CN106629682B - A kind of method that confinement catalysis prepares hollow graphite alkene nanosphere - Google Patents
A kind of method that confinement catalysis prepares hollow graphite alkene nanosphere Download PDFInfo
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The invention discloses a kind of confinements to be catalyzed the method for preparing hollow graphite alkene nanosphere, which includes the following steps：First divalent metal salt, surfactant, precipitating reagent are completely dissolved in solvent, obtain mixed liquor；Reflux condensation mode stirs after mixed liquor is heated again, obtains suspension；Then suspension is handled by suction filtration, is smashed after taking filtration cakes torrefaction；Then powder is passed through into carbonization treatment, obtains black powder；Black powder is handled by acid etch finally, obtains the hollow graphite alkene nanosphere in black powder.Preparation method of the present invention prepares hollow graphite alkene nanosphere by inorganic/organic layer compound confinement carbonization catalysis technique, the diameter range of prepared hollow graphite alkene nanosphere can be controlled in 4 25nm, and by selecting different surfactants, the hollow graphite alkene nanosphere of different Heteroatom dopings may finally be obtained, the preparation method is simple for process, is suitable for industrialization large-scale production.
Description
Technical field
The present invention relates to the technical fields of nano material, are catalyzed in particular to a kind of confinement and prepare hollow graphite alkene nanosphere
Method.
Background technology
Russian two physicist in 2004, Andrei Geim and Kostya Novoselov are by using adhesive tape
Stripping means obtains single-layer graphene, and graphene causes the extensive interest of people from then on.Graphene is a kind of by carbon original
Sub- SP2Hydridization composition hexagon is in the flat film of honeycomb lattice, carbon atom thickness 2D carbon materials there are one, other dimensions
Carbon material such as carbon nanotube, fullerene and graphite etc. can regard the derivative of graphene as.Since single-layer graphene is not easy
It obtains, it is considered that graphite all can be considered by the crystal with several atomic layers (usually less than 10 layers) that carbon atom is constituted
Alkene.Graphene has higher specific surface area (2630m2/ g), superior electric conductivity (200-3000S/cm), BREATHABLE BANDWIDTH and
High mechanical strength, these features make graphene be had broad application prospects in fields such as energy storage, catalysis and environmental protections.
The preparation method of graphene mainly has：Chemical vapour deposition technique (CVD), arc discharge method, mechanical stripping method, oxidation
Remove graphite reduction method, SiC epitaxial growth methods etc..The graphene-structured that these usual methods prepare is largely with sheet
Or belt-like form exists, and the preparation of hollow spheres graphene is also relatively difficult using CVD method.China Patent Publication No.
A kind of preparation method of graphene nanospheres is disclosed in CN102120573B, and the method reacted under microwave radiation is used to obtain
The graphite of graphene nanospheres attachment, is then prepared graphene nanospheres by disperseing centrifugation, what this method prepared
A diameter of 100nm-500nm of graphene nanospheres.Jae-Young Choi et al. report it is a kind of use simple substance nickel particle for
Template, polyalcohol are carbon source, and multi-layer graphene nanosphere has been synthesized by high temperature cabonization.The graphene that this method prepares is received
Rice bulb diameter is bigger in 100-200nm (ACS Nano, 2012,6 (8), 6803-6811).
Currently, there is following deficiency in the hollow graphite alkene nanosphere technique prepared：(1) by hard mold plate technique, need by
Template prepares, and then carries out carbon coated processing again and needs to carry out graphitization processing at high temperature, finally carves template
Eating away increases process complexity and cost of material；(2) chemical vapour deposition technique (CVD) technical matters is complicated, needs clean behaviour
Make environment, cost is higher, is not suitable for mass producing；(3) the hollow graphite alkene nanosphere prepared at present is relatively large in diameter (100-
200nm), the application range of hollow graphite alkene nanosphere is limited.
Invention content
Present invention aim to provide a kind of method that confinement catalysis prepares hollow graphite alkene nanosphere, the preparation side
Method prepares inorganic/organic layer compound by being co-precipitated intercalation, then carries out carbonization confinement catalysis under an inert atmosphere
Inorganic metal is finally etched away to obtain hollow graphite alkene nanosphere by graphitization, prepared hollow graphite alkene nanosphere it is straight
Diameter is 4-25nm, and the preparation method is simple for process, is suitable for industrialization large-scale production, and by selecting different surfaces
Activating agent can obtain the hollow graphite alkene of different Heteroatom dopings.
