CN104258807A - Magnetic nano material solid phase extracting agent as well as preparation method and application thereof - Google Patents
Magnetic nano material solid phase extracting agent as well as preparation method and application thereof Download PDFInfo
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- CN104258807A CN104258807A CN201410539224.XA CN201410539224A CN104258807A CN 104258807 A CN104258807 A CN 104258807A CN 201410539224 A CN201410539224 A CN 201410539224A CN 104258807 A CN104258807 A CN 104258807A
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Abstract
The invention provides a magnetic nano material solid phase extracting agent used for absorbing phthalate organic pollutants in an environmental water sample and a preparation method of the extracting agent. The magnetic nano material solid phase extracting agent comprises magnetic silicon dioxide particles serving as the inner core and layered bi-metal hydroxide serving as the shell layer, wherein the magnetic silicon dioxide particles are formed by coating a magnetic nano core with silicon dioxide; and the layered bi-metal hydroxide shell layer adopts Mg-Al bi-metal hydroxide. The preparation method for the solid phase extraction absorbent is simple, the raw material cost is low, a designed extraction process is fast and convenient, a small quantity of organic solvent is required to be used in the whole process, and environment friendliness is achieved.
Description
Technical field
The invention belongs to chemical analysis test instrument and equipment field, relate to a kind of novel mixed micelle formula Fe
3o
4@SiO
2@Mg-Al LDH composite solid extracting agent.
Background technology
SPE is the more novel environmental sample pre-treating method be most widely used at present.Compared with traditional liquid-liquid extraction, SPE has that extraction time is short, the rate of recovery is high, enrichment times is high and the advantage such as organic reagent consumption is few.In recent years, magnetic Nano material due to the physicochemical property and magnetic material that combine nano material uniqueness magnetic property and cause the extensive concern of every field.The absorption property of its brilliance and higher specific area make it in enriching pollutants and sample pre-treatments, have very large application potential.The superparamagnetism of material makes its rapid subsidence under additional magnetic fields to beaker bottom, overcome the shortcoming that general nano material solid phase extraction techniques loading resistance is large, operate consuming time, extractant and mother liquor separation difficulty.
Ionic surfactant becomes study hotspot in recent years in the absorption self assembly behavior on metal oxide particle surface.It can form mixed micelle on surfaces such as aluminium oxide, iron oxide, silica, titanium dioxide.There is bibliographical information to regulate the selective of extractant by controlling solution ph, kinds of surfactants and concentration etc., and then ionic, hydrophobic type, organic extraction that amphiphilic is different with Acidity of Aikalinity can be applied to.Have the specific area of research surfactant adsorption self assembly behavior and nano material closely related, specific area is larger, also higher to the loading capacity of pollutant.Therefore, large to reference area nano material will be well worth doing after carrying out hemi-micelle/adsorb micelle modified modification in SPE.With Fe
3o
4for magnetic layered double-metal hydroxide (the Layered double hydroxide of core, LDH) because specific area is large, cost is low, surface is easy to the concern that the advantages such as modification cause numerous researcher, and be widely used in absorption, catalysis, molecules and field of biology, it can be used as solid extracting agent to have huge potentiality.
Summary of the invention
Fe prepared by the present invention
3o
4@SiO
2@Mg-Al LDH magnetic nano solid extracting agent, has that layered double hydroxide specific area is large concurrently, an advantage such as strong extracting power of the Magneto separate ability of magnetic material, nano material quick adsorption and easily wash-out and mixed micelle.
Technical scheme disclosed by the invention is: a kind of magnetic Nano material solid extracting agent, and it comprises the magnetic silica particles as kernel, as the layered double hydroxide of shell; Described magnetic silica particles is formed in magnetic Nano core by coated with silica; Layered double-metal hydroxide shell is Mg-Al double-metal hydroxide.
Preferably, the magnetic Nano core in described magnetic silica particles is Fe
3o
4, one in Co, FeCo, Ni, FeCo, FeO.
Preferably, described magnetic Nano core adopts solvent-thermal method preparation.
Preferably, the diameter of described magnetic Nano core is between 150nm-250nm.
