CN106976857B - A kind of novel sp3Carbon material and its high pressure method for preparing - Google Patents

A kind of novel sp3Carbon material and its high pressure method for preparing Download PDF

Info

Publication number
CN106976857B
CN106976857B CN201710127353.1A CN201710127353A CN106976857B CN 106976857 B CN106976857 B CN 106976857B CN 201710127353 A CN201710127353 A CN 201710127353A CN 106976857 B CN106976857 B CN 106976857B
Authority
CN
China
Prior art keywords
sample
carbon
swnts
novel
pressure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201710127353.1A
Other languages
Chinese (zh)
Other versions
CN106976857A (en
Inventor
刘冰冰
姚明光
杨西贵
刘世杰
刘然
吴香英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN201710127353.1A priority Critical patent/CN106976857B/en
Publication of CN106976857A publication Critical patent/CN106976857A/en
Application granted granted Critical
Publication of CN106976857B publication Critical patent/CN106976857B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A kind of novel sp of the invention3Carbon material and its high pressure method for preparing belong to the technical field of superhard carbon material preparation.With C60@SWNTs or C70@SWNTs is that sample using diamond anvil cell as pressurizing device is packed into sample cavity by raw material, takes the hard pressure mode of no transmission medium, is forced into and is depressed into normal pressure more than or equal to unloading after 60GPa, obtains the novel sp with superhard characteristic3Carbon material.The raw materials used in the present invention is common, reactant is at low cost, preparation process is simple and safe, it does not need that temperature variable is 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 under normal pressure.

