CN105439115B - The carbon nano-particle and its production method of a kind of Heteroatom doping - Google Patents

The carbon nano-particle and its production method of a kind of Heteroatom doping Download PDF

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CN105439115B
CN105439115B CN201410390123.0A CN201410390123A CN105439115B CN 105439115 B CN105439115 B CN 105439115B CN 201410390123 A CN201410390123 A CN 201410390123A CN 105439115 B CN105439115 B CN 105439115B
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carbon nano
acid
alkyl
nano
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CN105439115A (en
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乔金樑
张江茹
张晓红
戚桂村
宋志海
蔡传伦
赖金梅
李秉海
王亚
王湘
高建明
张红彬
蒋海斌
茹越
何谷
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The present invention relates to a kind of carbon nano-particle of Heteroatom doping, it is characterized in that, the carbon nano-particle has the macropore that the mesoporous and aperture that aperture is less than 1nm micropore, aperture is 2 50nm is more than 50nm, and the BET specific surface area of the carbon nano-particle is 300 1500m2Content of heteroatoms in/g, the carbon nano-particle is 2 25wt%, at least middle one kind of the hetero atom in nitrogen phosphate and sulfur and boron.The invention further relates to a kind of production method of the carbon nano-particle.

Description

The carbon nano-particle and its production method of a kind of Heteroatom doping
Technical field
It is to be related to one kind there is hierarchical porous structure and big ratio further the invention belongs to the preparation field of carbon material Carbon nano-particle of surface area and preparation method thereof.
Background technology
Porous carbon materials are generally with specific surface area is big, heat endurance and chemical stability are good, resistance is low, surface hydrophobic The excellent property such as good, in poison gas absorption, wastewater treatment, lithium ion battery, ultracapacitor, CO2Seizure, catalyst and catalysis There is good application prospect in terms of agent carrier.Nearest researcher has found electronic structure, crystalline texture and the hydrophily of carbon material It can be changed by Heteroatom doping.With undoped with carbon material compared with the specific capacitance of carbon material after chemical doping would generally Improve.Recent years, the element such as phosphorus, sulphur, boron, nitrogen is all used to doping carbon material to improve its chemical property.For example, nitrogen The electronegativity (3.0) of element is higher than carbon (2.5), and atomic diameter is smaller, therefore, by nitrogen-doping carbon material with The interaction of lithium ion is stronger, is more beneficial for the insertion of lithium ion, in addition, nitrogen-doping can improve the hydrophilic of carbon material Property, therefore be also to receive much concern in numerous doped chemicals.The carbon material of N doping can be rich in nitrogen by direct thermal cracking Presoma or polymer, such as acrylonitrile, melamine, gelatin, but the product porosity that Direct Pyrolysis is obtained is relatively low, therefore often Often need to introduce extra sacrificial template (such as Nano-meter CaCO33And SiO2) improve the porosity (Energy of product Environ.Sci.2012,5:7950-7955；Electrochim.Acta.2012,78:147-153； Micropor.Mesopor.Mat.2012,163:140-146), cause preparation process complicated, time-consuming.Without using the mould of sacrificial Plate, the product after charing is accomplished by just obtaining porous carbon materials by high-temperature activation.The method of activation has physically activated and changed Learn activation.Physically activated usually used CO2, air or vapor be activator, and chemical activation is usually using KOH, ZnCl2、 K2CO3、H3PO4Deng for activator.Such as Long Qie (Adv.Mater.2012,24:2047-2050) etc. it have studied with polypyrrole Nano wire is presoma, is activator by using KOH, and high-temperature activation has obtained the porous carbon fiber material of N doping, the material Electrode material of the material as lithium ion battery has very high electric capacity and good large current discharging capability.But a large amount of highly basic KOH addition is, it is necessary to using substantial amounts of acid progress neutralization washing when post-processing, make preparation process become complicated.It can be seen that, use letter The porous carbon materials that single method prepares Heteroatom doping are still a challenge.Structural conductive macromolecular is due to its molecule master Generally there are the cyclic structures such as big conjugatedπbond structure and five-membered ring, hexatomic ring on chain, and intermolecular π-π interactions are big, because This in high temperature pyrolysis, is easily carbonized under an inert atmosphere.In addition, structural conductive macromolecular, including polypyrrole (PPy), polyaniline (PANI) and polythiophene (PTh) etc., are to prepare Heteroatom doping carbon all containing hetero atoms such as N, S in molecule The excellent presoma of material.Using structural conductive macromolecular, for presoma, we are prepared for hierarchical porous structure first Heteroatom doping carbon nano-particle.
