CN112758915A - Preparation method of highly-graphitized mesoporous-rich nano-carbon onion - Google Patents
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Abstract
The invention relates to a preparation method of a highly-graphitized mesoporous-rich nanocarbon onion. The invention provides a multi-mesoporous and high-graphitization nano carbon onion which is prepared by preparing solid nano carbon spheres by a chemical vapor deposition method, strengthening a carbon sphere graphite structure by a discharge plasma sintering process and removing amorphous carbon in the carbon spheres by an etching method. The method has the advantages of simplicity, convenience, easy expansion, environmental protection and the like. And the obtained nano carbon material with the novel structure has good electrical and mechanical properties and huge potential application value.
Description
Technical Field
The invention relates to a preparation method for synthesizing high-graphitization nano carbon onions rich in mesopores by a template-free method, which can be used for large-scale production.
Background
The nano carbon onion is a novel zero-dimensional carbon nano material formed by nesting graphite-like carbon spheres with different diameters layer by layer in a Russian nesting doll mode (the spacing is between 0.34 and 0.37). The material has the advantages of good electric and thermal conductivity, excellent chemical stability, low density and high compression strength, and can be widely applied to various fields such as electromagnetic shielding, energy storage, solid lubricants, novel alkali metal battery electrode materials, electrocatalytic materials, biocompatible nanocapsules for drug delivery and the like. And thus has received a wide range of attention.
Various methods for synthesizing nanocarbon onions have been reported, including arc discharge, electron beam irradiation, plasma method, nanodiamond vacuum heat treatment, organometallic polymer pyrolysis or laser irradiation method, and vacuum ball milling method. The synthesis conditions of the methods are harsh, and the prepared nanocarbon onion has low purity and low graphitized layering degree, so that the wide application of the nanocarbon onion is limited. On the other hand, the nano carbon onions prepared by the methods are mostly in a solid structure or a thick-wall-wrapped internal hollow structure. The carbon onion with the atomic structure seriously limits the application of the carbon onion in the fields of energy materials, electrocatalysis, drug delivery and the like. Although porous spherical carbon nanomaterials can be prepared by a template method, the materials prepared by the methods generally have the defects of low graphitized stratification degree, complex preparation process, environmental pollution and the like. For example, Jianan-Ying Miao et al synthesized mesoporous carbon nanospheres with a size of 400 nm to 2000 nm by CVD using a transition metal as a catalyst. The group of w.m. Qiao subjects synthesized carbon nanoballs having excellent monodispersity by an arc discharge technique. Another class is low temperature pyrolysis and catalytic decomposition of organic compounds. For example, Chen et al obtained mesoporous carbon nanospheres by heat treatment followed by microwave reaction. Wang et al reported that porous carbon nanospheres were synthesized by a microemulsion-hydrothermal method, with an average size of 20 nm and pore sizes between 0.7 and 3.4 nm. Hai-lacing Liu et al synthesized a three-dimensional ordered array of mesoporous carbon nanospheres about 10.4 nm in size with a sphere-to-sphere spacing of about 60 nm by a dual-template method. Although there are many methods for synthesizing mesoporous carbon nanospheres, the problems of complicated synthesis steps, uneven particle size, low yield, low graphitization degree of the obtained carbon spheres, unclear synthesis mechanism and the like still exist. These disadvantages limit the application of the carbon nanoball.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a highly graphitized mesoporous-rich nanocarbon onion.
The technical scheme adopted by the invention is as follows: a preparation method of highly graphitized nano carbon onion rich in mesopores comprises the following steps:
(1) preparing solid carbon nanospheres by a two-stage chemical vapor deposition method;
(2) sintering the solid carbon nanospheres obtained in the step (1) by using a spark plasma sintering technology;
(3) and (3) etching the sintered solid carbon nanospheres obtained in the step (2) into onion-like mesoporous carbon nanospheres by using methods such as hydrothermal method, air high-temperature oxidation method, chemical etching (oxidant or alkali) and the like.
In the step (1), a two-stage chemical vapor deposition method is adopted: putting a quartz boat containing catalyst ferrocene into a quartz tube of a tube furnace, and placing the quartz boat in a low-temperature area at a gas inlet; introducing inert gas and raising the temperature at a temperature rise rate of 10 ℃ per minute (the set temperature of the low-temperature region is 150-oC, the temperature of a high-temperature area is 700-900 ℃; after the temperature is stable, injecting o-dichlorobenzene into the furnace body through an injection pump, and finishing the reaction after the injection is finished; and (3) closing the power supply of the high-temperature furnace, cooling to room temperature in the inert gas atmosphere, and collecting the product on the wall of the quartz tube, namely the solid carbon nanosphere powder.
In the step (2), the solid carbon nanospheres obtained in the step (1) are placed in an SPS sintering mould, the mould is placed between an upper large electrode and a lower large electrode of a sintering furnace, the pressure is 2 KN, and the pressure is 50-100 DEGoThe temperature rise rate of C/min is increased to the reaction temperature of 1000-2000 ℃, then the reaction temperature is kept for 10 min, the power supply is closed, and the sample is taken out to be the sintered solid carbon nanosphere.
In the step (2), the reaction temperature is 1000-.
In the step (3), the solid carbon nanospheres sintered in the step (2) are placed in a reaction kettle, and deionized water, NaOH (or KOH) solution and H are added2O2Screwing down the reaction kettle, reacting for 18-30h at the temperature of 150-And washing the material with deionized water to be neutral, and drying to obtain the highly graphitized mesoporous-rich nano carbon onion. Or, the solid carbon nanospheres sintered in the step (2) can be placed in a high-temperature furnace in an air atmosphere, heated to 400 ℃ at a heating rate of 10 ℃/min and kept for one hour, and then cooled to room temperature to obtain the highly graphitized mesoporous-rich nanocarbon onion.
The invention has the following beneficial effects: the invention provides a method for preparing solid nano carbon spheres by adopting a two-stage chemical vapor deposition method, which is characterized in that a graphite structure of the carbon spheres is strengthened by spark plasma sintering, and amorphous carbon in the carbon spheres is removed by an etching method, so that a multi-mesoporous and high-graphitization nano carbon onion is obtained. The method has the advantages of simplicity, convenience, easy expansion, environmental protection and the like. And the obtained nano carbon material with the novel structure has good electrical and mechanical properties and huge potential application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a transmission picture of highly graphitized mesoporous-rich nanocarbon onion prepared in example 1;
FIG. 2 is an electron micrograph of a porous nanocarbon onion CNS-SPS 1600 prepared in example 1: (a) SEM picture; (b) a low magnification TEM image; (c) high magnification TEM images (d) high resolution TEM images;
FIG. 3 is a thermogravimetric analysis plot of the porous nanocarbon onion CNS-SPS 1600 prepared in example 1;
FIG. 4 is a Raman plot of porous nanocarbon onion CNS-SPS 1600 prepared in example 1;
FIG. 5 is an XRD pattern of the porous nanocarbon onion CNS-SPS 1600 prepared in example 1;
fig. 6 is a nitrogen adsorption-desorption isotherm of the porous nanocarbon onion CNS-SPS 1600 prepared in example 1, with the inset being its pore size distribution curve.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Weighing 1g of ferrocene (ferrocene), paving the ferrocene in a quartz boat, and placing the quartz boat in a quartz tube, wherein the quartz boat is positioned at the low-temperature section (close to an injection end) of the two-section chemical vapor deposition system. The temperature of the low-temperature furnace is set to be 150 ℃, the temperature of the high-temperature furnace is set to be 800 ℃, and the heating rates of the two sections of electric furnaces are both 15 ℃/min. In the process of heating the tubular furnace, introducing inert gas (such as nitrogen, argon, carbon dioxide and the like, wherein the gas flow is 500 sccm) all the time, injecting o-dichlorobenzene (with the injection rate of 0.08 mL/min) into the furnace body through an injection pump when the set temperature is 800 ℃, ending the reaction after the injection is finished, closing the high-temperature furnace, and cooling to the room temperature in the inert gas atmosphere. The product collected on the wall of the quartz tube was about 500 mg, which is named as the solid carbon nanoball powder CNS.
Weighing 60 mg of the sample, putting the sample into an SPS sintering mould (the diameter of the mould is 8 mm), placing the mould between an upper large electrode and a lower large electrode of a sintering furnace, setting the pressure to be 2 KN and the reaction temperature to be 1600 ℃, opening a water cooling machine, vacuumizing, and then carrying out temperature programming at the temperature rise rate of 50 ℃/min. And when the temperature reaches the set temperature, keeping the temperature for 10 min, turning off the power supply, turning off the water chiller when the temperature in the cavity is reduced to room temperature under the action of the water chiller, taking out a product, and naming the obtained material as CNS-SPS 1600 according to the sintering temperature.
Placing the synthesized CNS-SPS 1600 into a 50 mL reaction kettle, then respectively adding 25mL of deionized water, 1mL of 1M NaOH solution and 2mL of H2O2 into the kettle, screwing the reaction kettle, placing the reaction kettle into an electric heating constant temperature forced air drying box, reacting for 24 hours at 200 ℃, closing the drying box, cooling to room temperature, filtering the mixture in the kettle, washing to be neutral by using deionized water, and drying to obtain 43 mg of black powder, wherein the obtained material is MCNS-SPS 1600.
As shown in FIG. 2, the synthesized carbon nanosphere has good monodispersity, uniform morphology and size of 50-120 nm. TEM observation revealed that 100% of the obtained carbon spheres had carbon nanoballs having a structure similar to an onion. The high resolution transmission plot shows that the MCNS-SPS 1600 has a graphite layer structure with a distance between graphite layers of about 0.33-0.35 nm, similar to the interlayer spacing of graphite crystals. The carbon sphere structure is similar to a porous carbon nanosphere which is formed by convoluting multiple graphene layers (5-10 layers) and has a gap (the gap is 1-10 nm) in the middle.
And carrying out thermogravimetric analysis on the obtained carbon spheres to obtain the component and purity information of each sample. FIG. 3 is a thermogravimetric analysis plot. It can be seen from the figure that the quality of the porous carbon nanospheres prepared by sintering at 1600 degrees is reduced after 580 ℃. The good stability is shown, which indicates that the graphitization degree of the sample is higher. The sample is finally and completely oxidized into CO2, which shows that the synthesized carbon spheres have high purity and less impurities.
The resulting samples were subjected to raman testing at a laser wavelength of 532 nm. By normalizing the G peak, fig. 4 was obtained. It can be seen from the figure that MCNS-SPS 1600 also has a sharp G peak and a small ID/IG value (0.7), indicating that the material is better in crystallinity. The internal structure and composition of the crystal can be known by analyzing the X-ray diffraction pattern of the sample shown in fig. 5. For ordered graphitic carbon, it has two characteristic peaks at 2 θ = 26.6 ° (002) and 2 θ = 43.75 ° (100), respectively. As can be seen from fig. 5, the characteristic peak of the obtained sample is narrow and sharp, and the full width at half maximum of the (002) peak is 0.609, which shows that after SPS, the structure becomes more ordered, the graphitization degree is improved, and the crystallinity is better, which is consistent with our raman and transmission results. It also proves that the structure is similar to graphite and the degree of order is high.
The nitrogen adsorption-desorption isotherm reflects the change in pore structure. As shown in FIG. 6, the nitrogen adsorption-desorption isotherm of the porous carbon nanosphere is an IV-type isotherm, which indicates that the sample is mainly of a mesoporous structure, the pore size distribution of the sample is mainly about 48 nm, and the specific surface area of the sample is 35.6 m2/g。
Example 2:
60 mg of the CNS sample obtained in example 1 was weighed, placed in an SPS sintering mold (mold aperture 8 mm), the reaction temperature was set to 1200 ℃ and the heating rate was set to 50 ℃ per min under the same pressure as in example 1, and the material was sintered at 1200 ℃ for 10 min, and the obtained material was named CNS-SPS 1200 according to the sintering temperature.
The CNS-SPS 1200 synthesized as above was placed in a 50 ml reaction vessel, subjected to hydrothermal etching as in example 1, and dried to obtain 45 mg of black powder, and the obtained material was named MCNS-SPS 1200.
The obtained carbon spheres are uniform in appearance, have the size of 50-120 nm and 100% of carbon nanospheres with onion-like structures through observation of a transmission electron microscope. The crystal structure was similar to that obtained in example 1. The results of the Raman measurement showed that the ID/IG value was 0.75, and the results of the XRD measurement showed that the full width at half maximum of the (002) peak was 0.63. The specific surface test shows that the pore size distribution is mainly about 48 nm, and the specific surface area is 35.8 m2(ii) in terms of/g. The thermogravimetric analysis results were the same as those of example 1.
Example 3:
60 mg of the CNS sample obtained in example 1 was weighed, placed in an SPS sintering mold (mold aperture 8 mm), the reaction temperature was set to 1000 ℃ and the temperature rise rate was set to 50 ℃ per min under the same pressure as in example 1, and sintered at 1000 ℃ for 10 min, and the obtained material was named CNS-SPS 1000 according to the sintering temperature.
The synthesized CNS-SPS 1000 was placed in a 50 ml reactor, subjected to hydrothermal etching as in example 1, and dried to obtain 40 mg of black powder, and the obtained material was named MCNS-SPS 1000.
The obtained carbon spheres are uniform in appearance, have the size of 50-120 nm and 100% of carbon nanospheres with onion-like structures through observation of a transmission electron microscope. The crystal structure was similar to that obtained in example 1. The results of the Raman measurement showed that the ID/IG value was 0.83, and the results of the XRD measurement showed that the full width at half maximum of the (002) peak was 0.69. The specific surface test shows that the pore size distribution is mainly about 48 nm, and the specific surface area is 37.1 m2(ii) in terms of/g. The thermogravimetric analysis results were the same as those of example 1.
Example 4:
60 mg of the CNS sample obtained in example 1 was weighed, placed in an SPS sintering mold (mold aperture 8 mm), the reaction temperature was set to 2000 ℃ and the temperature rise rate was set to 50 ℃ per min under the same pressure as in example 1, and the material was sintered at 2000 ℃ for 10 min, and the obtained material was named CNS-SPS 2000 according to the sintering temperature.
The CNS-SPS 2000 synthesized above was placed in a 50 ml reactor, subjected to hydrothermal etching as in example 1, and dried to obtain 46 mg of black powder, and the obtained material was named MCNS-SPS 2000.
The obtained carbon spheres are uniform in appearance, have the size of 50-120 nm and 100% of carbon nanospheres with onion-like structures through observation of a transmission electron microscope. The crystal structure was similar to that obtained in example 1. The results of the Raman test showed that the ID/IG value was 0.65, and the results of the XRD test showed that the full width at half maximum of the (002) peak was 0.6. The specific surface test shows that the pore size distribution is mainly about 48 nm, and the specific surface area is 35.3 m2(ii) in terms of/g. The thermogravimetric analysis results were the same as those of example 1.
Example 5:
weighing 60 mg of the synthesized CNS-SPS 1600 sample, placing the weighed sample into a 50 mL reaction kettle, respectively adding 25mL of deionized water, 5mL of 1M NaOH solution and 2mL of H2O2 into the kettle, screwing the reaction kettle, placing the reaction kettle into an electric heating constant temperature air blowing drying oven, reacting for 72 hours at 200 ℃, closing the drying oven, cooling to room temperature, filtering the mixture in the kettle, washing with deionized water to be neutral, and drying to obtain 43 mg of black powder.
The obtained carbon spheres are uniform in appearance, have the size of 50-120 nm and 100% of carbon nanospheres with onion-like structures through observation of a transmission electron microscope. The crystal structure was similar to that obtained in example 1. The results of the Raman test showed that the ID/IG value was 0.7, and the results of the XRD test showed that the full width at half maximum of the (002) peak was 0.609. The specific surface test shows that the pore size distribution is mainly about 48 nm, and the specific surface area is 35.6 m2(ii) in terms of/g. The thermogravimetric analysis results were the same as those of example 1.
Example 6:
100mg of the CNS-SPS 1600 sample synthesized above was weighed out under air atmosphere at 10 deg.CoHeating to 400 ℃ at a C/min heating rateoC, keeping for half an hour, then turning off the power supply, naturally cooling to room temperature in an air atmosphere, and collecting a sample to obtain 56 mg of black powder.
The obtained carbon spheres are uniform in appearance, have the size of 50-120 nm and 100% of carbon nanospheres with onion-like structures through observation of a transmission electron microscope. The crystal structure was similar to that obtained in example 1. The results of the Raman measurement revealed that the ID/IG value was 0.84, and the results of the XRD measurement revealed that the full width at half maximum of the (002) peak was 0.923. The specific surface test shows that the pore size distribution is mainly about 50 nm, and the specific surface area is 42.3 m2(ii) in terms of/g. The thermogravimetric analysis results were the same as those of example 1.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (6)
1. A preparation method of highly graphitized nano carbon onion rich in mesopores is characterized by comprising the following steps:
(1) preparing solid carbon nanospheres by a chemical vapor deposition method;
(2) sintering the solid carbon nanospheres obtained in the step (1) by using a spark plasma sintering technology;
(3) and (3) etching the solid carbon nanospheres sintered in the step (2) into onion-like mesoporous carbon nanospheres.
2. The method for preparing highly graphitized carbon nano-onion rich in mesopores according to claim 1, wherein: in the step (1), a two-stage chemical vapor deposition method is adopted, a quartz boat containing catalyst ferrocene is placed in a quartz tube of a tube furnace and placed in a low-temperature region at a gas inlet, inert gas is introduced, the temperature is simultaneously raised, the temperature of the low-temperature region is set to be 150-.
3. The method of claim 1The preparation method of the highly graphitized mesoporous-rich nano carbon onion is characterized by comprising the following steps: in the step (2), the solid carbon nanospheres obtained in the step (1) are placed in an SPS sintering mould, the mould is placed between an upper large electrode and a lower large electrode of a sintering furnace, the pressure is 2 KN, and the pressure is 50-100 DEGoAnd raising the temperature to the reaction temperature at the temperature raising rate of C/min, then keeping the temperature for 10 minutes, turning off the power supply and taking out a sample, wherein the sample is the sintered solid carbon nanosphere.
