CN107481827B - The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs - Google Patents
The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs Download PDFInfo
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- CN107481827B CN107481827B CN201710772691.0A CN201710772691A CN107481827B CN 107481827 B CN107481827 B CN 107481827B CN 201710772691 A CN201710772691 A CN 201710772691A CN 107481827 B CN107481827 B CN 107481827B
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- 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
- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
- H01F1/0045—Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
- H01F1/0054—Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
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- H—ELECTRICITY
- 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
Abstract
The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs, belongs to nano material production technical field, by FeCl3·6H2O, ethylene glycol, ethyl alcohol and sodium acetate mixing carry out hydro-thermal reaction, obtain Fe3O4Ball mixes with ethyl alcohol, deionized water, ammonium hydroxide, obtains Fe3O4Ball mixed liquor adds resorcinol and formaldehyde is reacted, obtain Fe after silicon source reaction is added dropwise thereto3O4@SiO2@resorcinol formaldehyde resin ball obtains Fe through calcining under argon gas3O4@SiO2@C ball, etches through sodium hydrate aqueous solution, obtains magnetic nano cages；Magnetic nano cages are reacted with metal nitrate and 2-methylimidazole finally, obtain that size is uniform, is evenly distributed and pattern controls the hollow magnetic Nano carbon balls of good internal confinement growth MOFs.The process is easy, and reaction process material requested is less toxic, harmless.
Description
Technical field
The invention belongs to nano material production technical fields, and in particular to a kind of magnetic Nano cage inside confinement growth MOFs
Technology.
Background technique
Metal organic framework compound (MOFs) is a kind of coordination polymer quickly grown nearly ten years, refers to transition gold
Belong to ion and organic ligand passes through the crystalline porous material with periodic network structure being self-assembly of.It has high hole
Rate, low-density, bigger serface, duct rule, aperture is adjustable and topological structure diversity and the advantages that Scalability, has
Three-dimensional pore structure, generally using metal ion as tie point, it is that zeolite and carbon are received that organic ligand support, which constitutes space 3D and extends,
The important novel porous materials of another class except mitron, are all widely used in catalysis, energy storage and separation.Currently, MOFs
Have become the important research direction of multiple chemical branches such as inorganic chemistry, organic chemistry.Metal organic framework compound (MOFs)
The catalyst and catalytic carrier, nanocages reactor, negative electrode of lithium ion battery of catalysis are had been used for as a series of composite material
Material, the controllable function in adjustable aperture make it better than traditional porous material.
But MOFs material does not have electric conductivity, limits its application in electrochemical field.The size of MOFs material
It is smaller, it is more difficult from the separation in reaction system.MOFs material stability in strong acid and strong basicity solvent is poor, will cause
The decomposition of MOF, when as adsorbent, catalyst, catalyst carrier, slow releasing carrier of medication or lithium ion battery electrode material,
The stability of material cannot be guaranteed.In addition, MOFs material does not have magnetism, can not in magnetic field displacement, also can not be from
Magnetic Isolation in reaction system.Therefore, it is necessary to design to synthesize a kind of MOFs composite material with magnetism, electric conductivity.
Summary of the invention
For the disadvantages described above of the prior art, it is an object of the invention to propose a kind of magnetic Nano cage inside confinement growth
The preparation method of the preparation method ball of MOFs.
The present invention the following steps are included:
1) by FeCl3·6H2O, hydro-thermal reaction is carried out after ethylene glycol, ethyl alcohol and sodium acetate mixing, centrifugation is washed after reaction
It washs, takes solid phase dry, obtain Fe3O4Ball.
The present invention Fe uniform by diameter that hydro-thermal method synthesizes3O4Ball, with Fe3O4Ball is the template of subsequent reactions.
With Fe3O4For magnetic kernel and template, SiO is successively wrapped up conducive on its surface2With resorcinol-formaldehyde oligomer.
2) by ethyl alcohol, deionized water, ammonium hydroxide and Fe3O4Ball mixes under ultrasound condition, obtains Fe3O4Ball mixed liquor；Again will
Silicon source is added dropwise in above-mentioned mixed liquor, is reacted under stirring condition, and the Fe containing core-shell structure is obtained3O4@SiO2Nanosphere is anti-
Answer system；Resorcinol and formaldehyde are added in above-mentioned reaction system under stirring condition again and reacted, after reaction from
Heart washing takes solid phase dry, obtains Fe3O4@SiO2@resorcinol formaldehyde resin ball.