The content of the invention
Preparation method in the prior art on the carbon nano-particle of the Heteroatom doping with hierarchical porous structure is less, and And existing preparation method is generally required for the physics or chemical activating process in the template either later stage of sacrificial, prepares Journey is lengthy and tedious.The present invention provides a kind of simple to operation for Heteroatom doping carbon nano-particle of the preparation with hierarchical porous structure Method.
First embodiment of the present invention is to provide a kind of carbon nano-particle of Heteroatom doping, the carbon nanometer Grain has the macropore that the mesoporous and aperture that aperture is less than 2nm micropore, aperture is 2-50nm is more than 50nm, and carbon nanometer The BET specific surface area of grain is 300-1500m2Content of heteroatoms in/g, the carbon nano-particle is 2-25wt%, the miscellaneous original At least middle one kind of son in nitrogen phosphate and sulfur and boron.
In a preferred embodiment of the present invention, the carbon nano-particle is in P/P0Aperture at=0.97 is 70nm The single-point absorption total pore volume in following hole is 0.2-0.7cm3g-1, wherein, the pore volume of micropore is 0.1-0.4cm3g-1, it is mesoporous and big The total pore volume in hole is 0.2-0.8cm3g-1。
In another preferred embodiment of the present invention, the BET specific surface area of the nano particle is 400-1000m2/ g。
In a preferred embodiment of the present invention, the particle diameter of the nano particle is 10-500nm, preferably 20- 300nm, more preferably 30-100nm.
In some preferred embodiments of the present invention, the hetero atom in the carbon nano-particle of the Heteroatom doping is nitrogen Atom, and the content of the nitrogen-atoms is 2-23%, more preferably preferably 3-20%, 4-15%.
In other preferred embodiments of the present invention, the hetero atom in the carbon nano-particle of the Heteroatom doping is Sulphur atom, and the content of the sulphur atom is 2-25%, more preferably preferably 3-22%, 4-17%.
Second embodiment of the present invention is related to a kind of production method of the carbon nano-particle of the Heteroatom doping, wraps Include：
1) reaction solution containing decentralized medium, oxidant, dopant, stabilizer and conductive high polymer monomer is subjected to oxygen Change polymerization, the speed that control reaction is carried out, it is ensured that obtained conducting polymer particle is dispersed spherical and/or spherical Particle；
2) high temperature carbonization of structural conductive macromolecular nano particle is directly carried out in an inert atmosphere, obtains that there is multistage The Heteroatom doping carbon nano-particle of pore structure.
The method that the control reaction carries out speed includes using different raw material addition manners, selects suitable oxysome It is, selects suitable stabilising system and the consumption of stabilizer and control to react condition of progress etc..
Research before shows that structural conductive macromolecular is almost not dissolved in all solvents, that is, allows to dissolving, its Solubility is also low-down.Therefore, structural conductive macromolecular can not be swelled as common polymer by monomer, into Kernel mode is mainly nonhomogen-ous nucleation, and particle is increased by colliding to combine.Therefore, polymerization is controlled well during the course of the reaction Speed, it is to avoid too fast reaction rate.Reaction rate is too fast, and that product can be caused to reunite is serious, it is impossible to obtains spherical or spherical receives Rice grain.
