CN100537411C - Nanometer carbon ball with heteroatom and its preparation method - Google Patents
Nanometer carbon ball with heteroatom and its preparation method Download PDFInfo
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- CN100537411C CN100537411C CNB2004100568139A CN200410056813A CN100537411C CN 100537411 C CN100537411 C CN 100537411C CN B2004100568139 A CNB2004100568139 A CN B2004100568139A CN 200410056813 A CN200410056813 A CN 200410056813A CN 100537411 C CN100537411 C CN 100537411C
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- heteroatomic
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- carbon microsphere
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 125000005842 heteroatom Chemical group 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract 2
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 61
- 239000010439 graphite Substances 0.000 claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 125000004429 atom Chemical group 0.000 claims abstract description 22
- 150000001721 carbon Chemical group 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000004005 microsphere Substances 0.000 claims description 61
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000010891 electric arc Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001247 metal acetylides Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052776 Thorium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052770 Uranium Inorganic materials 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910021386 carbon form Inorganic materials 0.000 claims description 2
- 150000002829 nitrogen Chemical class 0.000 claims 3
- 239000002131 composite material Substances 0.000 abstract description 5
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 description 6
- -1 and for example Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011796 hollow space material Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002088 nanocapsule Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical compound O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- DAIXJPRSBARELR-UHFFFAOYSA-N [N].[B]=O Chemical compound [N].[B]=O DAIXJPRSBARELR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 230000009149 molecular binding Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a nanometer carbon sphere containing heteroatom and the preparation. The nanometer carbon sphere has a closed structure and no less than one layer of graphite layer, the graphite layer expressed by chemical formula C(D)x, among, C representing carbon atom, having a sp2 composite orbit, D representing an atom from triels or pentels, the atom bonding to carbon atom, x representing a digit among 0.0001 to 0.1. The nanometer carbon sphere can be hollow, in which metal or metallic compound can be filled.
Description
Technical field
The present invention is about a kind of nano carbon microsphere, particularly has heteroatomic nano carbon microsphere and a method for making thereof about a kind of, and nano carbon microsphere can be hollow, and has metal, alloy or metallic compound at hollow space.
Background technology
The polyhedron carbon that nano carbon microsphere is made up of with the structure of ball in the ball the multilayer graphite linings bunch.Particle diameter is mainly 30-40nm between 1-100nm.Its inside can be hollow (hollownanocapsules) or fills metal (metal filled nanocapsules).The graphite linings of nano carbon microsphere shell, central part all are hexatomic rings, in the corner or turnover partly then form by five-membered ring, each carbon atom is all sp
2Structure.The special multilayer graphite-structure of nano carbon microsphere makes it have special advantages such as heat conductivity, electric conductivity, intensity are good, chemical stabilization, high surface, Stability Analysis of Structures, electromagnetic interference (EMI) capture-effect.The graphite shell of nano carbon microsphere forms a guard space; avoid inner metallic particles and the gathering of other metallic particles or diffuse to other place or be subjected to environmental oxidation destroying, character such as its inner nanometer metal structure and quantum effect are maintained.The chemical modification upgrading can be carried out in nano carbon microsphere graphite shell surface, make in solvent dispersedly improve, with the lifting of functions such as other molecular binding and conductive and heat-conductive.
Yet, the report of the heteroatomic nano carbon microsphere that mixes had not been arranged on the document.The report of boronation nitrogen ball (boron nitride (BN) fullerene nanomaterials) was once arranged, and it is a kind of nano material of tool core-shell structure, and shell is entirely boronation nitrogen (BN) or boron monoxide nitrogen (B-C-N), boron monoxide (BC
3), C
3N
4The crystal structure of being formed, but not the graphite-structure of carbon-coating.Again, the research of mixing N on onion carbon granules or CNT was arranged once, however the formed layer structure thing of this type of CNx, and its shell is not a polyhedral structure.
Summary of the invention
Main purpose of the present invention provides a kind of nano carbon microsphere, its doping hetero atom, and can outside having the advantage of known nano carbon microsphere, have more the characteristic in polyelectron or electric hole, and be easy to disperse to utilize, can be used in chemical sensing, chemisorbed material, conductive and heat-conductive material or light absorber.
Another purpose of the present invention provides a kind of method of making above-mentioned nano carbon microsphere, can make above-mentioned nano carbon microsphere with multiple advantages.
