CN104226262A - Preparing method and application thereof of functional magnetic MOFs (Metal-Organic Frameworks) material - Google Patents
Preparing method and application thereof of functional magnetic MOFs (Metal-Organic Frameworks) material Download PDFInfo
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Abstract
一种功能化磁性MOFs材料的制备方法，所述功能化磁性MOFs材料为羧基或氨基修饰的磁性MOFs材料，步骤如下：首先制备羧基或氨基功能化磁性粒子，然后制备功能化磁性MOFs材料。本发明的优点是：该功能化磁性MOFs材料的制备方法工艺简单、易于实施，制备的功能化磁性MOFs材料用于对雌激素进行磁性固相萃取，通过在Fe3O4粒子表面进行功能修饰，实现对磁性MOFs表面的疏水和亲水性、极性的调节，以达到对磁性MOFs材料吸附性能的调节和改善，可高效地吸附富集环境水中污染的痕量环境雌激素，为快速、灵敏、高效地检测环境水中痕量雌激素提供有力的技术支持。
A method for preparing a functionalized magnetic MOFs material, wherein the functionalized magnetic MOFs material is a magnetic MOFs material modified by a carboxyl group or an amino group, the steps are as follows: firstly prepare a carboxyl group or an amino group functionalized magnetic particle, and then prepare a functionalized magnetic MOFs material. The advantages of the present invention are: the preparation method of the functionalized magnetic MOFs material is simple and easy to implement, and the prepared functionalized magnetic MOFs material is used for magnetic solid-phase extraction of estrogen, by performing functional modification on the surface of Fe3O4 particles , realize the adjustment of the hydrophobicity, hydrophilicity and polarity of the surface of magnetic MOFs, in order to achieve the adjustment and improvement of the adsorption performance of magnetic MOFs materials, and can efficiently adsorb and enrich trace environmental estrogens polluted in environmental water. Sensitive and efficient detection of trace estrogen in environmental water provides strong technical support.
Description
Technical field
The present invention relates to estrogenic enrichment method, particularly a kind of preparation method of functional magnetic MOFs material and application thereof.
Background technology
In China along with industrialized high speed development, environmental pollution is on the rise, and the environmental estrogens class material wherein with endocrine disrupting causes the concern of people day by day.Environmental estrogens is that a class has bioactive sterid, can affect the nerves after entering human body and animal body, immunity and the normal regulation function of internal system, dysgenesia, dysplasia, some cancer and relevant Ecology Action can be caused.Environmental estrogens is extensively present in occurring in nature, and stable in properties is not easily degraded destruction, has very strong toxicity and bioconcentration, disturbs the internal system of animals and humans by drinking water and food chain enrichment.Serious harm can be produced at much lower concentrations to organism.Therefore quick, sensitive, trace estrogen that is that pollute in testing environment water efficiently becomes one of the difficult point and focus of environmental monitoring.
Estrogen content in environment is usually all very low, is generally μ gL
-1or ngL
-1the order of magnitude, in addition owing to there is matrix effect and other interference, even use highly sensitive analytical instrument to be also difficult to obtain measurement result accurately, therefore separation and concentration remains indispensable important step in trace analysis.Traditional sample treatment technology is as surname extraction, ultrasonic extraction etc., and most complicated operation, working strength are large, long processing period, needs to use the shortcomings such as a large amount of volatile organic solvent.Along with the fast development of material science, various organic and inorganic and hybrid material, particularly magnetic composite all for enriched with trace environmental estrogens with get rid of chromatogram detect time other materials interference.
Metal-organic framework materials (MOFs) is a kind of material emerging in recent years.Owing to having that specific area is large, structure diversity, pore size are adjustable and skeleton such as can to modify at the advantage, it is made to become a kind of sorbing material of excellence.In sample separation is analyzed, magnetic MOFs material is due to without the need to high speed centrifugation or membrane filtration, cause the great interest of people, more because it with the magnetic response characteristic of magnetic particle and MOFs material excellent absorption property and enjoy favor, it shows huge potentiality in sample preconcentration, environmental contaminants compartment analysis.Adopt functional magnetic MOFs material to carry out magnetic SPE to estrogenic, quick, sensitive, efficiently in testing environment water trace estrogen can be realized.