Further, to preparation method of the invention, details are as follows：
In a preferred embodiment of the present invention, the structural conductive macromolecular is selected from following monomer The conducting polymer of at least one composition：Pyrroles, thiophene, 3,4- ethene dioxythiophenes, indoles, carbazole, aniline etc. and these The derivative of monomer；Structural conductive macromolecular monomer can be when using it is a kind of can also be several monomers mixture.It is excellent Select the one or more in pyrroles, aniline, thiophene, 3,4-rthylene dioxythiophene, carbazole and its in derivative, it is contemplated that monomer and One kind or several in the stability of polymer, more preferably pyrroles, aniline, thiophene and 3,4-rthylene dioxythiophene and its derivative Kind.
In a preferred embodiment of the present invention, the structure of the pyrroles, thiophene and their derivative such as Formulas I It is shown：
Wherein, X is N-R2Or S；R2For C1-C20Alkyl, the aryl that either replaces of aryl, preferably H or C1- C12- alkyl；More preferably H or C1-C8- alkyl, most preferably H；
4 R existed1It may be the same or different, H, alkyl, cycloalkyl, alkenyl, aryl, alkane can be each independently selected from Base aromatic radical, hydroxyl, alkoxy, halogen, nitro, it should be noted that wherein at least two R1Be necessary for H, halogen or Alkoxy, the two R1Can be with identical, can also be different；It is preferred that, 4 R existed1H, C can be each independently selected from1- C20Alkyl, hydroxyl, C1-C4Alkoxy, chlorine or nitro, it should be noted that four R1In, two R at least at X ortho positions1 Must be H, halogen or alkoxy respectively, but two R1Can be with identical, can also be different；It is further preferred that 4 R existed1All H, methyl, hydroxyl, chlorine or nitro can be each independently selected from, it should be noted that four R1In, at least at X ortho positions Two R1Must be H.
In a preferred embodiment of the present invention, the derivative of pyrroles and thiophene in following compound at least It is a kind of：N- methylpyrroles, N- N-ethyl pyrrole Ns, N- n-propyls pyrroles, N- normal-butyls pyrroles, N- phenylpyrroles, N- benzyls pyrroles, N- naphthylpyrroles, N- carboxy pyrroles, 3- methylpyrroles, 3- carboxy pyrroles, 3,4- dimethyl pyrroles, 3- N-ethyl pyrrole Ns, 3- positive third Base pyrroles, 3- normal-butyls pyrroles, 3- phenylpyrroles, 3- benzyls pyrroles, 3- naphthylpyrroles, 3- methoxypyrroles, 3- ethyoxyls Pyrroles, 3- propoxyl group pyrroles, 3- phenoxy groups pyrroles, 3,4- dimethoxys pyrroles, 3- methyl-N-methyls pyrroles, 3- methoxyl groups-N- Methylpyrrole, 3- chlorine pyrroles, 3- bromines pyrroles, 3- alkylthrophenes (3 methyl thiophene, 3- ethylthiophenes, 3- propyl group thiophene, 3- hexyls Thiophene etc.), 2,2 '-Dithiophene, -2,2 '-Dithiophene of 3- methyl, 3,3 '-dimethyl -2,2 '-Dithiophene, 3,4- dimethyl -2, 2 '-Dithiophene, 3,4- dimethyl -3 ', 4 '-dimethyl -2,2 '-Dithiophene, 3- methoxyl groups -2,2 '-Dithiophene, 3,3 '-diformazan Epoxide -2,2 '-Dithiophene, 2,2 ', 5,5 '-three thiophene, 3- methyl -2,2 ', 5 ', 2 "-three thiophene, 3,3 '-dimethyl -2,2 ', 5 ', 2 "-three thiophene etc..Most preferably pyrroles and thiophene.
In a preferred embodiment of the present invention, the present invention in aniline and its derivatives structural formula such as Formula II institute Show：
Wherein, R3Can be H, C1-C20- alkyl, aryl or substituted aryl；Preferably H or C3-C12Alkyl；More Preferably H or C4-C8Alkyl；Most preferably H；
4 R existed4It may be the same or different, be each independently selected from H, alkyl, cycloalkyl, alkenyl, aryl, alkyl Substituted aryl, hydroxyl, alkoxy, halogen or nitro, it should be noted that at least one R4It is necessary for H, halogen or alkane Epoxide.4 R existed4Can be independently selected from H, C1-C4Alkyl, hydroxyl, C1-C4Alkoxy, chlorine or nitro, and extremely Less in NHR3The R of contraposition4It is H, halogen or alkoxy.It is further preferred that 4 R existed4Can be independently selected from H, methyl, second Base, hydroxyl, chlorine, bromine or nitro, and NHR3The R of contraposition4For H.Most preferably, all R4All it is H.