To achieve the above object, a kind of method that confinement catalysis prepares hollow graphite alkene nanosphere provided by the present invention,
It is characterised in that it includes following steps：First divalent metal salt, surfactant, precipitating reagent are completely dissolved in solvent, obtained
Mixed liquor；Reflux condensation mode stirs after mixed liquor is heated again, obtains suspension；Then suspension is handled by suction filtration, takes filter
It is smashed after biscuit is dry；Then powder is passed through into carbonization treatment, obtains black powder；Black powder is finally passed through into acid etch
Processing obtains the hollow structure graphene nanospheres in black powder.
Further, the divalent metal salt, surfactant, precipitating reagent additive amount by mole the ratio between be divalent metal
Salt：Surfactant：Precipitating reagent=1：2-5：3-5.
Further, the solvent is distilled water or distilled water and ethyl alcohol is 2-3 by volume:1 mixed liquor.
Further, the mixed liquor is first heated to 90-120 DEG C, then reflux condensation mode stirs 2-12h, obtains suspension.
Further, the carbonization treatment the specific steps are：Powder is placed in tube furnace, under an inert gas, from room
Temperature is warming up to 600-1000 DEG C, and keeps 2-10h, and cooled to room temperature obtains black powder.
Further, the one kind of the inert gas in nitrogen, argon gas, helium.
Further, acid etch processing the specific steps are：It is molten that black powder is placed in a concentration of 3-10mol/L hydrochloric acid
In liquid, 24-48h is reacted at 60-100 DEG C, is cooled to room temperature, then passes through suction filtration and handles, filter cake is taken repeatedly to be washed with water
Until filtrate pH=6.8-7.2, finally dry 10-24h under conditions of temperature is 60-80 DEG C, obtains in black powder
Hollow graphite alkene nanosphere.
Further, the one kind of the divalent metal salt in ferrous salt, mantoquita, nickel salt or cobalt salt；Wherein, the Asia
Molysite is selected from one or more of frerrous chloride, ferrous sulfate；The mantoquita is selected from copper chloride, copper sulphate, copper nitrate, vinegar
One or more of sour copper.The nickel salt is selected from one or more of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate；
The cobalt salt is selected from one or more of cobalt nitrate, cobalt chloride, cobaltous sulfate, cobalt acetate；
Further, the surfactant is selected from lauryl sodium sulfate, neopelex, dodecyl phosphorus
One or more of sour sodium, dodecyl sodium sulfate, n-octyl amine, lauryl amine.
Still further, the precipitating reagent is in urea, potassium hydroxide, sodium hydroxide, hexamethylenetetramine, ammonium chloride
One kind.
Further, the method that confinement catalysis prepares hollow graphite alkene nanosphere, specifically comprises the following steps：
1) dissolving of reactant：
First by divalent metal salt, surfactant, precipitating reagent by mole the ratio between be divalent metal salt：Surfactant：It is heavy
Shallow lake agent=1：2-5：3-5 is completely dissolved in solvent, obtains mixed liquor；
Wherein, the divalent metal salt is one or more in ferrous salt, mantoquita, nickel salt or cobalt salt；Wherein, described
Ferrous salt is selected from one or more of frerrous chloride, ferrous sulfate；The mantoquita be selected from copper chloride, copper sulphate, copper nitrate,
One or more of copper acetate；The nickel salt is a kind of or more in nickel chloride, nickel sulfate, nickel nitrate, nickel acetate
Kind；The cobalt salt is selected from one or more of cobalt nitrate, cobalt chloride, cobaltous sulfate or cobalt acetate；The surfactant choosing
From lauryl sodium sulfate, neopelex, ferric tri-dodecanesulfonate, dodecyl sodium sulfate, n-octyl amine, lauryl amine
One or more of；The precipitating reagent is in urea, potassium hydroxide, sodium hydroxide, hexamethylenetetramine, ammonium chloride
It is a kind of；
2) reflux condensation mode and suction filtration processing：
Mixed liquor obtained by step 1) is first heated to 90-120 DEG C, then reflux condensation mode stirs 2-12h, obtains suspension,
Then suspension is handled by suction filtration, is smashed after taking filtration cakes torrefaction；
3) carbonization treatment：
By in powder merging tube furnace obtained by step 2), under an inert gas, from room temperature to 600-1000 DEG C, and protect
2-24h is held, cooled to room temperature obtains black powder；
4) acid etch is handled：
Black powder obtained by step 3) is placed in a concentration of 3-10mol/L hydrochloric acid solutions, is stirred at 60-100 DEG C
24-48h is reacted, room temperature is cooled to, then passes through suction filtration and handles, filter cake water is taken repeatedly to wash the pH=6.8- up to filtrate
7.2, finally dry 10-24h under conditions of temperature is 60-80 DEG C, obtains the hollow graphite alkene nanosphere in black powder.