Preferably, the silicon dioxide layer in described magnetic silica particles is that TEOS hydrolysis obtains.TEOS described in the present invention refers to: ethyl orthosilicate, also known as silester; Tetraethyl orthosilicate; Sub-silester; Tetraethoxysilane; Tetraethyl orthosilicate; Its chemical formula is Si (OC
2h
5)
4; Colourless liquid; Fusing point-77 DEG C, boiling point 168.5 DEG C, density 0.9346gcm
-3; More stable to air; Be slightly soluble in water, in pure water, hydrolysis slowly, can accelerate hydrolysis in the presence of acids and bases; Obtain there is no electrolytical silica sol with boiling water effect.The invention also discloses a kind of preparation method of magnetic Nano material solid extracting agent, comprise the following steps:
(1) magnetic Nano core is prepared: solvent-thermal method prepares magnetic Nano core;
(2) obtained magnetic silica particles: utilize TEOS to be hydrolyzed in the mixed liquor of ethanol and water in the basic conditions and form silicon dioxide layer, magnetic Nano core prepared by step (1) is embedded in described silicon dioxide layer, obtained magnetic silica particles;
(3) magnetic silica particles Surface coating double-metal hydroxide layer: utilize Mg (NO
3)
26H
2o, Al (NO
3)
39H
2o is the magnetic silica particles surface of co-precipitation prepared by step (2) in the basic conditions, forms double-metal hydroxide layer.
The invention also discloses the self-assembling method of a kind of surfactant on the top layer of above-mentioned magnetic Nano material solid extracting agent, in the method, in acid condition, there is absorption self assembly behavior in magnetic double-metal hydroxide shell layer surface, form mixed micelle in surfactant SDS.
The invention also discloses a kind of Fe
3o
4@SiO
2the preparation method of@Mg-Al LDH composite nano materials extractant, comprises the following steps:
(1) solvent-thermal method prepares Fe
3o
4nano particle: by FeCl
36H
2o, NaAc and natrium citricum are dissolved in ethylene glycol solvent, magnetic stirring 20min-60min; Gained solution is transferred in sealed reactor, at 180-240 DEG C, reacts 6-14h, after reaction terminates, by the Fe of preparation
3o
4nano particle is separated and is cleaned up, drying for standby;
(2) obtained magnetic silica particles: the Fe getting above-mentioned preparation
3o
4nano particle joins in the mixed liquor of ethanol and deionized water, then adds the NH of 25%
3h
2o solution, adds TEOS after ultrasonic agitation, stirred at ambient temperature 10-15h; Obtain magnetic silica particles (Fe
3o
4@SiO
2); The magnetic silica particles of preparation is cleaned up, drying for standby;
(3) magnetic silica particles Surface coating double-metal hydroxide layer: get above-mentioned magnetic silica particles, be distributed in deionized water, drips alkaline solution to solution alkaline, under agitation by Mg (NO
3)
26H
2o, Al (NO
3)
39H
2the mixed liquor of O drops to described alkaline solution; After being added dropwise to complete, after ultrasonic 20-40min, collect product, product is dispersed in deionized water again and continues ultrasonic 20-40min, finally prepare Fe3O4 SiO2 Mg-Al LDH composite nano materials extractant.
Preferably, in above-mentioned steps (1), FeCl
36H
2mol ratio between O, NaAc and natrium citricum is (1-1.5): (3.4-3.8): (0.3-0.5).Preferably, FeCl
36H
2mol ratio between O, NaAc and natrium citricum is 1:3.5:0.4.
Preferably, in above-mentioned steps (2), in the mixed liquor of ethanol and deionized water, the volume ratio of ethanol and deionized water is (3-4): (0.8-1), and preferably, the volume ratio of ethanol and deionized water is 4:1.In preparation process, the amount that TEOS adds is larger, SiO
2the thickness of layer is larger.
Preferably, in above-mentioned steps (3), Mg (NO
3)
26H
2o and Al (NO
3)
39H
2the mol ratio of O is (2-3): (1-1.5); Preferably, Mg (NO
3)
26H
2o and Al (NO
3)
39H
2the mol ratio of O is 3:1.
Preferably, in above-mentioned steps (3), drip alkaline solution to solution ph between 9-11; Preferred, solution ph=10.Described alkaline solution is by Na
2cO
3be dissolved in NaOH and obtain in methanol aqueous solution.Further, described alkaline solution is by Na
2cO
3being dissolved in volume ratio with NaOH is obtain in the methanol aqueous solution of 1:1.
The invention also discloses the magnetic Fe of above-mentioned preparation
3o
4@SiO
2@Mg-Al LDH composite nano materials is the purposes of solid extracting agent organic pollution in enrichment or isolating environment water sample.
Preferably, the organic pollution in described environmental water sample is phthalate compound.Described phthalate pollutant comprises phthalandione n-propyl (DPP), the positive butyl ester of phthalandione (DBP), phthalandione cyclohexyl (DCP) and phthalandione n-octyl (DOP).
