CN110075814A - A kind of two dimension N doping magnetic ionic liquids class zeolite imidazole ester nano material and preparation method thereof, purposes - Google Patents

A kind of two dimension N doping magnetic ionic liquids class zeolite imidazole ester nano material and preparation method thereof, purposes Download PDF

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CN110075814A
CN110075814A CN201910371957.XA CN201910371957A CN110075814A CN 110075814 A CN110075814 A CN 110075814A CN 201910371957 A CN201910371957 A CN 201910371957A CN 110075814 A CN110075814 A CN 110075814A
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preparation
nano material
ionic liquids
zeolite imidazole
imidazole ester
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高仕谦
邵子纯
吴怡秋
严雨濛
张占恩
卢建
王俊霞
徐蕊
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Suzhou University of Science and Technology
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Abstract

The invention discloses a kind of two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nano materials and preparation method thereof, purposes, it is placed in ultrapure water the preparation method comprises the following steps: weighing ZIF-8, ultrasonic disperse is uniform, -3 methylimidazole of bromo -1- hexyl and -3 methylimidazole titanium tetrachloride salt of 1- hexyl is added, continue ultrasound uniformly, by above-mentioned mixed solution in N2FeSO is added under protection and high-speed stirred4•7H2O, while ammonium hydroxide stirring is added, black magnetic microballoon is collected after washing vacuum drying with magnet, and MILZIF is obtained after grinding.Porous magnetic Core-shell structure material one step of synthetic method that the present invention synthesizes is quick, and not needing same conventional method, equally first building magnetic core constructs nano material particle on surface again.Double imidazole groups are constructed by the combination of ZIF-8 and IL, so that material functional group is more abundant and diversified.The material of preparation has magnetic and bigger specific surface area, while facilitating separation, recycling.