Compared with prior art, the invention has the advantages that：
First, the preparation method of the present invention is in-situ inserted into laminated metal by surfactant by coprecipitation reaction
Between closing nitride layer, a kind of inorganic/organic layer structure compound is obtained；Then interlayer surface activating agent is carried out under the high temperature conditions
Carbonization, and it is amorphous to be carbonized by the surfactant of metal (such as iron, cobalt, nickel) between laminate in lamellar compound
Carbon carries out confinement catalyzed graphitization processing, finally etches away metallic compound, obtains the graphene nanospheres of hollow structure；Phase
Than traditional hard template method and chemical vapor deposition (CVD), the preparation method is simple for process, without preparing template, both reduces original
The cost for expecting production, in turn avoids polluting the environment, and is suitable for industrialization large-scale production.
Second, the hollow graphite alkene nanosphere size and graphene number of plies that the present invention obtains are controllable, by controlling carbonization temperature
Degree and different surfaces activating agent can obtain size 4-25nm hollow graphite alkene nanosphere and graphene number of plies in 4-6
Layer is consequently belonging to few layer graphene, and the specific surface area and electric conductivity of graphene all can be compared with multilayer (7-10 layers) graphene
It improves；It, can be more preferable when filling some non-conductive material (such as sulphur powders) since obtained hollow graphite alkene size is smaller
Ground promotes the electric conductivity of material by its dispersed filler to this some holes；In addition, preventing particle agglomeration from forming very bulky grain, avoid
Material in internal deeper cannot efficiently use.
Third, in terms of application field, obtained hollow graphite alkene nanosphere can be as battery or the electrode of capacitor
Material or additive, hoist capacity and high rate performance can be used as sulphur to carry such as due to it is smaller to obtain graphene nano bulb diameter
Body is applied in lithium-sulfur cell, since aperture is smaller, so can reduce lithium ion expansion for bigger hollow ball
It is scattered to the distance of internal sulphur, promotes battery performance；In addition, since hollow graphite alkene nanosphere has more empty properties, can also use
Applied to fields such as pollutant absorption.
Fourth, due to there is hetero atom (such as nitrogen, sulphur, phosphorus element) in organic matter, so finally obtained graphene is
With Heteroatom doping, heteroatomic doping can improve the wetability and electric conductivity of graphene；In addition hetero atom can be with
As " anchor ", strong interaction, especially some noble metal catalysts are generated with some metals, reduce what it reunited at high temperature
Possibility；In energy storage field, with electrolyte ion redox reaction can occur for hetero atom, can be into for ultracapacitor
One step promotes specific capacitance, can adsorb more lithium sulfides for lithium-sulfur cell, inhibit shuttle effect etc..
Description of the drawings
Fig. 1 is the electron scanning micrograph of hollow graphite alkene nanosphere prepared by embodiment 1；
Fig. 2 is the transmission electron microscope photo of hollow graphite alkene nanosphere prepared by embodiment 1；
Fig. 3 is the electron scanning micrograph of hollow graphite alkene nanosphere prepared by embodiment 2；
Fig. 4 is the transmission electron microscope photo of hollow graphite alkene nanosphere prepared by embodiment 2；
Fig. 5 is the transmission electron microscope photo of hollow graphite alkene nanosphere prepared by embodiment 3；
Fig. 6 is the transmission electron microscope photo of hollow graphite alkene nanosphere prepared by embodiment 4；
Fig. 7 is the transmission electron microscope photo of hollow graphite alkene nanosphere prepared by embodiment 5；
Fig. 8 is the transmission electron microscope photo of hollow graphite alkene nanosphere prepared by embodiment 6；
Fig. 9 is the transmission electron microscope photo of hollow graphite alkene nanosphere prepared by embodiment 7；
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail.