The present invention adjusts the polarity of reaction system using ethyl alcohol and deionized water, thus when controlling tetraethyl orthosilicate hydrolysis
Hydrolysis rate, and the purpose that ammonium hydroxide is added is to provide tetraethyl orthosilicate and hydrolyzes necessary alkaline condition.
The high temperature cabonization for the oligomer that carbon-coating is formed from resorcinol and formaldehyde, the thickness of carbon-coating and carbon-coating surface
Mesoporous size is adjusted by the way that formalin, the dosage of resorcinol and reaction time is added.Meso-porous hollow Nano carbon balls carbon
2 ~ 5 nm of layer intermediary hole size, mesoporous size can meet subsequent reactions metal ion, small organic molecule enters magnetic carbon nanometer
Confinement reaction is carried out inside cage.
3) by Fe3O4@SiO2The high-temperature calcination under argon atmosphere protection of@resorcinol formaldehyde resin ball, obtains Fe3O4@SiO2@
C ball.Calcination process makes resorcinol formaldehyde resin carbonization become mesoporous carbon-coating.
4) by Fe3O4@SiO2@C ball, which is dispersed in sodium hydrate aqueous solution, to be performed etching, and the product centrifugation after etching is washed
It washs, then takes solid phase dry, obtain magnetic nano cages.
The present invention is using resorcinol and formaldehyde as carbon source, at room temperature to the SiO of tetraethyl orthosilicate (TEOS) formation2Ball
Cladding, high-temperature calcination forms Fe under an argon atmosphere3O4@SiO2Then@C ball forms yolk-egg with sodium hydroxide acid etch again
The magnetic Nano cage of shell structure.Prepared magnetic nano cages pattern is uniform, stable structure, carbon-coating surface be distributed with it is mesoporous,
There is the Fe of good pattern for subsequent preparation3O4/ MOFs/ meso-porous hollow carbon composite nano ball structure provides advantage.
5) magnetic nano cages are dispersed in methanol, metal nitrate then are added and 2-methylimidazole is reacted,
Centrifuge washing after reaction obtains solid phase drying, obtains hollow magnetic Nano carbon balls (the i.e. Fe of internal confinement growth MOFs3O4/
MOFs/ meso-porous hollow carbon composite nano ball).
In the step, using magnetic nano cages as nano-reactor, confinement growth is carried out to MOFs, it is equal to can get distribution
It is even, and pattern controls good Fe3O4/ MOFs/ meso-porous hollow carbon composite nano ball.
The present invention is with Fe3O4Magnetic nano-balls are template, in its inner surface coated Si O2And resorcinol formaldehyde resin, warp
It crosses high-temperature calcination to etch later, forms the magnetic Nano cage of yolk-eggshell structure, and with the magnetic Nano of yolk-eggshell structure
Cage is reaction vessel growth in situ MOFs, forms Fe3O4/ MOFs/ meso-porous hollow carbon composite nano ball.Yolk-eggshell structure
Magnetic nano cages inner wall growth in situ MOFs, realizes the micro nano structure of cage in cage.Nano cages and MOFs cage tool have can
The mesopore size of control and controllable carbon wall thickness, while magnetic nano cages provide field as micro-nano reactor for nanometer reaction
Institute may be implemented the confinement growth of nano material and as micro-nano reactor as nanometer reacting environment, as catalyst and urge
Agent carrier can effectively improve catalytic performance；Basket structure can play the effect of control medicament slow release in cage, carry in biology
It has a clear superiority in terms of medicine medicament slow release；Basket structure is also used as nano-reactor in cage, " cage " effect is utilized, in carbon cage
Interior confinement synthesizes other nano materials or organic reaction；The magnetic nano cages inner wall growth in situ of yolk-eggshell structure
MOFs can be used as lithium ion battery negative material, be conducive to the transfer of charge, and the diffusion of lithium ion can be improved, can high magnification fill
Electric discharge.
In short, production equipment of the present invention is simple, preparation cost is low, and operating process is easy, reaction process material requested low toxicity,
It is harmless, and the stoichiometric ratio of multi-component material can be effectively controlled, acquisition size is uniform, is evenly distributed and pattern control is good
Good Fe3O4/ MOFs/ meso-porous hollow carbon composite nano ball, this ternary that can be used for industrial mass production high quality are multiple
Condensation material.