Description

A kind of two dimension N doping magnetic ionic liquids class zeolite imidazole ester nano material and its system Preparation Method, purposes
Technical field
The invention belongs to field of nanometer material technology, and in particular to two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nanometer Material and preparation method thereof, purposes.
Background technique
Class zeolitic imidazolate framework material (Zeolitic imidazolate frameworks, ZIFs) is that one kind has The metal-organic framework materials of skeleton structure of zeolite.With traditional zeolite comparatively, transition metal ions is boiled instead of tradition Element silicon and aluminium element in stone, imidazate are connected into instead of the oxygen bridge in traditional zeolite by the nitrogen-atoms on imidazole ring A kind of zeolite structured material of new class.Therefore ZIF material combines the dual of metal-organic framework materials and traditional zeolite material Advantage, while it being provided with MOFs material high porosity and great specific surface area, and have the characteristics that zeolitic material stability is high, So that having when the material is applied in complex matrices sample be enriched with trace or ultra trace organic pollutant preferable Efficiency.
The solvent that ionic liquid is made of specific organic cation and inorganic anion.By adjusting cation and yin It is various to reach high chemical stability and thermal stability, low viscosity, insignificant vapour pressure, and dissolution for the chemical structure of ion The ability of compound.Due to these properties, so that ionic liquid is different from conventional solvent, it is a kind of " green solvent ".These are special Point since ionic liquid has its unique physicochemical property, is very suitable for so that the research of ionic liquid becomes more and more active Solvent as separating-purifying.ZIFs material is a kind of nano material containing imidazoles group, we arrive ionic liquid loaded Among ZIFs material hole, the stability of ZIFs on the one hand can be improved, on the other hand by the introducing of ionic liquid, with script ZIFs material constitute a kind of double glyoxaline structures.Ionic liquid is also a kind of nitrogen dopant simultaneously, adds a small amount of nitrogen and is used as and mixes The miscellaneous dose of performance that can be further improved carbonaceous material.Although the effect of N doping is not fully understood, has multinomial research Show that N doping will affect the surface nature and activity of material.MILZIF compared with ZIF, although due to ionic liquid exist, hole Gap rate can be lower than ZIFs, but its adsorption capacity is more superior, this is because nitrogen caused by the combination of IL and MOF/oxygen species are deposited , while the adsorption energy of MILZIF can be explained with the bonding action (donor of MILZIF:H, object: the receptor of H) of H key Power is more superior, and the interaction of pi-pi bond also plays certain contribution to absorption.ZIFs material ratio with higher after introducing IL Surface area and nitrogen content, have a good application prospect.
Summary of the invention
Technical problems to be solved: since traditional absorption and extracting process expend time and complicated for operation, this material draws Enter Fe3O4It as magnetic source, is supported on outside ZIFs material, there is ZIF material magnetic convenient for recycling, separately One side magnetic nano-particle little particle increases the specific surface area of ZIFs material, makes it have wider application field with before Scape.
Technical solution: for above-mentioned problem, this application discloses a kind of two-dimentional N doping magnetic ionic liquids class zeolites Imidazate nano material and preparation method thereof, purposes, the preparation method include the steps that following:
ZIF-8 is accurately weighed to be placed in ultrapure water, after ultrasound makes ZIF-8 be uniformly dispersed in ultrapure water, be added bromo -1- oneself - 3 methylimidazole titanium tetrachloride salt of -3 methylimidazole of base and 1- hexyl continues ultrasound to being uniformly mixed, above-mentioned mixed solution is existed N2FeSO is added under protection and high-speed stirred4•7H2O, while ammonium hydroxide is added dropwise, it is stirred at room temperature, collects black magnetic with magnet Then microballoon is alternately washed with dehydrated alcohol and deionized water, after vacuum drying, MILZIF is obtained after grinding.
Preferably, the ZIF-8 weight is 0.3019-0.6025g.
Preferably, -3 methylimidazole 2.0350-4.0792g of bromo -1- hexyl.
Preferably, -3 methylimidazole titanium tetrachloride salt 2.2506-4.5161g of 1- hexyl.
Preferably, the concentration that ammonium hydroxide is added is 25%, volume 5mL.
Preferably, dehydrated alcohol and deionized water alternating washing times are 2-5 times.
Compared with prior art, the present invention has the advantages that:
1. the innovation of synthetic method: introducing magnetic fluid as magnetic mother matrix, water-soluble imidazole ion liquid provides micro emulsion and prepares ring Border, using nano aperture organic framework material as kernel, by glyoxaline ion liquid, by magnetic ionic liquids as ferric After source loads on ZIF-8, while drawing ferrous iron and make the area load ionic liquid of ZIF-8, magnetic Fe is grown3O4。 Porous magnetic Core-shell structure material one step of synthetic method of synthesis is quick, and not needing same conventional method, equally first building magnetic core exists again Surface constructs nano material particle.
2. double imidazole groups are constructed by the combination of ZIF-8 and IL, so that material functional group is more abundant and diversified.
3. being Fe by introducing magnetic ionic liquids3O4Synthesis provide Fe3+Ion does not need to additionally introduce ferric iron, It only needs to introduce ferrous ion and produces Fe3O4, so that material has magnetic and bigger specific surface area, while convenient point From, recycle.
4. by adjusting reaction condition, reactant ratio, the magnetism and specific surface area of the nanoparticle of adjustable generation Size allows to select to be suitble to the optimal conditions of different pollutant absorption.
Detailed description of the invention
Fig. 1 is the surface sweeping electron microscope of ZIF-8, and ZIF-8 particle is uniform regular octahedron structure in figure, and surface texture is smooth Without obvious particle,
Fig. 2 is the surface sweeping electron microscope of MILZIF, can't see the regular octahedron structure of ZIF-8 in figure, can only see spherical Fe3O4? Grain, through comparison it can be seen that under identical amplification factor, the specific surface area of MILZIF is significantly increased, and surface Fe3O4Particle is equal It is even and abundant.
Fig. 3 is the transmission electron microscope picture of MILZIF, and material granule is uniform, and no magnetic core occurs but can see Fe3O4Microballoon.
Fig. 4 is the FTIR spectrum of MILZIF, 2852 and 2929cm-1For be saturated C-H stretching vibration peak, 1617 and 1570 cm-1The entire imidazole ring stretching vibration peak of ionic liquid, 1126 and 1400cm-1The plane deformation that place is imidazole ring C-H vibrates, card Bright IL is successfully carried on ZIF, and there are N dopings to constitute C-N key (sp2 and sp3) in MILZIF；568 be the flexible vibration of Fe-O Dynamic peak, it was demonstrated that successfully synthesize Fe3O4。
Specific embodiment
Embodiment 1
One one step preparation method of MILZIF magnetic nano-particle
It accurately weighs 0.3019gZIF-8 to be placed in 50mL ultrapure water, ultrasound makes ZIF-8 be uniformly dispersed in ultrapure water in 1 hour Afterwards, -3 methylimidazole of 2.0405g bromo -1- hexyl and -3 methylimidazole titanium tetrachloride salt of 2.2511g1- hexyl is added, continues to surpass Above-mentioned mixed solution is transferred in 250mL four-hole boiling flask, to being uniformly mixed in N within sound 2 hours2Add under protection and high-speed stirred Enter 0.8775gFeSO4•7H2O, while the ammonium hydroxide of 5mL 25% is added dropwise, 3h is stirred at room temperature, collects black magnetic with magnet Then microballoon is dried in vacuo 12h at dehydrated alcohol and deionized water alternately washing 3 times, 105 DEG C, obtains 0.7074g after grinding MILZIF.Residual ion liquid passes through rotary evaporation purification.
Embodiment 2
It accurately weighs 0.4027gZIF-8 to be placed in 50mL ultrapure water, ultrasound makes ZIF-8 be uniformly dispersed in ultrapure water in 1 hour Afterwards, -3 methylimidazole of 2.0350g bromo -1- hexyl and -3 methylimidazole titanium tetrachloride salt of 2.2506g1- hexyl is added, continues Above-mentioned mixed solution is transferred in 250mL four-hole boiling flask, to being uniformly mixed in N within ultrasound 2 hours2Under protection and high-speed stirred 0.8750g FeSO is added4•7H2O, while the ammonium hydroxide of 5mL 25% is added dropwise, 3h is stirred at room temperature, collects black magnetic with magnet Property microballoon obtained after grinding then with 12h is dried in vacuo at dehydrated alcohol and deionized water alternately washing 3 times, 105 DEG C 0.7486g MILZIF.Residual ion liquid passes through rotary evaporation purification.Residual ion liquid is purified by rotary evaporation Reuse.
Embodiment 3
It accurately weighs 0.6022gZIF-8 to be placed in 100mL ultrapure water, ultrasound makes ZIF-8 be uniformly dispersed in ultrapure water in 1 hour Afterwards, -3 methylimidazole of 4.0792g bromo -1- hexyl and -3 methylimidazole titanium tetrachloride salt of 4.5071g1- hexyl is added, continues to surpass Above-mentioned mixed solution is transferred in 250mL four-hole boiling flask to being uniformly mixed within sound 2 hours, is added under N2 protection and high-speed stirred Enter 1.7551gFeSO4•7H2O, while the ammonium hydroxide of 10mL 25% is added dropwise, 3h is stirred at room temperature, collects black magnetic with magnet Then microballoon is dried in vacuo 12h at dehydrated alcohol and deionized water alternately washing 3 times, 105 DEG C, obtains 1.4786g after grinding MILZIF.Residual ion liquid passes through rotary evaporation purification.