Summary of the invention
The object of the invention is for above-mentioned technical Analysis and existing problems, provide a kind of preparation method and application thereof of functional magnetic MOFs material, the functional magnetic MOFs material of preparation is used for carrying out Magnetic solid phases extraction to estrogen.By at Fe
3o
4particle surface carries out functionalized modification, realize the adjustment to the hydrophobic of magnetic MOFs surface and hydrophily, polarity, to reach adjustment to magnetic MOFs materials adsorption performance and improvement, the trace amount environment estrogen that can pollute in adsorption and enrichment ambient water efficiently, for quick, sensitive, efficiently testing environment underwater trace estrogen strong technical support is provided.
Technical scheme of the present invention:
A preparation method for functional magnetic MOFs material, described functional magnetic MOFs material is carboxyl or amido modified magnetic MOFs material, and step is as follows:
1) preparation of carboxyl-functional magnetic particle
By FeCl
36H
2o and natrium citricum are dissolved in ethylene glycol, add anhydrous sodium acetate stirring and dissolving, then proceed to and are equipped with in teflon-lined reactor, 10 h are reacted at 200 DEG C, Magneto separate solid, uses 60 DEG C of vacuum drying 12 h, obtained carboxyl-functional Fe after water and ethanol purge 3 times successively
3o
4magnetic particle;
2) preparation of amino functional magnetic particle
By FeCl
36H
2o, 1,6-hexamethylene diamine and anhydrous sodium acetate add in ethylene glycol, stir until dissolve, then proceed to and be equipped with in teflon-lined reactor, at 200 DEG C, react 6 h, Magneto separate solid, use 60 DEG C of vacuum drying 12 h, obtained amino functional Fe after water and ethanol purge 3 times successively
3o
4magnetic particle;
3) preparation of functional magnetic MOFs material
By Cr (NO
3)
39H
2o, terephthalic acid (TPA) and hydrofluoric acid are dissolved in deionized water, magnetic agitation is dissolved, then carboxyl-functional magnetic particle or amino functional magnetic particle prepared by above-mentioned steps is added, proceed to after being uniformly dispersed and be equipped with in teflon-lined reactor, react 18 h at 218 DEG C, after cool to room temperature, by external magnet collecting reaction product, use water and ethanol purge 3 times successively, vacuum drying 12 h at 100 DEG C, obtained carboxyl or amido modified functional magnetic MOFs material.
Described FeCl
36H
2the amount ratio of O, natrium citricum, anhydrous sodium acetate and ethylene glycol is 1 g:0.1-0.3 g:1-3 g:20 mL.
Described FeCl
36H
2the amount ratio of O, 1,6-hexamethylene diamine, anhydrous sodium acetate and ethylene glycol is 1 g:3-6 g:2-4 g:3 0 mL.
Described Cr (NO
3)
39H
2the mol ratio of O, terephthalic acid (TPA), hydrofluoric acid and deionized water is 1:0.67:0-2:278; Cr (NO
3)
39H
2the amount ratio of O and carboxyl or amino functional magnetic particle is 1mol:20-60 mg.
An application for prepared functional magnetic MOFs material, for carrying out Magnetic solid phases extraction to estrogen in ambient water, step is as follows:
1) pH value is adjusted to 5.0-8.0 with the membrane filtration in 0.45 μm of aperture by the water sample of collection, add estrogen standard specimen to concentration 50 ppb, described estrogen standard specimen comprises oestrone, 17 beta estradiols, estriol and bisphenol-A;
2) get 2-10 mg carboxyl or amido modified magnetic MOFs homogenize material is scattered in 30 mL water samples, put into digital display type gas bath constant temperature oscillator room temperature and carry out oscillation extraction, revolution is 250 rpm, and extraction time is 10-30 min;
3) with external magnet, separation and concentration is carried out to functional magnetic MOFs material, with 500 μ L methyl alcohol or acetonitrile, and adopt organic membrane filtration of 0.45 μm to be measured in sample bottle.