Fe is prepared disclosed in the present invention
3o
4@SiO
2the method of@Mg-Al LDH solid extracting agent is: first prepared the magnetic Fe of diameter at about 200nm with solvent-thermal method
3o
4particle; Then by Hydrolyze method, in the basic conditions, by SiO
2the coated Fe of layer
3o
4particle surface, the SiO obtained
2layer thickness is at about 25nm; Finally utilize ultrasonic method, at pH constant be 10 condition synthesis Mg-Al LDH layer.Ionic surfactant very easily forms mixed micelle at metal oxide surface, only need immerse in the solution of certain density surfactant by obtained magnetic layered double-metal hydroxide, and absorption self assembly behavior can occur.Just the selective of extractant can be regulated quickly and easily by control solution ph and the extraction conditions such as kinds of surfactants, concentration.Because the kind of extractant is different, the pollutant being suitable for extraction is different, therefore need regulate the selective of extractant, in general: anionic surfactant is suitable for extraction anionic compound, and cationic surface active agent is suitable for extracting cationic compound; PH value difference, the kinds of surfactants of easily absorption is also just different, thus causes the pollutant of extraction different.Object to be extracted from water sample, only need by the dispersion of obtained nano solid extracting agent in aqueous, leave standstill and within 10 minutes, can complete organic absorption, then under additional magnetic fields, in 5 minutes, the quick Magneto separate of solid-liquid can complete the process of extraction; In Separation of Solid and Liquid process, the extractant combining target contaminant is separated fast from the aqueous solution.The a small amount of organic solvent wash-out of the nano material separated, then enter liquid chromatogram measuring target concentration after being concentrated by eluent.Whole pretreatment process very quick, therefore, mixed micelle formula Fe
3o
4@SiO
2good application prospect is had in the concentration and separation of@Mg-Al LDH solid extracting agent organic pollution in large volume environmental sample.
Compared with existing traditional SPE material sample pre-treating method, solid extracting agent of the present invention has the following advantages:
1. Solvent quantity is few, and extraction efficiency is high.In current commercial solid-phase extraction column, the quality of extractant is generally between 200-500mg, and Fe prepared by the present invention
3o
4@SiO
2@Mg-Al LDH only needs 30mg just can the organic pollution of trace in quantitative recovery 300mL water sample.
2. environmental friendliness.In solid phase extraction procedure, only need consume the organic solvent of minute quantity, other poisonous and hazardous materials can not be introduced, environmentally friendly.
3. easy and simple to handle, rate of extraction is fast.On the one hand, because nano material particle diameter is little, diffusion path is short, therefore, it is possible to realize quick adsorption; On the other hand, obtained Fe
3o
4@SiO
2@Mg-Al LDH magnetic Nano material has good superparamagnetism, uses a strong magnet just can easily realize extractant and is separated with mother liquor is quick and complete.
4. with low cost, preparation is simple.The primary raw material used in preparation process is FeCl
36H
2o, ammoniacal liquor, tetraethoxysilane (TEOS), cheap, it is convenient to buy.
5. good stability, renewable and recycling.The object be adsorbed in nano material can elute with a small amount of organic solvent easily, forms the surfactant of mixed micelle itself also by complete wash-out, and during extraction next time, mixed micelle is very easily formed on double-metal hydroxide surface again again.Overcome short, the not reproducible utilization in service life of general SPE Stationary liquid, expensive shortcoming to a certain extent.
Select phthalate pollutant phthalandione n-propyl (DPP), the positive butyl ester of phthalandione (DBP), phthalandione cyclohexyl (DCP) and phthalandione n-octyl (DOP), Deng the representative as common contaminant, the Fe that Surfactant lauryl sodium sulfate (SDS) is modified
3o
4@SiO
2the extraction ability of the magnetic layered double-metal hydroxide solid extracting agent of@Mg-Al LDH is tested.Result proves that this extractant has good extracting power, uses 30mg extractant in 400mL ambient water sample, and the extraction yield for majority of organic pollutants all can reach more than 90%.Its desorption process is also fairly simple, and organic pollution just can elute by usual 12mL (4mL × 3) organic solvent completely.Under the effect of additional magnet, extractant and ambient water sample can realize being separated completely in 5min.After being concentrated to 0.5mL, namely can be used for the analysis of liquid chromatogram sample introduction.
