CN105498694A - Temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof - Google Patents

Temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof Download PDF

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CN105498694A
CN105498694A CN201510854281.1A CN201510854281A CN105498694A CN 105498694 A CN105498694 A CN 105498694A CN 201510854281 A CN201510854281 A CN 201510854281A CN 105498694 A CN105498694 A CN 105498694A
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陈相峰
贾玉倩
苏浩
曹莹莹
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Shandong Analysis and Test Center
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    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
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    • B01J20/285—Porous sorbents based on polymers
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • G—PHYSICS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N30/02—Column chromatography
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography

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Abstract

The invention discloses a temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof. A temperature-sensitive polymer and a magnetic material are introduced into a metal organic framework, and the obtained composite material has a high specific surface area and can realize enrichment and separation of target pollutants; through introduction of magnetic ferriferrous oxide, enrichment and separation become more convenient and faster under the action of an applied magnetic field, so time for enrichment is substantially shortened, and an adsorbent material can be easily recovered for cyclic usage; and through introduction of the temperature-sensitive polymer, the prepared material has hydrophilic groups on the surface, which enables dispersibility and stability of the material in water to be improved, and temperature-sensitive changes unique to the polymer enable the adsorbent material to have high enrichment efficiency to the target pollutants at low temperature, volatilization of organic solvents in the process of extraction and elution to be reduced and secondary pollution to the environment to be reduced.

Description

A kind of metallic organic framework magnetic material of temperature sensitive polymer parcel and application thereof
Technical field
The present invention relates to metallic organic framework magnetic material and the application thereof of a kind of temperature sensitive polymer parcel.
Background technology
PBDE (PBDEs) can be divided into ten homology groups according to bromine atoms quantity, has 209 kinds of homologue isomers, has persistence, hydrophobicity and bioaccumulation.Because it is cheap and efficient fire resistance, be widely used in during electronics industry produces, but PBDEs in the product and there is not the effect of chemical bond between material, so produce, be inevitably released in environment in the process of transport and use.Their chemical property is extremely stable, is difficult in the environment by organism degrades, and can remains by all means, finally cause the pollution of global range, therefore most important with detection to the enrichment of PBDE in environment.
At present, liquid-liquid extraction (LLE), SPE (SPE), SPME (SPME), stirring rod SPE (SBSPE) are mainly contained to the enrichment mode of PBDE in water body.But, liquid-liquid extraction method is the earliest for the extraction of hydrophobic organic compound, by ethyl acetate, carrene and n-hexane equal solvent target contaminant is transferred in organic solvent and carries out enrichment method, but the quantity of solvent that consumes of liquid-liquid extraction more greatly and easily occur emulsion; SPE is based on column chromatography principle, utilize the different of ability that to interact between solid absorbent from target contaminant in fluid sample, the concentration and separation of realize target pollutant, can collect sampling, extract and be enriched in one, but expends time in long and load the reappearance that quality can affect experiment; SPME is a kind of novel extraction and separation technology grown up based on SPE, integrate sampling, extraction, enrichment and sample introduction, convenient and swift without the need to organic reagent, but extraction time is longer and experimentation cost is higher; Stirring rod SPE dimethyl siloxane (PDMS) is enclosed within interior envelope to have on the glass tube of magnetic core as extracting coating, it is a kind of novel SPME pretreatment technology, relative to SPME, there is larger extraction stationary phase volume, but comparatively slow then needs consumes longer extraction time due to mass transfer rate.And magnetic SPE (MSPE) is incorporated in solid adsorbent materials by magnetic-particle, make enrichment process become convenient and swift, required solvent is less, extraction time is short, cost is lower and the feature such as favorable reproducibility therefore to adopt magnetic solid phase extraction to have.