Have heteroatomic nano carbon microsphere for reaching above-mentioned purpose, the invention provides, it has the graphite linings of one deck at least structure of sealing, and the composition of this graphite linings is with chemical formula C (D)
xRepresent that wherein, C represents carbon atom, has sp
2The hybridized orbit structure, D is the atom of the 3rd or five families, forms bond with carbon atom, as forming shell at shell C-N jointly in SP2 covalent bond bond mode; X is 0.0001 to 0.1 numeral.
Provided by the invention have a heteroatomic nano carbon microsphere, and this graphite linings is the polyhedral structure that hexatomic ring and five-membered ring constitute, and wherein five-membered ring is positioned at polyhedral corner.
Provided by the invention have a heteroatomic nano carbon microsphere, and it has 12 corners.
Provided by the invention have a heteroatomic nano carbon microsphere, and wherein D is nitrogen, phosphorus or boron.
Provided by the invention have a heteroatomic nano carbon microsphere, and wherein nitrogen, phosphorus or boron and carbon form pentacyclic bond.
According to another feature of the present invention, of the present invention have a heteroatomic nano carbon microsphere, further can comprise being selected from following filler: metal, metal oxide, metal carbides (metal carbide), metal sulfide, metal nitride, metal boride, and metal alloy.
Method according to manufacturing nano carbon microsphere of the present invention, comprise an electric arc reaction chamber with graphite anode and graphite cathode is provided, and in this electric arc reaction chamber, feed an inert gas, wherein this graphite anode contains the compound and the graphite of the 3rd or five family's atoms, and the 3rd or five family's atom contents are 2 to 5 moles of % of carbon content; Apply a voltage between above-mentioned negative electrode and the anode with a pulse current, and produce the arc discharge reaction; And the sedimental step that is collected in graphite cathode.
According to another feature of the present invention, the method of manufacturing nano carbon microsphere of the present invention, comprise an electric arc reaction chamber with graphite anode and graphite cathode is provided, and in this electric arc reaction chamber, feed an inert gas, wherein this graphite anode contains compound, metal-powder, and the graphite of the 3rd or five family's atoms, the 3rd or five family's atom contents are 2 to 5 moles of % of carbon content, and this metal-powder atom content is 1 to 5 mole of % of carbon content; Apply a voltage between above-mentioned negative electrode and the anode with a pulse current, to produce the arc discharge reaction; And the sedimental step that is collected in graphite cathode.
Shell with heteroatomic nano carbon microsphere provided by the invention is the polyhedral structure of complete closure, this point is identical with the nano carbon microsphere of full carbon, but in the outside graphite shell of the polyhedron carbon of this nano carbon microsphere bunch, the carbon atom of part is replaced by the element atom of nitrogen (N) or boron (B) or phosphorus (P) grade in an imperial examination three or five families, then be different from general nano carbon microsphere, as shown in Figure 1.Make the graphite shell of original pure carbon structure have the characteristic in polyelectron or electric hole, and become a kind of nano carbon microsphere of tool three, five family's characteristics.There is a spot of carbon to be replaced on the nano carbon microsphere graphite linings by for example nitrogen, boron or phosphorus, and six ring or five rings structures of unlikely change graphite, each atom still is sp on it
2(hetero atom that comprises doping) hybridized orbit structure still has the characteristic of class graphite and the structure of many unsaturated double bonds.Because N or B atom can be inclined to sp
3Configuration, therefore, hetero atom appears at nano carbon microsphere polyhedron corner can be the most stable.For example, the inventor finds in experiment, and the assorted element N that is mixed mainly can appear at the five-membered ring position of polyhedron graphite shell corner.By inferring in theory, electron rich N can be inclined to sp
3Configuration, therefore appearing at the corner can be the most stable.This kind appears at the N of polyhedron graphite linings corner five-membered ring position, and be different fully with other six-membered ring structure.The number of corner for example has 12, but is not limited to this.In addition, having heteroatomic nano carbon microsphere surface and only have a kind of three races hetero atom or the 5th family's hetero atom, is not the structure that possesses the assorted element of two kinds of differences simultaneously.