Further, in step 2 of the present invention, the silicon source is tetraethyl orthosilicate (TEOS), in addition, in order to adjust
Save the diameter ratio of magnetic core and nano cages, Fe3O4The mass ratio that feeds intake of ball and tetraethyl orthosilicate (TEOS) are 1: 1~10.
Tetraethyl orthosilicate is common silylating reagent, the available effective control of the hydrolysis rate in mild alkaline conditions, thus
Obtain the silicon dioxide layer being evenly coated.Also other silicon sources, such as tetrapropoxysilane (TPOS) may be selected.
The diameter of magnetic core and nano cages is adjusted than receiving between core and carbon-coating can be efficiently controlled for product
Rice gap.The size of nanovoids can grow MOFs for subsequent confinement and provide suitable spatial volume, more in growth inside
MOFs, improve the mass fraction of MOFs, be more advantageous to improve product application performance.In addition, adjusting magnetic core and carbon nanometer
Integrality and magnetism of the diameter of cage than advantageously ensuring that sphere.
SiO is generated in order to control2With a thickness of 50~150 nm, in the step 2, tetraethyl orthosilicate is added
(TEOS) afterwards to Fe of the acquirement containing core-shell structure3O4@SiO2The reaction time of nanosphere reaction system is 10~20 min.Control
System generates SiO2Thickness, can mainly effectively obtain the nanovoids of suitable size, for subsequent confinement grow MOFs mention
The mass fraction of MOFs is improved in the more MOFs of growth inside for suitable spatial volume, is more advantageous to and improves answering for product
Use performance.If the thickness of SiO2 is less than 50 nm, it is unfavorable for the confinement growth of MOFs material；Such as SiO2Thickness be greater than 150 nm,
Entire sphere diameter is excessive, is unfavorable for the cladding of resorcinol formaldehyde resin, leads to subsequent carbonisation, and carbon ball is crushed.
In order to make the carbon wall thickness control of manufactured product in 10~35nm, the surface mesoporous magnitude range control of carbon-coating exists
2~5 nm, in the step 2, the feed ratio of the resorcinol, formaldehyde and tetraethyl orthosilicate (TEOS) is 0.5~1.5
Ml: 0.2~0.8 g: 1~10 g.The surface mesoporous size of the thickness and carbon-coating of carbon wall influences the confinement growth of MOFs material
And subsequent applications.Firstly, the thickness of carbon wall is thicker, carbon-coating is surface mesoporous smaller, and MOFs just will receive limit in internal confinement growth
System causes MOFs very few in internal quantity, to just lose the effect that MOFs is played as main material.Secondly,
In subsequent application, either molecule and ion need to just can enter inside by carbon wall, therefore carbon layers having thicknesses and mesoporous size need
It controls, carbon layers having thicknesses are excessive, influence the diffusion and migration of molecule and ion.It is mesoporous too small, less than 2 nm, the big molecule of size
It cannot pass through, mesoporous excessive, carbon-coating structure is easily destroyed.Therefore, it is necessary to effectively control carbon layers having thicknesses and surface apertures size.
It states in step 3), the temperature condition of the high-temperature calcination is 500~700 DEG C.Under this condition, carbon layer material can be made
It is carbonized more complete, while generating a large amount of mesoporous.Not exclusively, carbonization time is too long for such as lower than 500 DEG C carbonizations；And such as it is higher than
700 DEG C, ferroso-ferric oxide is easily reduced to cementite or fe by carbon, loses magnetic.
In the step 4), the temperature of the sodium hydrate aqueous solution for etching is 40~90 DEG C, the hydrogen-oxygen for etching
The concentration for changing sodium water solution is 1~5mol/L.It, can be with by the adjusting of reaction time and naoh concentration in this temperature range
Realize SiO2Complete etching.Lower than 40 DEG C etch periods are too long, are higher than 90 DEG C, water-bath generates a large amount of aqueous vapors.This sodium hydroxide
In concentration range, SiO may be implemented by the adjusting of reaction time and reaction temperature2Complete etching.Naoh concentration mistake
Low, etch period is too long, and concentration is higher than 5mol/L, and alkalinity is too strong, there is certain corrosion to carbon-coating, magnetic core.