Metal-organic framework materials (MOFs) is the polymer formed by coordinate bond by metal ion and organic ligand, because of the difference of its coordination mode, thus obtain different secondary construction units, further assembling obtains the different porous material of various structures, hole.Due to the advantage that its regulatable frame structure, special internal environment, good heat endurance and chemical stability and rear rhetorical function etc. are many, possessed inorganic matter, organic matter and both unexistent characteristics, thus be widely used in gas storage and adsorbing separation, organic molecule identification be separated, the exchange of ion and the research of the aspect such as identification, catalytic activity.But when using it for the enrichment of organic pollution, for dispersion extraction mode, usually by modes such as centrifugal or suction filtrations, MOFs can be extracted from sample solution, owing to reclaiming not exclusively, easily cause the loss of object and enrichment degree lower.
At present, gas chromatography (GC), gas chromatography-mass spectrography (GC-MS) and gas-chromatography-tandem mass spectrometry (GC-MS/MS) etc. are had to the analyzing detecting method of PBDE.But the selective and specificity that gas chromatography or gas chromatography-mass spectrography detect is poor, comparatively large to the interference ratio of complex sample, easily there is false positive results.Therefore adopt gas chromatography tandem mass spectrometry method to the mensuration of PBDE, the ambient interferences decreased in complex sample is scanned by second order ms, there is the features such as highly sensitive, good stability, the range of linearity are wide, improve the detection sensitivity of PBDE.
Summary of the invention
Object of the present invention is exactly to solve the problem, the metallic organic framework magnetic material providing a kind of temperature sensitive polymer to wrap up and application thereof, the present invention passes through metal-organic framework materials external growth temperature sensitive polymer, inner introducing magnetic ferroferric oxide, thus achieve the conveniently concentration and separation of target contaminant, make material in water, have pollutant well dispersed and at low temperatures and there is the very high rate of recovery.
To achieve these goals, the present invention adopts following technical scheme:
A kind of metallic organic framework magnetic material (Fe of temperature sensitive polymer parcel 3o 4siO 2uiO-66-PNIPAM) preparation method, step is as follows:
(1) carboxyl modified Fe 3o 4siO 2preparation: succinic anhydride and 3-aminopropyl triethoxysilane (APTES) are dissolved in DMF (DMF), add Fe 3o 4siO 2(SiO 2parcel Fe 3o 4core-shell material) DMF solution reaction, obtain black product carboxyl modified Fe 3o 4siO 2particle; The consumption mol ratio of preferred succinic anhydride and 3-aminopropyl triethoxysilane is 5:4.
(2) zirconium chloride (ZrCl 4), the amino terephthalic acid (TPA) of 2-and acetic acid is dissolved in DMF, adds the carboxyl modified Fe that step (1) is synthesized 3o 4siO 2after dispersion, be obtained by reacting Fe by under above-mentioned mixed solution 110-150 DEG C (preferably 130 DEG C) 3o 4siO 2uiO-66-NH 2; Preferred: the mol ratio of zirconium chloride and the amino terephthalic acid (TPA) of 2-is 1:1.
(3) NIPA (PNIPAM-NHS) (preferably: the concentration of the chloroform soln of PNIPAM-NHS is 10mM) of N-hydroxy-succinamide ester end-blocking is dissolved in chloroform, adds the Fe that step (2) is synthesized 3o 4siO 2uiO-66-NH 2dispersion, after being transferred to 50-70 DEG C (preferably 60 DEG C) reaction 24 afterwards, obtains product Fe 3o 4siO 2uiO-66-PNIPAM.PNIPAM-NHS and chloroform, Fe 3o 4siO 2uiO-66-NH 2consumption mol ratio be 1:1:3.
Fe in described step (1) 3o 4siO 2the preparation method of particle: Fe 3o 4be scattered in ethanol, add catalyst (preferred ammoniacal liquor) and tetraethyl orthosilicate (TEOS) reacts to obtain product Fe 3o 4siO 2, wash dry Fe 3o 4siO 2particle.Preferred: the volume ratio of tetraethyl orthosilicate and ammoniacal liquor is 1:1.