In a preferred embodiment of the present invention, the monomer of anil may be selected from least one in following material Kind：Aniline, 2-aminotoluene, 2- MEAs, 2- propyl group aniline, 2- aminoanisoles, 2- phenetidines, 3- methylbenzenes Amine, 3- MEAs, 3- propyl group aniline, 3- aminoanisoles, 3- phenetidines, 3- hexyls aniline, methylphenylamine, N- third Base aniline, N- butylanilines；It is preferred that aniline.
In a preferred embodiment of the present invention, the present invention in conductive high polymer monomer in step 1) in reaction system In mass concentration be 0.1-30%, preferred concentration is 0.5-20%, more preferably concentration be 1-10%, most preferable concentrations are 1- 5%.
In a preferred embodiment of the present invention, the reaction medium used in the present invention, i.e. solvent, being can not be by oxygen Change the oxidizing any solvent used during polymerization, can be water, organic solvent or mixed solvent.Preferred reaction Medium is water.
In further preferred embodiment, the organic solvent in the present invention includes ethanol, acetone, tetrahydrofuran, ring Fourth sulfone, acetonitrile, toluene, propene carbonate, ethylene carbonate, chloroform etc., preferred alcohol, acetonitrile.
There is no particular limitation for the oxidant used in the present invention, can use iron (III) salt of inorganic acid, inorganic acid Copper (II) salt, persulfate, periodate, hydrogen peroxide, ozone, six cyanogen close iron (III) potassium, the ammonium cerium of two hydrated sulfuric acid four (IV), bromine, iodine, iron (III) salt of organic acid, and metal ion compound one kind or several in oxidation system with hydrogen peroxide Kind.It is preferred that in iron (III) salt, persulfate and metal ion and hydrogen peroxide the compounding oxidation system of inorganic acid or organic acid It is one or more of.More preferably metal ion compounds the one or more in oxidation system with hydrogen peroxide.
Iron (III) salt of heretofore described inorganic acid includes anhydrous ferric chloride (III), ferric chloride hexahydrate (III), nine Water ferric nitrate (III), anhydrous nitric acid iron (III), n ferric sulfate hydrates (III) (n=3 to 12), 12 hydrated sulfuric acid ammonium iron (III), n perchloric acid hydrates iron (III) (n=1,6), tetrafluoro boric acid iron etc., more preferably ferric chloride hexahydrate (III)；The nothing Copper (II) salt of machine acid includes copper chloride (II), copper sulphate (II), copper nitrate (II), copper acetate (II), tetrafluoro boric acid copper (II) Deng more preferably copper chloride (II)；The persulfate includes ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate etc., more preferably over cure Sour ammonium；The periodate is including potassium metaperiodate etc.；Iron (III) salt of the organic acid includes p-methyl benzenesulfonic acid iron (III) etc.； The metal ion includes Fe with hydrogen peroxide compounding oxidation system2+-H2O2、Fe3+-H2O2、Cu2+-H2O2Deng more preferably Fe3+- H2O2。
Oxidant/the monomer mole ratio used in the present invention is 0.1-10, and preferred molar ratio is 0.2-5, more preferably mole Than for 0.5-2.
The dopant used in the present invention can be inorganic acid, lewis acid, organic acid and their derivative or iron (III) one kind in salt, alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, anthraquinone sulfonic acid and its derivative, tetracyanoethylene, trifluoromethanesulfonic acid Or it is several.It is preferred that the one or more in inorganic acid and alkyl sulfonic acid, benzene sulfonic acid and its derivative.