Embodiment 1：
By the nickel chloride of 0.0025mol, 0.0025mol nickel sulfates, 0.015mol hexamethylenetetramines and 0.02mol ten
Sodium dialkyl sulfate is dissolved in 50mL water, and is transferred in 100mL flasks, and reflux condensation mode stirs 12h at 90 DEG C.It is cooled to room
Wen Hou filters above-mentioned suspension, dries at room temperature for 24 hours.The powder after drying is put into tube furnace, in the protection of nitrogen
Under (nitrogen flow 50mL/min), from room temperature to 600 DEG C, and keep 5h at this temperature.Cooled to room temperature obtains
The sample powder of black.This black powder is put into 100mL beakers, the hydrochloric acid 50mL of 3mol/L is added, is stirred at 60 DEG C
48h.Later, it filters, and is repeatedly washed with distilled water until pH=6.8-7.2, drying is for 24 hours, final to make at 60 DEG C by filter cake
It is standby go out black powder hollow graphite alkene nanosphere.
The scanned Electronic Speculum of hollow graphite alkene nanosphere and transmission electron microscope of above-mentioned preparation are characterized, the side of sem test
Method is：Powder sample is adhered on carbonaceous conductive glue, metal spraying 60s is carried out on vacuum coater, is then scanned Electronic Speculum survey
Examination, voltage 10kV, enlargement ratio are 200k times.
The method of transmissioning electric mirror test is：By sample dispersion in ethanol solution, after ultrasonic disperse, drip in clean
On copper mesh, transmission electron microscope observing is carried out after to be dried.
Fig. 1 is the electron scanning micrograph (SEM) of the hollow graphite alkene nanosphere of above-mentioned preparation, can be with from Fig. 1
Be clearly seen the particle of graphene nanospheres, and it is mutually arranged together.Fig. 2 is the hollow graphite alkene nanosphere of above-mentioned preparation
Transmission electron microscope photo (TEM), be apparent that from Fig. 2 chondritic and be hollow structure, hollow graphite alkene
The diameter of nanosphere is about 4-5nm, and spherical shell is made of 5-6 layers of single-layer graphene.
Embodiment 2：
The ferric tri-dodecanesulfonate of the nickel acetate of 0.005mol, 0.015mol potassium hydroxide and 0.01mol is dissolved in 50mL
It in water, and is transferred in 100mL flasks, reflux condensation mode stirs 12h at 95 DEG C.After being cooled to room temperature, by above-mentioned suspension into
It is capable to filter, it dries at room temperature for 24 hours.The powder after drying is put into tube furnace, under nitrogen atmosphere, from room temperature to 700
DEG C, and 4h is kept at this temperature.After cooled to room temperature, black powder is obtained.This black powder is put into 100mL beakers
In, the hydrochloric acid 50mL of 5mol/L is added, stirs 48h.Later, it filters, and is repeatedly washed with distilled water up to pH=6.8-7.2,
Obtained filter cake dry 10h at 80 DEG C, final is in the hollow structure graphene nanospheres of black powder.
The scanned Electronic Speculum of hollow graphite alkene nanosphere and transmission electron microscope of above-mentioned preparation are characterized, the method for retouching Electronic Speculum test
For：Powder sample is adhered on carbonaceous conductive glue, metal spraying 60s is carried out on vacuum coater, is then scanned Electronic Speculum test,
Voltage 10kV, enlargement ratio are 110k times.The method of transmissioning electric mirror test is：By sample dispersion in ethanol solution, surpass
After sound dispersion, drips on clean copper mesh, transmission electron microscope observing is carried out after to be dried.
Fig. 3 is the electron scanning micrograph (SEM) of the graphene nanospheres of above-mentioned preparation, is can be found that from Fig. 3
Hollow graphite alkene nanometer ball particle is clearly demarcated and is closely connected together；Fig. 4 is the saturating of the hollow graphite alkene nanosphere of above-mentioned preparation
Electron micrograph (TEM) is penetrated, the diameter of hollow graphite alkene nanosphere is about 20nm, the stone of outside as can see from Figure 4
Black alkene shell number is at 4-5 layers.
Embodiment 3：
By the cobalt nitrate of 0.005mol, the neopelex of 0.015mol ammonium chlorides and 0.01mol, 0.01mol
Dodecyl sodium sulfate be dissolved in 50mL water, and be transferred in 100mL flasks, reflux condensation mode stirs 12h at 100 DEG C.It is cold
But to after room temperature, above-mentioned suspension is filtered, at room temperature it is dry for 24 hours.The powder after drying is put into tube furnace,
Under nitrogen atmosphere, from room temperature to 700 DEG C, and 10h is kept at this temperature.After cooled to room temperature, black powder is obtained
End.This black powder is put into 100mL beakers, the hydrochloric acid 80mL of 10mol/L is added, stirs 48h.Later, it filters, and repeatedly
It is washed with distilled water until filtrate pH=6.8-7.2, for 24 hours, final be in black powder to obtained filter cake for drying at 60 DEG C
Hollow graphite alkene nanosphere.
