CN107481827A - The preparation method of internal confinement growth MOFs hollow magnetic Nano carbon balls - Google Patents

The preparation method of internal confinement growth MOFs hollow magnetic Nano carbon balls Download PDF

Info

Publication number
CN107481827A
CN107481827A CN201710772691.0A CN201710772691A CN107481827A CN 107481827 A CN107481827 A CN 107481827A CN 201710772691 A CN201710772691 A CN 201710772691A CN 107481827 A CN107481827 A CN 107481827A
Authority
CN
China
Prior art keywords
balls
magnetic nano
preparation
sio
ball
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710772691.0A
Other languages
Chinese (zh)
Other versions
CN107481827B (en
Inventor
陈铭
李文龙
周克寒
张秀娥
姜晖
吴倩卉
赵荣芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou University
Original Assignee
Yangzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou University filed Critical Yangzhou University
Priority to CN201710772691.0A priority Critical patent/CN107481827B/en
Publication of CN107481827A publication Critical patent/CN107481827A/en
Application granted granted Critical
Publication of CN107481827B publication Critical patent/CN107481827B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036Magnets 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
    • H01F1/0045Zero dimensional, e.g. nanoparticles, soft nanoparticles for medical/biological use
    • H01F1/0054Coated nanoparticles, e.g. nanoparticles coated with organic surfactant
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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 internal confinement growth MOFs hollow magnetic Nano carbon balls, belongs to nano material production technical field, by FeCl3·6H2O, ethylene glycol, ethanol and sodium acetate are mixed into water-filling thermal response, obtain Fe3O4Ball, mixed with ethanol, deionized water, ammoniacal liquor, obtain Fe3O4Ball mixed liquor, after silicon source reaction is added dropwise thereto, adds resorcinol and formaldehyde is reacted, obtain Fe3O4@SiO2@resorcinol formaldehyde resin balls, through being calcined under argon gas, obtain Fe3O4@SiO2@C balls, are etched through sodium hydrate aqueous solution, obtain magnetic nano cages;Finally magnetic nano cages and metal nitrate and 2 methylimidazoles are reacted, obtain that size is homogeneous, is evenly distributed and pattern controls good inside confinement growth MOFs hollow magnetic Nano carbon balls.The process is easy, and course of reaction material requested is less toxic, harmless.