Advantage of the present invention is: preparation method's technique of this functional magnetic MOFs material is simple, easy to implement, and the functional magnetic MOFs material of preparation is used for carrying out Magnetic solid phases extraction to estrogen, by Fe
3o
4particle surface carries out functionalized modification, realize the adjustment to the hydrophobic of magnetic MOFs surface and hydrophily, polarity, to reach adjustment to magnetic MOFs materials adsorption performance and improvement, the trace amount environment estrogen that can pollute in adsorption and enrichment ambient water efficiently, for quick, sensitive, efficiently testing environment underwater trace estrogen strong technical support is provided.
[accompanying drawing explanation]
Fig. 1 is magnetic particle and the functional magnetic MOFs material Electronic Speculum figure of functionalization, in figure: (A) carboxyl-functional magnetic particle; (B) the magnetic MOFs material of carboxyl modified; (C) amino functional magnetic particle; (D) amido modified magnetic MOFs material.
Fig. 2 is functional magnetic MOFs material enrichment estrogen (1 estriol; 2 bisphenol-As; 3 17-β estradiol; 4 oestrone) before and after liquid chromatogram, in figure: four kinds of estrogenic chromatograms of 50 ppb before (A) enrichment; (B) chromatogram after the magnetic MOFs material enrichment of carboxyl modified; (C) chromatogram after amido modified magnetic MOFs material enrichment.
[detailed description of the invention]
Embodiment 1:
A preparation method for functional magnetic MOFs material, described functional magnetic MOFs material is the magnetic MOFs material of carboxyl modified, and step is as follows:
1) preparation of carboxyl-functional magnetic particle
By 1 g FeCl
36H
2o and 0.2 g natrium citricum are dissolved in 20 mL ethylene glycol, add 1.2 g anhydrous sodium acetate stirring and dissolving, then proceed to and be equipped with in teflon-lined reactor, 10 h are reacted at 200 DEG C, Magneto separate solid, use 60 DEG C of vacuum drying 12 h, obtained carboxyl-functional Fe after water and ethanol purge 3 times successively
3o
4magnetic particle; Fig. 1 (A) is carboxyl-functional magnetic particle Electronic Speculum figure, shows in figure: synthesized carboxyl-functional magnetic particle is spherical and even particle size distribution, pattern are neat.
2) preparation of the magnetic MOFs material of carboxyl modified
By 2.5 mmol Cr (NO
3)
39H
2o, 1.675 mmo terephthalic acid (TPA)s and 0.2 mL hydrofluoric acid are dissolved in 12.5 mL deionized waters, magnetic agitation is dissolved, then 60 mg carboxyl-functional magnetic particles prepared by above-mentioned steps are added, proceed to after being uniformly dispersed and be equipped with in teflon-lined reactor, react 18 h at 218 DEG C, after cool to room temperature, by external magnet collecting reaction product, use water and ethanol purge 3 times successively, vacuum drying 12 h at 100 DEG C, the functional magnetic MOFs material of obtained carboxyl modified.The magnetic MOFs material Electronic Speculum figure that Fig. 1 (B) is carboxyl modified, shows in figure: carboxyl-functional magnetic particle is attached to the surface of octahedra MOFs material.