The hollow graphite alkene nanometer ball warp transmission electron microscope of above-mentioned preparation is characterized, the method for transmissioning electric mirror test is：By sample
Product are scattered in ethanol solution, and after ultrasonic disperse, drop carries out transmission electron microscope sight on clean copper mesh after to be dried
It examines.
Fig. 5 is the transmission electron microscope photo of the above-mentioned hollow graphite alkene nanosphere being prepared, can from Fig. 5
Diameter to hollow graphite alkene nanosphere is about 25nm, and the graphene shell number of outside is at 5-6 layers.
Embodiment 4：
By the cobalt chloride of 0.005mol and 0.005mol cobaltous sulfates, 0.005mol cobalt acetates, 0.045mol potassium hydroxide and
The ferric tri-dodecanesulfonate of 0.015mol, 0.015mol lauryl sodium sulfate are dissolved in 50mL water, and are transferred to 100mL flasks
In, reflux condensation mode stirs 12h at 100 DEG C.After being cooled to room temperature, above-mentioned suspension is filtered, is dried at room temperature for 24 hours.
It is put into the powder after drying in tube furnace, under nitrogen atmosphere, from room temperature to 700 DEG C, and keeps at this temperature
2h.After cooled to room temperature, black powder is obtained.This black powder is put into 100mL beakers, the hydrochloric acid of 6mol/L is added
70mL stirs 48h.Later, it filters, and is repeatedly washed with distilled water until filtrate pH=6.8-7.2, obtained filter cake is at 60 DEG C
Lower dry 16h finally obtains the hollow graphite alkene nanosphere in black powder.
The hollow graphite alkene nanometer ball warp transmission electron microscope of above-mentioned preparation is characterized, the method for transmissioning electric mirror test is：By sample
Product are scattered in ethanol solution, and after ultrasonic disperse, drop carries out transmission electron microscope sight on clean copper mesh after to be dried
It examines.
Fig. 6 be above-mentioned preparation hollow graphite alkene nanosphere transmission electron microscope photo, as can see from Figure 6 in
The diameter of empty graphene nanospheres is about 25nm, and mutually heap is fallen together.
Embodiment 5：
By 0.01mol copper nitrates, the ferric tri-dodecanesulfonate of 0.01mol copper sulphate, 0.1mol sodium hydroxides and 0.05mol
It is dissolved in 50mL water, and is transferred in 100mL flasks, 10h is stirred at 100 DEG C.After being cooled to room temperature, by above-mentioned suspension into
It is capable to filter, it dries at room temperature for 24 hours.The powder after drying is put into tube furnace, under nitrogen atmosphere, from room temperature to 900
DEG C, and 3h is kept at this temperature.After cooled to room temperature, black powder is obtained.This black powder is put into 100mL beakers
In, the hydrochloric acid solution 50mL of 6mol/L is added, stirring is for 24 hours.Later, it filters, and is repeatedly washed with distilled water until filtrate pH=
6.8-7.2, for 24 hours, final be in the hollow graphite alkene nanosphere of black powder to obtained filter cake for drying at 60 DEG C.
The hollow graphite alkene nanometer ball warp transmission electron microscope of above-mentioned preparation is characterized, the method for transmissioning electric mirror test is：By sample
Product are scattered in ethanol solution, and after ultrasonic disperse, drop carries out transmission electron microscope sight on clean copper mesh after to be dried
It examines.
Fig. 7 be above-mentioned preparation hollow graphite alkene nanosphere transmission electron microscope photo, as can see from Figure 7 in
The diameter of empty graphene nanospheres is about 10nm, and the graphene shell number of outside is at 4-6 layers.
Embodiment 6：
The n-octyl amine of the copper acetate of 0.01mol, 0.04mol urea and 0.05mol is dissolved in 50mL water and 20mL ethyl alcohol mixes
It closes in solution, and is transferred in 100mL flasks, reflux condensation mode stirs 2h at 100 DEG C.It, will be above-mentioned suspended after being cooled to room temperature
Liquid is filtered, and is dried at room temperature for 24 hours.The powder after drying is put into tube furnace, under nitrogen atmosphere, from room temperature
To 1000 DEG C, and 5h is kept at this temperature.After cooled to room temperature, black powder is obtained.This black powder is put into
In 100mL beakers, 50mL concentrated hydrochloric acids are added, stir 48h.Later, it filters, and is repeatedly washed with distilled water until filtrate pH=
6.8-7.2, the drying at 60 DEG C of obtained filter cake for 24 hours, finally obtain the hollow graphite alkene nanosphere in black powder.