Description

The preparation method of internal confinement growth MOFs hollow magnetic Nano carbon balls
Technical field
The invention belongs to nano material production technical field, and in particular to confinement growth MOFs inside a kind of magnetic Nano cage Technology.
Background technology
Metal organic framework compound(MOFs)It is a kind of coordination polymer quickly grown nearly ten years, refers to transition gold Category ion and organic ligand passes through the crystalline porous material with periodic network structure that is self-assembly of.It has high hole Rate, low-density, bigger serface, duct rule, aperture is adjustable and the advantages that topological structure diversity and Scalability, has Three-dimensional pore structure, typically using metal ion as tie point, organic ligand support Special composition 3D extensions, are that zeolite and carbon are received The important novel porous materials of another class outside mitron, are all widely used in catalysis, energy storage and separation.At present, MOFs The important research direction of multiple chemical branches such as inorganic chemistry, organic chemistry is turned into.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, the controllable function in its adjustable aperture, it is set to be better than traditional porous material.
But MOFs materials do not have electric conductivity, its application in electrochemical field is limited.The size of MOFs materials It is smaller, it is more difficult from the separation in reaction system.MOFs materials less stable in strong acid and strong basicity solvent, can be caused MOF decomposition, 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 materials do not have magnetic, can not in magnetic field displacement, also can not be from Magnetic Isolation in reaction system.Therefore, it is necessary to design synthesis it is a kind of have magnetic, the MOFs composites of electric conductivity.
The content of the invention
For the disadvantages described above of prior art, it is an object of the invention to propose confinement growth inside a kind of magnetic Nano cage The preparation method of MOFs preparation method ball.
The present invention comprises the following steps:
1)By FeCl3·6H2O, ethylene glycol, ethanol and sodium acetate mix laggard water-filling thermal response, and reaction terminates rear centrifuge washing, Take solid phase to dry, obtain Fe3O4Ball.
The present invention passes through the homogeneous Fe of the diameter of hydro-thermal method synthesis3O4Ball, with Fe3O4Ball is the template of subsequent reactions. With Fe3O4For magnetic kernel and template, SiO is wrapped up successively beneficial on its surface2With resorcinol-formaldehyde oligomer.
2)By ethanol, deionized water, ammoniacal liquor 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, obtains the Fe containing core shell structure3O4@SiO2Nanosphere is anti- Answer system;Resorcinol and formaldehyde are added in above-mentioned reaction system under stirring condition again and reacted, reaction terminate after from The heart washs, and takes solid phase to dry, obtains Fe3O4@SiO2@resorcinol formaldehyde resin balls.
The present invention using ethanol and deionized water regulation reaction system polarity, during so as to control tetraethyl orthosilicate to hydrolyze Hydrolysis rate, and the purpose for adding ammoniacal liquor is to provide tetraethyl orthosilicate and hydrolyzes necessary alkalescence condition.
The high temperature cabonization for the oligomer that carbon-coating is formed from resorcinol with formaldehyde, the thickness of carbon-coating and carbon-coating surface Mesoporous size is adjusted by adding formalin, the dosage of resorcinol and reaction time.Meso-porous hollow Nano carbon balls carbon The nm of layer intermediary hole size 2 ~ 5, mesoporous big I meet that subsequent reactions metal ion, organic molecule enter magnetic carbon nanometer Confinement reaction is carried out inside cage.
3)By Fe3O4@SiO2The high-temperature calcination under argon gas atmosphere protection of@resorcinol formaldehyde resins ball, obtains Fe3O4@SiO2@ C balls.Calcination process makes resorcinol formaldehyde resin carbonization be changed into mesoporous carbon-coating.
4)By Fe3O4@SiO2@C balls, which are dispersed in sodium hydrate aqueous solution, to be performed etching, and the product centrifugation after etching is washed Wash, then take solid phase to 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, under an argon atmosphere high-temperature calcination form Fe3O4@SiO2@C balls, then form yolk-egg with sodium hydroxide acid etch again The magnetic Nano cage of shell structure.Prepared magnetic nano cages pattern is homogeneous, Stability Analysis of Structures, carbon-coating surface distributed have it is mesoporous, The Fe with good pattern is prepared to be follow-up3O4/ MOFs/ meso-porous hollow carbon composite nano ball structures provide advantage.
5)Magnetic nano cages are dispersed in methanol, then metal nitrate is added and 2-methylimidazole is reacted, Reaction terminates rear centrifuge washing, obtains solid phase and dries, and obtains internal confinement growth MOFs hollow magnetic Nano carbon balls(That is Fe3O4/ MOFs/ meso-porous hollow carbon composite nano balls).
In the step, using magnetic nano cages as nano-reactor, confinement growth is carried out to MOFs, it is equal that distribution can be obtained It is even, and pattern controls good Fe3O4/ MOFs/ meso-porous hollow carbon composite nano balls.
The present invention is with Fe3O4Magnetic nano-balls are template, in its inner surface coated Si O2And resorcinol formaldehyde resin, warp Cross high-temperature calcination to etch afterwards, form 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 balls.Yolk-eggshell structure Magnetic nano cages inwall growth in situ MOFs, realize the micro nano structure of cage in cage.Nano cages and MOFs cage tools 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, it is possible to achieve the confinement of nano material grows and is used as micro-nano reactor as catalyst and to be urged as nanometer reacting environment Agent carrier can effectively improve catalytic performance;Basket structure can play the effect of control medicament slow release in cage, be carried in biology Had 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 inwall growth in situ of yolk-eggshell structure MOFs can be used as lithium ion battery negative material, be advantageous to the transfer of electric charge, can improve the diffusion of lithium ion, can high magnification fill Electric discharge.