The application of the magnetic MOFs material of prepared carboxyl modified, for carrying out Magnetic solid phases extraction to estrogen in ambient water, step is as follows:
1) pH value is adjusted to 6.0 with the membrane filtration in 0.45 μm of aperture by the water sample of collection, add four kinds of estrogen standard specimens to concentration 50 ppb, described estrogen standard specimen comprises oestrone, 17 beta estradiols, estriol and bisphenol-A;
2) measure the water sample of 30 mL, be scattered in 30 mL water samples by the magnetic MOFs homogenize material of 5 mg carboxyl modified, put into digital display type gas bath constant temperature oscillator room temperature and carry out oscillation extraction, revolution is 250 rpm, and extraction time is 10 min;
3) carry out separation and concentration with the magnetic MOFs material of external magnet to carboxyl modified, by 500 μ L methanol-eluted fractions, and adopt organic membrane filtration of 0.45 μm in sample bottle, carry out liquid chromatogram separation determination.
Fig. 2 is functional magnetic MOFs material enrichment estrogen (1 estriol; 2 bisphenol-As; 3 17-β estradiol; 4 oestrone) before and after liquid chromatogram, in figure: four kinds of estrogenic chromatograms of 50 ppb before (A) enrichment; (B) chromatogram after the magnetic MOFs material enrichment of carboxyl modified, shows in figure: the magnetic MOFs material of carboxyl modified shows excellent sorption extraction performance to four kinds of estrogen.
Embodiment 2:
A preparation method for functional magnetic MOFs material, described functional magnetic MOFs material is amido modified magnetic MOFs material, and step is as follows:
1) preparation of amino functional magnetic particle
By 1.0 g FeCl
36H
2o, 5 g 1,6-hexamethylene diamine and 2.0 g anhydrous sodium acetates add in 30 mL ethylene glycol, stir until dissolve, then proceed to and be equipped with in teflon-lined reactor, 6 h are reacted at 200 DEG C, Magneto separate solid, uses 60 DEG C of vacuum drying 12 h, obtained amino functional Fe after water and ethanol purge 3 times successively
3o
4magnetic particle; Fig. 1 (C) is amino functional magnetic particle Electronic Speculum figure, shows in figure: amino functional magnetic particle is spherical and even particle size distribution, pattern are neat.
2) preparation of amino functional magnetic MOFs material
By 2.5 mmol Cr (NO
3)
39H
2o, 1.675 mmol terephthalic acid (TPA)s and 0.1 mL hydrofluoric acid are dissolved in 12.5 mL deionized waters, magnetic agitation is dissolved, then 80 mg amino functional magnetic particles prepared by above-mentioned steps are added, proceed to after being uniformly dispersed and be equipped with in teflon-lined reactor, react 18 h at 218 DEG C, after cool to room temperature, by external magnet collecting reaction product, use water and ethanol purge 3 times successively, vacuum drying 12 h at 100 DEG C, obtained amido modified magnetic MOFs material.Fig. 1 (D) is amido modified magnetic MOFs material Electronic Speculum figure, shows the surface that amino functional magnetic particle is attached to octahedra MOFs material in figure.
The application of prepared amido modified magnetic MOFs material, for carrying out Magnetic solid phases extraction to estrogen in ambient water, step is as follows:
1) pH value is adjusted to 7.0 with the membrane filtration in 0.45 μm of aperture by the water sample of collection, add four kinds of estrogen standard specimens to concentration 50 ppb, described estrogen standard specimen comprises oestrone, 17 beta estradiols, estriol and bisphenol-A;
2) measure the water sample of 30 mL, be scattered in 30 mL water samples by magnetic MOFs homogenize material amido modified for 5 mg, put into digital display type gas bath constant temperature oscillator room temperature and carry out oscillation extraction, revolution is 250 rpm, and extraction time is 10 min;
3) with external magnet, separation and concentration is carried out to amido modified magnetic MOFs material, by 500 μ L methanol-eluted fractions, and adopt organic membrane filtration of 0.45 μm in sample bottle, carry out liquid chromatogram separation determination.