In addition, metal nitrate of the present invention is Zn (NO3)2·6H2O or Co (NO3)2·6H2O。
When with Zn (NO3)2·6H2When O is metal nitrate, limited in hollow magnetic Nano carbon balls by step 5) ZIF-8
Domain growth, obtained is the hollow magnetic Nano carbon balls of internal confinement growth ZIF-8.
And when with Co (NO3)2·6H2When O is metal nitrate, by step 5) ZIF-67 in hollow magnetic Nano carbon balls
Interior confinement growth, obtained is the hollow magnetic Nano carbon balls of internal confinement growth ZIF-67.
Select Zn (NO3)2·6H2O or Co (NO3)2·6H2O is metal nitrate and 2-methylimidazole in meso-porous hollow carbon
The reason of confinement growth MOFs is because of ZIF-8 and ZIF-67 synthesis technology relative maturity, and ZIF-8 and ZIF-67 inside ball
And its derived material has begun and is widely used in gas absorption, hydrogen storage material, catalyst, catalyst carrier, medicament slow release load
Body or lithium ion battery electrode material.Also other zinc salts and cobalt salt can be selected.
In the step 5), magnetic nano cages and Zn (NO3)2·6H2The mass ratio of O is 1: 2~12.
In the step 2, magnetic nano cages and Co (NO3)2·6H2The mass ratio of O is 1: 2~12.
The confinement in hollow magnetic Nano carbon balls of described two kinds of MOFs materials of ZIF-8, ZIF-67 is grown, and does not change MOFs
The original composition of material, structure, pattern etc. are formed with Fe3O4For kernel, mesoporous carbon is shell, and MOFs material is new in the gap of middle part
Type trielement composite material.
In the hollow magnetic Nano carbon balls of formation, magnetic 300 ~ 500 nm of nano cages diameter, carbon wall thickness is 10 ~ 35
Nm, carbon ball surface apertures size 2 ~ 5 nm, 200 nm of magnetic core diameter.
In short, the present invention has the characteristics that raw material is cheap, simple process is environmentally friendly, yield is big, has excellent performance, preparation is provided
Fe3O4The new strategy of/MOFs/ meso-porous hollow carbon composite nano ball, and the potentiality with large-scale application.The Fe3O4/
ZIF-8/ meso-porous hollow carbon composite nano ball, Fe3O4/ ZIF-67/ meso-porous hollow carbon composite nano ball can be used as adsorbent, urge
The application of agent, catalyst carrier, slow releasing carrier of medication or lithium ion battery electrode material.
Detailed description of the invention
Fig. 1 is the Fe of preparation3O4Transmission electron microscope picture.
Fig. 2 is the transmission electron microscope picture of the magnetic nano cages of preparation.
Fig. 3 is the Fe of preparation3O4The transmission electron microscope picture of/ZIF-8/ meso-porous hollow carbon composite nano ball.
Fig. 4 is the Fe of preparation3O4The transmission electron microscope picture of/ZIF-67/ meso-porous hollow carbon composite nano ball.
Fig. 5 is the Fe of preparation3O4Charge-discharge performance figure under/ZIF-67/ meso-porous hollow Nano carbon balls different multiplying.
Fig. 6 is the Fe of preparation3O4Charge-discharge performance figure under/ZIF-8/ meso-porous hollow Nano carbon balls different multiplying.
Fig. 7 is the Fe of preparation3O4/ ZIF-67/ meso-porous hollow Nano carbon balls and Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls
It take quadracycline (TH) as the drug Cumulative release profile figure of model drug.
Specific embodiment
One, in order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments to this hair
It is bright to be described in detail.
Embodiment 1:
1. preparing magnetic nano cages:
By 3.6 g FeCl3·6H2O, 90 ml ethylene glycol, 10 ml ethyl alcohol and the mixing of 2.4 g sodium acetates, it is mechanical at room temperature
30 min are stirred, mixed solution are transferred to reaction kettle, 10 h of hydro-thermal reaction at 200 DEG C.To centrifuge washing after reaction, do
The Fe of 200 nm is obtained after dry3O4Ball.
75 ml of ethyl alcohol, 30 ml of deionized water and 3 ml of ammonium hydroxide mixing, by 0.3 g Fe3O4Ball is distributed in mixed solution；
0.6 g tetraethyl orthosilicate (TEOS) uniform speed slow is added dropwise to containing Fe3O4Mixed liquor in, mechanical stirring at room temperature, reaction
10 min form the Fe of core-shell structure3O4@SiO2Nanosphere.
