CN105965009A - Preparation method of magnetic carbon-covering nano material - Google Patents
Preparation method of magnetic carbon-covering nano material Download PDFInfo
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- CN105965009A CN105965009A CN201610326121.4A CN201610326121A CN105965009A CN 105965009 A CN105965009 A CN 105965009A CN 201610326121 A CN201610326121 A CN 201610326121A CN 105965009 A CN105965009 A CN 105965009A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
Abstract
The invention discloses a preparation method of a magnetic carbon-covering nano material, and belongs to the field of preparation of nanocarbon@metal composites. The preparation method of the magnetic carbon-covering nano material is characterized in that the magnetic carbon-covering nano material is obtained through carrying out high-temperature pyrolysis on a metal-organic framework compound in the atmosphere of inert protection. According to the preparation method, the metal-organic framework compound is utilized as a precursor, and the carbon-covering nano material with a uniform size is prepared through a one-step high-temperature pyrolysis process; and according to a product obtained through the method, the phase is single, the impurities are extremely few, the collection is particularly easy, the yield is high, the large-scale synthesis is facilitated, the product has quite good ferromagnetism, the dispersity is quite good, the response time is short, and the magnetic carbon-covering nano material has quite typical ferromagnetism hysteresis loop and relatively high saturation magnetization intensity, and is a kind of quite potential biomagnetic nano material.
Description
Technical field
The invention belongs to nano-sized carbon metallic composite preparation field, be specifically related to the preparation of a kind of magnetic Carbon en capsulated nanomaterials
Method.
Background technology
At the eighties of last century initial stage eighties, nanosecond science and technology are born and progressively emerge.It is research material in 1～100nm range scale
The science of technical problem in the characteristics of motion of compositional system and interaction and actual application.In recent years, nanosecond science and technology and other
Subject intersects infiltration so that it is develop rapidly in fields such as medical science, biology, material, chemistry.Nano material is due to tool itself
Have small-size effect, quantum effect, skin effect etc. and show the characteristic that is different from its body phase material, as light, thermal and magnetic,
Electricity and surface nature etc., widely should have in fields such as magnetic fluid, structural ceramics, optical material, electricity material, catalyst
With.Wherein, magnetic Nano material magnetic memory material, biosensor, cell and Separation of Proteins labelling, pharmaceutical carrier,
The aspects such as nuclear magnetic resonance have a high potential, by the very big concern of domestic and international scientist.
Recently, a kind of novel nano-sized carbon@metallic composite carbon-clad metal nano particle, become magnetic Nano material
Study hotspot.This material typically has nucleocapsid structure or class Bulbus Allii Cepae structure, and wherein metal nanoparticle constitutes the core of composite
The heart, and several layers of graphite flake layer are closely around the shell of metal nanoparticle ordered arrangement composition material.This have core/shell structure and receive
Nano composite material, on the one hand can keep the independence of metal nanoparticle individual particle, it is to avoid reuniting effect occurs；On the other hand can
Protection metallic, from the impact of external environment, occurs some chemical reaction to lose efficacy.There is the carbon-clad metal of magnetic property
Nanoparticle has important application prospect at industrial circle, for example, it is possible to be scattered in oil carrier fluid, utilizes extra electric field to make magnetic
The feature that fluid viscosity increases is as damping material or braking automobile liquid；Lubricant can be protected as magnetic and reduce coefficient of friction and abrasion
Rate, extends the service life of friction material；It is also used as catalyst or carrier and urges to solve nanocatalyst particles participation liquid
After changing reaction, it is often difficult to this difficult problem separating, recycling.