In a word, production equipment of the present invention is simple, and preparation cost is low, and operating process is easy, course of reaction material requested low toxicity, It is harmless, and the stoichiometric proportion of multi-component material can be effectively controlled, acquisition size is homogeneous, is evenly distributed and pattern control is good Good Fe3O4/ MOFs/ meso-porous hollow carbon composite nano balls, this ternary that can be used for industrial mass production high quality are answered Condensation material.
Further, step 2 of the present invention)In, 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) is 1: 1~10. Tetraethyl orthosilicate is conventional silylating reagent, and its hydrolysis rate in mild alkaline conditions can be effectively controlled, so as to 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 space.The size of nanovoids can grow MOFs for follow-up confinement and provide suitable spatial volume, and internally growth is more MOFs, improve MOFs mass fraction, be more beneficial for improving the application performance of product.In addition, regulation magnetic core and carbon nanometer Integrality and magnetic of the diameter of cage than advantageously ensuring that spheroid.
In order to control generation SiO2Thickness be 50~150 nm, the step 2)In, add tetraethyl orthosilicate (TEOS) afterwards to Fe of the acquirement containing core shell structure3O4@SiO2The reaction time of nanosphere reaction system is 10~20 min.Control System generation SiO2Thickness, can mainly effectively obtain the nanovoids of suitable size, growing MOFs for follow-up confinement carries For suitable spatial volume, more MOFs are internally grown, improve MOFs mass fraction, are more beneficial for improving answering for product Use performance.Thickness such as SiO2 is less than 50 nm, is unfavorable for the confinement growth of MOFs materials;Such as SiO2Thickness be more than 150 nm, Whole sphere diameter is excessive, is unfavorable for the cladding of resorcinol formaldehyde resin, causes follow-up carbonisation, and carbon ball crushes.
In order that the carbon wall thickness control of manufactured product exists in 10~35nm, the surface mesoporous magnitude range control of carbon-coating 2~5 nm, the step 2)In, the rate of charge 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 materials And subsequent applications.First, the thickness of carbon wall is thicker, and carbon-coating is surface mesoporous smaller, and MOFs confinements internally growth will be limited System, causes the quantity of MOFs internally very few, so as to just lose the effect that MOFs is played as main material.Secondly, exist In follow-up application, either molecule and ion need to could enter inside by carbon wall, therefore carbon layers having thicknesses and mesoporous size need Control, 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 Can not be by the way that mesoporous excessive, carbon-coating structure is easily destroyed.It is therefore desirable to have effect control carbon layers having thicknesses and surface apertures size.
State step 3)In, the temperature conditionss of the high-temperature calcination are 500~700 DEG C.Under the conditions of this, carbon layer material can be made Carbonization is more complete, while produces substantial amounts of mesoporous.Such as less than 500 DEG C carbonizations are incomplete, and carbonization time is long;And such as it is higher than 700 DEG C, ferroso-ferric oxide is easily reduced to cementite or fe by carbon, loses magnetic.
The step 4)In, the temperature for the sodium hydrate aqueous solution of etching is 40~90 DEG C, the hydrogen-oxygen for etching The concentration for changing sodium water solution is 1~5mol/L., can be with by the regulation of reaction time and naoh concentration in this temperature range Realize SiO2Complete etching.Less than 40 DEG C etch periods are long, and higher than 90 DEG C, water-bath produces a large amount of aqueous vapors.This sodium hydroxide In concentration range, SiO can be realized by the regulation of reaction time and reaction temperature2Complete etching.Naoh concentration mistake Low, etch period is long, and concentration is higher than 5mol/L, and alkalescence 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, by step 5)ZIF-8 is limited in hollow magnetic Nano carbon balls Domain grows, and obtained is internal confinement growth ZIF-8 hollow magnetic Nano carbon balls.
And when with Co (NO3)2·6H2When O is metal nitrate, by step 5)ZIF-67 is in hollow magnetic Nano carbon balls Interior confinement growth, obtained is internal confinement growth ZIF-67 hollow magnetic Nano carbon balls.
From Zn (NO3)2·6H2O or Co (NO3)2·6H2O is metal nitrate and 2-methylimidazole in meso-porous hollow carbon The reason for ball inside confinement growth MOFs is because of ZIF-8 and ZIF-67 synthesis technique relative maturities, and ZIF-8 and ZIF-67 And its derived material has begun to be 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.
The step 5)In, magnetic nano cages and Zn (NO3)2·6H2O mass ratio is 1: 2~12.
The step 2)In, magnetic nano cages and Co (NO3)2·6H2O mass ratio is 1: 2~12.
The confinement in hollow magnetic Nano carbon balls of described two kinds of MOFs materials of ZIF-8, ZIF-67 grows, and does not change MOFs The original composition of material, structure, pattern etc., are formed with Fe3O4For kernel, mesoporous carbon is shell, and MOFs materials are new in the space of middle part Type trielement composite material.
In the hollow magnetic Nano carbon balls of formation, the nm of magnetic nano cages diameter 300 ~ 500, carbon wall thickness is 10 ~ 35 Nm, carbon ball surface apertures size 2 ~ 5 nm, the nm of magnetic core diameter 200.
In a word, the present invention has the characteristics of raw material is cheap, technique is simple and environmentally-friendly, yield is big, excellent performance, there is provided prepares Fe3O4The new strategy of/MOFs/ meso-porous hollow carbon composite nano balls, and the potentiality with large-scale application.Described Fe3O4/ ZIF-8/ meso-porous hollow carbon composite nanos ball, Fe3O4/ ZIF-67/ meso-porous hollow carbon composite nanos ball can be used as adsorbent, urge The application of agent, catalyst carrier, slow releasing carrier of medication or lithium ion battery electrode material.
Brief description of the drawings
