CN106237993B - A kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite - Google Patents
A kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite Download PDFInfo
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- CN106237993B CN106237993B CN201610743155.3A CN201610743155A CN106237993B CN 106237993 B CN106237993 B CN 106237993B CN 201610743155 A CN201610743155 A CN 201610743155A CN 106237993 B CN106237993 B CN 106237993B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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Abstract
A kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite, including 1, use FeCl3·6H2O, ethylene glycol and sodium acetate prepare Fe3O4Nanoparticle.2, again with 1,3,5-equal benzoic acid, N, N-=toluic acid amide, ethyl alcohol, the Fe prepared3O4Fe is made in nanoparticle and triethylamine3O4@MOF-199.3, with chlorine (dimethyl) octadecylsilane and Fe3O4Fe is made in@MOF-1993O4@MOF-199@C18 nanocomposite.Operation of the present invention is simple, at low cost, prepared Fe3O4@MOF-199 C18 nanocomposite partial size is in Nano grade, and particle is uniform, is easily isolated and collects, and good dispersion, adsorption capacity is strong, and not will cause environmental pollution when preparation, harmless to the health of operator.
Description
Technical field
The present invention relates to a kind of preparation method of metal organic framework composite material, in particular to a kind of magnetic metal is organic
Skeleton nanocomposite (Fe3O4@MOF-199@C18) preparation method.
Background technique
The synthetic method of metal-organic framework materials has very much, and common method has hydro-thermal method, diffusion method, microwave-assisted
Method, ultrasonic wave added method is stirred at room temperature etc. in method.
(1) hydro-thermal method
Hydro-thermal method (also known as hydrothermal method), which refers to, to be taken water as a solvent, and under conditions of closed, makes reactant by high temperature and pressure
It reacts, cultivates a kind of method of crystal.Till now, it the reactive mode of hydro-thermal method and is not solely restricted to and is with water
Solvent, may some or all of organic solvent, i.e. described hot solvent method in reaction.The knot occurred under the conditions of hydro-thermal method
Crystalline substance reaction, thermal stress is small, and the crystal of synthesis has good crystal face, and internal flaw is few.Therefore, generally using hydro-thermal method preparation gold
Belong to organic framework material.
(2) diffusion method
Diffusion method is exactly that the substance of two kinds of different shapes is made to contact with each other, and then will be slow crystallization at two kinds of material interfaces
And generate the process of product.This method is milder, is readily synthesized the crystal of larger particles, but the conventionally used time is all
It is long, therefore some limitations are received in some aspects.
(3) microwave assisting method
Microwave assisting method is a kind of synthetic method for being considered transitory efficient, usually be exactly under the action of high-frequency microwave,
So that the particle of electrification is mutually hit with very high speed, the process of product is then generated.Since the frequency of microwave is very high,
General reactions were occurred in moment, and temperature gradient is very low, and can selectively heat reactant, and capacity usage ratio is very
It is high.
(4) method is stirred at room temperature
The method of being stirred at room temperature is also a kind of method of rapid synthesis metal-organic framework materials, and easy to operate, equipment letter
It, certainly can also be in system under conditions of room temperature or heating as long as single be dissolved in reactant in specific solvent
Proton-removed agent is added to accelerate the progress of reaction.
Summary of the invention
The purpose of the present invention is to provide a kind of magnetic metal organic framework nanocomposite (Fe3O4@MOF-199@C18)
Preparation method.This method, which can be prepared, provides a kind of metal organic framework nanocomposite (Fe for having fine magnetism3O4@MOF-
199@C18), and composite material partial size is in Nano grade, particle is uniform, and absorbent properties are good.
The technical solution of use:
A kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite, comprising the following steps:
The first step, Fe3O4The preparation of nanoparticle:
1, FeCl is taken according to mass ratio 1.35:83.625:3.636H2O, ethylene glycol and sodium acetate powder, are made FeCl3、
The mixed solution of ethylene glycol and sodium acetate.
2, magnetic agitation mixed solution, revolving speed 200rpm, magnetic agitation to whole dissolutions.Then by mixed solution ultrasound
It to being completely dispersed, goes in ptfe autoclave, the isothermal reaction 8 hours of 200 DEG C of temperature.
3, it is cooled to room temperature, reactant is separated and collected under external magnetic field, and successively use distilled water after reaction
And ethanol washing, it is dry in 60 DEG C of drying boxes；Obtain Fe3O4Nanoparticle is spare.