Above-mentioned reaction system is added in 1 ml of formalin and 0.5 g of resorcinol, at room temperature 24 h of mechanic whirl-nett reaction.
60 DEG C of solid phase dry 12h after centrifuge washing form Fe3O4@SiO2@resorcinol-formaldehyde resin magnetic microsphere.
By the Fe after drying3O4@SiO2@resorcinol formaldehyde resin magnetic microsphere is 500 DEG C of high temperature under argon atmosphere protection
8 h are calcined, 2 DEG C/min of heating rate is to get Fe3O4@SiO2@C ball.
By calcined Fe3O4@SiO2@C ball magnetic microsphere is dispersed in 50 ml, in 2 mol/L sodium hydrate aqueous solutions, 60
DEG C etching 16 h, to after reaction use water and ethyl alcohol difference centrifuge washing three times, obtain solid phase after 60 DEG C of dry 12h, i.e. magnetic
Property nano cages.
400 nm of nano cages diameter, carbon wall thickness are 18 nm, 2.8 nm of carbon ball surface apertures size, magnetic kernel 200
nm。
2. confinement growth of the ZIF-8 in magnetic nano cages:
Magnetic Nano cage 50mg is dispersed in 30ml methanol solution, Zn (NO is added after being uniformly dispersed3)2·6H2O
149 mg(0.5 mmol) and 162 mg(2 mmol of 2-methylimidazole) reacted, distinguish to water after reaction and ethyl alcohol
Three times, 60 DEG C of dry 12h grow the hollow magnetic Nano carbon balls of ZIF-8 to get internal confinement to centrifuge washing after acquirement solid phase
(Fe3O4/ ZIF-8/ meso-porous hollow carbon composite nano ball).
3. confinement growth of the ZIF-67 in magnetic nano cages:
50 mg of magnetic Nano cage is dispersed in 30ml methanol solution, Co (NO is added after being uniformly dispersed3)2·6H2O
146 mg(0.5 mmol) and 162 mg(2 mmol of 2-methylimidazole) reacted, distinguish to water after reaction and ethyl alcohol
Three times, 60 DEG C of dry 12h grow the hollow magnetic Nano carbon balls of ZIF-67 to get internal confinement to centrifuge washing after acquirement solid phase
(Fe3O4/ ZIF-67/ meso-porous hollow carbon composite nano ball).
Embodiment 2:
1. preparing magnetic nano cages:
By 3.6 g FeCl3·6H2O, 90 ml ethylene glycol, 10 ml ethyl alcohol and the mixing of 2.4 g sodium acetates, it is mechanical at room temperature
30 min are stirred, mixed solution are transferred to reaction kettle, 10 h of hydro-thermal reaction at 200 DEG C.To centrifuge washing after reaction,
The Fe of 200 nm is obtained after drying3O4Ball.
75 ml of ethyl alcohol, deionized water 30 ml and ammonium hydroxide 3ml mixing, by 0.3 g Fe3O4Ball is distributed in mixed solution；
0.6 g tetraethyl orthosilicate (TEOS) uniform speed slow is added dropwise to containing Fe3O4Mixed liquor in, mechanical stirring at room temperature, reaction
10 min form the Fe of core-shell structure3O4@SiO2Nanosphere.
Above-mentioned reaction system is added in 1 ml of formalin and 0.5 g of resorcinol, at room temperature 24 h of mechanic whirl-nett reaction.
60 DEG C of 12 h of drying of solid phase after centrifuge washing form Fe3O4@SiO2@resorcinol-formaldehyde resin magnetic microsphere.
By the Fe after drying3O4@SiO2@resorcinol formaldehyde resin magnetic microsphere is forged for 600 DEG C of high temperature under argon atmosphere protection
6h is burnt, 2 DEG C/min of heating rate is to get Fe3O4@SiO2@C ball.
By calcined Fe3O4@SiO2@C ball magnetic microsphere is dispersed in 50 ml, in 2 mol/L sodium hydrate aqueous solutions, 60
DEG C etching 16 h, to after reaction use water and ethyl alcohol difference centrifuge washing three times, obtain solid phase after 60 DEG C of dry 12h, i.e. magnetic
Property nano cages.