Up to the present, the method preparing carbon-clad metal nano particle mainly has arc discharge method, chemical vapour deposition technique, heat
Solution etc..Arc discharge method is the method the most successfully preparing carbon-clad metal nano particle, is also the most the most commonly used one
The method of kind, it is possible to prepare the carbon-coated nano metallic that particle diameter is less, it is homogeneous to be distributed, shell carbon degree of graphitization is higher,
But due to the complexity of pyroreaction, product inevitably generates with CNT, fullerene and white carbon black etc., product
Purity the lowest.The equipment that arc process uses simultaneously is the most complicated, and technological parameter is wayward, and power consumption is big, and cost is high, thus
It is difficult to synthesize on a large scale.It is a kind of the more commonly used that chemical vapour deposition technique prepares Carbon en capsulated nanomaterials, is also to study relatively
Many methods, compared with arc discharge method, technique is relatively easy, and productivity is the highest.But the carbon cladding that the method is prepared is received
Particle diameter and the distribution of rice metallic are limited by metallic catalyst, can be with CNT and unbodied carbon in late-stage products
Particles generation and separate with substrate and catalyst carrier be also need solve problem.By contrast, pyrolysismethod is expected to most realize
The large-scale production of carbon-clad metal nano particle, because pyrolysismethod has, technique is simple, preparation cost is low, tenor is controlled,
Carbonization productivity height etc. advantage.But only drawback is that, degree that product particle is coated with by carbon-coating and the microstructure of carbon-coating are all
Depend heavilying on persursor material, the quality of persursor material directly determines quality and the performance of final products.
Utilize that metal-organic framework compound then can solve as persursor material to be that pyrolysismethod is faced well above-mentioned asks
Topic.Metal-organic framework compound is to be connected by self assembly with organic ligand by inorganic metal ion (or metal cluster), constructs
The inorganic-organic hybridization porous material with periodic network structure.Such material has structured designability and controllable
Property, mainly has a following advantage as the persursor material of pyrolysismethod: 1) metal center has multiformity, and we can basis
Application demand is screened, and selects space big；2), during high temperature, organic ligand molecule can be carbonized formation carbon-coating and be coated in metal
Heart surface, metal center is then reduced generation metal nanoparticle under the reproducibility effect of carbon, need not volume in preparation process
Outer introducing source metal or carbon source；3) synthesis condition of major part MOFs material is the gentleest, and some even can be normal in room temperature
Synthesize under the conditions of pressure, have the potentiality accomplished scale production.If the magnetic metal ion needed for our selection is as metal-organic bone
The metal center of frame compound, only i.e. can get preferable magnetic Carbon en capsulated nanomaterials by a step pyrolytic process after synthesis.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of magnetic Carbon en capsulated nanomaterials.
In the present invention, technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of magnetic Carbon en capsulated nanomaterials, it is characterised in that described preparation method be employing include metal-
The compound of organic backbone, under inert protective atmosphere, high temperature pyrolysis obtains.
Further, the compound of described metal-organic framework is, the two-dimensional layer chemical combination that metallic compound and Organic substance are formed
Thing, and the three dimensional skeletal structure built by the pillared effect of organic ligand.
Further, described metal-organic framework compound is [Ni2(L-asp)2(bpy)]·CH3OH·H2O, is by basic carbonate
The two-dimensional layer compound that nickel and aspartic acid L-asp are formed connects, by organic ligand 4,4'-, the three-dimensional that the pillared effect of pyridine is built
Framing structure.
Further, the duct size of described three dimensional skeletal structure is
Further, described preparation method comprises the following steps:
(1)Ni(L-asp)(H2O)2·H2The preparation of O: by NiCO3·2Ni(OH)2·xH2O, L-asp and H2O in mass ratio 1:
0.5～3:100～400 mixing, and heated and stirred 0.5～4 hours under the conditions of being maintained at 70～100 DEG C, be dissolved in water to major part powder
Heating and stirring is stopped after in；The insoluble matter that Filtration removes in solution obtains settled solution, and puts in 60～120 DEG C of baking ovens
Stand 0.5～2 day, after aqueous solvent volatilization completely, i.e. obtain green Ni (L-asp) (H2O)2·H2O crystal, collects standby；
(2)[Ni2(L-asp)2(bpy)]·CH3OH·H2The preparation of O crystalline material: by prepare in step (1)
Ni(L-asp)(H2O)2·H2O joins in the mixed solution of first alcohol and water, continues to add 4,4'-under agitation after being partly dissolved
Even pyridine so that in final solution, the mass ratio of each material is Ni (L-asp) (H2O)2·H2O:4,4'-connects pyridine: methanol: water
=1:0.5～10:1～80:1～80；It is transferred to this solution in autoclave seal, crystallization 1～4 days in 80～180 DEG C of baking ovens；
After question response still is cooled to room temperature, obtain aeruginous [Ni by being filtered, washed and dried2(L-asp)2(bpy)]·CH3OH·H2O is brilliant
Body powder；
(3) preparation method of magnetic Carbon en capsulated nanomaterials: [Ni2 (L-asp) 2 (bpy)] CH3OH H2O that step (2) is obtained
Crystal powder is ground to exist without larger particles and be laid in bottom ceramic crucible, is placed in the middle part of tube furnace by this porcelain crucible, then
Removed the inner air of tube furnace by evacuation, replace with high pure nitrogen, repeat 2～5 times, then at 400～1200 DEG C of bars
It is pyrolyzed 2～8 hours under part.
