFs adsorbents and preparation method thereof
And application.
Background technology
Along with the fast development of modernization industry, substantial amounts of heavy metal is discharged into environment, at present heavy metal pollution
Have become and threaten one of several big harm of human health.By traditional method such as precipitate remove the aqueous solution in heavy metal from
Son, not only cost is high, complex operation, and often produces substantial amounts of poisonous discarded object, forms secondary pollution.Environmental work
Person and researcher are development cost is low, has done substantial amounts of work in terms of the Heavy Metal Pollution Control such as simple to operate.
Mercury, as a kind of hypertoxic heavy metal element, the mercury especially in water environment can be by directly taking in or giving birth to
Thing enrichment, the mode of biomagnification enter human body, and then cause various harm, such as eyesight and Hearing, influence people
Development even distortion, nervous system injury etc..Therefore developing the mercury that a kind of simple efficient technology is removed in water body has ten
Divide important meaning.At present, mainly there are precipitation, absorption, UF membrane etc. for the method that the mercury in water body is removed, wherein inhaling
It is attached because of the advantages that simple to operate, separation is quick, cost is low, the rate of recovery is high, be widely used.It is although existing at present a variety of
Material is applied to the removal of Mercury in Water Body, such as clay, activated carbon, graphene as adsorbent, but these materials are relatively
The selectivity and relatively low adsorption capacity of difference, the more difficult weight of separation, limit its extensive use.Therefore, develop to target stains
The new adsorbent being easily isolated that thing mercury has high selectivity, high-adsorption-capacity is of great practical significance.
Metal-organic framework materials (MOFs) be one kind using metal ion or metal cluster as part center, it is and oxygen-containing or nitrogenous
Organic ligand pass through formed with strong chemical bond act on porous organic-inorganic hybrid material.With traditional mesoporous material phase
Than because it has, extra specific surface area, synthetic method are simple, aperture is adjustable, are easy to the advantages such as Post functionalization modification, are adsorbing
It is widely applied with separation field.And MOFs is combined the magnetic MOFs composites of preparation with magnetic material
(magnetic MOFs composites, MFCs), can be by the advantage of magnetic material quick separating and specific surface area larger MOFs
Combined Deng Dominant Facies, prepared MFCs has a good application prospect in multiple fields.But MFCs prepared at present
Often lack certain functional unit, weak with the interaction of mercury, poor selectivity is not, it is therefore desirable to MFC is carried out further
Post functionalization, so as to improve its selectivity and adsorption capacity.On the other hand, most of MFCs materials are mainly based upon at present
HKUST-1 is decorative material, and is not particularly stable when HKUST-1 contacts with water, and the Cu of high concentration2+Itself is for life
Thing has certain toxicity, easily causes secondary pollution, therefore have some limitations in application.Therefore a kind of environment is developed
The friendly, MFCs that cost is cheap, stability is good has a good application prospect.
The content of the invention
The purpose of the present invention is to overcome the shortcomings of existing technology of preparing, there is provided a kind of selectivity is good, stability is strong, absorption is held
Measure high sulfhydryl modified magnetic Zr-MOF solid-phase adsorbents and its preparation method and application.The absorption of adsorbent prepared by this method
Speed is fast, and adsorption capacity is big, and applicable pH scopes are wide, is applicable to the quick removal of heavy metal ion in polluted-water.
The purpose of the present invention is achieved through the following technical solutions：
A kind of sulfhydryl modified magnetic MOFs adsorbents, including magnetic Fe3O4Core and Fe3O4Wrapped up successively from inside to outside on core
SiO2Layer and MOF layers, the MOF layers are UIO-66 or UIO-66-NH2, the UIO-66 is through mercaptoalkyl carboxylic acid functional.
The magnetic Fe3O4The particle diameter of core is 10-20 nm.