Fig. 1 is the Fe prepared3O4Transmission electron microscope picture.
Fig. 2 is the transmission electron microscope picture of the magnetic nano cages prepared.
Fig. 3 is the Fe prepared3O4The transmission electron microscope picture of/ZIF-8/ meso-porous hollow carbon composite nano balls.
Fig. 4 is the Fe prepared3O4The transmission electron microscope picture of/ZIF-67/ meso-porous hollow carbon composite nano balls.
Fig. 5 is the Fe prepared3O4Charge-discharge performance figure under/ZIF-67/ meso-porous hollow Nano carbon balls different multiplyings.
Fig. 6 is the Fe prepared3O4Charge-discharge performance figure under/ZIF-8/ meso-porous hollow Nano carbon balls different multiplyings.
Fig. 7 is the Fe prepared3O4/ ZIF-67/ meso-porous hollows Nano carbon balls and Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls With quadracycline(TH)For the medicine Cumulative release profile figure of model drug.
Embodiment
First, in order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments to this hair It is bright to be described in detail.
Embodiment 1:
1. prepare magnetic nano cages:
By 3.6 g FeCl3·6H2O, 90 ml ethylene glycol, 10 ml ethanol and 2.4 g sodium acetates mix, at room temperature mechanical agitation 30 min, mixed solution is transferred to reactor, the h of hydro-thermal reaction 10 at 200 DEG C.Question response terminates rear centrifuge washing, after drying Obtain 200 nm Fe3O4Ball.
The ml of ethanol 75, the ml of deionized water 30 and the ml of ammoniacal liquor 3 mixing, by 0.3 g Fe3O4Ball is distributed in mixed solution; 0.6 g tetraethyl orthosilicates (TEOS) uniform speed slow is added dropwise to containing Fe3O4Mixed liquor in, mechanical agitation at room temperature, reaction 10 min, form the Fe of core shell structure3O4@SiO2Nanosphere.
The ml of the formalin 1 and g of resorcinol 0.5 is added into above-mentioned reaction system, at room temperature the h of mechanic whirl-nett reaction 24. The dry 12h of 60 DEG C of solid phase after centrifuge washing, form Fe3O4@SiO2@resorcinol-formaldehyde resin magnetic microspheres.
By dried Fe3O4@SiO2@resorcinol formaldehyde resins magnetic microsphere 500 DEG C of high temperature under argon gas atmosphere protection 8 h are calcined, 2 DEG C/min of heating rate, produce Fe3O4@SiO2@C balls.
By the Fe after calcining3O4@SiO2@C ball magnetic microspheres are dispersed in 50 ml, 2 mol/L sodium hydrate aqueous solutions, 60 DEG C etching 16 h, question response terminate after with water and ethanol difference centrifuge washing three times, obtain solid phase after 60 DEG C of dry 12h, i.e. magnetic Property nano cages.
The nm of nano cages diameter 400, carbon wall thickness are 18 nm, the nm of carbon ball surface apertures size 2.8, magnetic kernel 200 nm。
2. confinement growths of the ZIF-8 in magnetic nano cages:
Magnetic Nano cage 50mg is dispersed in 30ml methanol solutions, Zn (NO are added after being uniformly dispersed3)2·6H2O 149 mg (0.5 mmol)With the mg of 2-methylimidazole 162(2 mmol)Reacted, question response terminates rear water and ethanol and centrifuged respectively to wash Wash three times, obtain 60 DEG C of dry 12h after solid phase, produce internal confinement growth ZIF-8 hollow magnetic Nano carbon balls(Fe3O4/ ZIF-8/ meso-porous hollow carbon composite nano balls).
3. confinement growths of the ZIF-67 in magnetic nano cages:
The mg of magnetic Nano cage 50 is dispersed in 30ml methanol solutions, Co (NO are added after being uniformly dispersed3)2·6H2O 146 mg(0.5 mmol)With the mg of 2-methylimidazole 162(2 mmol)Reacted, question response terminates rear water and ethanol and centrifuged respectively Washing three times, obtains 60 DEG C of dry 12h after solid phase, produces internal confinement growth ZIF-67 hollow magnetic Nano carbon balls(Fe3O4/ ZIF-67/ meso-porous hollow carbon composite nano balls).
Embodiment 2:
1. prepare magnetic nano cages:
By 3.6 g FeCl3·6H2O, 90 ml ethylene glycol, 10 ml ethanol and 2.4 g sodium acetates mix, at room temperature mechanical agitation 30 min, mixed solution is transferred to reactor, the h of hydro-thermal reaction 10 at 200 DEG C.Question response terminates rear centrifuge washing, dries 200 nm Fe is obtained afterwards3O4Ball.
The ml of ethanol 75, the ml of deionized water 30 and ammoniacal liquor 3ml mixing, by 0.3 g Fe3O4Ball is distributed in mixed solution; 0.6 g tetraethyl orthosilicates (TEOS) uniform speed slow is added dropwise to containing Fe3O4Mixed liquor in, mechanical agitation at room temperature, reaction 10 min, form the Fe of core shell structure3O4@SiO2Nanosphere.
The ml of the formalin 1 and g of resorcinol 0.5 is added into above-mentioned reaction system, at room temperature the h of mechanic whirl-nett reaction 24. 60 DEG C of 12 h of drying of solid phase after centrifuge washing, form Fe3O4@SiO2@resorcinol-formaldehyde resin magnetic microspheres.
By dried Fe3O4@SiO2@resorcinol formaldehyde resins magnetic microsphere 600 DEG C of high temperature under argon gas atmosphere protection is forged 6h is burnt, 2 DEG C/min of heating rate, produces Fe3O4@SiO2@C balls.
By the Fe after calcining3O4@SiO2@C ball magnetic microspheres are dispersed in 50 ml, 2 mol/L sodium hydrate aqueous solutions, 60 DEG C etching 16 h, question response terminate after with water and ethanol difference centrifuge washing three times, obtain solid phase after 60 DEG C of dry 12h, i.e. magnetic Property nano cages.
The nm of nano cages diameter 400, carbon wall thickness are 18 nm, the nm of carbon ball surface apertures size 2.8, magnetic kernel 200 nm。
2. confinement growths of the ZIF-8 in magnetic nano cages:
The mg of magnetic Nano cage 50 is dispersed in 30ml methanol solutions, Zn (NO are added after being uniformly dispersed3)2·6H2O 297 mg(1 mmol)With the mg of 2-methylimidazole 324(4 mmol)Reacted, question response terminates rear water and ethanol and centrifuged respectively to wash Wash three times, obtain 60 DEG C of dry 12h after solid phase, produce internal confinement growth ZIF-8 hollow magnetic Nano carbon balls(Fe3O4/ ZIF-8/ meso-porous hollow carbon composite nano balls).
3. confinement growths of the ZIF-67 in magnetic nano cages:
The mg of magnetic Nano cage 50 is dispersed in 30 ml methanol solutions, Co (NO are added after being uniformly dispersed3)2·6H2O 291 mg(1 mmol)With the mg of 2-methylimidazole 324(4 mmol)Reacted, question response terminates rear water and ethanol and centrifuged respectively to wash Wash three times, obtain 60 DEG C of dry 12h after solid phase, produce internal confinement growth ZIF-67 hollow magnetic Nano carbon balls(Fe3O4/ ZIF-67/ meso-porous hollow carbon composite nano balls).