Further, in described step (3) by room temperature to pyrolysis heating mode be temperature programming, programming rate is 2～10 DEG C per second.
Further, [Ni in described step (3) temperature-rise period2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is at 100～200 DEG C
Stop 0.5～4 hour, with the solvent molecule remained in removing plane of crystal and duct.
Further, in described step (3), the flow velocity of nitrogen is controlled by suspended body flowmeter, and flow velocity is per minute 20～120ml.
Further, described magnetic Carbon en capsulated nanomaterials is nucleocapsid structure, and external shell is the carbon with certain degree of graphitization
Layer, internal core is metallic nickel simple substance.
Further, described magnetic Carbon en capsulated nanomaterials a size of 10～20nm.
Beneficial effects of the present invention is as follows:
The present invention is predecessor by utilizing metal-organic framework compound [Ni2 (L-asp) 2 (bpy)] CH3OH H2O, by one
Step high temperature pyrolysis process prepares the Carbon en capsulated nanomaterials of size uniform.The product that the method obtains is mutually single, and impurity is few,
Being especially susceptible to collect, and yield is high, be conducive to extensive synthesis, have good ferromagnetism, dispersibility is fabulous, during response
Between short, there is very typical ferromagnetism hysteresis curve and higher saturation magnetization, be the most potential biological magnetic of a class
Property nano material.
Accompanying drawing explanation
Fig. 1 (a): [Ni2(L-asp)2(bpy)]·CH3OH·H2O crystal structure simulation X-ray diffraction spectrogram.
[the Ni of synthesis in Fig. 1 (b): embodiment 12(L-asp)2(bpy)]·CH3OH·H2The X-ray diffraction spectrogram of O crystal powder.
The X-ray diffraction spectrogram of the Carbon en capsulated nanomaterials prepared in Fig. 2 (a): embodiment 1.
The X-ray diffraction spectrogram of the Carbon en capsulated nanomaterials prepared in Fig. 2 (b): embodiment 2.
The X-ray diffraction spectrogram of the Carbon en capsulated nanomaterials prepared in Fig. 2 (c): embodiment 3.
The X-ray diffraction spectrogram of the Carbon en capsulated nanomaterials prepared in Fig. 2 (d): embodiment 4.
The X-ray diffraction spectrogram of the Carbon en capsulated nanomaterials prepared in Fig. 2 (e): embodiment 5.
The X-ray diffraction spectrogram of the Carbon en capsulated nanomaterials prepared in Fig. 2 (f): embodiment 6.
The X-ray diffraction spectrogram of the Carbon en capsulated nanomaterials prepared in Fig. 2 (g): embodiment 7.
The transmission electron micrograph of the Carbon en capsulated nanomaterials prepared in Fig. 3 (a): embodiment 1.
The transmission electron micrograph of the Carbon en capsulated nanomaterials prepared in Fig. 3 (b): embodiment 2.
The transmission electron micrograph of the Carbon en capsulated nanomaterials prepared in Fig. 3 (c): embodiment 3.
The transmission electron micrograph of the Carbon en capsulated nanomaterials prepared in Fig. 3 (d): embodiment 4.
The transmission electron micrograph of the Carbon en capsulated nanomaterials prepared in Fig. 3 (e): embodiment 5.
The transmission electron micrograph of the Carbon en capsulated nanomaterials prepared in Fig. 3 (f): embodiment 6.
The transmission electron micrograph of the Carbon en capsulated nanomaterials prepared in Fig. 3 (g): embodiment 7.