A kind of method for preparing above-mentioned sulfhydryl modified magnetic MOFs adsorbents, comprises the following steps：
（1）Using tetraethoxysilane as coupling agent, the magnetic Fe using particle diameter as 10-20 nm3O4Nanosphere is core, using St
Ber silica gel coupling methods prepare the Fe with nucleocapsid structure3O4@SiO2；
（2）By step（1）The Fe of preparation3O4@SiO2Ultrasonic disperse adds soluble gold into DMF
Belong to salt, ultrasonic mixing, obtain solution；Organic ligand is added in DMF and dissolved, ultrasonic disperse, obtains solution；
（3）Under agitation, by solutionAdd solutionIn, suspension is formed, is stirred, is heated, is washed, is activated, is done
It is dry, obtain magnetic MOFs materials MFC-O；
（4）Mercaptoalkyl carboxylic acid is dispersed in water, adds KOH to adjust pH, then adds MFC-O, is stood, is heated, washing,
Dry, produce sulfhydryl modified magnetic MOFs adsorbents.
Described particle diameter is 10-20 nm magnetic Fe3O4Nanosphere is prepared by coprecipitation；The step（2）
Middle Fe3O4@SiO2Mass ratio with soluble metallic salt is 1：1-3；The soluble metallic salt is ZrCl4；Described is organic
Part is carboxyl ligand.
Described carboxyl ligand is terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)s, and the mol ratio with metal salt is 1：1.
The step（3）Specially：Room temperature, under the stirring condition of 400-600 revs/min of rotating speed, by solutionAdd solutionIn, suspension is formed, continues to stir 12-24 hours, 110-150oC is heated, and is washed successively with DMF and methanol；Exist at room temperature
Activated 24 hours in methanol, repetition of activation 3 times, drying at room temperature, obtain magnetic MOFs materials MFC-O.
Step（4）Described mercaptoalkyl carboxylic acid is TGA, mercaptopropionic acid or DMSA, sulfydryl alkane
Yl carboxylic acid and step（4）UIO-66 mol ratio contained by middle MFC-O is 1-3：1.
The step（4）Specially：Mercaptoalkyl carboxylic acid is dispersed in water, it is 7 to add KOH regulations pH；Then add
MFC-O, stand, 25-60 is heated under Ar gas shieldedsoC, kept for 3-72 hours；Then washed successively with water and methanol, room temperature
Dry, produce sulfhydryl modified magnetic MOFs adsorbents.
Application of the above-mentioned sulfhydryl modified magnetic MOFs adsorbents in containing heavy metal containing wastewater treatment.
The heavy metal is Hg2+。
The preparation method of magnetic MOFs solid extracting agents provided by the invention is（Its synthetic route schematic diagram such as Fig. 1 institutes
Show）：（1）Using coprecipitation（Liu, X.; Ma, Z.; Xing, J.; Liu, H., "Preparation and
Characterization of Amino–Silane Modified Superparamagnetic Silica
Nanospheres". [J] J. Magn. Magn. Mater.2004,270(1), 1-6.）It is 10-20 to be prepared for particle diameter
Nm magnetic Fe3O4Nanosphere；（2）Using tetraethoxysilane as coupling agent, it is prepared for having by St ber silica gel coupling methods
The Fe of nucleocapsid structure3O4@SiO2；（3）Using soluble metallic salt as raw material, pass through the method for the room temperature growth in situ in water, system
Standby magnetic MOFs adsorbents, by adjusting metal salt and Fe3O4@SiO2Ratio, can effectively adjust the thickness of shell；（4）It is logical
Solvent assistant ligand is crossed to exchange to step（3）The magnetic MOFs of middle gained carries out Post functionalization, i.e., sulfydryl is modified on MOF.
, can be by adjusting metal salt and Fe in preparation method provided by the invention3O4@SiO2Mass ratio, effectively regulation
The thickness of shell；By adjusting the ratio of mercaptoalkyl carboxylic acid and MFC-O, the functional group sulfydryl ratio in material can be entered
Row regulation, realize the optimization of material property.