Embodiment 3:
1. prepare magnetic nano cages:
By 3.6 g FeCl3·6H2O, 90 ml ethylene glycol, 10 ml ethanol and 2.4 g sodium acetates mix, at room temperature mechanical agitation 30 min, mixed solution is transferred to reactor, the h of hydro-thermal reaction 10 at 200 DEG C.Question response terminates rear centrifuge washing, dries 200 nm Fe is obtained afterwards3O4Ball.
The ml of ethanol 75, the ml of deionized water 30 and ammoniacal liquor 3ml mixing, by 0.3 g Fe3O4Ball is distributed in mixed solution; 0.6 g tetraethyl orthosilicates (TEOS) uniform speed slow is added dropwise to containing Fe3O4Mixed liquor in, mechanical agitation at room temperature, reaction 10 min, form the Fe of core shell structure3O4@SiO2Nanosphere.
The ml of the formalin 1 and g of resorcinol 0.5 is added into above-mentioned reaction system, at room temperature the h of mechanic whirl-nett reaction 24. The dry 12h of 60 DEG C of solid phase after centrifuge washing, form Fe3O4@SiO2@resorcinol-formaldehyde resin magnetic microspheres.
By dried Fe3O4@SiO2@resorcinol formaldehyde resins magnetic microsphere 700 DEG C of high temperature under argon gas atmosphere protection is forged 5h is burnt, 2 DEG C/min of heating rate, produces Fe3O4@SiO2@C balls.
By the Fe after calcining3O4@SiO2@C ball magnetic microspheres are dispersed in 50 ml, 2 mol/L sodium hydrate aqueous solutions, 60 DEG C etching 16 h, question response terminate after with water and ethanol difference centrifuge washing three times, obtain solid phase after 60 DEG C of dry 12h, i.e. magnetic Property nano cages.
The nm of nano cages diameter 400, carbon wall thickness are 18 nm, the nm of carbon ball surface apertures size 2.8, magnetic kernel 200 nm。
2. confinement growths of the ZIF-8 in magnetic nano cages:
The mg of magnetic Nano cage 50 is dispersed in 30 ml methanol solutions, Zn (NO are added after being uniformly dispersed3)2·6H2O 594 mg(2 mmol)With the mg of 2-methylimidazole 648(8 mmol)Reacted, question response terminates rear water and ethanol and centrifuged respectively to wash Wash three times, obtain 60 DEG C of dry 12h after solid phase, produce internal confinement growth ZIF-8 hollow magnetic Nano carbon balls(Fe3O4/ ZIF-8/ meso-porous hollow carbon composite nano balls).
3. confinement growths of the ZIF-67 in magnetic nano cages
The mg of magnetic Nano cage 50 is dispersed in 30ml methanol solutions, Co (NO are added after being uniformly dispersed3)2·6H2O 582 mg(2 mmol)With 2-methylimidazole 648mg(8 mmol)Reacted, question response terminates rear water and ethanol difference centrifuge washing Three times, 60 DEG C of dry 12h after acquirement solid phase, internal confinement growth ZIF-67 hollow magnetic Nano carbon balls are produced(Fe3O4/ZIF- 67/ meso-porous hollow carbon composite nano ball).
2nd, product is verified:
Fig. 1 is the Fe prepared using the inventive method3The transmission electron microscope picture of O magnetic microspheres.From figure:Prepared Fe3O4Particle diameter About 200 nm.
Fig. 2 is the transmission electron microscope picture of the nucleocapsid structure magnetic Nano cage prepared using the inventive method.From figure:Magnetic Property nanocages pattern it is homogeneous, still keep C hollow magnetic micro-sphere structures, prepared product be particle diameter 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 inventive method3O4The transmission electron microscope picture of/ZIF-8/ meso-porous hollow carbon composite nano balls. From figure:Successfully confinement is grown in inside magnetic Nano cage ZIF-8, and magnetic Nano basket structure keeps complete, forms Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls tri compound nanostructureds.ZIF-8/ meso-porous hollow carbon composite nano balls.
Fig. 4 is the Fe prepared using the inventive method3O4The transmission electron microscope of/ZIF-67/ meso-porous hollow carbon composite nano balls 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 nanostructureds.
Fig. 5 is the Fe prepared3O4Charge-discharge performance figure under/ZIF-67/ meso-porous hollow Nano carbon balls different multiplyings.
Fig. 6 is the Fe prepared3O4Charge-discharge performance figure under/ZIF-8/ meso-porous hollow Nano carbon balls different multiplyings.
3rd, apply:
Confinement growth MOFs in inside prepared by the inventive method hollow magnetic Nano carbon balls are assembled into button cell.
Fig. 5 and Fig. 6 is respectively the Fe prepared3O4/ ZIF-67/ meso-porous hollows Nano carbon balls and Fe3O4The mesoporous skies of/ZIF-8/ Charge-discharge performance figure under heart Nano carbon balls different multiplying, by material Fe3O4/ ZIF-67/ meso-porous hollows 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 each circulation 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 hollows 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 each circle of circulation 10, reversible specific capacity is respectively 843, 646th, 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 there is fabulous high rate performance.
Fig. 7 is the Fe prepared3O4/ ZIF-67/ meso-porous hollows Nano carbon balls and Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls With quadracycline(TH)For the medicine 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 hollows Nano carbon balls are using quadracycline as model drug, medicine The trend of release is extension over time and increased.Fe3O4/ ZIF-67/ meso-porous hollow Nano carbon balls are as medicament slow release During 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 hollows 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 contrasting, In insoluble drug release 10h, Fe3O4The release amount of medicine of/ZIF-67/ meso-porous hollow Nano carbon balls is more than Fe3O4The mesoporous skies of/ZIF-8/ Heart Nano carbon balls, and rate of release is very fast;In insoluble drug release 10h-20h, Fe3O4/ ZIF-8/ meso-porous hollow Nano carbon balls Release amount of medicine be more 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 more than Fe3O4/ZIF- 8/ meso-porous hollow Nano carbon balls.This is probably caused by pore structures different MOFs with metal ion difference.This explanation Fe3O4/ ZIF-67/ meso-porous hollows Nano carbon balls and Fe3O4Carrier of/ZIF-8/ meso-porous hollows the Nano carbon balls as medicament slow release Medicine can be made slowly to discharge, there is good slow release effect.