Above-mentioned Fe 3o 4preparation method: by Iron(III) chloride hexahydrate (FeCl 36H 2o) be dissolved in after in ethylene glycol, add sodium acetate (NaAC) and stir, afterwards mixed liquor is transferred in reactor, after reacting 6-10 hour (preferably 8 hours) under 180-220 DEG C (preferably 200 DEG C), obtain product.The mol ratio of preferred Iron(III) chloride hexahydrate and sodium acetate is 1:8.8.
Metallic organic framework magnetic material based on temperature sensitive polymer parcel prepared by said method.
The application of described material in enriching pollutants is separated.
The application of described material in persistence organic pollutant enrichment is analyzed.
Described pollutant is PBDE.
Detect a method for PBDE in water, the material first utilizing the present invention to prepare carries out concentration and separation, then detects with GC-MS/MS.Concrete detection method: material ultrasonic disperse the present invention prepared, in the 10mL mark-on aqueous solution or actual water sample, after ultrasonic 10 minutes, is separated and obtains sorbing material, to be joined in 2mL n-hexane ultrasonic wash-out afterwards 5 minutes under additional magnetic fields.The eluent obtained by magnetic fields nitrogen at 30 DEG C is blown and is concentrated into 100 μ L, gets 1 μ L and detects for gas-chromatography tandem mass spectrum.
Beneficial effect of the present invention:
The present invention introduces the metallic organic framework-magnetic nanoparticle of temperature sensitive polymer parcel in the material, in extraction process, due to the existence of hydrophilic polymer, makes adsorbent in solution system, have better dispersed and stability.Under the effect of externally-applied magnetic field, this composite can be separated comparatively fast preferably from sample solution, makes separation and elution process become simple and efficient.In addition, this temperature sensitive polymer has low temperature and opens duct, and high temperature closes the effect in duct, realizes low-temperature extraction, and effectively can avoid secondary pollution in extraction.
Composite prepared by the present invention has higher specific area, realizes the concentration and separation to target contaminant; The introducing of magnetic ferroferric oxide, makes concentration and separation process become convenient and swift under the effect of externally-applied magnetic field, substantially reduces the time of enrichment process and easily reclaims sorbent material and reach and recycle; The introducing of temperature sensing polymer, make material surface with hydrophilic group, enhance its dispersiveness in water and stability, and the distinctive change to temperature of polymer makes sorbent material have very high bioaccumulation efficiency to target contaminant at low temperatures, avoid the volatilization of organic solvent in the process of extraction and wash-out simultaneously, reduce the secondary pollution to environment; In conjunction with gas chromatography-mass spectrum, for the PBDE in ambient water sample detection, method has very high sensitivity and reappearance, can reach very low detectability and superior bioaccumulation efficiency.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of composite of the present invention;
Fig. 2 is the high resolution transmission electron microscopy photo of composite of the present invention;
Fig. 3 is the x-ray diffractogram of powder of composite of the present invention;
Fig. 4 is the hysteresis curve figure of composite of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing and embodiment, the invention will be further described.
