CN107572509A - A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof - Google Patents
A kind of hollow carbon graphite ball nano material of N doping and preparation method thereof Download PDFInfo
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- CN107572509A CN107572509A CN201710955253.8A CN201710955253A CN107572509A CN 107572509 A CN107572509 A CN 107572509A CN 201710955253 A CN201710955253 A CN 201710955253A CN 107572509 A CN107572509 A CN 107572509A
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Abstract
The invention discloses hollow carbon graphite ball nano material of a kind of N doping and preparation method thereof.The present invention is first using spherical cuprous oxide as hard mould agent, organic/inorganic composite is formed by hydro-thermal reaction with organic carbon source, organic nitrogen source, then high-temperature roasting is carried out under an inert atmosphere, copper/spherical nano composite material of nitrogenous carbon graphite is obtained, the copper in above-mentioned composite is finally removed and obtains the hollow carbon graphite nano material of spherical N doping.The material of the present invention has boring structure, and shell thickness can adjust, and have higher N doping amount.In addition, the preparation method used in the present invention is simple and easy, template used is recyclable, and cost is low, reproducible, is easy to large-scale production.
Description
Technical field
The present invention relates to hollow carbon graphite ball nano material of a kind of N doping and preparation method thereof, belong to inorganic nano material
Expect technical field.
Background technology
The utilization of new energy are an important topics of mankind nowadays society.The storage of the energy and be converted to new energy
Appearance and application provide guarantee basis.In numerous energy-storage systems, ultracapacitor is due to having extended cycle life, environment friend
Well, the advantages that safety and high specific energy density, the very big concern of people is received.Electrode material is the performance of ultracapacitor
One key influence factor, thus for high-specific capacitance super electrode material preparation and performance study be ultracapacitor research
Emphasis.
Carbon graphite material is constantly subjected to the extensive concern of people, according to carbon graphite due to its unique pattern and performance
The form of material is different, can be divided into carbon pipe, carbosphere, carbon fiber etc., wherein carbosphere can be divided into again according to the difference of its structure
Solid carbosphere and hollow carbosphere.Wherein, hollow carbosphere is due to big cavity structure, big specific surface area, good
Chemically and thermally stability, therefore be widely used in gas storage mediums, ultracapacitor, fuel cell, the neck such as catalyst
Domain.And combination of the hollow porous carbon graphite ball as both structures, possess more excellent performance, be more widely applied neck
Domain.
In recent years, with hollow carbosphere material preparation and its functional modification correlative study increasingly deep, miscellaneous original
Son such as N, S and B adulterate carbon material and played a very important role in terms of material property is determined, because they can be by changing
Become electronics and crystal structure improves the performances such as surface polarity, electric conductivity, surface alkalinty and the biocompatibility of material.For example mix
Miscellaneous nitrogen enhances electric conductivity, stability, catalytic activity etc. in the skeleton of carbon so that nitrogen-doped carbon is in catalyst carrier, CO2Inhale
Attached, ultracapacitor etc. has potential application prospect.
By research and development these years, the preparation method of hollow carbosphere is increasingly ripe, on the whole, can be divided into
Under several classes:Template (soft template and hard template), chemical vapour deposition technique (CVD) and hydro-thermal method.Wherein chemical vapour deposition technique
It is higher to prepare the temperature of hollow carbon sphere, and hollow fibre is easily formed in product；Hydro-thermal method prepares hollow carbon sphere pattern can
Control property is poor, and template prepares that hollow carbon sphere morphology controllable is preferable, and can be by changing the method control of template and carbon source
Every structural parameters of hollow carbon sphere processed.At present, soft template method makees template frequently with organic surface active agent, passes through presoma point
Self assembling process between son and surfactant, produce hole or hollow-core construction.Template is removed after baking, so as to obtain
The carbon ball of hollow-core construction.This method repeatability is poor, and hollow ball is not easily controlled synthesis.Hard mould agent method is typically to act
For example spherical SiO of the monodisperse spheres first synthesized2, polymer latex particles (PS) etc. do hard mould agent.Preparing hollow carbon sphere
During, toward the floor height Molecularly Imprinted Polymer of parcel one on hard mould agent surface, then by high-temperature roasting so that hard mould agent table
The organic polymer in face is carbonized, so as to obtain the composite sphere of carbon coating hard mould agent.After removing the templates such as silica
Just obtain hollow carbon sphere.This method is reproducible, and the size of hard mould agent spheroid is used as by control, can obtain different big
Small hollow carbon sphere.