Under mild conditions, using water as solvent, the novel nano prepared by by way of solvent assistant ligand exchanges
MFCs materials, by nanometer Fe3O4Advantage and the MOFs materials high selectivity of magnetic quick separating, larger adsorption capacity, quick
Absorption property be combined, method is simple to operate, and cost is cheap, has extraordinary application prospect.
Prepared magnetic MOFs solid-phase adsorbents water stability is good, containing the sulfydryl strong with heavy metal affinity, therefore
The various heavy in water body is can remove, there is good application prospect in field of waste water treatment.
The present invention is had the following advantages that relative to prior art and beneficial effect：
（1）Preparation method provided by the invention has that reaction condition is gentle, energy consumption is low, synthetic method is simple, cost is low, easy
The advantages that realizing industrialized production.
（2）The Hg of magnetic Zr-MOFs solid-phase adsorbents prepared by the present invention in aqueous systems are removed2+Aspect, show to inhale
Attached speed is fast, adsorption capacity is big, the pH value of solution scope of application is wide, the good, strong antijamming capability of selectivity and the repeatable advantage such as utilize.
Brief description of the drawings
Fig. 1 is the synthetic route schematic diagram of MFCs solid-phase adsorbents of the present invention；
Fig. 2 is the Fe prepared by embodiment 13O4@SiO2Transmission electron microscope picture；
Fig. 3 is the transmission electron microscope picture of the MFC-S-3 prepared by embodiment 3；
Fig. 4 is the scanning electron microscope (SEM) photograph of the MFC-S-3 prepared by embodiment 3；
Fig. 5 is the FT-IR spectrograms of the MFC-S-X solid extracting agents prepared by embodiment 1-3；
Fig. 6 is the XRD spectra of the MFC-S-X prepared by embodiment 1-3；
Fig. 7 is the hysteresis curve of the MFC-S-3 prepared by embodiment 3；
Fig. 8 is Hg2+PH value of solution and prepared MFC-S-3 absorption properties graph of a relation in embodiment 3；
MFC-S-3 solid-phase adsorbents of the Fig. 9 prepared by embodiment 3 is to Hg2+Absorption property graph of a relation.
Embodiment
It is below in conjunction with accompanying drawing and specifically real the invention provides a kind of preparation method of magnetic Zr-MOFs solid-phase adsorbents
Apply example and the present invention is expanded on further, but these embodiments are only limitted to the explanation present invention, can not limit the scope of the invention.
Embodiment l
Coprecipitation prepares the magnetic Fe that particle diameter is 10-20 nm3O4Nanosphere：By 11.68 g iron chloride and 4.30 g chlorine
Change ferrous iron to be dissolved in 200 mL high purity waters, be heated with stirring to 85 DEG C under nitrogen protection.Then add 20 mL's 30%
NH3·H2O, the color of solution become black by crocus rapidly.After reacting half an hour, stop reaction, be cooled to room temperature, gained
Nano-particle uses high purity water and 0.02 mol L successively-1NaCl wash to neutrality, finally preserved with high purity water.
St ber silica gel coupling methods prepare the Fe with nucleocapsid structure3O4@SiO2：Pipette the Fe of half3O4Nano-particle is thrown
Enter the in the mixed solvent containing 160 mL ethanol and 40 mL high purity waters, under agitation, 5 mL are added dropwise successively into mixed liquor
30 % NH3·H2O and 6 mL tetraethoxysilanes（TEOS）, then at room temperature, the h of mechanical agitation 12.After reaction terminates, according to
It is secondary to be washed with high purity water and ethanol to neutrality, by the Fe of gained3O4@SiO2Nano-particle is stored in high purity water with standby.Its
TEM figures are shown in Fig. 2.