The inorganic acid used in the present invention includes HCl, H2SO4、HNO3、HClO4, chlorosulfonic acid etc.；Lewis acid includes BF3、 PCl5、AlCl3、SnCl4、WCl6、MoCl5Deng；Organic acid include alkyl sulfonic acid, benzene sulfonic acid, anthraquinone sulfonic acid, camphorsulfonic acid and Their derivative or their iron (III) salt；Sulfonic acid includes single sulfonic acid, disulfonic acid or trisulfonic acid；The derivative of alkyl sulfonic acid Including 2- acrylamide-2-methyl propane sulfonics etc.；The derivative of benzene sulfonic acid includes phenolsulfonic acid, styrene sulfonic acid, to toluene sulphur Acid, to ethyl phenenyl azochlorosulfonate acid, DBSA etc.；The derivative of naphthalene sulfonic acids includes 1-naphthalene sulfonic aicd, 2- naphthalene sulfonic acids, 1,3- naphthalenes two Sulfonic acid, 1,3,6- naphthalene trisulfonic acids and 6- ethyls -1-naphthalene sulfonic aicd etc.；The example of the derivative of anthraquinone sulfonic acid include anthraquinone-1-sulfonic acid, Anthraquinone-2-sulfonic acid, anthraquinone 2,6 disulfonic acid and 2-methylanthraquinone -6- sulfonic acid etc..It is preferred that HCl, p-methyl benzenesulfonic acid, camphorsulfonic acid, One or more in DBSA.More preferably p-methyl benzenesulfonic acid.
Dopant/monomer mole ratio is 0.05-10 in the present invention, and preferred molar ratio is 0.1-5, and more preferably mol ratio is 0.2-2。
There is no particular limitation for the stabilizer used in the present invention, can use all stabilizers disclosed in prior art, Including one kind or several in anionic emulsifier, nonionic emulsifier and various macromolecular stabilizer agent and polyanion Kind.One or more in preferred anionic type emulsifying agent and macromolecular stabilizer agent.One kind more preferably in macromolecular stabilizer agent Or it is several.
The anionic emulsifier used in the present invention includes lauryl sodium sulfate, neopelex, 12 Alkyl benzene sulphonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate etc..Cationic emulsifier includes DTAB, ten Six alkyl trimethyl ammonium bromides etc..Nonionic emulsifier has OP series, NP series, Trixon series, Span series and tween Series etc..Macromolecular stabilizer agent include polyoxyethylene (PEO), PVP (PVP), polyvinyl acetate (PVAc, Degree of hydrolysis：70-99%), poly 4 vinyl pyridine, poly 2 vinyl pyridine, poly- (4-vinylpridine-co- methacrylic acid fourths Ester), polyacrylamide, methylcellulose, cyclodextrin etc..Polyanion includes Sodium Polyacrylate, poly (sodium 4-styrenesulfonate) etc.. Wherein preferred neopelex, DBSA, PVP, PVAc, methylcellulose and poly (sodium 4-styrenesulfonate) In one or more.One or more more preferably in DBSA, PVP and PVAc.
The molecular weight for the macromolecular stabilizer agent that the present invention is used is 5000-5000000.It is preferred that 10000-2500000；It is more excellent Select 10000-1000000.
The concentration of the stabilizer used in the present invention is 0.1%-30%, and optimization concentration is 0.2%-20%, is more optimized dense Spend for 0.2%-10%.
The reaction temperature used in the present invention is -20 DEG C -150 DEG C, and preferable reaction temperature is -10 DEG C -100 DEG C, more preferably Reaction temperature is -5 DEG C -50 DEG C.
Reaction time for being used in the present invention is needed depending on the reaction condition that is carried out according to oxidation polymerization, the bar of polymerisation Part is different, and corresponding change can also occur for the speed of polymerisation, typically between several hours to several days.
Structural conductive macromolecular nano particle in the present invention is spherical or spherical.
The size range of the structural conductive macromolecular nano particle prepared in the present invention is 10-500nm, the size of optimization Scope is 20-300nm, and the size range more optimized is 30-100nm.
The inert atmosphere of structural conductive macromolecular high temperature carbonization is carried out in the present invention includes nitrogen and argon gas etc., compared to it The purity of lower argon gas is higher, impurity content is few, therefore preferably argon gas, but argon gas cost is higher, can also using nitrogen.