The Carbon en capsulated nanomaterials prepared in Fig. 4: embodiment 3 dispersion in water and the response condition digital photograph to Magnet.
The magnetic performance test result of the Carbon en capsulated nanomaterials prepared in Fig. 5 (a): embodiment 1.
The magnetic performance test result of the Carbon en capsulated nanomaterials prepared in Fig. 5 (b): embodiment 2.
The magnetic performance test result of the Carbon en capsulated nanomaterials prepared in Fig. 5 (c): embodiment 3.
The magnetic performance test result of the Carbon en capsulated nanomaterials prepared in Fig. 5 (d): embodiment 4.
The magnetic performance test result of the Carbon en capsulated nanomaterials prepared in Fig. 5 (e): embodiment 5.
The magnetic performance test result of the Carbon en capsulated nanomaterials prepared in Fig. 5 (f): embodiment 6.
The magnetic performance test result of the Carbon en capsulated nanomaterials prepared in Fig. 5 (g): embodiment 7.
Detailed description of the invention
Being embodied as the following detailed description of the present invention, it is necessary to it is pointed out here that, below implement to be only intended to entering of the present invention
One step explanation, it is impossible to be interpreted as the restriction to invention protection domain, this art skilled person is according to the invention described above content pair
Some nonessential improvement and adjustment that the present invention makes, still fall within protection scope of the present invention.
The relevant testing conditions that the present invention relates to and method:
X-ray diffraction (XRD): XRD test uses the Ultima IV type diffractometer of Rigaku company.Use Cu-KaLaunching site, fixed power source is 40kV and 30mA, and scanning 2theta scope is 4～40 °.
Transmission electron microscope (SEM): SEM test uses FEI Co.'s Tecnai F20 type transmission electron microscope.
Accelerating potential is 200kV.
Magnetic performance is tested: the magnetic performance of nano material is the SQUID-VSM Magnetic Measurement by Quantum Design, Inc. of the U.S.
(the temperature range: 1.8～400K that system characterizes；Magnetic field intensity: ± 7T；AC frequency range: 0.1Hz～1kHz；AC magnetic
Field amplitude: 0.1Oe～10Oe)
Embodiment 1:
(1)Ni(L-asp)(H2O)2·H2The preparation of O: by NiCO3·2Ni(OH)2·xH2O, L-asp and H2O 1:1 in proportion:
200 mixing, and heated and stirred 2.5 hours under the conditions of being maintained at 95 DEG C, to major part powder soluble in water after stop heating and stir
Mix.Filtration removes the insoluble matter in solution and obtains settled solution, and puts into standing 1 day in 100 DEG C of baking ovens, treats aqueous solvent
Green Ni (L-asp) (H is i.e. obtained after volatilization completely2O)2·H2O crystal, collects standby.
(2)[Ni2(L-asp)2(bpy)]·CH3OH·H2The preparation of O crystalline material: by prepare in previous step
Ni(L-asp)(H2O)2·H2O joins in the mixed solution of first alcohol and water, continues to add under agitation necessarily after being partly dissolved
The 4 of amount, 4'-connects pyridine so that in final solution, the mass ratio of each material is Ni (L-asp) (H2O)2·H2O:4,4'-connects pyridine: methanol:
Water=1:1.4:21.7:27.4.It is transferred to this solution in autoclave seal, crystallization 2 days in 150 DEG C of baking ovens.Question response still
After being cooled to room temperature, obtain aeruginous [Ni by the operation such as being filtered, washed and dried2(L-asp)2(bpy)]·CH3OH·H2O crystal
Powder.
(3) preparation method of magnetic the Carbon en capsulated nanomaterials: [Ni that will synthesize2(L-asp)2(bpy)]·CH3OH·H2O crystal powder
End is lightly ground to existing without larger particles and being laid in bottom ceramic crucible, is placed in the middle part of tube furnace by this porcelain crucible, then leads to
Cross evacuation and remove the inner air of tube furnace, replace with high pure nitrogen, be repeated 3 times to ensure sufficient oxygen-free environment,
The flow speed control of nitrogen is at 80ml per minute, and programming rate is 5 DEG C per second, first stops 2 hours at 150 DEG C, after at 500 DEG C of bars
It is pyrolyzed 5 hours under part, obtains magnetic Carbon en capsulated nanomaterials.