Claims (9)

1. the preparation method of inside confinement growth MOFs hollow magnetic Nano carbon balls, it is characterised in that comprise the following steps:
1)By FeCl3·6H2O, ethylene glycol, ethanol and sodium acetate mix laggard water-filling thermal response, and reaction terminates rear centrifuge washing, Take solid phase to dry, obtain Fe3O4Ball;
2)By ethanol, deionized water, ammoniacal liquor 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, obtains 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, reaction is centrifuged after terminating and washed Wash, take solid phase to dry, obtain Fe3O4@SiO2@resorcinol formaldehyde resin balls;
3)By Fe3O4@SiO2The high-temperature calcination under argon gas atmosphere protection of@resorcinol formaldehyde resins ball, obtains Fe3O4@SiO2@C balls;
4)By Fe3O4@SiO2@C balls, which are dispersed in sodium hydrate aqueous solution, to be performed etching, by the product centrifuge washing after etching, then Take solid phase to dry, obtain magnetic nano cages;
5)Magnetic nano cages are dispersed in methanol, then metal nitrate is added and 2-methylimidazole is reacted, are reacted Centrifuge washing after end, obtain solid phase and dry, obtain internal confinement growth MOFs hollow magnetic Nano carbon balls.
2. preparation method according to claim 1, it is characterised in that:The step 2)In, 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 the step 2)In, add 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 the step 2)In, the resorcinol, formaldehyde and The rate of charge 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 the step 3)In, 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 step 4)In, the sodium hydroxide water for etching The temperature of solution is 40~90 DEG C, and the concentration for the sodium hydrate aqueous solution of etching is 1~5mol/L.
7. preparation method according to claim 1, it is characterised in that:The step 5)In, metal nitrate Zn (NO3)2·6H2O or Co (NO3)2·6H2O。
8. preparation method according to claim 7, it is characterised in that:The step 5)In, magnetic nano cages and Zn (NO3)2·6H2O mass ratio is 1: 2~12.
9. preparation method according to claim 7, it is characterised in that the step 2)In, magnetic nano cages and Co (NO3)2·6H2O mass ratio is 1: 2~12.
CN201710772691.0A 2017-08-31 2017-08-31 The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs Active CN107481827B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710772691.0A CN107481827B (en) 2017-08-31 2017-08-31 The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710772691.0A CN107481827B (en) 2017-08-31 2017-08-31 The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs

Publications (2)

Publication Number Publication Date
CN107481827A true CN107481827A (en) 2017-12-15
CN107481827B CN107481827B (en) 2019-04-19

Family

ID=60603444

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710772691.0A Active CN107481827B (en) 2017-08-31 2017-08-31 The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs

Country Status (1)

Country Link
CN (1) CN107481827B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109894085A (en) * 2019-03-22 2019-06-18 武汉理工大学 Monodisperse bakelite resin nano stick is embedded in the simple universality preparation method of MOF composite material in situ
CN110034287A (en) * 2019-04-10 2019-07-19 扬州大学 ZIF-67 coats potassium phosphomolybdate microballoon composite material and preparation method
CN111056545A (en) * 2019-08-21 2020-04-24 洛阳师范学院 Preparation method of MOFs-derived hollow porous carbon microspheres
CN111097528A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Nano cage-limited catalyst, preparation method and application
CN111804279A (en) * 2020-08-19 2020-10-23 湖南三五二环保科技有限公司 Preparation method of carbon material for dye wastewater, product and application thereof
CN112093934A (en) * 2020-09-11 2020-12-18 广州绿然环保新材料科技有限公司 Heavy metal sewage treatment method
CN112736259A (en) * 2020-12-28 2021-04-30 陕西师范大学 Method for preparing metal monoatomic electrocatalytic oxygen reduction catalyst through confined space
CN113659155A (en) * 2021-08-10 2021-11-16 大连理工大学 Metal-nitrogen-carbon coated carbon nanocage electrocatalyst and preparation method and application thereof
CN113856707A (en) * 2021-09-18 2021-12-31 深圳市东有新材料科技有限公司 Hollow nano aluminum fluoride ball with high catalytic efficiency and preparation method thereof
CN114133584A (en) * 2021-12-24 2022-03-04 贵州大学 Method for green, efficient and uniform synthesis of ZIF-8 material
CN114804070A (en) * 2022-04-06 2022-07-29 北京化工大学 Preparation method of carbon nano hemispherical particles

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080295692A1 (en) * 2007-06-01 2008-12-04 Chunqing Liu Uv cross-linked polymer functionalized molecular sieve/polymer mixed matrix membranes for sulfur reduction
CN105251420A (en) * 2015-09-08 2016-01-20 哈尔滨工程大学 Preparation method for multifunctional composite microspheres
CN105565265A (en) * 2016-03-17 2016-05-11 齐鲁工业大学 Preparation method of composite microsphere lithium ion battery cathode material in yolk structure
CN105754560A (en) * 2016-02-03 2016-07-13 易达(福建)旅游集团有限公司 Self-heating hot compress material and preparation method thereof
CN106311248A (en) * 2016-08-15 2017-01-11 浙江师范大学 Zinc ferrite/carbon/zinc oxide nanocomposite material and preparation method thereof
CN106620702A (en) * 2017-02-14 2017-05-10 扬州大学 Preparation method of gold/nitrogen-doped hollow carbon nanosphere core-shell material
CN106970215A (en) * 2017-03-26 2017-07-21 合肥学院 A kind of preparation method for the Fe3O4@PEG@SiO2 artificial antibodies for detecting thifensulfuronmethyl
CN106984261A (en) * 2017-05-16 2017-07-28 浙江工业大学 A kind of CoFe2O4/ N/C hollow nano-spheres and its preparation and application