In a word, the good hollow ball of repeatability can be obtained with hard mould agent, but due to presently used hard template master
If silica or high score bulbec, not more than 850 degree of heating-up temperature, hollow plumbago ball can not be obtained.Hard template simultaneously
Agent is not recyclable and reuses, and this increases the cost that template prepares method to a certain extent.Many people are simply concerned about in addition
The formation of hollow ball, seldom pay close attention to the thickness problem of hollow ball shell.
The content of the invention
Can be adjusted it is an object of the invention to provide a kind of shell thickness, the controllable miscellaneous element of N doping amount it is hollow
Carbon graphite ball nano material and preparation method thereof.The size of hollow ball can be modulated according to the size of selected template.
In the present invention, using cuprous oxide as hard mould agent, by being combined between organic nitrogen source and organic carbon source,
The surface coating organic emulsion of cuprous oxide, is then carried out under the atmosphere of inert gas the product of acquisition by hydro-thermal reaction
High-temperature roasting, in heating process, for presoma in pyrocarbon/graphitization, cuprous oxide is reduced to copper, and carbon graphite is coated on
Thereon, carbon graphite coated is formed, then logical overetched method removes template hollow-core construction, and it is hollow to finally give N doping
Carbon graphite ball nano material.By changing the ratio of organic carbon source and nitrogen source etc. in building-up process, different-thickness can be obtained
Hollow carbon graphite ball.Wherein, in preparation process, by hard mould agent is etched be dissolved into copper chloride after, may be used as making again
The raw material of standby cuprous oxide micro-and nano-particles, so as to continue to serve as the hard mould agent of hollow carbon graphite ball, reaches recycling
Effect.
Technical scheme is specifically described as follows.
A kind of preparation method of the hollow carbon graphite ball nano material of N doping, comprises the following steps：
(1) in a solvent, using cuprous oxide micro-and nano-particles as hard mould agent, organic nitrogen source and organic carbon source are being added
Under the conditions of alkaline matter, 12~30h of stirring reaction, then, mixed liquor is transferred in water heating kettle and carries out hydro-thermal process at room temperature,
It is 50-200 DEG C to control hydrothermal temperature, reaction 2-12h, and after natural cooling, resulting reaction solution washing, is dried, i.e., through filtering
Obtain organic/inorganic composite；
(2) organic/inorganic composite obtained in step (1) is calcined under an inert atmosphere, that is, obtain copper/nitrogenous carbon/
The spherical nano composite material of graphite；
(3) by step (2) to copper/spherical nano composite material of nitrogenous carbon graphite mixed with hydrochloric acid, room temperature
Lower stirring, hydrogenperoxide steam generator is then added dropwise, continues stirring reaction 24h~48h, reaction solution washing, produces through filtering after drying
To the spherical rice material of the hollow carbon graphite of N doping.
In the present invention, in step (1), 20~26h of stirring reaction；Hydrothermal temperature is 80~120 DEG C, reacts 10~12h.
In the present invention, in step (1), alkaline matter is the one or more in concentrated ammonia liquor, sodium hydroxide or potassium hydroxide；
Organic nitrogen source is the one or more in aniline, m-aminophenol or melamine；Organic carbon source is in formaldehyde, acetaldehyde or furfural
One kind；Solvent is one or both of methanol, ethanol, ethylene glycol or deionized water.
In the present invention, in step (1), hard mould agent, alkaline matter, organic nitrogen source, the mass ratio of organic carbon source and solvent
For 1:(0.01-1)：(0.1-5)：(0.1-5):(1-120).
In the present invention, in step (2), calcination procedure is as follows：It is 1-5 DEG C/min to control programming rate, is warming up to 295 first
~305 DEG C, after keeping 50~70min, be continuously heating to 600 DEG C~1000 DEG C 6~20h of roasting, then natural cooling, obtain copper/
The nitrogenous spherical nano composite material of carbon graphite.Preferably, when sintering temperature is 600~850 DEG C, copper/nitrogenous carbon ball is prepared
Shape composite；When sintering temperature is more than 850 DEG C less than or equal to 1000 DEG C, the spherical nano composite material of copper/graphite is prepared.
In the present invention, in step (3), the molar concentration of hydrochloric acid is 1~6mol/L, and the mass fraction of hydrogenperoxide steam generator is
1-30%；The rate of charge of copper/spherical nano-complex of nitrogenous carbon graphite, hydrochloric acid and hydrogenperoxide steam generator is 1g:(10-100)
ml:(10-100)ml。
In the present invention, in step (3), continue 24~48h of stirring reaction.