Accompanying drawing explanation
Below, describe embodiments of the invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is the synthesis schematic diagram of magnetic nano-material extractant of the present invention;
Fig. 2 is TEM and the SEM photo of magnetic nano-material extractant of the present invention and various intermediate product, (A) Fe
3o
4, (B) Fe
3o
4@SiO
2, (C) Fe
3o
4@SiO
2@Mg-Al LDH;
Fig. 3 is the infrared spectrum of magnetic nano-material extractant of the present invention and various intermediate product;
Fig. 4 is the hysteresis curve of magnetic nano-material extractant of the present invention and various intermediate product;
Fig. 5 is the N of magnetic nano-material extractant of the present invention
2adsorption-desorption curve map;
Fig. 6 is the XRD spectra of magnetic nano-material extractant of the present invention and various intermediate product;
Fig. 7 is the XPS spectrum figure of magnetic nano-material extractant of the present invention and various intermediate product;
Fig. 8 is magnetic Nano material SPE flow chart of the present invention.
Detailed description of the invention
Set forth the present invention further below in conjunction with preferred embodiment, but these embodiments are only limitted to the present invention is described, can not limit the scope of the invention.Please refer to accompanying drawing 1 to accompanying drawing 8, the embodiment of the present invention comprises:
Embodiment 1: a kind of magnetic Nano material solid extracting agent, comprises the magnetic silica particles as kernel, as the layered double hydroxide of shell; Described magnetic silica particles is formed in magnetic Nano core by coated with silica; Layered double-metal hydroxide shell is Mg-Al double-metal hydroxide.In the present embodiment, described magnetic Nano core is Fe
3o
4.
Embodiment 2: a kind of magnetic Nano material solid extracting agent, comprises the magnetic silica particles as kernel, as the layered double hydroxide of shell; Described magnetic silica particles is formed in magnetic Nano core by coated with silica; Layered double-metal hydroxide shell is Mg-Al double-metal hydroxide.In the present embodiment, described magnetic Nano core is Fe
3o
4, one in Co, FeCo, Ni, FeCo, FeO.In the present embodiment, magnetic Nano core is prepared by solvent-thermal method.
Embodiment 3: the difference of the present embodiment and above-described embodiment is, in the present embodiment, the diameter of magnetic Nano core is between 150nm-250nm, and the diameter of magnetic Nano core can be 150nm, 180nm, 200nm, 220nm, 250nm.In the present embodiment, the silicon dioxide layer in magnetic silica particles is that TEOS hydrolysis obtains.
embodiment 4: the preparation method of magnetic nano-material extractant of the present invention
Fe provided by the present invention
3o
4@SiO
2as shown in Figure 1, its concrete preparation method can be divided into following steps to the synthesis schematic diagram of@Mg-Al LDH magnetic nano-material extractant:
First, nano ferriferrous oxide is prepared.First by 4.05g FeCl
36H
2o, 5.2g NaAc and 1.25g natrium citricum are dissolved in 90mL ethylene glycol solvent, magnetic stirring 60min, yellow for gained mixed liquor is transferred in the polytetrafluoroethylene (PTFE) reactor of sealing, 180 DEG C of reaction 6h, after reaction terminates, externally-applied magnetic field is utilized to be separated by obtained ferroferric oxide magnetic nanoparticle; With ethanol the ferroferric oxide magnetic nanoparticle of gained cleaned that to be placed on 60 DEG C of dryings in vacuum desiccator for 3 times for subsequent use after 12 hours.
Secondly, by Fe
3o
4magnetic nanoparticle coated with silica, obtained embedding formula magnetic silica particles.Get above-mentioned Fe
3o
4magnetic nanoparticle 1.02g, joins in the mixed liquor of 250mL ethanol and 50mL deionized water, then adds the NH of 3.6mL 25% volume fraction
3h
2o solution, ultrasonic agitation adds the TEOS of 3.0mL after 30 minutes, at room temperature stir 10h; It is for subsequent use after 12 hours that the magnetic silica gel particle obtained with washes of absolute alcohol is placed on 60 DEG C of dryings in vacuum desiccator for 3 times.