400 nm of nano cages diameter, carbon wall thickness are 18 nm, 2.8 nm of carbon ball surface apertures size, magnetic kernel 200
nm。
2. confinement growth of the ZIF-8 in magnetic nano cages:
50 mg of magnetic Nano cage is dispersed in 30ml methanol solution, Zn (NO is added after being uniformly dispersed3)2·6H2O
297 mg(1 mmol) and 324 mg(4 mmol of 2-methylimidazole) reacted, to water after reaction and ethyl alcohol respectively from
The heart washs three times, and 60 DEG C of dry 12h grow the hollow magnetic Nano carbon balls of ZIF-8 to get internal confinement after acquirement solid phase
(Fe3O4/ ZIF-8/ meso-porous hollow carbon composite nano ball).
3. confinement growth of the ZIF-67 in magnetic nano cages:
50 mg of magnetic Nano cage is dispersed in 30 ml methanol solutions, Co (NO is added after being uniformly dispersed3)2·6H2O
291 mg(1 mmol) and 324 mg(4 mmol of 2-methylimidazole) reacted, to water after reaction and ethyl alcohol respectively from
The heart washs three times, and 60 DEG C of dry 12h grow the hollow magnetic Nano carbon balls of ZIF-67 to get internal confinement after acquirement solid phase
(Fe3O4/ ZIF-67/ meso-porous hollow carbon composite nano ball).
Embodiment 3:
1. preparing magnetic nano cages:
By 3.6 g FeCl3·6H2O, 90 ml ethylene glycol, 10 ml ethyl alcohol and the mixing of 2.4 g sodium acetates, it is mechanical at room temperature
30 min are stirred, mixed solution are transferred to reaction kettle, 10 h of hydro-thermal reaction at 200 DEG C.To centrifuge washing after reaction,
The Fe of 200 nm is obtained after drying3O4Ball.
75 ml of ethyl alcohol, deionized water 30 ml and ammonium hydroxide 3ml mixing, by 0.3 g Fe3O4Ball is distributed in mixed solution；
0.6 g tetraethyl orthosilicate (TEOS) uniform speed slow is added dropwise to containing Fe3O4Mixed liquor in, mechanical stirring at room temperature, reaction
10 min form the Fe of core-shell structure3O4@SiO2Nanosphere.
Above-mentioned reaction system is added in 1 ml of formalin and 0.5 g of resorcinol, at room temperature 24 h of mechanic whirl-nett reaction.
60 DEG C of solid phase dry 12h after centrifuge washing form Fe3O4@SiO2@resorcinol-formaldehyde resin magnetic microsphere.
By the Fe after drying3O4@SiO2@resorcinol formaldehyde resin magnetic microsphere is forged for 700 DEG C of high temperature under argon atmosphere protection
5h is burnt, 2 DEG C/min of heating rate is to get Fe3O4@SiO2@C ball.
By calcined Fe3O4@SiO2@C ball magnetic microsphere is dispersed in 50 ml, in 2 mol/L sodium hydrate aqueous solutions, 60
DEG C etching 16 h, to after reaction use water and ethyl alcohol difference centrifuge washing three times, obtain solid phase after 60 DEG C of dry 12h, i.e. magnetic
Property nano cages.
400 nm of nano cages diameter, carbon wall thickness are 18 nm, 2.8 nm of carbon ball surface apertures size, magnetic kernel 200
nm。
2. confinement growth of the ZIF-8 in magnetic nano cages:
50 mg of magnetic Nano cage is dispersed in 30 ml methanol solutions, Zn (NO is added after being uniformly dispersed3)2·6H2O
594 mg(2 mmol) and 648 mg(8 mmol of 2-methylimidazole) reacted, to water after reaction and ethyl alcohol respectively from
The heart washs three times, and 60 DEG C of dry 12h grow the hollow magnetic Nano carbon balls of ZIF-8 to get internal confinement after acquirement solid phase
(Fe3O4/ ZIF-8/ meso-porous hollow carbon composite nano ball).
3. confinement growth of the ZIF-67 in magnetic nano cages
50 mg of magnetic Nano cage is dispersed in 30ml methanol solution, Co (NO is added after being uniformly dispersed3)2·6H2O
582 mg(2 mmol) and 2-methylimidazole 648mg(8 mmol) reacted, it is centrifuged respectively to water after reaction and ethyl alcohol
Three times, 60 DEG C of dry 12h grow the hollow magnetic Nano carbon balls (Fe of ZIF-67 to get internal confinement after acquirement solid phase for washing3O4/
ZIF-67/ meso-porous hollow carbon composite nano ball).
