CN105712317B - A kind of preparation method of the carbon material containing hollow nano - Google Patents
A kind of preparation method of the carbon material containing hollow nano Download PDFInfo
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- CN105712317B CN105712317B CN201610067079.9A CN201610067079A CN105712317B CN 105712317 B CN105712317 B CN 105712317B CN 201610067079 A CN201610067079 A CN 201610067079A CN 105712317 B CN105712317 B CN 105712317B
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- C01P2002/00—Crystal-structural characteristics
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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Abstract
The invention belongs to field of novel carbon material, and in particular to a kind of preparation method of carbon material containing hollow nano.The problem of there is preparation method complexity, low carbon hollow ball purity, high cost and low yield present invention mainly solves current preparation method.The preparation method of the carbon material of the invention containing hollow nano, comprises the following steps：(1) surfactant, metal salt, urea and oxygen-bearing organic matter, are dissolved in water, are added in stainless steel cauldron；(2) stainless steel cauldron that, will be equipped with raw material is put into reaction in the air dry oven with temperature programming function；(3), suction filtration reaction solution, and with deionized water and ethanol washed product, dry；(4), take) drying after product be heat-treated in an inert atmosphere；(5), by the sample after heat treatment, soaked with excessive dilute acid soln, then carry out suction filtration drying, obtain carbon material containing hollow nano.
Description
Technical field
The invention belongs to field of novel carbon material, and in particular to a kind of preparation method of carbon material containing hollow nano.This hair
The hollow carbon material of bright preparation can be widely applied to electrode of super capacitor, lithium ion cell electrode, electrochemical energy storage hydrogen storage,
The every field such as catalyst carrier, sewage purification, absorption.
Background technology
Following nanosecond science and technology will be increasingly dependent on the synthesis of the nano material of new different structure and functional characteristic.
Carbon material is due to a variety of bonding form (sp, sp of carbon2、sp3Hydridization) and various structures form is shown, such as CNT, graphite
Alkene, carbon nano rod etc., therefore cause the extensive concern of people.Hollow nano carbon ball structure is special, with low-density, certain big
Small cavity, high-specific surface area, its internal lar nanometric cavities can be used as even one reactor of a memory space, Ke Yiguang
The every field such as general use biologic medical, catalyst carrier, absorption, energy storage hydrogen storage, ultracapacitor, lithium ion battery.
Nowadays it is template using widest preparation method, template can be divided into hard template method and soft template method again,
Hard template method is usually to apply some monodispersed silicon ball, polymer drops, metal oxides etc. to be template, then polymer is existed
Its surface aggregate, obtains the composite balls that polymer embeds hard template, carbonizes afterwards, and the suitable method of reselection removes hard template and obtained
To Carbon Hollow ball.[Jang J, Lim the B.Advanced Materials, 2002,14 (19) such as Jang:1390-1393.] utilize
The SiO that surface was modified2As template, divinylbenzene is carbon source, is prepared for size about 22nm hollow carbon balls, gained production
Thing is than more uniform, but its carbon source used is noxious material, and template also needs to be removed with hydrofluoric acid, comparatively laborious, time-consuming, yield compared with
It is low.[WhiteR J, Tauer K, Antonietti M, the et al.Journal of the American such as White
Chemical Society,2010,132(49):17360-17363] by the use of polystyrene latex as template, using glucose as
Carbon source, is prepared for the hollow carbon balls of 100nm or so cavitys, more than ten nanometers of wall thickness, carbon ball prepared by this method, pattern and structure
Than more uniform, method is simple, and template can decompose removal in heat treatment, but be to need to prepare template in advance eventually.
Chemical vapor deposition (CVD) method is another common method for synthesizing carbon hollow ball, under flowing atmosphere, with organic
Gas is pyrolyzed as carbon source in high-temperature region, in the process of catalyst surface deposition growing solid carbon.[Wang the Z L, Yin such as Wang
J S.Chemical physics letters,1998,289(1):189-192.] MnO is used at first2As catalyst, pass through
CH4The carbon hollow ball and hollow calabash shaped carbon structure for having synthesized a diameter of 800nm are pyrolyzed at 900-1050 DEG C.It is general to use gold
Category oxide makees catalyst, is generated more with a large amount of accessory substances, and carbon hollow ball purity is not high.
In addition, the preparation method of carbon ball also has metal deoxidization, supercritical methanol technology, dispersion copolymerization method, laser gasification method, electric arc
The shortcomings of electric discharge, the different degrees of presence manufacturing cost height of these methods, low yield.
The content of the invention
Have that preparation method is complicated, carbon hollow ball purity is low, cost is high present invention is generally directed to current preparation method and
The problem of low yield, there is provided a kind of preparation method of carbon material containing hollow nano.
The technical scheme taken to solve the above problems of the present invention is：
A kind of preparation method of carbon material containing hollow nano, comprises the following steps：
(1) it is, 1 according to mol ratio:(2~200):(8~800):The ratio of (5~500) is by surfactant, metal
Salt, urea and oxygen-bearing organic matter are dissolved in water, are added to afterwards in stainless steel cauldron；
(2) stainless steel cauldron that, will be equipped with raw material is put into the air dry oven with temperature programming function, from room temperature
70 DEG C are warming up to 1~10 DEG C/min programming rate, then are warming up to 90 DEG C with 0.1~0.5 DEG C/min programming rate, then with
1~10 DEG C/min programming rate is warming up to 160~200 DEG C, and in 160~200 DEG C of constant temperature 2~12 hours, it is then naturally cold
But to room temperature；
(3), the reaction solution of suction filtration step (2), and with deionized water and ethanol washed product, finally by product at 60 DEG C
Drying；
(4), take the product after step (3) drying to be heat-treated in an inert atmosphere, be warming up to 5~10 DEG C/min temperature
600~1200 DEG C, then constant temperature 1~4 hour be cooled to 500 DEG C, then be naturally cooling to room with 5~10 DEG C/min cooling rates
Temperature；
(5) sample after, step (4) is heat-treated, with excessive dilute acid soln soaking and stirring 10~12 hours, Ran Houjin
Row suction filtration is dried, and obtains carbon material containing hollow nano.
Surfactant of the present invention be cationic surface active agent, anionic surfactant or it is non-from
Sub- surfactant；Described metal salt is water-soluble inorganic salts and organic salt；Described oxygen-bearing organic matter is unitary sugar
Class, binary carbohydrate or starch.
Described dilute acid soln is the one kind or several of concentration in more than 0.5mol/L watery hydrochloric acid, dilute sulfuric acid, dust technology
Plant mixture.
Described cationic surface active agent is neopelex or lauryl sodium sulfate；Described the moon
Ionic surfactant is cetyl trimethylammonium bromide；Described nonionic surfactant polyvinylpyrrolidone.
Described inorganic salts are hydrochloride, nitrate or sulfate, and organic salt is oxalates or acetate, described gold
It is transition metal ions to belong to metal ion in salt.
The major technique advantage of the present invention for preparing hollow carbon balls method is embodied in：1st, with surfactant and metal
Ion is common template, and prepared lar nanometric cavities are smaller, below 50nm；2nd, using oxygen-bearing organic matters such as glucose as carbon source, raw material
Cost is low；3rd, hollow carbon balls are prepared in the method for hydro-thermal, the reaction time is short；4th, the medicine of severe corrosive need not be used, safety
Environmental protection；5th, technological process is short, and postprocessing working procedures are simple.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of product of the present invention, and wherein A and B are Sample Scan electromicroscopic photograph after gained heat treatment,
C and D is the stereoscan photograph of sample after pickling；
Fig. 2 is the transmission electron microscope photo of product of the present invention, and wherein A is the transmission electron microscope photo of sample after heat treatment, and B is acid
Wash the transmission electron microscope photo of rear sample；
Fig. 3 be hydro-thermal after, heat treatment after, after pickling three phases product x-ray diffraction pattern；
Fig. 4 for after heat treatment, the nitrogen adsorption desorption curve of pickling latter two stage product；
Fig. 5 is the graph of pore diameter distribution of product after pickling.
Embodiment
Embodiment 1
A kind of preparation method of carbon material containing hollow nano, comprises the following steps：
(1) 1.0g neopelexes (SDBS), 1.666g nickel nitrates, 1.3798g urea, 2.5g grapes, are weighed
Sugar is dissolved in 35ml deionized waters successively, is added to after being well mixed in 40ml stainless steel cauldrons；
(2), above-mentioned stainless steel cauldron is put into the air dry oven with temperature programming function, heating rate is set
For 2 DEG C/min, rise to after 70 DEG C, then 90 DEG C are risen to 0.2 DEG C/min heating rate, then with 2 DEG C/min heating rate liter
To 180 DEG C, then constant temperature 5 hours stop heating, reactor is naturally cooled to room temperature in an oven；
(3) suction filtration, is carried out to above-mentioned reaction product, and is washed with deionized 3 times, then 3 times are washed to clarification with ethanol,
Finally product is dried 4 hours at 60 DEG C；
(4), dried product is put into tube furnace, logical argon gas is heat-treated, from room temperature with 8 DEG C of heatings per minute
To 800 DEG C, constant temperature 2 hours is cooled to 500 DEG C with 10 DEG C/min speed, then naturally cools to room temperature；
(5), the product after heat treatment is dissolved with 1mol/L hydrochloric acid, and a whole night is stirred at 50 DEG C；
(6), to the sample suction filtration after pickling, and it is 7 to be washed with deionized 3 times to pH, finally does product at 60 DEG C
Dry 3 hours, obtain product.
The pattern of gained sample is shown in accompanying drawing, its ESEM of Figure 1A, B correspondence after step (4) heat treatment operation in embodiment 1
Figure, it can be seen that adhere to many nickel particles on carbon, its transmission electron microscope picture of Fig. 2A correspondences is more clearly seen on hollow carbon structure
There are many nickel particles for melting simultaneously globulate in face.Sample Scan electron microscope after step (6) pickling processes as shown in Fig. 1 C, D, with
Money laundering contrast is calculated, porosity is abundant a lot, and the product finally given is in the pattern of carbon ball aggregation；Its transmission electron microscope picture such as Fig. 2 B
It is shown, it can clearly see that nickel particle is removed completely compared with A, and obtain highly uniform carbon hollow structure.Fig. 3 show this
After embodiment step (3) hydro-thermal washing and drying treatment, step (4) heat treatment after, three phases product after step (6) pickling processes
X-ray diffraction pattern (XRD), from XRD it can be seen that, through Overheating Treatment, the characteristic peak of nickel and its substantially, and have certain
Graphitization, can confirm-have at 26 degree or so the characteristic peak of graphitized carbon from the later diffraction curve of pickling.Fig. 4 is heat
After processing, the nitrogen adsorption desorption curve of pickling latter two stage product, it can be verified that through overpickling, the hole of product structure
Degree improves a lot, and the curve pattern of the two show to have meso-hole structure in product it is in the majority.Fig. 5 is the aperture point of product after pickling
Butut, it is seen that the aperture integrated distribution in final product is at 1-5 nanometers, in 3.7 nanometers pore-size distributions at most, further displaying
The size of products therefrom cavity.
Embodiment 2
A kind of preparation method of carbon material containing hollow nano, comprises the following steps：
(1) 0.01g neopelexes (SDBS), 1.548g ferric trichlorides, 1.3798g urea, 2.5g fruits, are weighed
Sugar is once dissolved in 35ml deionized waters, is added to after being well mixed in 40ml stainless steel cauldrons；
(2), above-mentioned stainless steel cauldron is put into the air dry oven with temperature programming function, heating rate is set
For 5 DEG C/min, rise to after 70 DEG C, then 90 DEG C are risen to 0.4 DEG C/min heating rate, then with 5 DEG C/min heating rate liter
To 160 DEG C, then constant temperature 7 hours stop heating, reactor is naturally cooled to room temperature in an oven；
(3) suction filtration, is carried out to above-mentioned reaction product, and is washed with deionized 4 times, then 4 times are washed to clarification with ethanol,
Finally product is dried 5 hours at 60 DEG C；
(4), dried product is put into tube furnace, logical argon gas is heat-treated, from room temperature with 5 DEG C of heatings per minute
To 1000 DEG C, constant temperature 3 hours is cooled to 500 DEG C with 8 DEG C/min speed, then naturally cools to room temperature；
(5), the product after heat treatment is dissolved with 1mol/L hydrochloric acid, and a whole night is stirred at 50 DEG C；
(6), to the sample suction filtration after pickling, and it is 7 to be washed with deionized 4 times to pH, finally does product at 60 DEG C
Dry 3 hours, obtain product.