Again, double-metal hydroxide layer is formed on magnetic silica particles surface.Get above-mentioned magnetic silica particles 0.1g, be distributed to 50mL deionized water, drip alkaline solution subsequently until pH=10, with 1mLmin under mechanical agitation
-1speed by 20mL containing 1.44mmol Mg (NO
3)
26H
2o and 0.72mmolAl (NO
3)
39H
2the mixed liquor of O drops to above-mentioned solution; Collect product by after ultrasonic for above-mentioned mixed liquor half an hour, be again distributed in 50mL deionized water and continue ultrasonic 40min.It is for subsequent use after 12 hours that last products therefrom is placed in vacuum desiccator 60 DEG C of dryings.
embodiment 5: the preparation method of magnetic nano-material extractant of the present invention
Fe provided by the present invention
3o
4@SiO
2as shown in Figure 1, its concrete preparation method can be divided into following steps to the synthesis schematic diagram of@Mg-Al LDH magnetic nano-material extractant:
First, nano ferriferrous oxide is prepared.First by 2.7g FeCl
36H
2o, 4.67g NaAc and 0.75g natrium citricum are dissolved in 100mL ethylene glycol solvent, magnetic stirring 50min, yellow for gained mixed liquor is transferred in the polytetrafluoroethylene (PTFE) reactor of sealing, 180 DEG C of reaction 6h, after reaction terminates, externally-applied magnetic field is utilized to be separated by obtained ferroferric oxide magnetic nanoparticle; With ethanol the ferroferric oxide magnetic nanoparticle of gained cleaned that to be placed on 60 DEG C of dryings in vacuum desiccator for 3 times for subsequent use after 12 hours.
Secondly, by Fe
3o
4magnetic nanoparticle coated with silica, obtained embedding formula magnetic silica particles.Get above-mentioned Fe
3o
4magnetic nanoparticle 1.25g, joins in the mixed liquor of 150mL ethanol and 50mL deionized water, then adds the NH of 3.6mL 25% volume fraction
3h
2o solution, ultrasonic agitation adds the TEOS of 3.0mL after 30 minutes, at room temperature stir 10h; It is for subsequent use after 12 hours that the magnetic silica gel particle obtained with washes of absolute alcohol is placed on 60 DEG C of dryings in vacuum desiccator for 3 times.
Again, double-metal hydroxide layer is formed on magnetic silica particles surface.Get above-mentioned magnetic silica particles 0.2g, be distributed to 80mL deionized water, drip alkaline solution subsequently until pH=10, with 1mLmin under mechanical agitation
-1speed by 40mL containing 1.44mmol Mg (NO
3)
26H
2o and 1.08mmol Al (NO
3)
39H
2the mixed liquor of O drops to above-mentioned solution; Collect product by after ultrasonic for above-mentioned mixed liquor half an hour, be again distributed in 50mL deionized water and continue ultrasonic 40min.It is for subsequent use after 12 hours that last products therefrom is placed in vacuum desiccator 60 DEG C of dryings.
embodiment 6:the preparation method of magnetic nano-material extractant of the present invention
Fe provided by the present invention
3o
4@SiO
2as shown in Figure 1, its concrete preparation method can be divided into following steps to the synthesis schematic diagram of@Mg-Al LDH magnetic nano-material extractant:
First, nano ferriferrous oxide is prepared.First by 2.7g FeCl
36H
2o, 4.8g NaAc and 1.0g natrium citricum are dissolved in 80mL ethylene glycol solvent, magnetic stirring 30min, yellow for gained mixed liquor is transferred in the polytetrafluoroethylene (PTFE) reactor of sealing, 200 DEG C of reaction 10h, after reaction terminates, externally-applied magnetic field is utilized to be separated by obtained ferroferric oxide magnetic nanoparticle; With ethanol the ferroferric oxide magnetic nanoparticle of gained cleaned be placed on for 3 times in vacuum desiccator for subsequent use after 60 DEG C of dry 12h.
Secondly, by Fe
3o
4magnetic nanoparticle coated with silica, obtained embedding formula magnetic silica particles.Get above-mentioned Fe
3o
4magnetic nanoparticle 0.85g, joins in the mixed liquor of 200mL ethanol and 50mL deionized water, then adds the NH of 3.6mL 25% volume fraction
3h
2o solution, ultrasonic agitation adds the TEOS of 2.5mL after 30 minutes, at room temperature stir 12h; The magnetic silica gel particle obtained with washes of absolute alcohol is placed on for 3 times in vacuum desiccator for subsequent use after 60 DEG C of dry 12h.