(4) sign of material: to [Ni2(L-asp)2(bpy)]·CH3OH·H2O crystal powder carries out X-ray diffraction sign, to magnetic
Property Carbon en capsulated nanomaterials carry out transmission electron microscope characterize and magnetic performance characterize.
Embodiment 2:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)]·CH3OH·H2O crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is lightly ground to existing without larger particles and being laid in
Bottom ceramic crucible, this porcelain crucible is placed in the middle part of tube furnace, is then removed the inner air of tube furnace by evacuation, with height
Pure nitrogen gas is replaced, and is repeated 3 times to ensure sufficient oxygen-free environment, and the flow speed control of nitrogen is at 80ml per minute, and heat up speed
Degree for 5 DEG C per second, first stops 2 hours at 150 DEG C, after be pyrolyzed 5 hours under the conditions of 600 DEG C, obtain magnetic carbon-coated nano
Material.
The magnetic Carbon en capsulated nanomaterials prepared is carried out transmission electron microscope sign and magnetic performance characterizes.
Embodiment 3:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)]·CH3OH·H2O crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is lightly ground to existing without larger particles and being laid in
Bottom ceramic crucible, this porcelain crucible is placed in the middle part of tube furnace, is then removed the inner air of tube furnace by evacuation, with height
Pure nitrogen gas is replaced, and is repeated 3 times to ensure sufficient oxygen-free environment, and the flow speed control of nitrogen is at 80ml per minute, and heat up speed
Degree for 5 DEG C per second, first stops 2 hours at 150 DEG C, after be pyrolyzed 5 hours under the conditions of 700 DEG C, obtain magnetic carbon-coated nano
Material.
The magnetic Carbon en capsulated nanomaterials prepared is carried out transmission electron microscope sign and magnetic performance characterizes.
Embodiment 4:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)]·CH3OH·H2O crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is lightly ground to existing without larger particles and being laid in
Bottom ceramic crucible, this porcelain crucible is placed in the middle part of tube furnace, is then removed the inner air of tube furnace by evacuation, with height
Pure nitrogen gas is replaced, and is repeated 3 times to ensure sufficient oxygen-free environment, and the flow speed control of nitrogen is at 80ml per minute, and heat up speed
Degree for 5 DEG C per second, first stops 2 hours at 150 DEG C, after be pyrolyzed 5 hours under the conditions of 800 DEG C, obtain magnetic carbon-coated nano
Material.
The magnetic Carbon en capsulated nanomaterials prepared is carried out transmission electron microscope sign and magnetic performance characterizes.
Embodiment 5
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)]·CH3OH·H2O crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is lightly ground to existing without larger particles and being laid in
Bottom ceramic crucible, this porcelain crucible is placed in the middle part of tube furnace, is then removed the inner air of tube furnace by evacuation, with height
Pure nitrogen gas is replaced, and is repeated 3 times to ensure sufficient oxygen-free environment, and the flow speed control of nitrogen is at 80ml per minute, and heat up speed
Degree for 5 DEG C per second, first stops 2 hours at 150 DEG C, after be warming up to 500 DEG C, stop heating subsequently, obtain magnetic carbon cladding and receive
Rice material.
The magnetic Carbon en capsulated nanomaterials prepared is carried out transmission electron microscope sign and magnetic performance characterizes.
Embodiment 6:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)]·CH3OH·H2O crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is lightly ground to existing without larger particles and being laid in
Bottom ceramic crucible, this porcelain crucible is placed in the middle part of tube furnace, is then removed the inner air of tube furnace by evacuation, with height
Pure nitrogen gas is replaced, and is repeated 3 times to ensure sufficient oxygen-free environment, and the flow speed control of nitrogen is at 80ml per minute, and heat up speed
Degree for 10 DEG C per second, first stops 2 hours at 150 DEG C, after be warming up to 500 DEG C, stop heating subsequently, obtain magnetic carbon cladding
Nano material.
The magnetic Carbon en capsulated nanomaterials prepared is carried out transmission electron microscope sign and magnetic performance characterizes.