Description

A kind of novel sp3Carbon material and its high pressure method for preparing
Technical field
The invention belongs to sp3The technical field of carbon material preparation, and in particular to utilize C60The carbon nanotube or C of doping70It mixes Miscellaneous carbon nanotube is the new method that raw material has the superhard carbon material of new structure by the method preparation of high pressure.
Background technique
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, carbon nanotube and graphene, their excellent physics, chemical property have in every field It is widely applied.The property of material depends on its structure, therefore designing synthesis, there is new structural carbon material to cause people The carbon material that strong scientific interest, especially synthesis have superhard characteristic.
Currently, people using different carbon nanomaterials as presoma, explored using the means of high pressure there may be Superhard carbon phase.Using graphite as raw material in experiment, synthesis under high pressure has a cenotype of superhard characteristic, however this cenotype It can not be intercepted and captured in normal pressure, simultaneously because that there is X-ray diffraction peak number amounts is few, the weaker and serious widthization of signal in experiment Problem, this high voltage structures not can determine that.It is the superhard carbon materials of precursor preparation that similar situation, which is also occurred in carbon nanotube, In material.So far, the carbon material preparation with superhard characteristic is still a job with challenge.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of using C60The carbon nanotube of doping (is denoted as C60@SWNTs) Or C70The carbon nanotube of doping (is denoted as C70@SWNTs) it is that presoma synthesizes the novel sp with superhard characteristic under high pressure3 The new method of carbon material.
Technical solution of the present invention is specific as follows.
A kind of novel sp3The high pressure method for preparing of carbon material, with C60@SWNTs or C70@SWNTs is raw material, with diamond pair Top anvil is pressurizing device, and sample is packed into sample cavity, the hard pressure mode of no transmission medium is taken, is forced into and is greater than or equal to It is unloaded after 60GPa and is depressed into normal pressure, obtain the novel sp with superhard characteristic3Carbon material.
A kind of novel sp of the invention3The high pressure method for preparing of carbon material, more specific step are:Using diamond to top Anvil press precompressed rhenium metal piece, thickness reaches 40-60 μm, and taking diameter in impression centre drill is 60-100 μm of aperture conduct Sample cavity, then by C60@SWNTs or C70@SWNTs sample fills up sample cavity, is pressure calibration material using diamond, takes and do not add Add the hard pressure mode of any transmission medium to pressurize, when pressure reaches 60GPa-70GPa, then unloads and be depressed into normal pressure, obtain Novel sp with superhard characteristic3Carbon material.
A kind of novel sp of the invention3The high pressure method for preparing of carbon material, the C60@SWNTs or C70@SWNTs can be with It is prepared by the method for common vapor- phase synthesis in the art, the specific steps are：Select after purification, diameter be distributed as 1.3- The single-walled carbon nanotube sample of 1.5nm is put in the quartz ampoule of both ends open, is subsequently placed in tube furnace after being warming up to 450 DEG C and is protected Holding 30 minutes makes carbon nanotube be open；By the carbon nanotube and C after opening60Fullerene or C70Fullerene sample in mass ratio 1：2 It is respectively charged into the pipe of U-tube two sides, is vacuumized U-tube using molecular pump, while carbon nanotube-sample is equipped with 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 placed in tube furnace In, it is heated 2 hours at 650 DEG C, makes C60Fullerene or C70Fullerene becomes gaseous state and enters in carbon nanotube；By sample obtained Product are placed in the C that ultrasonic hour removing in toluene solution is adsorbed on carbon nano tube surface60Fullerene or C70Fullerene, after filtering Sample keep 650 DEG C of calcinings to obtain C in 30 minutes under vacuum environment in Muffle furnace60@SWNTs or C70@SWNTs sample.
A kind of novel sp3Carbon material, it is characterised in that have following structural formula：
The structure have monocline, C2/m symmetry, each primitive unit cell kind include 18 atoms, all carbon atoms completely with sp3Hybrid form bonding constitutes the topological structure mode of 5+6+7 carbon unit, a pair of adjacent 7 ring quilt of 5 ring of carbon and carbon in structure 6 member ring of carbon surrounds and along b axis direction.
The present invention is with C60@SWNTs or C70@SWNTs is raw material, and using diamond anvil cell as pressurizing device, preparation has 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, determine that the sample prepared is the new structure carbon with superhard characteristic Material.
Beneficial effect：
1, the present invention using HIGH PRESSURE TREATMENT method obtain can be stable under normal pressure new structure carbon material；It is prepared Superhard carbon material has clear and legible X-ray diffraction peak, and sample crystallization is good.
2, the present invention does not need that temperature variable is added.
3, the raw materials used in the present invention is common, reactant is at low cost, preparation process is simple and safe.
4, new structure carbon material prepared by the present invention has excellent mechanical performance.
Detailed description of the invention
Fig. 1 is C70The high resolution electron microscopy photo of@SWNTs sample.
Fig. 2 is C70The Raman spectrum of@SWNTs sample.
Fig. 3 is C60The high resolution electron microscopy photo of@SWNTs sample.
Fig. 4 is C60The Raman spectrum of@SWNTs sample.
Fig. 5 is novel sp made from embodiment 13The high resolution electron microscopy photo of carbon material.
Fig. 6 is novel sp made from embodiment 13The X-ray diffraction spectrum of carbon material.
Fig. 7 is novel 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 obtains.
Fig. 9 is the transmission electron microscope photo for the product that embodiment 4 obtains.
Figure 10 is novel sp made from embodiment 53The high resolution electron microscopy photo of carbon material.
Figure 11 is novel sp made from embodiment 53The X-ray diffraction spectrum of carbon material.
Figure 12 is that novel sp has been prepared in embodiment 13The optical photograph of diamond anvil face after carbon material.
Figure 13 is that novel sp has been prepared in embodiment 53The optical photograph of diamond anvil face after carbon material.
Specific embodiment
It is next combined with specific embodiments below that the present invention is further explained.
Embodiment 1
The diamond anvil cell precompressed rhenium metal piece for being 200 μm using anvil face, and 60 μm of diameter are taken in impression centre drill Aperture is as sample cavity.By C70@SWNTs sample fills up sample cavity, is pressure calibration substance using diamond, takes not add and 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 that there is superhard characteristic New carbon, hardness reaches Vickers hardness 90GPa.The electromicroscopic photograph and X-ray diffraction spectrum of new carbon obtained are shown in Fig. 5 and Fig. 6.
Embodiment 2
Raw material, press and sample cavity are the same as embodiment 1.By C70@SWNTs sample fills up sample cavity, is pressure using diamond Substance is demarcated, the hard pressure mode for not adding any transmission medium is taken to pressurize.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 new carbon obtained is shown in Fig. 7.
Conclusion：When pressurization reaches 60GPa, novel super-hard carbon material still can be obtained after release.
Embodiment 3
Raw material, press and sample cavity are the same as embodiment 1.By C70@SWNTs sample fills up sample cavity, is pressure using diamond Substance is demarcated, the hard pressure mode for not adding any transmission medium is taken to pressurize.When pressure rise is to 50GPa, unloads and be depressed into The X-ray diffraction spectrum of normal pressure, 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 carbon nanotube, can not Obtain the new carbon with superhard characteristic.
Embodiment 4
The diamond anvil cell precompressed T301 steel disc for being 300 μm using anvil face, and 100 μm of diameter are taken in impression centre drill Aperture as sample cavity.By C70@SWNTs sample fills up sample cavity, is pressure calibration substance using diamond, takes and do not add The hard pressure mode of any transmission medium is pressurizeed.When pressure rise is to 40GPa, unloads and be depressed into normal pressure, the electricity of product obtained Mirror photo is shown in Fig. 9.
Conclusion：When pressurization reaches 40GPa, it is mostly recoverable raw material that the product of release, which keeps tubular structure, can not Obtain the new carbon with superhard characteristic.
Embodiment 5：
Using press and sample cavity same as Example 1.By C60@SWNTs sample fills up sample cavity, is using diamond Pressure calibration substance takes the hard pressure mode for not adding any transmission medium to pressurize.When pressure rise is to 80GPa, unload It is depressed into normal pressure, obtains the new carbon with superhard characteristic.New carbon electromicroscopic photograph and X-ray diffraction spectrum obtained 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 press side of the invention After the completion of method preparation, optical photograph shooting is carried out to the diamond used, is had as shown in Figure 12,13, on anvil face obvious cyclic annular Impression illustrates that the product of preparation has superhard characteristic.
Embodiment 6：C used in each embodiment60@SWNTs or C70The preparation of@SWNTs
Select after purification, diameter is distributed as the single-walled carbon nanotube sample of 1.3-1.5nm and is put in the quartz of both ends open Guan Zhong is subsequently placed in tube furnace after being warming up to 450 DEG C and keeps making carbon nanotube be open in 30 minutes；By the carbon nanotube after opening With C70Fullerene sample in mass ratio 1：2 are respectively charged into the pipe of U-tube two sides, using molecular pump from U-tube top end opening It vacuumizes, while the side equipped with carbon nanotube-sample of U-tube is heated, when being evacuated to U-shaped intraductal pressure less than 1 ×10-6It seals U-tube melting at the top of U-tube after Pa, and is placed in tube furnace, heated 2 hours at 650 DEG C, make C70 Fullerene becomes gaseous state and enters in carbon nanotube；Sample obtained is placed in toluene solution ultrasonic hour removing and is adsorbed on carbon The C of nanotube surface70Fullerene keeps filtered sample 650 DEG C of calcinings 30 minutes in Muffle furnace under vacuum environment To C70@SWNTs sample, the high resolution electron microscopy photo and Raman spectrum of sample are as depicted in figs. 1 and 2.It will be in the present embodiment C70Fullerene changes C into60Fullerene, other conditions are constant, finally obtain C60The high resolution electron microscopy of@SWNTs sample, sample shines Piece and Raman spectrum are as shown in Figure 3 and Figure 4.