Again, double-metal hydroxide layer is formed on magnetic silica particles surface.Get above-mentioned magnetic silica particles 0.1g, be distributed to 50mL deionized water, drip alkaline solution subsequently until pH=10, under mechanical agitation, with the speed of 1mL/min, 20mL is contained 1.44mmolMg (NO
3)
26H
2o and 0.48mmolAl (NO
3)
39H
2the mixed liquor of O drops to above-mentioned solution; Collect product by after ultrasonic for above-mentioned mixed liquor 30min, be again distributed in 50mL deionized water and continue ultrasonic 30min.Last products therefrom is for subsequent use after being placed in vacuum desiccator 60 DEG C of dry 12h.
embodiment 7: the structural characterization of magnetic nano-material extractant of the present invention and intermediate product thereof
The present embodiment is the structural characterization to magnetic nano-material extractant and intermediate product thereof, specific as follows:
1.TEM and SEM photo
Adopt NEC JEOL.JEM-200CX type transmission electron microscope (TEM) and Hitachi S-2400 field emission scanning electron microscope (SEM), to Fe
3o
4@SiO
2particle diameter and the appearance structure of the magnetic layered double-metal hydroxide of@Mg-Al and intermediate product are analyzed.
Can find out from Fig. 2 (A, D), prepared magnetic Fe
3o
4globulate, dispersiveness is very good, particle diameter at about 200nm, even particle size; Can find out from Fig. 2 (B, E), SiO
2after coated, grain diameter becomes large, and surface becomes smooth, SiO
2layer thickness, at about 25nm, is formed typical in Fe
3o
4for core, silica gel are the nucleus-shell structure of shell, dispersiveness is still fine.Fe
3o
4@SiO
2form similar petal-like structure after the transmission electron microscope picture (Fig. 2 C) of@Mg-Al LDH can find out LDH nanometer sheet vertical deposition to silicon surface, spherical core is tight, and shell density is obviously smaller.Can find out that nanometer sheet pattern is comparatively regular from scanning electron microscopic picture (Fig. 2 F), and between different nanometer sheet, have sufficient space, can be the some position that follow-up modification provides enough.
2. infrared spectrum
Utilize Nicolet 170 SX Fourier transformation infrared spectrometer (FT-IR) to Fe
3o
4, Fe
3o
4@SiO
2and Fe
3o
4@SiO
2@Mg-AlLDH particle characterizes, and use KBr pressed disc method, assay method and setting parameter are shown in Yonghui Deng, et al, J.Am.Chem.Soc., and 2008,130 (1), 28-29.
The infrared spectrum of various magnetic-particle as shown in Figure 3.At Fe
3o
4spectrogram on, 1400cm
-1the absworption peak at place is by being modified at Fe
3o
4surperficial COO-produces, at 1626cm
-1what locate is that COO-and O-H group overlapped vibration produces.585 and 3434cm
-1place observe peak time Fe-O and O-H group stretching vibration formed.585cm
-1the peak at place can be seen in three kinds of materials, but intensity is along with SiO
2layer and LDH layer coated and decrease.With Fe
3o
4standard IR collection of illustrative plates contrast, the Fe of synthesis
3o
4@SiO
2magnetic silica gel particle and Fe
3o
4@SiO
2@Mg-Al LDH magnetic double-metal hydroxide particle is at 1080cm
-1place has obviously had more the characteristic peak of Si-O key, but COO-absworption peak disappears simultaneously.Along with the introducing of LDH layer, 3434 and 1626cm
-1the peak at place increases by force, simultaneously at 1384cm
-1place add one new for NO
3 -group produces absworption peak, and the LDH synthesis simultaneously also demonstrating us is successful.
3. hysteresis curve
Vibrating specimen magnetometer (vibration sample magnetometer, Lake shore VSM 7300 series) is adopted to measure Fe
3o
4, Fe
3o
4@SiO
2and Fe
3o
4@SiO
2the magnetic hysteresis regression curve of@Mg-Al LDH particle, assay method and setting parameter are shown in Yonghui Deng, et al, J.Am.Chem.Soc., 2008,130 (1), 28-29.
The hysteresis curve of various magnetic-particle as shown in Figure 4.As can be seen from Figure 4, various magnetic-particle all shows typical superparamagnetism, and the remanent magnetism of its magnetization curve and coercivity are all almost nil.Along with increasing of non-magnetic constituents, Fe
3o
4@SiO
2and Fe
3o
4@SiO
2@Mg-Al LDH contrasts Fe
3o
4magnetic-particle declines slightly to some extent.The Fe of final preparation
3o
4@SiO
2the saturated magnetic intensity of@Mg-Al LDH is 29.62emug
-1, meet the requirement of Magnetic Isolation completely, its superparamagnetism makes MLDH extractant being well dispersed in water without during externally-applied magnetic field, can be separated fast again, complete extraction process after extraction terminates by magnetic sedimentation with mother liquor.