Using the method for solvent heat growth in situ, MFC-O is prepared：By 1.0 g Fe3O4@SiO2Add to 150 mLDMF
In, 1.16 g ZrCl are added after ultrasonic disperse4, by mixed liquor ultrasonic mixing 20 minutes, obtain solution I；By 0.83 g terephthaldehydes
Acid is added in 50 mL DMF, ultrasonic disperse, obtains solution II.Room temperature, under the stirring condition of 400 revs/min of rotating speed, by solutionAdd
Enter solutionIn, suspension is formed, continues to stir 12-24 hours, 110-150oC is heated, and is washed successively with DMF and methanol；Room
Activated in methyl alcohol under temperature 24 hours, repetition of activation 3 times, drying at room temperature, obtain magnetic MOFs materials MFC-O.
1 mmol sulfydryl second carboxylic acids are dispersed in water, add KOH to adjust pH to 7, the rear magnetic for adding 400 mg activation
MOFs, stand, 60 are heated under Ar gas shieldedsoC, kept for 3 hours；Then washed successively with water and methanol, drying at room temperature, i.e.,
Obtain sulfhydryl modified magnetic MOFs adsorbents MFC-S-1.
The synthesis schematic diagram of magnetic Nano material adsorbent of the present invention is as shown in figure 1, method provided by the invention has instead
Answer that mild condition, energy consumption are low, synthetic method is simple, cost is low, environment-friendly and the advantages that can realize industrialized production.
Embodiment 2
Difference from Example 1 is：Synthesize MFC-S-2：2 mmol sulfydryl second carboxylic acids are dispersed in water, add KOH to adjust
PH to 7 is saved, the rear MFC-O for adding 400 mg activation, stands, 40 is heated under Ar gas shieldedsoC, kept for 40 hours；Then according to
It is secondary to be washed with water and methanol, drying at room temperature, produce sulfhydryl modified magnetic MOFs adsorbents MFC-S-2.
Embodiment 3
Difference from Example 1 is：Synthesize MFC-S-3：3 mmol sulfydryl second carboxylic acids are dispersed in water, add KOH to adjust
PH to 7 is saved, the rear MFC-O for adding 400 mg activation, stands, 25 is heated under Ar gas shieldedsoC, kept for 72 hours；Then according to
It is secondary to be washed with water and methanol, drying at room temperature, produce sulfhydryl modified magnetic MOFs adsorbents MFC-S-3.Its TEM is shown in that Fig. 3, SEM are shown in
Fig. 4, FT-IR are shown in that Fig. 5, XRD are shown in Fig. 6, and magnetic property is shown in Fig. 7.
Performance test：MFC-S-3 adsorbents are to Hg2+Absorption property test
Select Hg2+As the representative of common heavy metal, to the absorption property of the MFC-S-3 adsorbents prepared in embodiment 3
It is tested.The operating procedure of test is as follows：
1）The MFC-S-3 solid-phase adsorbents of drying are taken to be dispersed in water (10 g L-1), form MFC-S-3 solid-phase adsorbents
Suspension；
2）Using the method diluted step by step, 10 ppm of preparation Hg2+Solution：Take 1.0 mg/mL Hg2+Storing solution 1.5
ML is diluted to 15 mL, then takes 4 mL to be diluted to 40 mL, and repetition is diluted to Hg2+Concentration be 10 ppm, use HNO3Solution or ammonia
It is respectively 2,3,4,5,6,7 and 8 that the aqueous solution, which adjusts its pH,；
3）Take 10 mL 10 ppm Hg2+Solution adds 100 μ L MFC-S-3 solid-phase adsorbents into 10 mL centrifuge tubes
Suspension, shaking table shake Magneto separate after 6 h, take supernatant to be introduced in plasma atomic emission spectrometer (ICP-OES) and determine
The concentration of remaining target analytes, removal effect are good in solution（As Fig. 8 shows）.
Hg of the MFC solid-phase adsorbents to various concentrations is determined according to the method described above2+The removal effect of solution, see Fig. 9, it is real
Test result and show that MFC-S-3 condition maximum adsorption capacities in pH3 are 282 mg g-1。
The adsorption capacity of prepared MFC-S-3 solid phase vapors is big, and can quickly realize mother liquor quick separating, adsorption effect
Reappearance is good, as a result satisfactory.