The present invention also provides N doping made from a kind of above-mentioned preparation method hollow carbon graphite ball nano material, and it is black
Color powder, powder diameter 600nm or so, inside configuration spherical in shape is hollow, and size is evenly distributed, and product purity is high.
Compared to the prior art, the beneficial effects of the present invention are：
Using the hollow carbon graphite ball nano material of N doping prepared by the inventive method, apparatus and process is simple, and cost is low
Honest and clean, the cycle is shorter and yield is higher, can continuous large-scale production, be easy to industrializing implementation.And obtained product structure is uniform
Controllable, crystallinity is good, has a good application prospect.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of N doping hollow carbon sphere nano material prepared by embodiment 1.
Fig. 2 is N doping hollow carbon sphere nano material transmission electron microscope photo prepared by embodiment 1.
Fig. 3 is N doping hollow carbon sphere nano material X ray diffracting spectrum prepared by embodiment 1.
Fig. 4 is the stereoscan photograph of N doping hollow carbon sphere nano material prepared by embodiment 2.
Fig. 5 is the stereoscan photograph of N doping hollow carbon sphere nano material prepared by embodiment 3.
Fig. 6 is the Raman spectrogram that nitrogen prepared by embodiment 4 mixes hollow plumbago ball nano material.
Embodiment
Below by way of specific implementation, with reference to accompanying drawing, the present invention will be further described, but the present invention is not limited in following reality
Apply example.
Method described in various embodiments of the present invention is conventional method unless otherwise instructed.
Raw material used unless otherwise instructed, can be bought from disclosed commercial sources in various embodiments of the present invention
Arrive.
The value of chemical substance used is determined by the scope pre-set in various embodiments of the present invention, with
Gram, milliliter etc. is measurement unit.
Instrument used or unit type and the information of manufacturer are as follows in various embodiments of the present invention：
Air dry oven, model DHG-9920A, manufacturer：Shanghai Yiheng Scientific Instruments Co., Ltd；
Vacuum drying chamber, DZF-6030A, Shanghai Yiheng Scientific Instruments Co., Ltd；
Tube furnace, the types of SL1700 II, Shanghai Sheng Li testers Co., Ltd；
X-ray diffractometer (XRD), PANalytical company of X PERT PRO Holland；
Transmission electron microscope (TEM) JEM-2100 Japan Electronics Corporations；
SEM (SEM), S-3400N HITs；
Raman spectrometers, DXR-Raman, Thermo Fisher Scientific companies.
Embodiment 1
A kind of preparation method of the hollow carbon graphite ball nano material of N doping, specifically comprises the following steps：
(1) sodium hydroxide solution of 50ml0.4M/L copper chloride dihydrate solution, then 100ml 1M/L amounts, is measured,
Under the conditions of surfactant is existing, high-speed stirred, is made mixed emulsion at room temperature.Then, 60ml 0.5M/L Portugal is added
Grape sugar juice, continue to stir 10min, the hydrazine hydrate solution for adding 15ml 0.1M/L is used as reducing agent, is further continued for stirring 1h, molten
Liquid is changed into brick-red suspension, through standing, filters, washing, after drying, that is, it is sub- for 600nm or so spherical oxidation to obtain particle diameter
Copper.
(2), in a solvent, using the cuprous oxide obtained by above-mentioned steps (1), organic nitrogen source is organic for hard mould agent
Carbon source is presoma, and in the presence of alkaline substances, stirring reaction 24h, then, polytetrafluoro is transferred to by this liquid at room temperature
In the container of ethene liner, it is placed in stainless steel cauldron, seals, carry out hydro-thermal process, it is 180 DEG C to control temperature, reaction
12h, after natural cooling, resulting reaction solution is through filtering, and after cleaning, filter cake is dried in vacuo in less than 60 DEG C, that is, obtain it is organic/
Inorganic composite.
(3), by organic/inorganic composite resulting in step (2) under the atmosphere of nitrogen or argon gas, control heating speed
Spend for 1 DEG C/min, be warming up to 300 DEG C first, after keeping 1h, be continuously heating to 850 DEG C of roasting 6h, make programming rate for 2 DEG C/
min.Then room temperature is naturally cooled to, that is, obtains copper/nitrogenous carbon ball nano composite material.