4. specific area, mesopore diameter and pore volume
Specific area and the pore volume of magnetic nanoparticle is measured by Gemini 2375V4.01 type N2 adsorption BET specific surface area analyzer (Norcross company of the U.S.), assay method and setting parameter are shown in Ian J.Bruce, et al, Journal of Magnetism and Magnetic Materials 284 (2004) 145-160.
Measure the result of magnetic nano-material extractant of the present invention: Fe
3o
4@SiO
2it is 354.82 (m that@Mg-Al LDH magnetic mesoporous carbon specific grain surface amasss
2g
-1); Pore volume is 1.63 (cm
3g
-1).Its N
2adsorption-desorption curve is typical IV type closed curve (Fig. 5 A), demonstrates the meso-hole structure of material.The mesoporous pore size distribution of material presents a sharp-pointed peak type (Fig. 5 B), and average pore size is respectively 2.73nm.
5.XRD spectrogram
X-ray diffraction (XRD) collection of illustrative plates of magnetic nano-material extractant is in the upper acquisition of b/max-RB Diffractometer (Japanese Rigaku), nickel is used to filter Cu K alpha ray, sweep limits is from 10 ° to 80 °, and sweep speed is 4 °/min.Assay method and setting parameter are shown in Yonghui Deng, Dawei Qi, Chunhui Deng, et al, J.Am.Chem.Soc., 2008,130 (1), 28-29.
As shown in Figure 6, Fe can be found out from the diffraction maximum of curve a
3o
4the cube structure of the atom center of area.After coated Si glue-line, curve has more amorphous Si O
2diffraction maximum.On curve c, in 2 θ=10.25 °, 23.01 °, 38.43 ° and 61.77 ° there is typical LDH diffraction maximum.With Fe
3o
4the XRD spectra contrast of magnetic particle, after can seeing coated Si glue-line and LDH layer, material still has Fe
3o
4characteristic peak, show Fe
3o
4the spinel crystal structure of nano particle does not change after clad is modified.
6.XPS spectrogram
Utilize x-ray spectrometer to carry out the scanning of full spectrum and narrow spectrum to synthetic material, its surface-element is analyzed.
As shown in Figure 7, Fe
3o
4@SiO
2on the spectrogram of@Mg-Al LDH, the diffraction maximum of O1s, Mg1s and Al2p appears at 539.95,1308.76 and 79.95 eV respectively, and this shows that Mg-Al LDH has successfully been modified at Fe
3o
4@SiO
2surface.
embodiment 8: the extraction ability test of magnetic nano-material extractant of the present invention
The present embodiment selects phthalate pollutant phthalandione n-propyl (DPP), the positive butyl ester of phthalandione (DBP), phthalandione cyclohexyl (DCP) and phthalandione n-octyl (DOP) as the representative of common contaminant, test the absorption property preparing magnetic nano-material extractant in embodiment 4,5,6, test data record is shown in as following table 1.
The operating procedure of test as shown in Figure 8, specific experiment process is as follows: the magnetic LDH particle and the 20mg SDS that get 30mg embodiment 4 or embodiment 5 or embodiment 6 preparation join in 400mL PAEs water sample, ultrasonic agitation makes it dispersed and forms suspension in the solution, then pH value of solution is regulated to be 4.5 with 0.1M HCl or NaOH, leave standstill after within 10 minutes, reaching adsorption equilibrium, be placed in high-intensity magnetic field and make extractant and solution quick separating (can realize within 5 minutes being separated completely); Discard mother liquor, divide 3 drip washing extractants (each 4mL) repeatedly with 12mL acetonitrile, the PAEs be adsorbed on extractant is eluted, after being merged by eluent, use N
2blow to 0.5mL, get 20 μ L sample introductions, adopt HPLC-UV detection system (HPLC-UV) to measure content.Utilize the concentration of object in high-performance liquid chromatogram determination concentrate, then calculate the rate of recovery of each pollutant.The Fe using 30mg is only needed in 400mL ambient water sample
3o
4@SiO
2@Mg-Al LDH magnetic Nano extractant, pollutant rate of recovery major part can reach more than 80%.Reclaim result to the mark-on of the ambient water such as running water, river sample satisfactory, the rate of recovery is greater than 80%, reappearance RSD≤10% of analysis result.
The condition of phthalate ester pollution determination is as follows:
Enlightening horse DIKMA Diamonsil C18 chromatographic column (4.6mm × 250mm, 5 μm);
Column temperature 30 DEG C; Sample size 20 μ L, flow rate of mobile phase 1mLmin
-1.