Claims (8)
- A kind of 1. sulfhydryl modified magnetic MOFs adsorbents, it is characterised in that：Including magnetic Fe3O4Core and Fe3O4On core from inside to outside The SiO wrapped up successively2Layer and MOF layers, the MOF layers are UIO-66 or UIO-66-NH2, the UIO-66 is through mercaptoalkyl carboxylic acid Functionalization；Described sulfhydryl modified magnetic MOFs adsorbents are prepared by following steps：(1) using tetraethoxysilane as coupling agent, the magnetic Fe using particle diameter as 10-20nm3O4Nanosphere is core, is usedSilicon Glue coupling method prepares the Fe with nucleocapsid structure3O4@SiO2；(2) Fe for preparing step (1)3O4@SiO2Ultrasonic disperse adds soluble metallic salt into DMF, Ultrasonic mixing, obtain solution I；Carboxyl ligand is added in DMF and dissolved, ultrasonic disperse, obtains solution II；(3) under agitation, solution I is added in solution II, forms suspension, stirred, heated, washed, activated, dried, Obtain magnetic MOFs materials MFC-O；(4) mercaptoalkyl carboxylic acid is dispersed in water, adds KOH to adjust pH, then add MFC-O, stood, heated, washed, done It is dry, produce sulfhydryl modified magnetic MOFs adsorbents.
- 2. sulfhydryl modified magnetic MOFs adsorbents according to claim 1, it is characterised in that：Described particle diameter is 10- 20nm magnetic Fe3O4Nanosphere is prepared by coprecipitation；Fe in the step (2)3O4@SiO2With soluble metallic salt Mass ratio be 1：1-3；The soluble metallic salt is ZrCl4。
- 3. sulfhydryl modified magnetic MOFs adsorbents according to claim 1, it is characterised in that：The carboxyl ligand is to benzene Dioctyl phthalate or 2- amino terephthalic acid (TPA)s, the mol ratio with metal salt are 1：1.
- 4. sulfhydryl modified magnetic MOFs adsorbents according to claim 1, it is characterised in that：The step (3) is specially： Room temperature, under the stirring condition of 400-600 revs/min of rotating speed, solution I is added in solution II, suspension is formed, continues to stir 12-24 hours, 110-150 DEG C of heating, washed successively with DMF and methanol；Activate 24 hours in methyl alcohol at room temperature, repetition of activation 3 times, drying at room temperature, obtain magnetic MOFs materials MFC-O.
- 5. sulfhydryl modified magnetic MOFs adsorbents according to claim 1, it is characterised in that：Sulfydryl described in step (4) Alkyl carboxylic acid is TGA, mercaptopropionic acid or DMSA, mercaptoalkyl carboxylic acid and MFC-O institutes in step (4) Mol ratio containing UIO-66 is 1-3：1.
- 6. sulfhydryl modified magnetic MOFs adsorbents according to claim 1, it is characterised in that：The step (4) is specially： Mercaptoalkyl carboxylic acid is dispersed in water, it is 7 to add KOH regulations pH；Then MFC-O is added, is stood, is heated under Ar gas shieldeds 25-60 DEG C, kept for 3-72 hours；Then washed successively with water and methanol, drying at room temperature, produce sulfhydryl modified magnetic MOFs absorption Agent.
- 7. application of the sulfhydryl modified magnetic MOFs adsorbents in containing heavy metal containing wastewater treatment described in claim 1.
- 8. application of the sulfhydryl modified magnetic MOFs adsorbents according to claim 7 in containing heavy metal containing wastewater treatment, It is characterized in that：The heavy metal is Hg2+。
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| CN104307481A (en) * | 2014-08-26 | 2015-01-28 | 武汉大学 | Magnetic MOFs solid-phase extractant, and preparation method and application thereof |
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