Described alkaline matter is the ammoniacal liquor that mass fraction is 25%；
Described organic nitrogen source is m-aminophenol；
Described organic carbon source is formaldehyde；
Described solvent is that ethanol and deionized water are 5 by volume:The mixed solution of 2 compositions；
The dosage of described template cuprous oxide, alkaline matter, organic nitrogen source, organic carbon/graphitic source and solvent, by matter
Amount is than calculating, i.e. cuprous oxide：Alkaline matter, organic nitrogen source, organic carbon source：Solvent is：1:0.04：0.5：0.7:100 ratio
Example is calculated
(4), by copper/nitrogenous carbon ball nano composite material obtained by step (3) with hydrochloric acid mixed, at room temperature
Stirring, appropriate hydrogenperoxide steam generator is then slowly added dropwise, continues more than stirring reaction 24h, the reaction solution of gained is washed through filtering
Wash, N doping hollow carbon sphere nano material is obtained after drying；
The molar concentration of described hydrochloric acid is 6mol/L；
The mass fraction of described hydrogenperoxide steam generator is 10%；
Copper/nitrogenous carbon ball the nano-complex obtained in described step (3) and hydrochloric acid and hydrogenperoxide steam generator dosage
By 1g:50ml:50ml ratio calculates.
The N doping hollow carbon sphere nano material of above-mentioned gained is observed using SEM, such as Fig. 1 institutes
Show, there it can be seen that the grain size of the N doping hollow carbon sphere nano material of above-mentioned gained is in 600nm or so, and size
It is evenly distributed, regular appearance is spherical in shape；
The N doping hollow carbon sphere nano material of above-mentioned gained is observed using transmission electron microscope.As shown in Fig. 2 therefrom
It can be seen that sample has than more uniform regular hollow ball shape form, carbon ball surface showed smooth is coarse, and average diameter is
600nm or so；
The N doping hollow carbon sphere nano material of above-mentioned gained is characterized using x-ray diffractometer, the sample of gained
Wide-angle XRD as shown in figure 3, have two diffraction maximums at about 24 ° 71 and 44 ° 92, show inorganic carbon graphite (002) and
(100) diffraction maximum, in addition, other peaks are not observed in XRD, show that no impurity is present.(100) peak value is relatively
It is weak, show its faulty feature.
Embodiment 2
The process that the present embodiment prepares N doping hollow plumbago ball nano material is identical with the process of embodiment 1, different
It is by the amount ratio of step (2) template cuprous oxide in embodiment 1, alkaline matter, organic nitrogen source, organic graphitic source and solvent
It is changed to：That is cuprous oxide：Alkaline matter, organic nitrogen source：Organic graphitic source：Solvent is：1:0.04：0.7：1.02:100, so as to
The N doping hollow carbon sphere nano material of different-thickness can be obtained.Hollow carbon sphere nano material is mixed by nitrogen manufactured in the present embodiment
SEM photograph is as shown in Figure 4.
Embodiment 3
The process that the present embodiment prepares the hollow carbon graphite ball nano material of N doping is identical with the process of embodiment 1, different
Be that step (3) sintering temperature in embodiment 1 is changed to 750 DEG C by 850 DEG C.N doping hollow carbon sphere finally is prepared to receive
Rice material.It is as shown in Figure 5 that hollow carbon sphere nano material SEM photograph is mixed by nitrogen manufactured in the present embodiment.
Embodiment 4
The process that the present embodiment prepares the hollow carbon graphite ball nano material of N doping is identical with the process of embodiment 1, different
Be that step (3) sintering temperature in embodiment 1 is changed to 1000 DEG C by 850 DEG C.The hollow stone of N doping being finally prepared
Tampon nano material.The Raman spectrum of hollow plumbago ball nano material is mixed by nitrogen manufactured in the present embodiment as shown in fig. 6, can see
Go out to belong to defect peak D relative intensity less than being used as graphite peaks G, relative intensity ID/IGIt is approximately equal to 0.81, shows using ours
Method, the high hollow plumbago ball nano material of order can be obtained.
In summary, the hollow carbon graphite ball nano material of N doping of the invention is spherical morphology, and internal to be hollow
Structure, this specific structure had both imparted the hollow more preferable chemical stability of carbon graphite ball nano material, and resistance to acids and bases is raw
Thing compatibility and surface-functionalized various selective, but also carbon graphite ball can be modified, therefore the nitrogen of the present invention
Doped hollow carbon graphite ball nano material will have in biology sensor, ultracapacitor, fuel cell and catalyst etc.