Provided by the invention have a heteroatomic nano carbon microsphere, has the graphite linings of one deck at least structure of sealing.If with the composition of this graphite linings with chemical formula C (D)
xRepresent that then C represents to have sp
2The carbon atom of hybridized orbit.D represents the atom of the 3rd or five families, and for example, nitrogen, phosphorus or boron form pentacyclic bond with a plurality of carbon atoms, and this has more the turning point of polyhedral in present carbon ball.The atom content of the 3rd or five families in the content of carbon atom it, account for 0.01 to 10% (mol ratio or atom number than), that is x is 0.0001 to 0.1, is preferably 0.005 to 0.05, is more preferred from 0.01 to 0.02 numeral.
Provided by the invention have a heteroatomic nano carbon microsphere, can be hollow shape, and external diameter can be 1 to 100nm, is preferably 30 to 40nm.Perhaps, have the graphite linings of sealing more than two layers, constitute the structure of ball in the ball.Hollow space can have filler, and for example, metal, metal oxide, metal carbides (metal carbide), metal sulfide, metal nitride, metal boride or metal alloy are positioned at this hollow space, and content can be 0.1wt% to 99wt%.Metal can be such as but not limited to Sc, V, Cr, Fe, Co, Ni, Y, Zr, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ta, Os, Ir, Pt, Au, Th, U or its combination.
The method that manufacturing has heteroatomic nano carbon microsphere mainly is to reach with the method for arc discharge (arc discharge), comprises the following steps:
At first, provide an electric arc reaction chamber with graphite anode and graphite cathode.Graphite anode contains the compound and the graphite of the 3rd or five family's atoms.The compound of the 3rd or five family's atoms can be such as but not limited to melamine, ammonium chloride, B
4C, B
2O
3, or P
2O
5Content ratio is calculated with the 3rd in the compound or five family's atoms, makes the amount of the 3rd or five family's atoms, in molal quantity it, be 2 to 5% of carbon atom total amount in the graphite anode.When desire is made hollow space and is comprised the nano carbon microsphere of metal etc., can make graphite anode comprise compound, metal-powder, and the graphite of the 3rd or five family's atoms, wherein the amount of the 3rd or five family's atoms is 2 to 5 moles of % of carbon atom total amount, and the amount of this metal-powder atom is 1 to 5 mole of % of the amount of carbon atom.In addition, the compound of the 3rd or five family's atoms comprises metal oxide, metal carbides (metal carbide), metal sulfide, metal nitride or metal boride.
Employed graphite cathode is then constituted by graphite.
In the electric arc reaction chamber, feed inert gas.The flow velocity of inert gas can be controlled in 10 to 200mm
3/ min preferablely is controlled at 30 to 120mm
3/ min.Be applicable to that inert gas of the present invention includes but not limited to: helium, argon gas, nitrogen etc.The pressure of electric arc reaction chamber can be controlled in 0.1 to 5 atmospheric pressure, preferable being controlled between 1 to 2 atmospheric pressure.
Then, apply a voltage between above-mentioned negative electrode and the anode, to produce the arc discharge reaction with a pulse current.The frequency range of pulse current is between 0.01 to 1000Hz.The controlled amount of electric current is built in 50 to 800 amperes, and the voltage between the electrode is controlled at 10 to 30 volts scope approximately.
After carrying out the arc discharge reaction, on negative carbon, can obtain product.Can be further purified, crude product is scattered in the solution, separate and purifying with CNT with the method for filtration chromatography nano carbon microsphere again different scale in the solution.
Provided by the invention have a heteroatomic nano carbon microsphere, because of having the 3rd or group-v element, characteristic with polyelectron or electric hole, and the nano carbon microsphere that generally only has carbon atom is easy to disperse to utilize, for example be scattered in easily that water, alcohols, chloroform, tetrahydrochysene are muttered, in the phenylamino solution, and can be favourable be applied to chemical sensing, chemisorbed material, conductive and heat-conductive material or light absorber etc.
Description of drawings
Fig. 1 is for having the layer structure schematic diagram of heteroatomic nano carbon microsphere in the specific embodiment of the invention.
Fig. 2 is for having the energy scatter spectra mensuration figure of heteroatomic nano carbon microsphere in the specific embodiment of the invention.
Fig. 3 is for having the SEM photo of heteroatomic nano carbon microsphere in the specific embodiment of the invention.
Fig. 4 is for having the TEM photo of heteroatomic nano carbon microsphere in the specific embodiment of the invention.