Two, product is verified:
Fig. 1 is the Fe prepared using the method for the present invention3The transmission electron microscope picture of O magnetic microsphere.From figure: prepared Fe3O4
Partial size is about 200 nm.
Fig. 2 is the transmission electron microscope picture of the nucleocapsid structure magnetic Nano cage prepared using the method for the present invention.From figure: magnetic
Property nanocages pattern it is uniform, still keep C hollow magnetic micro-sphere structure, prepared product be partial size be about 400 ~ 500 nm, carbon
Wall thickness is about 20 nm or so, and surface is smooth.
Fig. 3 is the Fe prepared using the method for the present invention3O4The transmission electron microscope picture of/ZIF-8/ meso-porous hollow carbon composite nano ball.
From figure: successfully confinement is grown in inside magnetic Nano cage ZIF-8, and magnetic Nano basket structure keeps complete, is formd
Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls tri compound nanostructure.ZIF-8/ meso-porous hollow carbon composite nano ball.
Fig. 4 is the Fe prepared using the method for the present invention3O4The transmission electron microscope of/ZIF-67/ meso-porous hollow carbon composite nano ball
Figure.From figure: successfully confinement is grown in inside magnetic Nano cage ZIF-67, and magnetic Nano basket structure keeps complete, is formed
Fe3O4/ ZIF-67/ meso-porous hollow Nano carbon balls tri compound nanostructure.
Fig. 5 is the Fe of preparation3O4Charge-discharge performance figure under/ZIF-67/ meso-porous hollow Nano carbon balls different multiplying.
Fig. 6 is the Fe of preparation3O4Charge-discharge performance figure under/ZIF-8/ meso-porous hollow Nano carbon balls different multiplying.
Three, it applies:
The hollow magnetic Nano carbon balls of the inside confinement growth MOFs of the method for the present invention preparation are assembled into button cell.
Fig. 5 and Fig. 6 is respectively the Fe prepared3O4/ ZIF-67/ meso-porous hollow Nano carbon balls and Fe3O4The mesoporous sky of/ZIF-8/
Charge-discharge performance figure under heart Nano carbon balls different multiplying, by material Fe3O4/ ZIF-67/ meso-porous hollow Nano carbon balls are dividing
Not in 0.1 A g-1、0.2 A g-1、0.5A g-1、1.0A g-1、2.0A g-1、0.1A g-1Current density under respectively recycle 10
Circle, reversible specific capacity is respectively 1021,870,833,682,577 and 817 mA h g-1.When being recycled to 50 circle, turn again to
100 mA g-1Under current density, specific capacity quickly recovers to 817 mA h g-1, about the 80% of initial capacity shows with pole
Good high rate performance.Equally by material Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls are respectively in 0.1 A g-1、0.2 A g-1、
0.5A g-1、1.0A g-1、2.0A g-1、0.1A g-1Current density under respectively recycle 10 circles, reversible specific capacity is respectively 843,
646,474,389,332 and 721 mA h g-1.When being recycled to 50 circle, 100 mA g are turned again to-1Under current density, specific volume
Amount quickly recovers to 817 mA h g-1, about the 96% of initial capacity shows the high rate performance for having fabulous.
Fig. 7 is the Fe of preparation3O4/ ZIF-67/ meso-porous hollow Nano carbon balls and Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls
It take quadracycline (TH) as the drug Cumulative release profile figure of model drug.By in figure we can see that Fe3O4/ZIF-67/
Meso-porous hollow Nano carbon balls and Fe3O4When/ZIF-8/ meso-porous hollow Nano carbon balls are using quadracycline as model drug, drug
The trend of release is the extension with the time and increases.Fe3O4/ ZIF-67/ meso-porous hollow Nano carbon balls are as medicament slow release
When carrier, drug release amount reaches 59.7% in preceding 10h, and after 24h, rate of releasing drug tends towards stability, within 32 h, highest drug release amount
Reach 83.2%；Fe3O4When/ZIF-8/ meso-porous hollow Nano carbon balls are as slow releasing carrier of medication, drug release amount reaches in preceding 10h
81.1%, after 24h, rate of releasing drug tends towards stability, and within 34 h, highest drug release amount reaches 86.7%.By comparison it is found that
In drug release 10h, Fe3O4The release amount of medicine of/ZIF-67/ meso-porous hollow Nano carbon balls is greater than Fe3O4The mesoporous sky of/ZIF-8/
Heart Nano carbon balls, and rate of release is very fast；In drug release 10h-20h, Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls
Release amount of medicine be greater than Fe3O4/ ZIF-67/ meso-porous hollow Nano carbon balls, and rate of release is very fast；Two kinds of materials exist
20h gradually tends to be steady later, but Fe3O4The release amount of medicine of/ZIF-67/ meso-porous hollow Nano carbon balls is greater than Fe3O4/ZIF-
8/ meso-porous hollow Nano carbon balls.Caused by this may be different with metal ion due to MOFs different pore structures.This explanation
Fe3O4/ ZIF-67/ meso-porous hollow Nano carbon balls and Fe3O4Carrier of/ZIF-8/ meso-porous hollow the Nano carbon balls as medicament slow release
Drug can be made slowly to discharge, there is good slow release effect.