Potential application prospect.
Described above is only the citing to embodiments of the present invention, it is noted that for the general skill of the art
For art personnel, on the premise of this technology principle is not departed from, some improvement and modification can also be made, these improve and become
Type is regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the hollow carbon graphite ball nano material of N doping, it is characterised in that specifically include following steps：
(1) in a solvent, using cuprous oxide micro-and nano-particles as hard mould agent, organic nitrogen source and organic carbon source are being added into alkalescence
Under material conditions, 12~30h of stirring reaction, then, mixed liquor is transferred in water heating kettle and carries out hydro-thermal process at room temperature, control
Hydrothermal temperature is 50-200 DEG C, reaction 2-12h, and after natural cooling, resulting reaction solution washing, is dried through filtering, that is, obtained
Organic/inorganic composite；
(2) organic/inorganic composite obtained in step (1) is calcined under an inert atmosphere, that is, obtains copper/nitrogenous carbon graphite
Spherical nano composite material；
(3) by step (2) to copper/spherical nano composite material of nitrogenous carbon graphite mixed with hydrochloric acid, stir at room temperature
Mix, hydrogenperoxide steam generator is then added dropwise, continue stirring reaction 24h~48h, reaction solution washing, nitrogen is obtained after drying through filtering
The spherical rice material of doped hollow carbon graphite.
2. preparation method according to claim 1, it is characterised in that in step (1), 20~26h of stirring reaction；Hydro-thermal temperature
Spend for 80~120 DEG C, react 10~12h.
3. preparation method according to claim 1, it is characterised in that in step (1), alkaline matter is concentrated ammonia liquor, hydrogen-oxygen
Change the one or more in sodium or potassium hydroxide；Organic nitrogen source is one kind or several in aniline, m-aminophenol or melamine
Kind；Organic carbon source is one kind in formaldehyde, acetaldehyde or furfural；Solvent is one kind in methanol, ethanol, ethylene glycol or deionized water
Or two kinds.
4. preparation method according to claim 1, it is characterised in that hard mould agent, alkaline matter, organic in step (1)
The mass ratio of nitrogen source, organic carbon source and solvent is 1:(0.01-1)：(0.1-5)：(0.1-5):(1-120).
5. preparation method according to claim 1, it is characterised in that in step (2), calcination procedure is as follows：Control heating
Speed is 1-5 DEG C/min, is warming up to 295~305 DEG C first, after keeping 50~70min, is continuously heating to 600 DEG C~1000 DEG C
6~20h, then natural cooling are calcined, obtains copper/spherical nano composite material of nitrogenous carbon graphite.
6. preparation method according to claim 5, it is characterised in that when sintering temperature is 600~850 DEG C, be prepared
Copper/nitrogenous carbon ball shape composite；When sintering temperature is more than 850 DEG C and is less than or equal to 1000 DEG C, it is prepared that copper/graphite is spherical to be received
Nano composite material.
7. preparation method according to claim 5, it is characterised in that sintering temperature is 6~10h.
8. preparation method according to claim 1, it is characterised in that in step (3), the molar concentration of hydrochloric acid for 1~
6mol/L, the mass fraction of hydrogenperoxide steam generator is 1-30%；Copper/spherical the nano-complex of nitrogenous carbon graphite, hydrochloric acid and mistake
The rate of charge of hydrogen peroxide solution is 1g:(10-100)ml:(10-100)ml.
9. preparation method according to claim 1, it is characterised in that in step (3), continue 24~48h of stirring reaction.
A kind of 10. hollow carbon graphite ball nanometer material of N doping that preparation method according to one of claim 1~9 obtains
Material.
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| CN110028053A (en) * | 2019-05-16 | 2019-07-19 | 济宁医学院 | A kind of preparation method and applications of high nitrogen doped amount nano cages material |
| CN110713176A (en) * | 2019-11-27 | 2020-01-21 | 北京航空航天大学 | Preparation of three-dimensional grading porous carbon material and method for regulating and controlling pore diameter of three-dimensional grading porous carbon material |
| CN117568694A (en) * | 2023-11-16 | 2024-02-20 | 北京科技大学顺德创新学院 | Three-dimensional graphite sphere reinforced copper-based heat conduction composite material and preparation method thereof |
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| CN117568694A (en) * | 2023-11-16 | 2024-02-20 | 北京科技大学顺德创新学院 | Three-dimensional graphite sphere reinforced copper-based heat conduction composite material and preparation method thereof |
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