Claims (3)

1. a kind of novel sp3The high pressure method for preparing of carbon material, with C60@SWNTs or C70@SWNTs is raw material, with diamond to top Anvil is pressurizing device, and sample is packed 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 novel sp with superhard characteristic3Carbon material；Specific step is:Utilize diamond anvil cell pressure Machine precompressed rhenium metal piece, thickness reach 40-60 μm, and take aperture that diameter is 60-100 μm as sample in impression centre drill Chamber, then by C60@SWNTs or C70@SWNTs sample fills up sample cavity, is pressure calibration material using diamond, takes not add and appoint The hard pressure mode of what transmission medium is pressurizeed, and when pressure reaches 60GPa-70GPa, is then unloaded and is depressed into normal pressure, is had The novel sp of superhard characteristic3Carbon material.
2. a kind of novel sp according to claim 13The high pressure method for preparing of carbon material, which is characterized in that the C60@ SWNTs or C70@SWNTs is prepared by the following method：Select after purification, diameter be distributed as the single wall carbon of 1.3-1.5nm Nanotube sample is put in the quartz ampoule of both ends open, is subsequently placed in tube furnace after being warming up to 450 DEG C and is kept making carbon in 30 minutes Nanometer tube opening；By the carbon nanotube and C after opening60Fullerene or C70Fullerene sample in mass ratio 1：2 be respectively charged into it is U-shaped In the pipe of pipe two sides, U-tube is vacuumized using molecular pump, while the side equipped with carbon nanotube-sample of U-tube is carried out Heating, when being evacuated to U-shaped intraductal pressure less than 1 × 10‐6U-tube is sealed after Pa, and is placed in tube furnace, at 650 DEG C Heating 2 hours, makes C60Fullerene or C70Fullerene becomes gaseous state and enters in carbon nanotube；Sample obtained is placed in toluene Ultrasonic hour removes the C for being adsorbed on carbon nano tube surface in solution60Fullerene or C70Fullerene, by filtered sample in horse Not 650 DEG C of calcinings is kept to obtain C in 30 minutes in furnace under vacuum environment60@SWNTs or C70@SWNTs sample.
3. a kind of novel sp prepared by method of claim 13Carbon material, it is characterised in that have 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 mode of 5+6+7 carbon unit, and a pair of adjacent 5 ring of carbon and 7 ring of carbon are by 6 yuan of carbon in structure Ring surrounds and along b axis direction.
CN201710127353.1A 2017-03-06 2017-03-06 A kind of novel sp3Carbon material and its high pressure method for preparing Expired - Fee Related CN106976857B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710127353.1A CN106976857B (en) 2017-03-06 2017-03-06 A kind of novel sp3Carbon material and its high pressure method for preparing