The specific embodiment
For above and other objects of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, be described in detail below:
Respectively with about 15 gram melamines (melamine) or 10 gram NH
4Cl mixes about 200 gram graphite powders, and the mol ratio of controlling its nitrogen content and carbon total amount is 2 to 5%, then the pressed by powder of mixing is become nitrogenous compound bar.With a pure graphite rod is negative electrode, and the nitrogenous compound bar of gained is an anode, and the graphite rod diameter is 1cm, and length about 8 places the electric arc reaction chamber to 10cm, carries out the arc discharge reaction.Arc discharge condition is: in flow-control in 60 to 90mm
3Under the Ar gas of/min (the about 1.2atm of pressure), with the pulse direct current of about 100Hz frequency, about 20 volts with about 120 amperes condition under carry out the arc discharge reaction.React and stop arc discharge after 30 minutes, can get deposit on negative carbon, deposit length about 3 is to 4cm, and diameter is approximately identical with carbon-point, cuts deposit, can obtain the crude product of black powder in its core, totally 10 restrains.
Identify with sweep electron microscope (SEM) and penetration type electron micro-(TEM) and to learn the nano carbon microsphere (N-doped carbon nanocapsule) that contains 80% the graininess doping nitrogen of having an appointment in the product and about 20% short CNT, and a spot of carbon granules.(SEM figure as shown in Figure 3)
Identify this crude product with energy dispersed light spectrometer (energy disperse X-ray (being called for short EDX)), obtaining this crude product energy scatter spectra is as shown in Figure 2.The nitrogen of this crude product (N) content is about 1.25%, but because of nitrogen (14) is close with carbon (12) atomic weight, so its signal almost overlaps together.And the size of signal depends on the size of relative amount, occupies the majority with carbon content in this case material, so just is difficult for seeing the amount that draws nitrogen on the collection of illustrative plates.
Crude product is scattered in the solution of water and methyl alcohol 1:1, with the filtration chromatography method solution separation and purification is gone out the nitrogenous nano carbon microsphere and the CNT of different scale again.
Product is observed the position of metal adsorption down again with after the ferric ion solutions dyeing in transmission electron microscopy (TEM), the position that iron ion can be adsorbed in N as shown in Figure 4.Photo shows the position of most metal adsorption in graphite shell corner, represents that electron rich N can be inclined to the five-membered ring position that appears at polyhedron graphite shell corner.
Repeat step, but change with 5 gram B as embodiment 1
4C (or 10 gram B
2O
3) mix the composite stone inker that 200 gram graphite powders are pressed into boracic (B), make nano carbon microsphere with boron atom.
Repeat step, but change with 10 gram P as embodiment 1
2O
5Mix the composite stone inker that 200 gram graphite powders are pressed into phosphorous (P), make nano carbon microsphere with phosphorus atoms.
Repeat step as embodiment 1, but manufacturing contain N or contain B, when containing the composite stone inker of P, further mix the metal-powder (being mainly Fe) of about 5mol%, comprise the heteroatomic composite stone inker of metal and N, B or P, make each and metal filled have a heteroatomic nano carbon microsphere to make.
Claims (14)
1, a kind of have a heteroatomic nano carbon microsphere, and it has the graphite linings of one deck at least structure of sealing, and the composition of this graphite linings is with chemical formula C (D)
xRepresent that wherein, C represents carbon atom, has sp
2The hybridized orbit structure, D is nitrogen, phosphorus or boron atom, forms bond with carbon atom, x is 0.0001 to 0.1 numeral.
2, as claimed in claim 1 have a heteroatomic nano carbon microsphere, and this graphite linings is the polyhedral structure that hexatomic ring and five-membered ring constitute, and wherein five-membered ring is positioned at polyhedral corner.
3, according to claim 2 have a heteroatomic nano carbon microsphere, and it has 12 corners.
4, according to claim 1 have a heteroatomic nano carbon microsphere, and wherein nitrogen, phosphorus or boron and carbon form pentacyclic bond.
5, according to claim 1 have a heteroatomic nano carbon microsphere, and it has the graphite linings of sealing more than two layers, constitutes the structure of ball in the ball.
6, according to claim 1 have a heteroatomic nano carbon microsphere, and wherein this has heteroatomic nano carbon microsphere and has 1 to 100nm external diameter.
7, according to claim 1 have a heteroatomic nano carbon microsphere, and wherein this graphite linings inside is hollow.