Embodiment 4
It accurately weighs 0.6025gZIF-8 to be placed in 100mL ultrapure water, ultrasound makes ZIF-8 be uniformly dispersed in ultrapure water in 1 hour Afterwards, -3 methylimidazole of 3.7190g bromo -1- hexyl and -3 methylimidazole titanium tetrachloride salt of 4.5161g1- hexyl is added, continues to surpass Above-mentioned mixed solution is transferred in 250mL four-hole boiling flask to being uniformly mixed within sound 2 hours, is added under N2 protection and high-speed stirred Enter 1.7554gFeSO4•7H2O, while the ammonium hydroxide of 10mL 25% is added dropwise, 3h is stirred at room temperature, collects black magnetic with magnet Then microballoon is dried in vacuo 12h at dehydrated alcohol and deionized water alternately washing 3 times, 105 DEG C, obtains 1.5060g after grinding MILZIF.Residual ion liquid passes through rotary evaporation purification.
Comparative example 1
0.2011g ZIF-8 is added to -3 methylimidazole of 2.9756g bromo -1- hexyl and 0.2051g 1- hexyl -3- methyl In imidazoles titanium tetrachloride salt, 50 mL ultrapure waters are added, are transferred to above-mentioned mixed solution to being uniformly mixed within ultrasound 2 hours In 250mL four-hole boiling flask, in N20.5014g FeSO is added under protection and high-speed stirred4•7H2O, while 5mL25% is added dropwise Ammonium hydroxide, 3h is stirred at room temperature, collects black magnetic microballoon with magnet, then with the alternately washing 3 of dehydrated alcohol and deionized water It is secondary, 12h is dried in vacuo at 105 DEG C, grinding saves.Obtained material is reunited, and dispersion is uneven, it may be possible to which imidazole ion liquid is thrown Adding excessively causes.Residual ion liquid passes through rotary evaporation purification.
Comparative example 2
It accurately weighs 0.4011g ZIF-8 to be placed in 50mL ultrapure water, ultrasound makes ZIF-8 be uniformly dispersed in ultrapure water in 1 hour Afterwards, -3 methylimidazole of 10.1045g bromo -1- butyl and -3 methylimidazole titanium tetrachloride salt of 1.3667g1- butyl is added, continues Above-mentioned mixed solution is transferred in 250mL four-hole boiling flask, to being uniformly mixed in N within ultrasound 2 hours2Under protection and high-speed stirred 0.6674g FeSO is added4•7H2O, while the ammonium hydroxide of 5mL 25% is added dropwise, 3h is stirred at room temperature, collects black magnetic with magnet Property microballoon, then with 12h is dried in vacuo at dehydrated alcohol and deionized water alternately washing 3 times, 105 DEG C, grinding is saved.It obtains Material is without magnetism.Residual ion liquid passes through rotary evaporation purification.
Application examples 1
MILZIF material prepared by embodiment 1, measurement Norfloxacin (NFX, Norfloxacin), Pazufloxacin (Pasil, Pazufloxacin), Ciprofloxacin (CIP, Ciprofloxacin), Sparfloxacin (Sparfloxacin), fleraxacin (FLE, Fleroxacin), Ofloxacin (Ofloxacin), Dan Nuosha star (Danofloxacin), Enrofloxacin (Enrofloxacin) this 8 kinds of fluoroquinolone antibiotics residuals.Material utilization amount is 50mg, and material investment 20mL is contained In the water of 50ppb fluoroquinolone antibiotics, mixing and absorption, material are carried out under the revolving speed of 1000r/min using magnetic agitation Magneton can be detached from high speed to be evenly distributed in solution, simultaneously close off stirring after material can rapidly using magnetic-adsorption to turn On son, facilitate recycling.1mL solution was taken to cross 0.22 μm of organic filter membrane at 0min, 10min and 1h hours respectively in whipping process The removal that fluoroquinolone antibiotics are removed in 10min is obtained into UHPLC-MS/MS detection level with brown sample introduction bottle Range is 77.2%-96%, and the removal efficiency range after 1h is 82.3%-98%.
The chromatography and Mass Spectrometry Conditions of UHLC-MS/MS is as follows:
Chromatographic column: Zorbax Eclipse XDB-C18Reverse-phase chromatographic column (50 mm × 3 mm, 1.8 μm)；Column temperature: 40 DEG C；Stream Dynamic phase: methanol (A) and 0.1% formic acid (B), gradient elution program is as follows: 0 ~ 1min 10%A- 75%A；1-6min 75%A； 6min- 6.5min 75%A- 10%A；6.5min- 9min 10%A；Flow velocity: 0.2 mL/min；Sample volume: 3 μ L.
Ion source: electrospray ionisation source (ESI+)；Scan pattern: cation scanning；Detection pattern: Selective reaction monitoring (SRM)；Ion transfer tube temperature: 350 DEG C；Vapo(u)rizing temperature: 300 DEG C；Spray voltage: 3500 V；Sheath atmospheric pressure: 25 MPa； Assist gas pressure power: 15 MPa；The parameter of SRM mode is as shown in table 1.
Retention time, parent ion, daughter ion and the collision energy result of 1: eight kind of quinolone antibiotics of table.