Embodiment 7:
[Ni is prepared by step (1) and (2) in embodiment 12(L-asp)2(bpy)]·CH3OH·H2O crystal powder material.
[the Ni that will synthesize2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is lightly ground to existing without larger particles and being laid in
Bottom ceramic crucible, this porcelain crucible is placed in the middle part of tube furnace, is then removed the inner air of tube furnace by evacuation, with height
Pure nitrogen gas is replaced, and is repeated 3 times to ensure sufficient oxygen-free environment, and the flow speed control of nitrogen is at 80ml per minute, and heat up speed
Degree for 5 DEG C per second, first stops 2 hours at 150 DEG C, after be pyrolyzed 5 hours under the conditions of 1100 DEG C, obtain magnetic carbon cladding and receive
Rice material.
The magnetic Carbon en capsulated nanomaterials prepared is carried out transmission electron microscope sign and magnetic performance characterizes.
From figure 1 it appears that [the Ni of synthesis in embodiment 12(L-asp)2(bpy)]·CH3OH·H2O crystal powder is at 7.96 °
Near occur the series of features peak that occurs after characteristic peak and 10 ° all with the X-ray diffraction spectrogram of simulation (simulation softward:
Materials studio 4.0) fit like a glove, there is no the appearance of any impurity peaks, synthesis is described
[Ni2(L-asp)2(bpy)]·CH3OH·H2O crystal powder is pure phase, and the high intensity of diffraction maximum also demonstrates the crystallization journey of crystal powder
Spend the highest.
From figure 2 it can be seen that the X-ray diffraction of the Carbon en capsulated nanomaterials prepared in embodiment 1～7 is after 30 °
It is evident that 5 characteristic peaks are corresponding in turn to (111), (200), (220) in metallic nickel, (311), (222) crystal face, card
The metal center of bright carbon cladding is nickel simple substance.The diffraction maximum of about 26 ° belongs to (002) crystal face of graphitic carbon, it was demonstrated that generation
Material with carbon element has certain degree of graphitization.Can obtain generally, along with the diffraction of the rising of temperature, graphitic carbon and metallic nickel
Peak intensity constantly strengthens, and crystallization degree increases the most accordingly.Even if it addition, also demonstrating that the platform having lacked pyrolysis temperature, the most also
The Carbon en capsulated nanomaterials that structure is similar can be prepared.
From figure 3, it can be seen that the Carbon en capsulated nanomaterials of synthesis in embodiment 1～7, it is that the nanometer by a large amount of size uniforms is little
Ball (10～20nm) is formed, and this nanometer bead has nucleocapsid structure, and external shell is graphited carbon-coating, and its internal core is
Metallic nickel simple substance.Along with the rising of pyrolysis temperature, the degree of graphitization of carbon-coating and the crystallization degree of metal core all gradually rise.Also
Can see at same temperature, even if not having the temperature platform of pyrolysis equally to generate similar structures.This microstructure ensure that
Such Carbon en capsulated nanomaterials has good ferromagnetism, and the protective effect of carbon-coating simultaneously hinders intergranular mutual reunion, point
Dissipate property fabulous.
Figure 4, it is seen that the degree of scatter that the Carbon en capsulated nanomaterials prepared in embodiment 3 is in water relatively other carbon material
Material is good a lot, can assemble the most rapidly under the effect of Magnet, and response time is short.Can reach after removing Magnet
To with the most the same dispersion effect in water, demonstrate again that the advantage of such core-shell material.
Return from figure 5 it can be seen that the Carbon en capsulated nanomaterials synthesized in embodiment 1～7 all has very typical ferromagnetism magnetic hysteresis
Line and higher saturation magnetization, along with the raising of synthesis temperature, saturation magnetization has the trend of increase, and remanent magnetization is strong
Degree and coercivity all have the trend of reduction, gradually close to paramagnetism.Result proves the most potential biomagnetism of class and receives
Rice material.
Description to the embodiment that disclosed in this invention is not intended to limit the scope of the present invention, but is used for describing the present invention.
Correspondingly, the scope of the present invention is not limited by embodiment of above, but is defined by claim or its equivalent.