(1) by 1.35g Iron(III) chloride hexahydrate (FeCl 36H 2o) be dissolved in 50mL ethylene glycol, after stirring to clarify, 3.6g sodium acetate (NaAC) slowly adds, and continues stirring 30 minutes.Be transferred to afterwards in reactor, react 8 hours at 200 DEG C.After normal temperature is down to by question response still, under the effect of externally-applied magnetic field, obtains black product and wash for several times with deionized water and ethanol, 60 DEG C of dried overnight;
(2) by the Fe of 20mg synthesis 3o 4ultrasonic disperse, in 20mL ethanol, adds 4mLH 2o and 100 μ L ammoniacal liquor continue ultrasonic 30 minutes, add 100 μ L tetraethyl orthosilicates (TEOS) afterwards and continue ultrasonic 5 hours.Product Fe 3o 4siO 2be separated under the effect of externally-applied magnetic field and use deionized water and ethanol washing for several times, 60 DEG C of dried overnight;
(3) 0.5g succinic anhydride and 1mL3-aminopropyl triethoxysilane (APTES) are dissolved in 30mLN, dinethylformamide (DMF), and mechanical agitation 3 hours in 30 DEG C of water-baths, by 40mgFe 3o 4siO 2ultrasonic disperse is in 20mLDMF and 3mLH 2be added to above-mentioned solution for continuous and stirred 12 hours in O.Be separated under externally-applied magnetic field effect and obtain black product carboxyl modified Fe 3o 4siO 2particle also washs for several times with deionized water and ethanol, 60 DEG C of dried overnight;
(4) 46.61mg zirconium chloride (ZrCl 4), the amino terephthalic acid (TPA) of 36.23mg2-and 30 μ L acetic acid are dissolved in 20mLDMF, add 10mg carboxyl modified Fe afterwards 3o 4siO 2ultrasonic disperse.Above-mentioned mixed solution to be transferred in flask under 130 DEG C of oil baths mechanic whirl-nett reaction 4 hours.Finally under additional magnetic fields, obtain Fe 3o 4siO 2uiO-66-NH 2and wash for several times with deionized water and ethanol, 60 DEG C of dried overnight;
(5) NIPA (PNIPAM-NHS) of 10mgN-hydroxysuccinimide eater end-blocking is dissolved in 500 μ L chloroforms, 3mgFe 3o 4siO 2uiO-66-NH 2ultrasonic disperse, in above-mentioned solution, is transferred to afterwards in 60 DEG C of oil baths and reacts 24 hours.After being down to normal temperature, end product Fe 3o 4siO 2uiO-66-PNIPAM is obtained by externally-applied magnetic field and uses chloroform and methyl alcohol cyclic washing, 60 DEG C of dried overnight.The block MOF material of the external growth of composite magnetic core of the present invention can be found out clearly by Fig. 1.Magnetic Fe can be distinguished more clearly by Fig. 2 3o 4core and outside SiO 2and the thickness of MOF shell (30 ~ 50nm).Composite of the present invention meets typical Fe as seen from Figure 3 3o 4with the X-ray diffraction peak of UiO66.This material has stronger magnetic as seen from Figure 4, can meet the follow-up requirement carrying out magnetometric analysis experiment.
The concentration and separation and the GC-MS/MS that material obtained above are used for PBDE in water sample detect.
(1) preparation of sample: standard P BDEs sample preparation concentration is the methanol solution of 20 μ g/L, stand-by.
(2) enrichment of sample: the magnetic microsphere compound material ultrasound that takes a morsel is scattered in the aqueous solution or actual water sample that concentration is 20ng/LPBDEs, ultrasonic disperse 10 minutes at 15 DEG C or 40 DEG C.Be separated under the effect of externally-applied magnetic field and obtain adsorbent, add the ultrasonic wash-out of 2mL n-hexane 5 minutes, be separated by magnetic fields and obtain eluant, eluent, at 30 DEG C, nitrogen blows and is concentrated into 100 μ L.
(3) GC-MS/MS detects: the eluent gas-chromatography tandem mass spectrum getting 1 μ L step (2) gained detects, and draws data analysis according to GC-MS/MS.
Setting GC-MS/MS operating condition is as follows: selected chromatographic column is: DB-5MS, (10m × 0.25mm × 0.25mm); Setting injector temperature is 280 DEG C; Setting Splitless injecting samples, sample size is 1 μ L; Setting post stream: 2mL/min, constant current; Setting column temperature: 150 DEG C, keep 1min, 20 DEG C/min rises to 300 DEG C, keeps 6min; Setting Mass Spectrometry Conditions: Salbutamol Selected Ion Monitoring pattern (SIM); Ion gun is CI (150 DEG C); Setting level Four bar is 150 DEG C; Setting interface temperature is 290 DEG C; Setting carrier gas is helium.The parameter of correlation analysis method is in table 1 and table 2.