Claims (8)

1. a kind of preparation method of two dimension N doping magnetic ionic liquids class zeolite imidazole ester nano material, the preparation method Include the steps that following:
ZIF-8 is accurately weighed to be placed in ultrapure water, after ultrasound makes ZIF-8 be uniformly dispersed in ultrapure water, be added bromo -1- oneself - 3 methylimidazole titanium tetrachloride salt of -3 methylimidazole of base and 1- hexyl continues ultrasound to being uniformly mixed, above-mentioned mixed solution is existed N2FeSO is added under protection and high-speed stirred4•7H2O, while ammonium hydroxide is added dropwise, it is stirred at room temperature, collects black magnetic with magnet Then microballoon is alternately washed with dehydrated alcohol and deionized water, after vacuum drying, MILZIF is obtained after grinding.
2. a kind of preparation of two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nano material according to claim 1 Method, which is characterized in that the ZIF-8 weight is 0.3019-0.6025g.
3. a kind of preparation of two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nano material according to claim 1 Method, which is characterized in that -3 methylimidazole 2.0350-4.0792g of bromo -1- hexyl.
4. a kind of preparation of two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nano material according to claim 1 Method, which is characterized in that -3 methylimidazole titanium tetrachloride salt 2.2506-4.5161g of 1- hexyl.
5. a kind of preparation of two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nano material according to claim 1 Method, which is characterized in that the concentration of the ammonium hydroxide is 25%, volume 5mL.
6. a kind of preparation of two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nano material according to claim 1 Method, which is characterized in that the dehydrated alcohol and deionized water alternating washing times be 2-5 times.
7. a kind of preparation of two-dimentional N doping magnetic ionic liquids class zeolite imidazole ester nano material according to claim 1 The ionic liquid class zeolite imidazole ester nano material that method is prepared.
8. according to right 7 it is a kind of two dimension N doping magnetic ionic liquids class zeolite imidazole ester nano material absorption pollute Purposes in object.
CN201910371957.XA 2019-05-06 2019-05-06 A kind of two dimension N doping magnetic ionic liquids class zeolite imidazole ester nano material and preparation method thereof, purposes Pending CN110075814A (en)

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Cited By (4)

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CN111185138A (en) * 2020-02-20 2020-05-22 苏州科技大学 Preparation method and application of two-dimensional nitrogen-doped metal organic framework magnetic nano material
CN113620820A (en) * 2021-08-11 2021-11-09 辽宁大学 Novel functionalized magnetic ionic liquid and preparation method and application thereof
CN113788956A (en) * 2021-10-11 2021-12-14 广东医科大学 Preparation method and application of metal organic framework compound based on modified eggshell
CN115073818A (en) * 2022-06-17 2022-09-20 山东海科创新研究院有限公司 Heat-conducting filler, high-heat-conductivity polyether sulfone composite material and preparation method thereof

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