8, according to claim 1 have a heteroatomic nano carbon microsphere, it also has a filler M, be positioned at the inner space of the graphite linings of sealing, M is selected from: metal, metal oxide, metal carbides, metal sulfide, metal nitride, metal boride and metal alloy.
9, according to claim 8 have a heteroatomic nano carbon microsphere, and wherein this metal is Sc, V, Cr, Fe, Co, Ni, Y, Zr, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ta, Os, Ir, Pt, Au, Th, U or its combination.
10, a kind of manufacturing has the method for heteroatomic nano carbon microsphere, comprise: an electric arc reaction chamber with graphite anode and graphite cathode (a) is provided, and in this electric arc reaction chamber, feed an inert gas, wherein this graphite anode contains the compound and the graphite of nitrogen, phosphorus or boron atom, and nitrogen, phosphorus or boron atom content are 2 to 5 moles of % of carbon content; (b) apply a voltage between above-mentioned negative electrode and the anode with a pulse current, to produce the arc discharge reaction; And the deposit that (c) is collected in graphite cathode.
11, manufacturing according to claim 10 has the method for heteroatomic nano carbon microsphere, and wherein the compound of this nitrogen, phosphorus or boron atom is melamine, ammonium chloride, B
4C, B
2O
3Or P
2O
5
12, a kind of manufacturing has the method for heteroatomic nano carbon microsphere, comprise: an electric arc reaction chamber with graphite anode and graphite cathode (a) is provided, and in this electric arc reaction chamber, feed an inert gas, wherein this graphite anode contains compound, metal-powder, and the graphite of nitrogen, phosphorus or boron atom, this nitrogen, phosphorus or boron atom content are 2 to 5 moles of % of carbon content, and this metal-powder atom content is 0.1 to 99 mole of % of carbon content; (b) apply a voltage between above-mentioned negative electrode and the anode with a pulse current, use producing the arc discharge reaction; And the deposit that (c) is collected in graphite cathode.
13, manufacturing according to claim 12 has the method for heteroatomic nano carbon microsphere, and wherein the compound of this nitrogen, phosphorus or boron atom is melamine, ammonium chloride, B
4C, B
2O
3Or P
2O
5
14, manufacturing according to claim 12 has the method for heteroatomic nano carbon microsphere, and wherein this metal-powder is the powder of Sc, V, Cr, Fe, Co, Ni, Y, Zr, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ta, Os, Ir, Pt, Au, Th, U or its combination.
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| CN101029218A (en) * | 2006-03-01 | 2007-09-05 | 财团法人工业技术研究院 | Heat-transferring solution containing heteroatomic nano-carbon ball |
| CN102432009B (en) * | 2010-09-29 | 2013-08-07 | 国家纳米科学中心 | Preparation method of carbon nitrogen micrometer spheres |
| CN109301216B (en) * | 2018-09-30 | 2021-10-12 | 西北有色金属研究院 | Preparation method of lithium iron phosphate electrode coated with carbon boron composite spheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062799A (en) * | 2001-08-27 | 2003-03-05 | Japan Science & Technology Corp | Lubrication system using carbon ball molecule or carbon tube molecule |
| CN1454839A (en) * | 2002-04-30 | 2003-11-12 | 财团法人工业技术研究院 | Hollow nano carbon ball manufacturing method |
| CN1477058A (en) * | 2002-06-28 | 2004-02-25 | Carbon nano particles, preparation method and transparent conductive polymer composite material containing said carbon nano particles | |
| CN1478593A (en) * | 2002-08-28 | 2004-03-03 | 财团法人工业技术研究院 | Manufacturing method of packed magnetic metal nanometer carbon ball |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003062799A (en) * | 2001-08-27 | 2003-03-05 | Japan Science & Technology Corp | Lubrication system using carbon ball molecule or carbon tube molecule |
| CN1454839A (en) * | 2002-04-30 | 2003-11-12 | 财团法人工业技术研究院 | Hollow nano carbon ball manufacturing method |
| CN1477058A (en) * | 2002-06-28 | 2004-02-25 | Carbon nano particles, preparation method and transparent conductive polymer composite material containing said carbon nano particles | |
| CN1478593A (en) * | 2002-08-28 | 2004-03-03 | 财团法人工业技术研究院 | Manufacturing method of packed magnetic metal nanometer carbon ball |
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