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080295692A1 (en) * 2007-06-01 2008-12-04 Chunqing Liu Uv cross-linked polymer functionalized molecular sieve/polymer mixed matrix membranes for sulfur reduction
CN105251420A (en) * 2015-09-08 2016-01-20 哈尔滨工程大学 Preparation method for multifunctional composite microspheres
CN105754560A (en) * 2016-02-03 2016-07-13 易达(福建)旅游集团有限公司 Self-heating hot compress material and preparation method thereof
CN105565265A (en) * 2016-03-17 2016-05-11 齐鲁工业大学 Preparation method of composite microsphere lithium ion battery cathode material in yolk structure
CN106311248A (en) * 2016-08-15 2017-01-11 浙江师范大学 Zinc ferrite/carbon/zinc oxide nanocomposite material and preparation method thereof
CN106620702A (en) * 2017-02-14 2017-05-10 扬州大学 Preparation method of gold/nitrogen-doped hollow carbon nanosphere core-shell material
CN106970215A (en) * 2017-03-26 2017-07-21 合肥学院 A kind of preparation method for the Fe3O4@PEG@SiO2 artificial antibodies for detecting thifensulfuronmethyl
CN106984261A (en) * 2017-05-16 2017-07-28 浙江工业大学 A kind of CoFe2O4/ N/C hollow nano-spheres and its preparation and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FUMIN XUE,ET AL: "One-pot modification of Fe3O4 to prepare Fe3O4/SiO2/C nanoparticles and their catalytic activity in Fenton-like process for dye decolouration", 《MICRO & NANO LETTERS》 *
WENXIAN LIU,ET AL: "Multi-shelled Hollow Metal–Organic Frameworks", 《ANGEW. CHEM. INT. ED.》 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111097528A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 Nano cage-limited catalyst, preparation method and application
CN111097528B (en) * 2018-10-25 2023-05-02 中国石油化工股份有限公司 Nano cage limited catalyst, preparation method and application
CN109894085B (en) * 2019-03-22 2022-03-11 武汉理工大学 Simple universal preparation method for in-situ embedding of monodisperse phenolic resin nanorods into MOF (Metal organic framework) composite material
CN109894085A (en) * 2019-03-22 2019-06-18 武汉理工大学 Monodisperse bakelite resin nano stick is embedded in the simple universality preparation method of MOF composite material in situ
CN110034287A (en) * 2019-04-10 2019-07-19 扬州大学 ZIF-67 coats potassium phosphomolybdate microballoon composite material and preparation method
CN111056545A (en) * 2019-08-21 2020-04-24 洛阳师范学院 Preparation method of MOFs-derived hollow porous carbon microspheres
CN111804279A (en) * 2020-08-19 2020-10-23 湖南三五二环保科技有限公司 Preparation method of carbon material for dye wastewater, product and application thereof
CN112093934A (en) * 2020-09-11 2020-12-18 广州绿然环保新材料科技有限公司 Heavy metal sewage treatment method
CN112736259A (en) * 2020-12-28 2021-04-30 陕西师范大学 Method for preparing metal monoatomic electrocatalytic oxygen reduction catalyst through confined space
CN113659155B (en) * 2021-08-10 2022-10-25 大连理工大学 Metal-nitrogen-carbon coated carbon nanocage electrocatalyst and preparation method and application thereof
CN113659155A (en) * 2021-08-10 2021-11-16 大连理工大学 Metal-nitrogen-carbon coated carbon nanocage electrocatalyst and preparation method and application thereof
CN113856707A (en) * 2021-09-18 2021-12-31 深圳市东有新材料科技有限公司 Hollow nano aluminum fluoride ball with high catalytic efficiency and preparation method thereof
CN114133584A (en) * 2021-12-24 2022-03-04 贵州大学 Method for green, efficient and uniform synthesis of ZIF-8 material
CN114133584B (en) * 2021-12-24 2023-02-28 贵州大学 Method for green, efficient and uniform synthesis of ZIF-8 material
CN114804070A (en) * 2022-04-06 2022-07-29 北京化工大学 Preparation method of carbon nano hemispherical particles

Also Published As

Publication number Publication date
CN107481827B (en) 2019-04-19

Similar Documents

Publication Publication Date Title
CN107481827B (en) The preparation method of the hollow magnetic Nano carbon balls of internal confinement growth MOFs
CN107522867B (en) Preparation method of hollow carbon nanospheres with MOFs growing in internal confinement
CN107359326B (en) Si @ C lithium ion battery cathode material with core-shell structure and preparation method thereof
CN110336032B (en) Preparation method of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon and application of nano-cobalt-loaded nitrogen-doped three-dimensional porous carbon in lithium-sulfur battery
CN112038648B (en) Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof
Hu et al. Functional carbonaceous materials from hydrothermal carbonization of biomass: an effective chemical process
CN105914358B (en) The preparation method of yolk eggshell structure nitrogen-doped carbon coated ferriferrous oxide@tin ash magnetic Nano boxes
CN104916828B (en) Three-dimensional grapheme hollow carbon sphere/sulphur composite and preparation method thereof and the application in lithium-sulfur cell
CN107611388A (en) A kind of shell has the preparation method of the carbon coating tungsten sulfide hollow nano-sphere of sandwich structure
CN105914345A (en) Hollow nano transition metal sulfide/carbon composite material and preparation method
CN107507686A (en) A kind of preparation method of magnetic nano cages
CN109920995B (en) Silicon or oxide @ titanium oxide core-shell structure composite material and preparation method thereof
CN105502342A (en) Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source
CN109473651B (en) Synthesis of bimetallic sulfide Co by ZIF-67 derivatization8FeS8Method for preparing/N-C polyhedral nano material
CN109243862B (en) Dual-modified carbon hollow sphere compound and preparation method and application thereof
CN108190963B (en) Multistage hollow CoFe2O4Material, CoFe2O4Preparation method and application of/C composite material
CN107628597B (en) By using SiO2Method for preparing biomass carbon material with micropore and mesopore structure by coating method
CN103840176B (en) Three-dimensional grapheme based combined electrode of a kind of area load Au nano particle and its preparation method and application
CN102020268B (en) Hollow carbon sphere and preparation method thereof
CN104868094A (en) Porous ruthenium dioxide and manganese dioxide combined electrode and preparation method and application thereof
CN110283288A (en) A kind of mass producible Heteroatom doping has cavity structure polymer nano-microspheres and preparation method thereof
CN103204490B (en) Preparation method of iron trioxide/carbon yolk-eggshell nano-composite structure
CN108585063A (en) The simple preparation method of hollow hydroxide derived from a kind of MOFs
CN106876676A (en) NiS classification micron balls of carbon shell cladding and its preparation method and application
CN103638988B (en) Magnetic mesoporous material, and preparation method and application of magnetic mesoporous material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant