CN106976857A - A kind of new sp3Carbon material and its high pressure method for preparing - Google Patents
A kind of new sp3Carbon material and its high pressure method for preparing Download PDFInfo
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- CN106976857A CN106976857A CN201710127353.1A CN201710127353A CN106976857A CN 106976857 A CN106976857 A CN 106976857A CN 201710127353 A CN201710127353 A CN 201710127353A CN 106976857 A CN106976857 A CN 106976857A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/06—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies
- B01J3/062—Processes using ultra-high pressure, e.g. for the formation of diamonds; Apparatus therefor, e.g. moulds or dies characterised by the composition of the materials to be processed
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
A kind of new sp of the present invention3Carbon material and its high pressure method for preparing, belong to technical field prepared by superhard carbon material.With C60@SWNTs or C70@SWNTs are raw material, and using diamond anvil cell as pressue device, sample is loaded into sample cavity, the hard pressure mode of no transmission medium is taken, and are forced into and are depressed into normal pressure more than or equal to being unloaded after 60GPa, obtain the new sp with superhard characteristic3Carbon material.Raw materials used common, the reactant cost of the present invention is low, preparation process is simple and safe, temperature variable need not be added, prepared superhard carbon material has clear and legible X-ray diffraction peak, and sample crystallization is good, it can be stabilized with excellent mechanical performance, and at ambient pressure.
Description
Technical field
The invention belongs to sp3Technical field prepared by carbon material, and in particular to utilize C60The CNT or C of doping70Mix
Miscellaneous CNT is that raw material prepares the new method with the superhard carbon material of new structure by the method for high pressure.
Background technology
Carbon is a kind of very common element.Due to its flexible bonding form, it can be widely present in a variety of forms.With
The discovery of later fullerene, CNT and graphene, their excellent physics, chemical property have in every field
It is widely applied.The property of material depends on its structure, therefore carbon material of the design synthesis with new structure causes people
Strong scientific interest, especially carbon material of the synthesis with superhard characteristic.
At present, people there may be by the use of different carbon nanomaterials as presoma using the means of high pressure to explore
Superhard carbon phase.By the use of graphite as raw material in experiment, cenotype of the synthesis with superhard characteristic under high pressure, but this cenotype
It can not be intercepted and captured in normal pressure, simultaneously because it is few, the weaker and serious widthization of signal to there is X-ray diffraction peak number amount in experiment
Problem, this high voltage structures not can determine that.It is that presoma prepares superhard carbon materials that similar situation, which is also occurred in CNT,
In material.So far, it is still the work with challenge that prepared by the carbon material with superhard characteristic.
The content of the invention
The technical problem to be solved in the present invention is to provide one kind and utilizes C60The CNT of doping (is designated as C60@SWNTs)
Or C70The CNT of doping (is designated as C70@SWNTs) the new sp with superhard characteristic is synthesized under elevated pressure conditions for presoma3
The new method of carbon material.
Technical scheme is specific as follows.
A kind of new sp3The high pressure method for preparing of carbon material, with C60@SWNTs or C70@SWNTs are raw material, with diamond pair
Top anvil is pressue device, and sample is loaded into sample cavity, the hard pressure mode of no transmission medium is taken, is forced into and is more than or equal to
Unloaded after 60GPa and be depressed into normal pressure, obtain the new sp with superhard characteristic3Carbon material.
A kind of new sp of the present invention3The high pressure method for preparing of carbon material, more specifically step are:Using diamond to top
Anvil press precompressed rhenium metal piece, thickness reaches 40-60 μm, and takes a diameter of 60-100 μm of aperture as sample in impression centre drill
Product chamber, then by C60@SWNTs or C70@SWNTs samples fill up sample cavity, using diamond be pressure calibration material, take without
The hard pressure mode of any transmission medium is pressurizeed, and when pressure reaches 60GPa-70GPa, is then unloaded and is depressed into normal pressure, had
There is the new sp of superhard characteristic3Carbon material.