The temperature range that structural conductive macromolecular charing is carried out in the present invention is 400-2300 DEG C, it is contemplated that heteroatomic Content can be reduced with the rise of carbonization temperature, and temperature range preferably is 500-1500 DEG C, and preferred carbonization temperature is 500-1000℃.If carbonization temperature is too low, the pore structure in product can not still be formed well.
Beneficial effects of the present invention：
The carbon nano-particle for the Heteroatom doping that the present invention is provided has hierarchical porous structure, at the same have micropore, it is mesoporous very To macroporous structure, Heteroatom doping amount is high, it is not necessary to which activation is with regard to that can obtain higher specific surface area, in CO2It is trapping, battery, super There is application prospect in terms of level capacitor, catalyst, catalyst carrier.
The method for the carbon nano-particle that the present invention is provided have technique it is simple, it is easily operated the features such as, directly carbonize It can be obtained by the porous carbon nano-particle of Heteroatom doping, it is to avoid cause using a large amount of templates to waste in art methods Shortcoming, it also avoid the process activated using the material such as alkali, simplify preparation process, and obtained carbon nano-particle Performance and structure are all very stable.
Brief description of the drawings
SEM (SEM) photo of porous carbon nano-particle prepared by Fig. 1 embodiments 1.
Embodiment
Describe embodiments of the present invention in detail below with reference to embodiment, whereby to the present invention how application technology hand Section solves technical problem, and reaches the implementation process of technique effect and can fully understand and implement according to this.It should be noted that with Lower embodiment is merely to illustrate the present invention, any limitation can not be constituted to the scope of the present invention, as long as not constituting conflict, this hair Each feature in each embodiment and each embodiment in bright can be combined with each other, and the technical scheme formed is in this hair Within bright protection domain.
Method of testing
SEM (SEM)：The shape and surface topography of product are by S-4800 type Flied emission scanning electrons Microscope (Hitachi, Japan) is directly observed under 1kV voltages, and the electric conductivity of product in itself is preferable, it is not necessary to which metal spraying can be straight Connect observation.
N2 adsorption desorption isothermal curves：On Micrometritics ASAP2020 adsorbent equipments, enter under the conditions of -196 DEG C The test of row N2 adsorption desorption isothermal curves.Before test, it is de-gassed place to sample under 180 DEG C, high vacuum condition first Manage at least 6h.
The specific surface area of product is calculated by Brunauer-Emmett-Teller (BET) method and obtained.
Micropore size and distribution be to be obtained by Horvath-Kawazoe (HK) calculating method.
Mesoporous pore size and distribution be to be obtained by Barrett-Joyner-Halenda (BJH) calculating method.
Total pore volume is by relative pressure P/P0Calculate what is obtained for the adsorbance at 0.97.
Micropore volume is then calculated by t-plot models.
Elementary analysis：By the EA1112 instruments of Thermo companies of the U.S. to the nitrogen and the content of element sulphur in product Analyzed.
In the present invention, described conducting polymer refers to structural conductive macromolecular or other kinds of conductive polymer Son, under the preferred conditions, it refers to structural conductive macromolecular or intrinsically conducting macromolecule.
Embodiment 1
Step one：Polypyrrole (PPy) nano particle is first prepared, preparation method is specially：Mechanical agitation is housed in 500ml In the reaction vessel of device add pyrroles, PVP (PVP, molecular weight 220,000), p-methyl benzenesulfonic acid and go from Sub- water, after stirring, sequentially adds ferric chloride hexahydrate (III) (FeCl3·6H2O) and 30% hydrogen peroxide solution, make most Pyrroles in end reaction solution, PVP, p-methyl benzenesulfonic acid, the concentration of ferric chloride hexahydrate (III) and hydrogen peroxide be respectively 0.3M, 0.018M, 0.3M, 0.001M and 0.36M (wherein PVP concentration be molecule in repeat unit concentration).Course of reaction uses six The oxidation system of Ferric Chloride Hydrated (III) and hydrogen peroxide compounding, reduces the speed of oxidation polymerization.Reaction is carried out at 23 DEG C, React and stop after 24h.By the method for centrifugation, 15min is centrifuged under 4000rpm speed, by PPy nanoparticle depositions, And make to be washed with deionized 2-3 times, the salt in product, residual monomer and other impurity are washed off.And dried in 60 DEG C of vacuum 24h is dried in vacuo in case.The size that obtained polypyrrole nano particle is characterized by SEM is about 70 ± 30nm.