Claims (9)
1. the preparation method that inside confinement grows the hollow magnetic Nano carbon balls of MOFs, it is characterised in that the following steps are included:
1) by FeCl3·6H2O, hydro-thermal reaction is carried out after ethylene glycol, ethyl alcohol and sodium acetate mixing, after reaction centrifuge washing,
It takes solid phase dry, obtains Fe3O4Ball；
2) by ethyl alcohol, deionized water, ammonium hydroxide and Fe3O4Ball mixes under ultrasound condition, obtains Fe3O4Ball mixed liquor；Again by silicon source
It is added dropwise in above-mentioned mixed liquor, is reacted under stirring condition, obtain the Fe containing core-shell structure3O4@SiO2Nanosphere reactant
System；Resorcinol and formaldehyde are added in above-mentioned reaction system under stirring condition again and reacted, centrifugation is washed after reaction
It washs, takes solid phase dry, obtain Fe3O4@SiO2@resorcinol formaldehyde resin ball；
3) by Fe3O4@SiO2The high-temperature calcination under argon atmosphere protection of@resorcinol formaldehyde resin ball, obtains Fe3O4@SiO2@C ball；
4) by Fe3O4@SiO2@C ball, which is dispersed in sodium hydrate aqueous solution, to be performed etching, by the product centrifuge washing after etching, then
It takes solid phase dry, obtains magnetic nano cages；
5) magnetic nano cages are dispersed in methanol, metal nitrate then is added and 2-methylimidazole is reacted, reacted
After centrifuge washing, obtain that solid phase is dry, obtain the hollow magnetic Nano carbon balls of internal confinement growth MOFs.
2. preparation method according to claim 1, it is characterised in that: in the step 2, the silicon source is positive silicic acid four
Ethyl ester, Fe3O4The mass ratio that feeds intake of ball and tetraethyl orthosilicate is 1: 1~10.
3. preparation method according to claim 2, it is characterised in that in the step 2, be added after tetraethyl orthosilicate extremely
Obtain the Fe containing core-shell structure3O4@SiO2The reaction time of nanosphere reaction system is 10~20 min.
4. preparation method according to claim 3, it is characterised in that in the step 2, the resorcinol, formaldehyde and
The feed ratio of tetraethyl orthosilicate is 0.5~1.5 ml: 0.2~0.8 g: 1~10 g.
5. preparation method according to claim 1, it is characterised in that in the step 3), the temperature strip of the high-temperature calcination
Part is 500~700 DEG C.
6. preparation method according to claim 1, it is characterised in that the sodium hydroxide water in the step 4), for etching
The temperature of solution is 40~90 DEG C, and the concentration of the sodium hydrate aqueous solution for etching is 1~5mol/L.
7. preparation method according to claim 1, it is characterised in that: in the step 5), metal nitrate Zn
(NO3)2·6H2O or Co (NO3)2·6H2O。
8. preparation method according to claim 7, it is characterised in that: in the step 5), magnetic nano cages and Zn
(NO3)2·6H2The mass ratio of O is 1: 2~12.
9. preparation method according to claim 7, it is characterised in that in the step 5), magnetic nano cages and Co
(NO3)2·6H2The mass ratio of O is 1: 2~12.
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| CN111056545A (en) * | 2019-08-21 | 2020-04-24 | 洛阳师范学院 | Preparation method of MOFs-derived hollow porous carbon microspheres |
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