A kind of new sp of the present invention3The high pressure method for preparing of carbon material, described C60@SWNTs or C70@SWNTs can be with
Prepared, concretely comprised the following steps by the method for vapor- phase synthesis conventional in the art：From after purification, diameter be distributed as 1.3-
1.5nm single-walled carbon nanotube sample is put in the quartz ampoule of both ends open, is subsequently placed in tube furnace to be warming up to after 450 DEG C and is protected
Holding 30 minutes makes CNT opening；By the CNT and C after opening60Fullerene or C70Fullerene sample in mass ratio 1：2
In the pipe for being respectively charged into U-tube both sides, U-tube is vacuumized using molecular pump, while being equipped with carbon nanotube-sample to U-tube
Side heated, when being evacuated to U-shaped intraductal pressure less than 1 × 10-6U-tube is sealed after Pa, and is positioned over tube furnace
In, heated 2 hours at 650 DEG C, make C60Fullerene or C70Fullerene becomes gaseous state and entered in CNT；By obtained sample
Product are placed in C of the ultrasonic hour removing absorption in carbon nano tube surface in toluene solution60Fullerene or C70Fullerene, after filtering
Sample in Muffle furnace under vacuum environment keep 650 DEG C of calcinings obtain C within 30 minutes60@SWNTs or C70@SWNTs samples.
A kind of new sp3Carbon material, it is characterised in that with following structural formula：
The structure has a monocline, C2/m symmetry, and each primitive unit cell kind includes 18 atoms, all carbon atoms completely with
sp3Hybrid form bonding, constitutes a pair of adjacent ring quilts of the ring of carbon 5 and carbon 7 in the topological structure pattern of 5+6+7 carbon units, structure
The yuan of rings of carbon 6 are surrounded and along b direction of principal axis.
The present invention is with C60@SWNTs or C70@SWNTs are raw material, using diamond anvil cell as pressue device, are prepared with super
The new structure carbon material of hardware features, to after release sample carry out X-ray diffraction (XRD), transmission electron microscope (TEM),
High resolution electron microscope (HRTEM) characterized, it is determined that the sample prepared is the new structure carbon with superhard characteristic
Material.
Beneficial effect：
1st, the present invention obtains the new structure carbon material that can stablize under normal pressure using the method for HIGH PRESSURE TREATMENT；It is prepared
Superhard carbon material has clear and legible X-ray diffraction peak, and sample crystallization is good.
2nd, the present invention need not add temperature variable.
3rd, raw materials used common, the reactant cost of the present invention is low, preparation process is simple and safe.
4th, new structure carbon material prepared by the present invention has excellent mechanical performance.
Brief description of the drawings
Fig. 1 is C70The high resolution electron microscopy photo of@SWNTs samples.
Fig. 2 is C70The Raman spectrum of@SWNTs samples.
Fig. 3 is C60The high resolution electron microscopy photo of@SWNTs samples.
Fig. 4 is C60The Raman spectrum of@SWNTs samples.
Fig. 5 is new sp made from embodiment 13The high resolution electron microscopy photo of carbon material.
Fig. 6 is new sp made from embodiment 13The X-ray diffraction spectrum of carbon material.
Fig. 7 is new sp made from embodiment 23The X-ray diffraction spectrum of carbon material.
Fig. 8 is the X-ray diffraction spectrum for the product that embodiment 3 is obtained.
Fig. 9 is the transmission electron microscope photo for the product that embodiment 4 is obtained.
Figure 10 is new sp made from embodiment 53The high resolution electron microscopy photo of carbon material.
Figure 11 is new sp made from embodiment 53The X-ray diffraction spectrum of carbon material.
Figure 12 is to have prepared new sp in embodiment 13The optical photograph of diamond anvil face after carbon material.
Figure 13 is to have prepared new sp in embodiment 53The optical photograph of diamond anvil face after carbon material.
Embodiment
The present invention is expanded on further with reference to specific embodiment.
Embodiment 1
It is 200 μm of diamond anvil cell precompressed rhenium metal piece using anvil face, and 60 μm of diameter is taken in impression centre drill
Aperture is used as sample cavity.By C70@SWNTs samples fill up sample cavity, using diamond be pressure calibration material, take without appoint
The hard pressure mode of what transmission medium is pressurizeed.When pressure rise is to 70GPa, unloads and be depressed into normal pressure, obtain with superhard characteristic
New carbon, hardness reaches Vickers hardness 90GPa.The electromicroscopic photograph and X-ray diffraction spectrum of obtained new carbon are shown in
Fig. 5 and Fig. 6.