Step 2: Fe3O4The preparation of@MOF-199:
4,1,3,5-equal benzoic acid solution is dissolved in N, in the mixed solution of N-=methylformamide and dehydrated alcohol；
5, the Fe for again preparing copper acetate monohydrate and step 13O4It is soluble in water, finally two kinds of solution are mixed；
6, it is added triethylamine into mixed solution, after ultrasonic 30min, reacts 8h at 120 DEG C.
Wherein, 1,3,5- equal benzoic acid, copper acetate monohydrate and Fe3O4Mass ratio be 5:8.6:4, N, N- diformazan
Base formamide, ethyl alcohol, deionized water and triethylamine volume ratio be 80:80:80:1；The equal benzoic acid of 1,3,5- and N, N- diformazan
The mass ratio of base formamide is 1:64；
7, it after reaction product is cooling, is washed for several times with dehydrated alcohol, is dried for standby at 60 DEG C to get Fe3O4@MOF-
199, it is spare.
Step 3: Fe3O4The preparation of@MOF-199@C18:
Chlorine (dimethyl) octadecylsilane, Fe are taken in mass ratio for the ratio of 4:3:23O4@MOF-199 and toluene, it is standby
With；
The Fe that chlorine (dimethyl) octadecylsilane and step 2 will be taken to prepare3O4@MOF-199 is dissolved in toluene, mechanical
Stir 12h, prepared Fe3O4@MOF-199@C18 particle by magnetic separation collect, with ethanol washing and dry to get.
The advantage is that:
Operation of the present invention is simple, at low cost, prepared Fe3O4@MOF-199@C18 nanocomposite partial size is in and receives
Meter level is other, and particle is uniform, is easily isolated and collects, good dispersion, and adsorption capacity is strong.Environment dirt is not will cause when preparation
Dye, it is harmless to the health of operator.
Specific embodiment
Embodiment one
A kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite, includes the following steps:
Step 1: Fe3O4The preparation of nanoparticle:
The FeCl that 1.35g is ground3·6H2O is put into the beaker equipped with 75mL ethylene glycol, after magnetic stirring clarification, to beaker
Middle addition 3.6g anhydrous sodium acetate, magnetic agitation to whole dissolutions.After ultrasonic 10min, it is anti-to be transferred to dry polytetrafluoroethylene (PTFE)
It answers in kettle, reacts 8h at being 200 DEG C in temperature.Cooling is stood in air after the reaction was completed, by product distilled water and ethyl alcohol
It washs 3 times respectively.It is put into 60 DEG C of vacuum ovens and dries, grind into powder dress, label saves.
Step 2: the preparation of Fe3O4@MOF-199:
It is molten for the N,N-dimethylformamide and ethyl alcohol of 1:1 that the equal benzoic acid 250mg of 1,3,5- is dissolved in 40mL volume ratio
In liquid.The Fe for again preparing copper acetate monohydrate 430mg and step 13O4It is dissolved in the water of 20mL.Two kinds of solution are mixed and are added
Enter 0.25mL triethylamine, ultrasonic 30min reacts 8h at 120 DEG C.After reaction product is cooling, dehydrated alcohol is washed 5 times,
Drying is at 60 DEG C with spare.
Step 3: Fe3O4The preparation of@MOF-199@C18:
By Fe made from 160mg chlorine (dimethyl) octadecylsilane and step 23O4@MOF-199 microballoon is dissolved in 80ml first
Benzene, by mixture mechanical stirring 12h at room temperature.Prepared Fe3O4@MOF-199@C18 particle is collected by magnetic separation,
It is dry with ethanol washing 5 times, and at 60 DEG C.
Embodiment two
A kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite, comprising the following steps:
Step 1: Fe3O4The preparation of nanoparticle:
The FeCl that 1.35g is ground36H2O is put into the beaker equipped with 75mL ethylene glycol, after magnetic stirring clarification, to burning
3.6g anhydrous sodium acetate, magnetic agitation to whole dissolutions are added in cup.After ultrasonic 10min, it is transferred to dry polytetrafluoroethylene (PTFE)
In reaction kettle, 8h is reacted at being 200 DEG C in temperature.Cooling is stood in air after the reaction was completed, by product distilled water and second
Alcohol washs 3 times respectively.It is put into 60 DEG C of vacuum ovens and dries, grind into powder dress, label saves.
It is molten for the N,N-dimethylformamide and ethyl alcohol of 1:1 that the equal benzoic acid 250mg of 1,3,5- is dissolved in 40mL volume ratio
In liquid.The Fe for again preparing copper acetate monohydrate 430mg and step 13O4200mg is dissolved in the water of 20mL.By two kinds of solution
0.25mL triethylamine is added in mixing, and ultrasonic 30min reacts 8h at 120 DEG C.After reaction product is cooling, dehydrated alcohol washing 5
Secondary, drying is at 60 DEG C with spare.