The hollow graphite alkene nanometer ball warp transmission electron microscope of above-mentioned preparation is characterized, the method for transmissioning electric mirror test is：By sample
Product are scattered in ethanol solution, and after ultrasonic disperse, drop carries out transmission electron microscope sight on clean copper mesh after to be dried
It examines.
Fig. 8 be above-mentioned preparation hollow graphite alkene nanosphere transmission electron microscope photo, as can see from Figure 8 in
The diameter of empty graphene nanospheres is about 20nm.
Embodiment 7：
By 0.01mol copper chlorides, 0.005mol copper sulphate, 0.005mol copper nitrates, 0.06mol potassium hydroxide and
The lauryl amine of 0.075mol is dissolved in 50mL water and 20mL ethanol solutions, and is transferred in 100mL flasks, at 120 DEG C
Reflux condensation mode stirs 12h.After being cooled to room temperature, above-mentioned suspension is filtered, is dried at room temperature for 24 hours.By the powder after drying
End is put into tube furnace, under argon atmosphere, from room temperature to 900 DEG C, and keeps 5h at this temperature.It naturally cools to
After room temperature, black powder is obtained.This black powder is put into 100mL beakers, 50mL concentrated hydrochloric acids are added, stirring is for 24 hours.Later,
It filters, and is repeatedly washed with distilled water, obtained filter cake dry 18h at 60 DEG C is finally obtained in the hollow of black powder
Graphene nanospheres.
The hollow graphite alkene nanometer ball warp transmission electron microscope of above-mentioned preparation is characterized, the method for transmissioning electric mirror test is：By sample
Product are scattered in ethanol solution, and after ultrasonic disperse, drop carries out transmission electron microscope sight on clean copper mesh after to be dried
It examines.
Fig. 9 be above-mentioned preparation hollow graphite alkene nanosphere transmission electron microscope photo, as can see from Figure 9 in
The diameter of empty graphene nanospheres is about 20nm, and mutually heap is fallen together.
Embodiment 8：
By 0.005mol frerrous chlorides, 0.005mol ferrous sulfate, 0.03mol hexamethylenetetramines and 0.02mol 12
Amine and 0.02mol n-octyl amines are dissolved in 50mL water and 20mL ethanol solutions, and are transferred in 100mL flasks, at 90 DEG C
Stir 10h.After being cooled to room temperature, above-mentioned suspension is filtered, is dried at room temperature for 24 hours.By the powder after drying, it is put into pipe
In formula stove, under argon atmosphere, from room temperature to 800 DEG C, and 3h is kept at this temperature.After cooled to room temperature, obtain
To black powder.This black powder is put into 100mL beakers, 50mL concentrated hydrochloric acids are added, stirring is for 24 hours.Later, it filters, and more
Secondary to be washed with distilled water, obtained filter cake dry 10h at 80 DEG C finally obtains the hollow graphite alkene nanometer in black powder
Ball.The graphene nano bulb diameter obtained under this condition is in 20nm.
Embodiment 9:
By 0.01mol nickel acetates, 0.005mol nickel chlorides, 0.005mol nickel sulfates, 0.1mol potassium hydroxide and 0.03mol
Ferric tri-dodecanesulfonate, 0.03mol neopelexes are dissolved in 50mL water, and are transferred in 100mL flasks, at 95 DEG C
Lower reflux condensation mode stirs 5h.After being cooled to room temperature, above-mentioned suspension is filtered, is dried at room temperature for 24 hours.By the powder after drying
End is put into tube furnace, under nitrogen atmosphere, from room temperature to 700 DEG C, and keeps 5h at this temperature.It naturally cools to
After room temperature, black powder is obtained.This black powder is put into 100mL beakers, the hydrochloric acid 50mL of 10mol/L is added, is stirred
48h.Later, it filters, and is repeatedly washed with distilled water up to pH=6.8-7.2, obtained filter cake dry 10h at 80 DEG C, most
It is in the hollow structure graphene nanospheres of black powder eventually.Obtained graphene nano mean diameter of a ball is 10nm.