Embodiment 2
Raw material, press and sample cavity be the same as Example 1.By C70@SWNTs samples fill up sample cavity, are pressure using diamond
Material is demarcated, takes the hard pressure mode without any transmission medium to be pressurizeed.When pressure rise is to 60GPa, unloads and be depressed into
Normal pressure, obtains the new carbon with superhard characteristic.The X-ray diffraction spectrum of obtained new carbon is shown in Fig. 7.
Conclusion：When pressurization reaches 60GPa, novel super-hard carbon material is still can obtain after release.
Embodiment 3
Raw material, press and sample cavity be the same as Example 1.By C70@SWNTs samples fill up sample cavity, are pressure using diamond
Material is demarcated, takes the hard pressure mode without any transmission medium to be pressurizeed.When pressure rise is to 50GPa, unloads and be depressed into
Normal pressure, the X-ray diffraction spectrum of obtained product is shown in Fig. 8.
Conclusion：When pressurization reaches 50GPa, the X-ray diffraction peak of release sample is the signal of raw material CNT, it is impossible to
Obtain the new carbon with superhard characteristic.
Embodiment 4
It is 300 μm of diamond anvil cell precompressed T301 steel discs using anvil face, and 100 μm of diameter is taken in impression centre drill
Aperture is used as sample cavity.By C70@SWNTs samples fill up sample cavity, using diamond be pressure calibration material, take without appoint
The hard pressure mode of what transmission medium is pressurizeed.When pressure rise is to 40GPa, unloads and be depressed into normal pressure, the Electronic Speculum of obtained product
Photo is shown in Fig. 9.
Conclusion：When pressurization reaches 40GPa, the product of release keeps tubular structure, is mostly recoverable raw material, it is impossible to
Obtain the new carbon with superhard characteristic.
Embodiment 5：
Using press and sample cavity same as Example 1.By C60@SWNTs samples fill up sample cavity, are using diamond
Pressure calibration material, takes the hard pressure mode without any transmission medium to be pressurizeed.When pressure rise is to 80GPa, unload
Normal pressure is depressed into, the new carbon with superhard characteristic is obtained.Obtained new carbon electromicroscopic photograph and X-ray diffraction spectrum are shown in
Figure 10 and Figure 11.
Above-described embodiment 1 and embodiment 5 use C respectively70@SWNTs and C60Two kinds of original materials of@SWNTs are by side of the invention
After the completion of prepared by method, optical photograph shooting is carried out to the diamond used, as shown in Figure 12,13, there is obvious ring-type on anvil face
Impression, illustrates that the product prepared has superhard characteristic.
Embodiment 6：C used in each embodiment60@SWNTs or C70@SWNTs preparation
From after purification, diameter is distributed as 1.3-1.5nm single-walled carbon nanotube sample and is put in the quartz of both ends open
Guan Zhong, be subsequently placed in tube furnace be warming up to after 450 DEG C keep make CNT opening within 30 minutes；By the CNT after opening
With C70Fullerene sample in mass ratio 1：2 are respectively charged into the pipe of U-tube both sides, using molecular pump at U-tube top end opening
Vacuumize, while being heated to the side equipped with carbon nanotube-sample of U-tube, be less than 1 when being evacuated to U-shaped intraductal pressure
×10-6Seal U-tube melting at the top of U-tube after Pa, and be positioned in tube furnace, heated 2 hours at 650 DEG C, make C70It is rich
Alkene is strangled to become gaseous state and enter in CNT；Obtained sample is placed in toluene solution into ultrasonic hour removing absorption to receive in carbon
The C of nanotube surface70Fullerene, keeps 650 DEG C of calcinings to obtain for 30 minutes in the sample after filtering in Muffle furnace under vacuum environment
C70@SWNTs samples, the high resolution electron microscopy photo and Raman spectrum of sample are as depicted in figs. 1 and 2.By the C in the present embodiment70
Fullerene changes C into60Fullerene, other conditions are constant, finally give C60@SWNTs samples, the high resolution electron microscopy photo of sample
With Raman spectrum as shown in Figure 3 and Figure 4.