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710127353.1A CN106976857B (en) 2017-03-06 2017-03-06 A kind of novel sp3Carbon material and its high pressure method for preparing

Publications (2)

Publication Number Publication Date
CN106976857A CN106976857A (en) 2017-07-25
CN106976857B true CN106976857B (en) 2018-11-27

Family

ID=59338636

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710127353.1A Expired - Fee Related CN106976857B (en) 2017-03-06 2017-03-06 A kind of novel sp3Carbon material and its high pressure method for preparing

Country Status (1)

Country Link
CN (1) CN106976857B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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
CN113896533B (en) * 2021-09-26 2023-04-14 吉林大学 Millimeter-scale sp 3 Amorphous carbon block and method for producing same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK1836239T3 (en) * 2005-01-13 2009-01-19 Cinv Ag Composite materials containing carbon nanoparticles
US20180265361A1 (en) * 2015-02-18 2018-09-20 Larry Burchfield Novel Carbon Allotrope

Also Published As

Publication number Publication date
CN106976857A (en) 2017-07-25

Similar Documents

Publication Publication Date Title
Zhang et al. Synthesis of aluminum nitride nanowires from carbon nanotubes
Yu et al. Diamond nanowires: fabrication, structure, properties, and applications
Ren et al. Aligned carbon nanotubes: physics, concepts, fabrication and devices
Qikun et al. Hydrogen storage by carbon nanotube and their films under ambient pressure
CN106976857B (en) A kind of novel sp3Carbon material and its high pressure method for preparing
Liang et al. Growth and characterization of TiC nanorods activated by nickel nanoparticles
Wang et al. SiC nanowires synthesized by rapidly heating a mixture of SiO and arc-discharge plasma pretreated carbon black
Zhong et al. Large-scale fabrication and utilization of novel hexagonal/turbostratic composite boron nitride nanosheets
Rahman et al. Synthesis and optical characterization of carbon nanotube arrays
Srivastava et al. Vacancy-mediated mechanism of nitrogen substitution in carbon nanotubes
CN110357074A (en) A kind of nano-onions carbon porous blocks material and preparation method thereof
Bokhonov et al. Formation of encapsulated molybdenum carbide particles by annealing mechanically activated mixtures of amorphous carbon with molybdenum
WO2004108593A1 (en) Nano-fiber or nano-tube comprising v group transition metal dichalcogenide crystals, and method for preparation thereof
CN112978715A (en) Carbon nano tube using alcohol solvent as carbon source and preparation method thereof
Aasmundtveit et al. Direct integration of carbon nanotubes in Si microstructures
CN102815698A (en) Method for synthesizing two-dimensional carbide through template restriction
Kharlamova et al. Diameter and metal-dependent growth properties of inner tubes inside metallocene-filled single-walled carbon nanotubes
Saikiran et al. Electronic excitation induced modifications in elongated iron nanoparticle encapsulated multiwalled carbon nanotubes under ion irradiation
KR101679693B1 (en) Method for preparing carbon nanotube and hybrid carbon nanotube composite
JP3890408B2 (en) Method for producing boron nitride nanotubes for hydrogen storage
Yen et al. Si–O–C nanotubes from pyrolyzing polycarbosilane in a mesoporous template
Chen et al. Synthesis of high-purity SiC nanowires via catalyst-free pyrolysis of SiO2/Si and sponge-like graphene oxide
Jain et al. Solid‐state synthesis of well‐defined carbon nanocapsules from organometallic precursors
CN101525767B (en) One-dimensional nano single-crystal tubular silicon carbide as well as preparation method
KR101626936B1 (en) Carbon nanofibers with sharp tip structure and carbon nanofibers growth method using of palladium catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20181127

Termination date: 20200306

CF01 Termination of patent right due to non-payment of annual fee