Step 3: Fe3O4The preparation of@MOF-199@C18:
By Fe made from 160mg chlorine (dimethyl) octadecylsilane and step 23O4@MOF-199 120mg microballoon is dissolved in
80ml toluene, by mixture mechanical stirring 12h at room temperature.Prepared Fe3O4@MOF-199@C18 particle passes through magnetic separation
It collects, it is dry with ethanol washing 5 times, and at 60 DEG C.
Claims (1)
1. a kind of Fe3O4The preparation method of@MOF-199@C18 nanocomposite, it is characterised in that include the following steps:
1) Fe3O4The preparation of nanoparticle:
(1), FeCl is taken according to mass ratio 1.35:83.625:3.63·6H2O, ethylene glycol and sodium acetate powder, are made FeCl3, second
The mixed solution of two pure and mild sodium acetates；
(2), magnetic agitation mixed solution, revolving speed 200rpm, time 1-1.5 hour；Then by mixed solution ultrasound to complete
Dispersion, goes in ptfe autoclave, the isothermal reaction 8 hours of 200 DEG C of temperature；
It is cooled to room temperature after reaction, reactant is separated and collected under external magnetic field, and successively use distilled water and ethyl alcohol
Washing, until oven drying is with spare；
2), Fe3O4The preparation of@MOF-199:
(1), first 1,3,5- equal benzoic acid solution is dissolved in n,N-Dimethylformamide and alcohol mixed solution, then one is hydrated
The Fe of copper acetate and step 1) preparation3O4It is soluble in water, finally two kinds of solution are mixed；
(2), it is added triethylamine into mixed solution, after ultrasonic 30min, reacts 8h at 120 DEG C；
(3), it after reaction product is cooling, is washed for several times with dehydrated alcohol, is dried at 60 DEG C；
Obtain Fe3O4@MOF-199 nanoparticle is spare；
Above-mentioned raw materials proportion are as follows:
The equal benzoic acid of 1,3,5-, copper acetate monohydrate and Fe3O4Mass ratio be 5:8.6:4, n,N-Dimethylformamide, second
The volume ratio of alcohol, water and triethylamine is 80:80:80:1；The wherein quality of 1,3,5- equal benzoic acid and N,N-dimethylformamide
Than for 1:64；
3), Fe3O4The preparation of@MOF-199@C18:
(1), it stocks up；
Chlorine (dimethyl) octadecylsilane and Fe are taken in mass ratio for the ratio of 4:3:23O4@MOF-199 and toluene, it is spare；
(2), by the Fe of chlorine (dimethyl) octadecylsilane and step 2 preparation3O4@MOF-199 is dissolved in toluene, and machinery stirs
Mix 12h, prepared Fe3O4@MOF-199@C18 particle by magnetic separation collect, with ethanol washing and dry to get.
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| CN107308987A (en) * | 2017-06-09 | 2017-11-03 | 沈阳理工大学 | A kind of Fe3O4The preparation method of the nano composite materials of@PDA@MOF 5 |
| CN108187752A (en) * | 2017-12-10 | 2018-06-22 | 江苏师范大学 | A kind of preparation method of novel synthesis gas catalyst for methanol |
| CN108554392A (en) * | 2018-01-03 | 2018-09-21 | 桂林理工大学 | The application of micro peacock green in a kind of preparation of magnetism copper base metal organic frame composite material and its separation and concentration environmental water sample |
| CN108341803A (en) * | 2018-03-21 | 2018-07-31 | 新沂市中诺新材料科技有限公司 | A kind of synthetic method of difenoconazole |
| CN113083237B (en) * | 2021-04-12 | 2022-12-02 | 太原理工大学 | MOFs desulfurizing agent based on organic amine in-situ modification, and preparation and application thereof |
| CN115722212A (en) * | 2022-11-29 | 2023-03-03 | 浙江工业大学 | Magnetic metal-organic framework material and preparation method and application thereof |
| CN115970662A (en) * | 2023-02-17 | 2023-04-18 | 中南大学 | UiO-67 loaded nano copper oxide material and preparation method and application thereof |
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| CN103537237B (en) * | 2013-09-29 | 2015-09-02 | 沈阳理工大学 | A kind of Fe 3o 4the preparation method of CPAM core-shell magnetic nano material |
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Effective date of registration: 20220623 Address after: 601, 603, 604, No. 3-6, Lane 96, Heping South Street, Heping District, Shenyang, Liaoning 110006 Patentee after: Shenyang Mao Yue Technology Co.,Ltd. Address before: 110159 No. 6 Nanping Road, Hunnan New District, Shenyang, Liaoning Patentee before: SHENYANG LIGONG University |