Claims (4)
1. a kind of new sp3The high pressure method for preparing of carbon material, with C60@SWNTs or C70@SWNTs are raw material, with diamond to top
Anvil is pressue device, and sample is loaded into sample cavity, takes the hard pressure mode of no transmission medium, is forced into more than or equal to 60GPa
After unload and be depressed into normal pressure, obtain the new sp with superhard characteristic3Carbon material.
2. a kind of new sp according to claim 13The high pressure method for preparing of carbon material, it is characterised in that specific step
It is:Using diamond anvil cell press precompressed rhenium metal piece, thickness reaches 40-60 μm, and takes a diameter of 60- in impression centre drill
100 μm of aperture is as sample cavity, then by C60@SWNTs or C70@SWNTs samples fill up sample cavity, are pressure using diamond
Material is marked, takes the hard pressure mode without any transmission medium to be pressurizeed, when pressure reaches 60GPa-70GPa, then
Unload and be depressed into normal pressure, obtain the new sp with superhard characteristic3Carbon material.
3. a kind of new sp according to claim 1 or 23The high pressure method for preparing of carbon material, it is characterised in that described
C60@SWNTs or C70@SWNTs are prepared by the following method：From after purification, diameter be distributed as 1.3-1.5nm list
Wall carbon nano tube sample is put in the quartz ampoule of both ends open, is subsequently placed in tube furnace and is warming up to holding 30 minutes after 450 DEG C
Make CNT opening；By the CNT and C after opening60Fullerene or C70Fullerene sample in mass ratio 1：2 are respectively charged into
In the pipe of U-tube both sides, U-tube is vacuumized using molecular pump, while entering to the side equipped with carbon nanotube-sample of U-tube
Row heating, is less than 1 × 10 when being evacuated to U-shaped intraductal pressure-6U-tube is sealed after Pa, and is positioned in tube furnace, 650 DEG C
Lower heating 2 hours, makes C60Fullerene or C70Fullerene becomes gaseous state and entered in CNT；Obtained sample is placed in first
Ultrasonic hour removes C of the absorption in carbon nano tube surface in benzole soln60Fullerene or C70Fullerene, the sample after filtering is existed
650 DEG C of calcinings are kept to obtain C in 30 minutes under vacuum environment in Muffle furnace60@SWNTs or C70@SWNTs samples.
4. new sp prepared by a kind of method by claim 13Carbon material, it is characterised in that with following structural formula：
The structure has monocline, C2/m symmetry, and each primitive unit cell kind includes 18 atoms, and all carbon atoms are completely with sp3It is miscellaneous
Change mode bonding, constitutes the topological structure pattern of 5+6+7 carbon units, and a pair adjacent rings of carbon 5 and the ring of carbon 7 are by 6 yuan of carbon in structure
Ring is surrounded and along b direction of principal axis.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330006A (en) * | 2019-08-05 | 2019-10-15 | 燕山大学 | The Gradia carbon and preparation method thereof of novel sp2-sp3 hydridization |
| CN113896533A (en) * | 2021-09-26 | 2022-01-07 | 吉林大学 | Millimeter-scale sp3Amorphous carbon block and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098916A (en) * | 2005-01-13 | 2008-01-02 | 金文申有限公司 | Composite materials containing carbon nanoparticles |
| WO2016134108A1 (en) * | 2015-02-18 | 2016-08-25 | AL FAHIM, Mohamed | A novel carbon allotrope |
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2017
- 2017-03-06 CN CN201710127353.1A patent/CN106976857B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101098916A (en) * | 2005-01-13 | 2008-01-02 | 金文申有限公司 | Composite materials containing carbon nanoparticles |
| WO2016134108A1 (en) * | 2015-02-18 | 2016-08-25 | AL FAHIM, Mohamed | A novel carbon allotrope |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110330006A (en) * | 2019-08-05 | 2019-10-15 | 燕山大学 | The Gradia carbon and preparation method thereof of novel sp2-sp3 hydridization |
| CN113896533A (en) * | 2021-09-26 | 2022-01-07 | 吉林大学 | Millimeter-scale sp3Amorphous carbon block and preparation method thereof |
| CN113896533B (en) * | 2021-09-26 | 2023-04-14 | 吉林大学 | Millimeter-scale sp 3 Amorphous carbon block and method for producing same |
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