4. The method for preparing highly graphitized carbon nano-onion rich in mesopores as claimed in claim 3, wherein: in the step (2), the reaction temperature is 1000-.
5. The method for preparing highly graphitized carbon nano-onion rich in mesopores according to claim 1, wherein: in the step (3), the solid carbon nanospheres sintered in the step (2) are placed in a reaction kettle, and deionized water, strong alkaline solution and H are added2O2Screwing the reaction kettle, reacting for 24-72h at the temperature of 150-.
6. The method for preparing highly graphitized carbon nano-onion rich in mesopores according to claim 1, wherein: and (3) placing the solid carbon nanospheres sintered in the step (2) in a high-temperature furnace in an air atmosphere, heating to 400 ℃ at a heating rate of 10 ℃/min, keeping for one hour, and cooling to room temperature to obtain the highly-graphitized mesoporous-rich nano carbon onion.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598046A (en) * | 2004-08-25 | 2005-03-23 | 太原理工大学 | Preparing onion shape fulven by chemical vapour phase deposition |
| CN1931716A (en) * | 2006-09-14 | 2007-03-21 | 太原理工大学 | Liquid benzene medium arc discharge process of preparing onion-shaped fullerene |
| CN101143385A (en) * | 2007-10-24 | 2008-03-19 | 太原理工大学 | Method for preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt |
| US20160141114A1 (en) * | 2014-11-14 | 2016-05-19 | Council Of Scientific & Industrial Research | Nanocomposite of multilayer fullerenes with transition metal oxide nanoparticles and a process for the preparation thereof |
| CN107857247A (en) * | 2017-11-29 | 2018-03-30 | 山西中兴环能科技股份有限公司 | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion |
| WO2018116240A1 (en) * | 2016-12-21 | 2018-06-28 | Fondazione Istituto Italiano Di Tecnologia | Methods for the preparation of carbon nano-onions |
| CN109147986A (en) * | 2018-09-13 | 2019-01-04 | 慈溪市万金电子元件有限公司 | A kind of carbon onion conductive material of embedded metal and preparation method thereof |
| CN109231185A (en) * | 2018-10-24 | 2019-01-18 | 深圳大学 | A kind of preparation method of nano-sized carbon onion |
| CN110255626A (en) * | 2019-07-08 | 2019-09-20 | 太原理工大学 | Method based on vapor deposition preparation surface-active onion shape Nano carbon balls |
| CN112028062A (en) * | 2020-01-17 | 2020-12-04 | 南通大学 | Method for preparing onion-shaped nano graphite nodules by hydrothermal method |
-
2020
- 2020-12-30 CN CN202011606132.0A patent/CN112758915B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598046A (en) * | 2004-08-25 | 2005-03-23 | 太原理工大学 | Preparing onion shape fulven by chemical vapour phase deposition |
| CN1931716A (en) * | 2006-09-14 | 2007-03-21 | 太原理工大学 | Liquid benzene medium arc discharge process of preparing onion-shaped fullerene |
| CN101143385A (en) * | 2007-10-24 | 2008-03-19 | 太原理工大学 | Method for preparing onion-shaped internal coating metal nickel carbon particle with deoiling asphalt |
| US20160141114A1 (en) * | 2014-11-14 | 2016-05-19 | Council Of Scientific & Industrial Research | Nanocomposite of multilayer fullerenes with transition metal oxide nanoparticles and a process for the preparation thereof |
| WO2018116240A1 (en) * | 2016-12-21 | 2018-06-28 | Fondazione Istituto Italiano Di Tecnologia | Methods for the preparation of carbon nano-onions |
| CN107857247A (en) * | 2017-11-29 | 2018-03-30 | 山西中兴环能科技股份有限公司 | A kind of method that catalystic pyrolysis prepares embedded magnetic metal carbon onion |
| CN109147986A (en) * | 2018-09-13 | 2019-01-04 | 慈溪市万金电子元件有限公司 | A kind of carbon onion conductive material of embedded metal and preparation method thereof |
| CN109231185A (en) * | 2018-10-24 | 2019-01-18 | 深圳大学 | A kind of preparation method of nano-sized carbon onion |
| CN110255626A (en) * | 2019-07-08 | 2019-09-20 | 太原理工大学 | Method based on vapor deposition preparation surface-active onion shape Nano carbon balls |
| CN112028062A (en) * | 2020-01-17 | 2020-12-04 | 南通大学 | Method for preparing onion-shaped nano graphite nodules by hydrothermal method |
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