Embodiment 10:
By 0.01mol frerrous chlorides, 0.04mol urea, 0.01mol ferric tri-dodecanesulfonates, 0.02mol detergent alkylates
Sodium sulfonate and 0.02mol dodecyl sodium sulfates are dissolved in 50mL water, and are transferred in 100mL flasks, the returned cold at 95 DEG C
Solidifying stirring 12h.After being cooled to room temperature, above-mentioned suspension is filtered, is dried at room temperature for 24 hours.By the powder after drying, it is put into
In tube furnace, under nitrogen atmosphere, from room temperature to 600 DEG C, and 10h is kept at this temperature.After cooled to room temperature,
Obtain black powder.This black powder is put into 100mL beakers, the hydrochloric acid 50mL of 3mol/L is added, stirs 36h.Later, it takes out
Filter, and be repeatedly washed with distilled water until pH=6.8-7.2, the drying at 80 DEG C of obtained filter cake is in finally black powder for 24 hours
The hollow structure graphene nanospheres of shape.The hollow graphite alkene nanometer mean diameter of a ball being prepared under this condition is in 15nm.
Embodiment 11:
By the nickel acetate of 0.01mol, 0.005mol nickel chlorides, 0.005mol nickel sulfates, 0.1mol potassium hydroxide and
Ferric tri-dodecanesulfonate, the 0.03mol neopelexes of 0.03mol is dissolved in 50mL water, and is transferred to 100mL flasks
In, reflux condensation mode stirs 8h at 90 DEG C.After being cooled to room temperature, above-mentioned suspension is filtered, is dried at room temperature for 24 hours.It will
Powder after drying, is put into tube furnace, under argon atmosphere, from room temperature to 900 DEG C, and keeps 4h at this temperature.
After cooled to room temperature, black powder is obtained.This black powder is put into 100mL beakers, the hydrochloric acid of 6mol/L is added
50mL, stirring is for 24 hours.Later, it filters, and is repeatedly washed with distilled water until pH=6.8-7.2, obtained filter cake are done at 80 DEG C
Dry 10h, final is in the hollow structure graphene nanospheres of black powder.The hollow graphite alkene nanosphere prepared under this condition is flat
Equal diameter is in 20nm.
Embodiment 12：
By the just pungent of the cobaltous sulfate of 0.005mol, 0.005mol cobalt chloride 0.015mol hexamethylenetetramines and 0.01mol
The dodecyl sodium sulfate of amine, 0.01mol lauryl amines and 0.01mol is dissolved in the mixed solution of 50mL water and 20mL absolute ethyl alcohols
In, and be transferred in 100mL flasks, reflux condensation mode stirs 6h at 100 DEG C.After being cooled to room temperature, above-mentioned suspension is carried out
It filters, dries at room temperature for 24 hours.The powder after drying is put into tube furnace, under helium atmosphere, from room temperature to 1000
DEG C, and 2h is kept at this temperature.After cooled to room temperature, black powder is obtained.This black powder is put into 100mL beakers
In, the hydrochloric acid 80mL of 10mol/L is added, stirs 48h.Later, it filters, and is repeatedly washed with distilled water until filtrate pH=6.8-
7.2, obtained filter cake dry 16h at 80 DEG C, final is in the hollow graphite alkene nanosphere of black powder.What the condition obtained
The average diameter of hollow graphite alkene nanosphere is 5nm.
The above description is merely a specific embodiment, it is noted that any technical person familiar with the field exists
Disclosed herein technical scope in, the change or replacement that can be readily occurred in, should all cover protection scope of the present invention it
It is interior.
Claims (8)
1. a kind of method that confinement catalysis prepares hollow graphite alkene nanosphere, which is characterized in that include the following steps：First by divalent
Metal salt, surfactant, precipitating reagent are completely dissolved in solvent, obtain mixed liquor；Reflux condensation mode after mixed liquor is heated again
Stirring obtains suspension；Then suspension is handled by suction filtration, is smashed after taking filtration cakes torrefaction；Then powder is passed through
Carbonization treatment obtains black powder；Black powder is handled by acid etch finally, obtains the hollow graphite in black powder
Alkene nanosphere；
Wherein, the divalent metal salt, surfactant, precipitating reagent additive amount by mole the ratio between be divalent metal salt：Surface
Activating agent：Precipitating reagent=1：2-5：3-5；
The divalent metal salt is one or more in ferrous salt, mantoquita, nickel salt or cobalt salt；Wherein, the ferrous salt choosing
From one or more of frerrous chloride, ferrous sulfate；The mantoquita is in copper chloride, copper sulphate, copper nitrate, copper acetate
One or more；The nickel salt is selected from one or more of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate；The cobalt
Salt is selected from one or more of cobalt nitrate, cobalt chloride, cobaltous sulfate or cobalt acetate.