Described actual water sample (be collected in the Huanghe water of Jinan City, and pond and sanitary wastewater.) comprise collection and the pretreatment in early stage of water sample: the actual water sample membrane filtration of 0.45 μm gathered in zones of different, and at 4 DEG C, be stored in use to be tested in Brown Glass Brown glass bottles and jars only.We adopt the method to analyze 3 kinds of water samples, and have carried out mark-on extraction test, and result of the test is in table 3.
The GC-MS/MS multiple reaction detection method of table 1.7 kind of PBDE.
The magnetic SPE parameter of table 2.7 kind of PBDE.
The analysis result of the PBDE in table 3.3 kind of water sample.
a: the rate of recovery (adds scalar 500ngL -1)
b: the rate of recovery (adds scalar 1000ngL -1)
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.

Claims (10)

1. a preparation method for the metallic organic framework magnetic material of temperature sensitive polymer parcel, is characterized in that: step is as follows:
(1) succinic anhydride and 3-aminopropyl triethoxysilane are dissolved in DMF, add Fe 3o 4siO 2dMF solution, be obtained by reacting black product carboxyl modified Fe 3o 4siO 2particle;
(2) zirconium chloride, the amino terephthalic acid (TPA) of 2-and acetic acid are dissolved in DMF, add the carboxyl modified Fe that step (1) is synthesized 3o 4siO 2after dispersion, be obtained by reacting Fe by above-mentioned mixed solution 110-150 DEG C 3o 4siO 2uiO-66-NH 2;
(3) NIPA of N-hydroxy-succinamide ester end-blocking is dissolved in chloroform, adds the Fe that step (2) is synthesized 3o 4siO 2uiO-66-NH 2dispersion, 50-70 DEG C of reaction, obtains product Fe afterwards 3o 4siO 2uiO-66-PNIPAM.
2. preparation method as claimed in claim 1, is characterized in that: in described step (1), the mol ratio of succinic anhydride and 3-aminopropyl triethoxysilane is 5:4.
3. preparation method as claimed in claim 1, is characterized in that: in described step (2), the mol ratio of zirconium chloride and the amino terephthalic acid (TPA) of 2-is 1:1.
4. preparation method as claimed in claim 1, is characterized in that: in described step (3), the concentration of the chloroform soln of PNIPAM-NHS is 10mM.
5. preparation method as claimed in claim 1, is characterized in that: Fe in described step (1) 3o 4siO 2the preparation method of particle: Fe 3o 4be scattered in ethanol, add catalyst and tetraethyl orthosilicate reacts to obtain product Fe 3o 4siO 2, the volume ratio of described tetraethyl orthosilicate and ammoniacal liquor is 1:1.
6. preparation method as claimed in claim 5, is characterized in that: described Fe 3o 4preparation method: Iron(III) chloride hexahydrate is dissolved in after in ethylene glycol, add sodium acetate to stir, be transferred in reactor by mixed liquor afterwards, react at 180-220 DEG C after 6-10 hour and obtain product, the mol ratio of described Iron(III) chloride hexahydrate and sodium acetate is 1:8.8.
7. the metallic organic framework magnetic material that the temperature sensitive polymer that prepared by the arbitrary described method of claim 1-6 wraps up.
8. the application of material according to claim 7 in enriching pollutants is separated.
9. apply as claimed in claim 8, it is characterized in that: described pollutant is PBDE.
10. detect a method for PBDE in water, it is characterized in that: first utilize material described in claim 7 to carry out concentration and separation, then detect with GC-MS/MS.
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CN112958038A (en) * 2021-02-08 2021-06-15 中国农业科学院农业质量标准与检测技术研究所 Preparation method of core-shell structure nano material based on nano particle/metal organic framework
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