Flow velocity is 1.0mL/min, UV detect wavelength 226nm; Mobile phase is acetonitrile aqueous systems, gradient mode: passage A is 50% acetonitrile solution, and channel B is 100% acetonitrile, 0-22min, and the B from 60% becomes the B of 100%, 22-35min, the B of 100%.
In several environmental water sample of table 1, the detectable concentration of PAEs and mark-on thereof reclaim concentration
Claims (10)
1. a magnetic Nano material solid extracting agent, is characterized in that, described magnetic Nano material solid extracting agent comprises the magnetic silica particles as kernel, as the layered double hydroxide of shell; Described magnetic silica particles is formed in magnetic Nano core by coated with silica; Layered double-metal hydroxide shell is Mg-Al double-metal hydroxide.
2. magnetic Nano material solid extracting agent according to claim 1, is characterized in that, the magnetic Nano core in described magnetic silica particles is Fe
3o
4, one in Co, FeCo, Ni, FeCo, FeO.
3. magnetic Nano material solid extracting agent according to claim 2, is characterized in that, described magnetic Nano core adopts solvent-thermal method preparation.
4. magnetic Nano material solid extracting agent according to claim 3, is characterized in that, the diameter of described magnetic Nano core is between 150nm – 250nm.
5. magnetic Nano material solid extracting agent according to claim 1, is characterized in that, the silicon dioxide layer in described magnetic silica particles is that TEOS hydrolysis obtains.
6. a preparation method for magnetic Nano material solid extracting agent, comprises the following steps:
(1) magnetic Nano core is prepared: solvent-thermal method prepares magnetic Nano core;
(2) obtained magnetic silica particles: utilize TEOS to be hydrolyzed in the mixed liquor of ethanol and water in the basic conditions and form silicon dioxide layer, magnetic Nano core prepared by step (1) is embedded in described silicon dioxide layer, obtained magnetic silica particles;
(3) magnetic silica particles Surface coating double-metal hydroxide layer: utilize Mg (NO
3)
26H
2o, Al (NO
3)
39H
2o is the magnetic silica particles surface of co-precipitation prepared by step (2) in the basic conditions, forms double-metal hydroxide layer.
7. the self-assembling method on the top layer of the magnetic Nano material solid extracting agent of a surfactant in above-mentioned power 1-power 6, it is characterized in that, in acid condition, there is absorption self assembly behavior in magnetic double-metal hydroxide shell layer surface, form mixed micelle in surfactant SDS.
8. a Fe
3o
4@SiO
2the preparation method of@Mg-Al LDH composite nano materials solid extracting agent, comprises the following steps:
(1) solvent-thermal method prepares Fe
3o
4nano particle: by FeCl
36H
2o, NaAc and natrium citricum are dissolved in ethylene glycol solvent, magnetic stirring 20min – 60min; Gained solution is transferred in sealed reactor, at 180-240 DEG C, reacts 6 – 14h, after reaction terminates, by the Fe of preparation
3o
4nano particle is separated and is cleaned up, drying for standby;
(2) obtained magnetic silica particles: the Fe getting above-mentioned preparation
3o
4nano particle joins in the mixed liquor of ethanol and deionized water, then adds the NH of 25%
3h
2o solution, adds TEOS after ultrasonic agitation, stirred at ambient temperature 10-15h; Obtain magnetic silica particles (Fe
3o
4@SiO
2); The magnetic silica particles of preparation is cleaned up, drying for standby;
(3) magnetic silica particles Surface coating double-metal hydroxide layer: get above-mentioned magnetic silica particles, be distributed in deionized water, drips alkaline solution to solution alkaline, under agitation by Mg (NO
3)
26H
2o, Al (NO
3)
39H
2the mixed liquor of O drops to described alkaline solution; After being added dropwise to complete, after ultrasonic 20-40min, collect product, product is dispersed in deionized water again and continues ultrasonic 20 – 40min, finally prepare Fe
3o
4@SiO
2@Mg-Al LDH composite nano materials extractant.
9. a magnetic Fe
3o
4@SiO
2@Mg-Al LDH composite nano materials is the purposes of solid extracting agent, it is characterized in that, for the organic pollution in enrichment or isolating environment water sample.
10. the purposes of solid extracting agent according to claim 9, is characterized in that, the organic pollution in described environmental water sample is phthalate compound.
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| CN104258807B (en) | 2015-07-01 |
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