2. the method that confinement catalysis according to claim 1 prepares hollow graphite alkene nanosphere, which is characterized in that described molten
Agent is distilled water or distilled water and ethyl alcohol is 2-3 by volume:1 mixed liquor.
3. the method that confinement catalysis according to claim 1 prepares hollow graphite alkene nanosphere, which is characterized in that described mixed
It closes liquid and is first heated to 90-120 DEG C, then reflux condensation mode stirs 2-12h, obtains suspension.
4. the method that confinement catalysis according to claim 1 prepares hollow graphite alkene nanosphere, which is characterized in that the carbon
Change processing the specific steps are：Powder is placed in tube furnace, under an inert gas, from room temperature to 600-1000 DEG C, and is protected
2-24h is held, cooled to room temperature obtains black powder.
5. the method that confinement catalysis according to claim 4 prepares hollow graphite alkene nanosphere, which is characterized in that described lazy
The one kind of property gas in nitrogen, argon gas, helium.
6. the method that confinement catalysis according to claim 1 prepares hollow graphite alkene nanosphere, which is characterized in that the acid
Etching processing the specific steps are：Black powder is placed in a concentration of 3-10mol/L hydrochloric acid solutions, is stirred at 60-100 DEG C anti-
24-48h is answered, room temperature is cooled to, then passes through suction filtration and handles, filter cake water is taken repeatedly to wash the pH=6.8- up to filtrate
7.2, finally dry 10-24h under conditions of temperature is 60-80 DEG C, obtains the hollow graphite alkene nanosphere in black powder.
7. the method that confinement catalysis according to claim 1 or 2 prepares hollow graphite alkene nanosphere, which is characterized in that institute
It states surfactant and is selected from lauryl sodium sulfate, neopelex, ferric tri-dodecanesulfonate, dodecyl sodium sulfonate
One or more of sodium, n-octyl amine, lauryl amine；The precipitating reagent is selected from urea, potassium hydroxide, sodium hydroxide, six first
One kind in urotropine, ammonium chloride.
8. the method that confinement catalysis according to claim 1 prepares hollow graphite alkene nanosphere, which is characterized in that specific packet
Include following steps：
1) dissolving of reactant：
First by divalent metal salt, surfactant, precipitating reagent by mole the ratio between be divalent metal salt：Surfactant：Precipitating reagent
=1：2-5：3-5 is completely dissolved in solvent, obtains mixed liquor；
Wherein, the divalent metal salt is one or more in ferrous salt, mantoquita, nickel salt or cobalt salt；Wherein, the ferrous iron
Salt is selected from one or more of frerrous chloride, ferrous sulfate；The mantoquita is selected from copper chloride, copper sulphate, copper nitrate, acetic acid
One or more of copper；The nickel salt is selected from one or more of nickel chloride, nickel sulfate, nickel nitrate, nickel acetate；Institute
It states cobalt salt and is selected from one or more of cobalt nitrate, cobalt chloride, cobaltous sulfate or cobalt acetate；The surfactant is selected from 12
One in sodium alkyl sulfate, neopelex, ferric tri-dodecanesulfonate, dodecyl sodium sulfate, n-octyl amine, lauryl amine
Kind is a variety of；The one kind of the precipitating reagent in urea, potassium hydroxide, sodium hydroxide, hexamethylenetetramine, ammonium chloride；
2) reflux condensation mode and suction filtration processing：
Mixed liquor obtained by step 1) is first heated to 90-120 DEG C, then reflux condensation mode stirs 2-12h, obtains suspension, then
Suspension is handled by suction filtration, is smashed after taking filtration cakes torrefaction；
3) carbonization treatment：
By in powder merging tube furnace obtained by step 2), under an inert gas, from room temperature to 600-1000 DEG C, and 2- is kept
For 24 hours, cooled to room temperature obtains black powder；
4) acid etch is handled：
Black powder obtained by step 3) is placed in a concentration of 3-10mol/L hydrochloric acid solutions, is stirred to react at 60-100 DEG C
24-48h is cooled to room temperature, then passes through suction filtration and handles, filter cake water is taken repeatedly to wash the pH=6.8-7.2 up to filtrate,
Finally dry 10-24h under conditions of temperature is 60-80 DEG C, obtains the hollow graphite alkene nanosphere in black powder.
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