Claims (10)
1. the preparation method of a magnetic Carbon en capsulated nanomaterials, it is characterised in that described preparation method be employing include metal-
The compound of organic backbone, under inert protective atmosphere, high temperature pyrolysis obtains.
2. the preparation method described in claim 1, it is characterised in that the compound of described metal-organic framework is, metal
The two-dimensional layer compound that compound and Organic substance are formed, and the three dimensional skeletal structure built by the pillared effect of organic ligand.
3. the preparation method described in claim 1, it is characterised in that described metal-organic framework compound is
[Ni2(L-asp)2(bpy)]·CH3OH·H2O, is that the two-dimensional layer compound formed by basic nickel carbonate and aspartic acid L-asp leads to
Cross organic ligand 4,4'-and connect the three dimensional skeletal structure that the pillared effect of pyridine is built.
4. the preparation method described in claim 1, it is characterised in that the duct size of described three dimensional skeletal structure is
5. according to the preparation method of the magnetic Carbon en capsulated nanomaterials described in any one of claim 1-4, it is characterised in that described
Preparation method comprises the following steps:
(1)Ni(L-asp)(H2O)2·H2The preparation of O: by NiCO3·2Ni(OH)2·xH2O, L-asp and H2O in mass ratio 1:
0.5～3:100～400 mixing, and heated and stirred 0.5～4 hours under the conditions of being maintained at 70～100 DEG C, be dissolved in water to major part powder
Heating and stirring is stopped after in；The insoluble matter that Filtration removes in solution obtains settled solution, and puts in 60～120 DEG C of baking ovens
Stand 0.5～2 day, after aqueous solvent volatilization completely, i.e. obtain green Ni (L-asp) (H2O)2·H2O crystal, collects standby；
(2)[Ni2(L-asp)2(bpy)]·CH3OH·H2The preparation of O crystalline material: by prepare in step (1)
Ni(L-asp)(H2O)2·H2O joins in the mixed solution of first alcohol and water, continues to add 4,4'-under agitation after being partly dissolved
Even pyridine so that in final solution, the mass ratio of each material is Ni (L-asp) (H2O)2·H2O:4,4'-connects pyridine: methanol: water
=1:0.5～10:1～80:1～80；It is transferred to this solution in autoclave seal, crystallization 1～4 days in 80～180 DEG C of baking ovens；
After question response still is cooled to room temperature, obtain aeruginous [Ni by being filtered, washed and dried2(L-asp)2(bpy)]·CH3OH·H2O is brilliant
Body powder；
(3) preparation method of magnetic Carbon en capsulated nanomaterials: [Ni2 (L-asp) 2 (bpy)] CH that step (2) is obtained3OH·H2O
Crystal powder is ground to exist without larger particles and be laid in bottom ceramic crucible, is placed in the middle part of tube furnace by this porcelain crucible, then
Removed the inner air of tube furnace by evacuation, replace with high pure nitrogen, repeat 2～5 times, then at 400～1200 DEG C of bars
It is pyrolyzed 2～8 hours under part.
The preparation method of magnetic Carbon en capsulated nanomaterials the most according to claim 5, it is characterised in that described step (3)
In by room temperature to pyrolysis heating mode be temperature programming, programming rate is 2～10 DEG C per second.
The preparation method of magnetic Carbon en capsulated nanomaterials the most according to claim 5, it is characterised in that described step (3)
[Ni in temperature-rise period2(L-asp)2(bpy)]·CH3OH·H2O crystal powder stops 0.5～4 hour at 100～200 DEG C, to remove crystalline substance
The solvent molecule of residual in surface and duct.
The preparation method of magnetic Carbon en capsulated nanomaterials the most according to claim 5, it is characterised in that described step (3)
The flow velocity of middle nitrogen is controlled by suspended body flowmeter, and flow velocity is per minute 20～120ml.
9. the magnetic Carbon en capsulated nanomaterials obtained by any one of claim 1-8 method, it is characterised in that described magnetic carbon
Cladding nano material is nucleocapsid structure, and external shell is the carbon-coating with certain degree of graphitization, and internal core is metallic nickel simple substance.
10. the material described in claim 9, it is characterised in that described magnetic Carbon en capsulated nanomaterials a size of 10～20nm.
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