The present embodiment products therefrom pattern is identical with example 1.
Embodiment 3
A kind of preparation method of carbon material containing hollow nano, comprises the following steps：
(1) 0.1g lauryl sodium sulfate (SDS), 1.611g cobaltous sulfates, 1.3798g urea, 1.25g starch one, are weighed
It is secondary to be dissolved in 35ml deionized waters, it is added to after being well mixed in 40ml stainless steel cauldrons；
(2), above-mentioned stainless steel cauldron is put into the air dry oven with temperature programming function, heating rate is set
For 8 DEG C/min, rise to after 70 DEG C, then 90 DEG C are risen to 0.5 DEG C/min heating rate, then with 8 DEG C/min heating rate liter
To 200 DEG C, then constant temperature 3 hours stop heating, reactor is naturally cooled to room temperature in an oven；
(3) suction filtration, is carried out to above-mentioned reaction product, and is washed with deionized 5 times, then 5 times are washed to clarification with ethanol,
Finally product is dried 3 hours at 60 DEG C；
(4), dried product is put into tube furnace, logical argon gas is heat-treated, from room temperature with 10 DEG C of liters per minute
Temperature is to 600 DEG C, and constant temperature 4 hours is cooled to 500 DEG C with 5 DEG C/min speed, then naturally cools to room temperature；
(5), the product after heat treatment is dissolved with 1mol/L hydrochloric acid, and a whole night is stirred at 50 DEG C；
(6), to the sample suction filtration after pickling, and it is 7 to be washed with deionized 5 times to pH, finally does product at 60 DEG C
Dry 3 hours, obtain product.
The present embodiment products therefrom pattern is identical with example 1.
Embodiment 4
A kind of preparation method of carbon material containing hollow nano, comprises the following steps：
(1) 0.1g lauryl sodium sulfate (SDS), 1.427g cobalt acetates, 1.3798g urea, 1.25g sucrose one, are weighed
It is secondary to be dissolved in 35ml deionized waters, it is added to after being well mixed in 40ml stainless steel cauldrons；
(2), above-mentioned stainless steel cauldron is put into the air dry oven with temperature programming function, heating rate is set
For 2 DEG C/min, rise to after 70 DEG C, then 80 DEG C are risen to 0.2 DEG C/min heating rate, then with 2 DEG C/min heating rate liter
To 160 DEG C, then constant temperature 2.5 hours stop heating, reactor is naturally cooled to room temperature in an oven；
(3) suction filtration, is carried out to above-mentioned reaction product, and is washed with deionized 3-5 times, then 3-5 times is washed extremely with ethanol
Clarification, finally dries product 5 hours at 60 DEG C；
(4), dried product is put into tube furnace, logical argon gas is heat-treated, from room temperature with 8 DEG C of heatings per minute
To 800 DEG C, constant temperature 3 hours is cooled to 500 DEG C with 10 DEG C/min speed, then naturally cools to room temperature；
(5), the product after heat treatment is dissolved with 1mol/L hydrochloric acid, and a whole night is stirred at 50 DEG C；
(6), to the sample suction filtration after pickling, and be washed with deionized 3-5 times to pH be 7, finally by product at 60 DEG C
Dry 3 hours, obtain product.
The present embodiment products therefrom pattern is identical with example 1.