Fig. 2 is functional magnetic MOFs material enrichment estrogen (1 estriol; 2 bisphenol-As; 3 17-β estradiol; 4 oestrone) before and after liquid chromatogram, in figure: four kinds of estrogenic chromatograms of 50 ppb before (A) enrichment; (C) chromatogram after the enrichment of amino-magnetic MOFs material, shows in figure: amido modified magnetic MOFs material shows excellent sorption extraction performance to four kinds of estrogen.
Claims (5)
1. a preparation method for functional magnetic MOFs material, is characterized in that: described functional magnetic MOFs material is carboxyl or amido modified magnetic MOFs material, and step is as follows:
1) preparation of carboxyl-functional magnetic particle
By FeCl
36H
2o and natrium citricum are dissolved in ethylene glycol, add anhydrous sodium acetate stirring and dissolving, then proceed to and are equipped with in teflon-lined reactor, 10 h are reacted at 200 DEG C, Magneto separate solid, uses 60 DEG C of vacuum drying 12 h, obtained carboxyl-functional Fe after water and ethanol purge 3 times respectively
3o
4magnetic particle;
2) preparation of amino functional magnetic particle
By FeCl
36H
2o, 1,6-hexamethylene diamine and anhydrous sodium acetate add in ethylene glycol, stir until dissolve, then proceed to and be equipped with in teflon-lined reactor, at 200 DEG C, react 6 h, Magneto separate solid, use 60 DEG C of vacuum drying 12 h, obtained amino functional Fe after water and ethanol purge 3 times respectively
3o
4magnetic particle;
3) preparation of functional magnetic MOFs material
By Cr (NO
3)
39H
2o, terephthalic acid (TPA) and hydrofluoric acid are dissolved in deionized water, magnetic agitation is dissolved, then carboxyl or amino functional magnetic particle prepared by above-mentioned steps is added, proceed to after being uniformly dispersed and be equipped with in teflon-lined reactor, react 18 h at 218 DEG C, after cool to room temperature, by external magnet collecting reaction product, use water and ethanol purge 3 times successively, vacuum drying 12 h at 100 DEG C, obtained carboxyl or amido modified functional magnetic MOFs material.
2. the preparation method of functional magnetic MOFs material according to claim 1, is characterized in that: described FeCl
36H
2the amount ratio of O, natrium citricum, anhydrous sodium acetate and ethylene glycol is 1 g:0.1-0.3 g:1-3 g:20 mL.
3. the preparation method of functional magnetic MOFs material according to claim 1, is characterized in that: described FeCl
36H
2the amount ratio of O, 1,6-hexamethylene diamine, anhydrous sodium acetate and ethylene glycol is 1 g:3-6 g:2-4 g:3 0 mL.
4. the preparation method of functional magnetic MOFs material according to claim 1, is characterized in that: described Cr (NO
3)
39H
2the mol ratio of O, terephthalic acid (TPA), hydrofluoric acid and deionized water is 1:0.67:0-2:278; Cr (NO
3)
39H
2the amount ratio of O and carboxyl or amino functional magnetic particle is 1mol:20-60 mg.
5. an application for the functional magnetic MOFs material prepared by claim 1, is characterized in that: for carrying out Magnetic solid phases extraction to estrogen in ambient water, step is as follows:
1) pH value is adjusted to 5.0-8.0 with the membrane filtration in 0.45 μm of aperture by the water sample of collection, add estrogen standard specimen to concentration 50 ppb, described estrogen standard specimen comprises oestrone, 17 beta estradiols, estriol and bisphenol-A;
2) get 2-10 mg carboxyl or amido modified magnetic MOFs homogenize material is scattered in 30 mL water samples, put into digital display type gas bath constant temperature oscillator room temperature and carry out oscillation extraction, revolution is 250 rpm, and extraction time is 10-30 min;
3) with external magnet, separation and concentration is carried out to functional magnetic MOFs material, with 500 μ L methyl alcohol or acetonitrile, and adopt organic membrane filtration of 0.45 μm to be measured in sample bottle.
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