Embodiment 5
A kind of preparation method of carbon material containing hollow nano, comprises the following steps：
(1) 1.0g neopelexes (SDBS), 1.031g ferric oxalates (II) dihydrate, 1.3798g urine, are weighed
Element, 2.5g glucose are once dissolved in 35ml deionized waters, are added to after being well mixed in 40ml stainless steel cauldrons；
(2), above-mentioned stainless steel cauldron is put into the air dry oven with temperature programming function, heating rate is set
For 1 DEG C/min, rise to after 70 DEG C, then 90 DEG C are risen to 0.1 DEG C/min heating rate, then with 10 DEG C/min heating rate liter
To 200 DEG C, then constant temperature 10 hours stop heating, reactor is naturally cooled to room temperature in an oven；
(3) suction filtration, is carried out to above-mentioned reaction product, and is washed with deionized 3 times, then 3 times are washed to clarification with ethanol,
Finally product is dried 4 hours at 60 DEG C；
(4), dried product is put into tube furnace, logical argon gas is heat-treated, from room temperature with 8 DEG C of heatings per minute
To 600 DEG C, constant temperature 4 hours is cooled to 500 DEG C with 5 DEG C/min speed, then naturally cools to room temperature；
(5), the product after heat treatment is dissolved with 1mol/L hydrochloric acid, and a whole night is stirred at 50 DEG C；
(6), to the sample suction filtration after pickling, and it is 7 to be washed with deionized 4 times to pH, finally does product at 60 DEG C
Dry 3 hours, obtain product.
The present embodiment products therefrom pattern is identical with example 1.
Claims (6)
1. the preparation method of a kind of carbon material containing hollow nano, it is characterised in that comprise the following steps：
(1) it is, 1 according to mol ratio：2~200：8~800：5~500 ratio is by surfactant, metal salt, urea and contains
Oxygen organic is dissolved in water, is added to afterwards in stainless steel cauldron；
(2) stainless steel cauldron that, will be equipped with raw material is put into the air dry oven with temperature programming function, from room temperature with 1
~10 DEG C/min programming rate is warming up to 70 DEG C, then is warming up to 90 DEG C with 0.1~0.5 DEG C/min programming rate, then with 1~
10 DEG C/min programming rate is warming up to 160~200 DEG C, and in 160~200 DEG C of constant temperature 2~12 hours, then naturally cools to
Room temperature；
(3), the reaction solution of suction filtration step (2), and with deionized water and ethanol washed product, finally dry product at 60 DEG C
It is dry；
(4), take step (3) dry after product be heat-treated in an inert atmosphere, be warming up to 600 with 5~10 DEG C/min temperature~
1200 DEG C, then constant temperature 1~4 hour be cooled to 500 DEG C, then be naturally cooling to room temperature with 5~10 DEG C/min cooling rates；
(5) sample after, step (4) is heat-treated, with excessive dilute acid soln soaking and stirring 10~12 hours, is then taken out
It is filtered dry dry, obtains carbon material containing hollow nano.
2. a kind of preparation method of carbon material containing hollow nano according to claim 1, it is characterised in that described surface
Activating agent is cationic surface active agent, anionic surfactant or nonionic surfactant；Described metal
Salt is water-soluble inorganic salts and organic salt；Described oxygen-bearing organic matter is unitary carbohydrate, binary carbohydrate or starch.
3. a kind of preparation method of carbon material containing hollow nano according to claim 1, it is characterised in that described diluted acid
Solution is one or more of mixtures of the concentration in more than 0.5mol/L watery hydrochloric acid, dilute sulfuric acid, dust technology.
4. a kind of preparation method of carbon material containing hollow nano according to claim 2, it is characterised in that described sun from
Subtype surfactant is neopelex or lauryl sodium sulfate；Described anionic surfactant is
Cetyl trimethylammonium bromide；Described nonionic surfactant polyvinylpyrrolidone.
5. the preparation method of a kind of carbon material containing hollow nano according to claim 2, it is characterised in that described is inorganic
Salt is hydrochloride, nitrate or sulfate, and organic salt is oxalates or acetate, and metal ion was in described metal salt
Cross metal ion.
6. a kind of preparation method of carbon material containing hollow nano according to claim 5, it is characterised in that described transition
Metal ion is iron ion, ferrous ion, cobalt ions, nickel ion.
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