Step 2：Dried PPy powder of nanometric particles is put in crucible, carbonized in box atmosphere furnace, charcoal Change condition is：In a nitrogen atmosphere, 800 DEG C are raised to 3 DEG C/min heating rate, and 3h is kept at 800 DEG C, it is then naturally cold But.Finally give the carbon nano-particle with hierarchical porous structure of N doping.The SEM of product characterizes as shown in Figure 1.Therefrom we The particle diameter of the product after charing can be measured, the adjoining dimensions with the polypyrrole nano particle before charing, are 70 ± 30nm.Product BET specific surface area, pore volume, the analysis result of aperture and nitrogen element content be shown in Table 1.
Embodiment 2
Step one：PPy nano particles are prepared, preparation method is same as Example 1, be simply 220,000 by molecular weight PVP replaces with domestic PVP (K30, molecular weight is about 10,000, Xilong Chemical Co., Ltd), and improves PVP concentration To 0.036M, reaction is carried out at 23 DEG C, is stopped after reaction 24h.Monomer is slowly added dropwise in form of an aqueous solutions in course of reaction Into reaction solution, rate of polymerization is reduced.Product washing methods and drying means are same as Example 1.Characterized and obtained by SEM PPy nano particles size be 60 ± 20nm.
Step 2：The condition that product is carbonized is same as Example 1.The particle diameter of product after charing is 60 ± 20nm. The BET specific surface area of product, pore volume, the analysis result of aperture and nitrogen element content are shown in Table 1.
Embodiment 3
Step one：The preparation method of PPy nano particles is same as Example 2, but pyrroles in end reaction solution, PVP, right The concentration of toluenesulfonic acid, ferric chloride hexahydrate (III) and hydrogen peroxide be respectively 0.3M, 0.036M, 0.06M, 0.001M and 0.36M (wherein PVP concentration be molecule in repeat unit concentration).
Step 2：The condition that product is carbonized is：In box atmosphere furnace, under nitrogen atmosphere, with 3 DEG C/min heating Speed is heated to 700 DEG C, and keeps 3h at 700 DEG C, then natural cooling.The particle diameter of product after charing is 60 ± 20nm.Production The BET specific surface areas of product, pore volume, the analysis result of aperture and nitrogen element content are shown in Table 1.
Embodiment 4
Step one：The preparation method of PPy nano particles is same as Example 2, but pyrroles in end reaction solution, PVP, right The concentration of toluenesulfonic acid, ferric chloride hexahydrate (III) and hydrogen peroxide is respectively 0.3M, 0.036M, 0.3M, 0.001M and 3.0M (wherein PVP concentration be repeat unit in molecule concentration), and oxidants hydrogen peroxide be slowly dropped to after dilution it is anti- Answer in solution, control oxidation polymerization speed is slower.
Step 2：The condition that product is carbonized is：In box atmosphere furnace, under nitrogen atmosphere, with 3 DEG C/min heating Speed is heated to 600 DEG C, and keeps 3h at 600 DEG C, then natural cooling.The particle diameter of product after charing is 60 ± 20nm.Production The BET specific surface areas of product, pore volume, the analysis result of aperture and nitrogen element content are shown in Table 1.
Embodiment 5
Step one：The preparation method of PPy nano particles is same as Example 2, but pyrroles in end reaction solution, PVP, right The concentration of toluenesulfonic acid, ferric chloride hexahydrate (III) and hydrogen peroxide be respectively 0.3M, 0.036M, 0.15M, 0.001M and 0.45M (wherein PVP concentration be molecule in repeat unit concentration), and react be in ice-water bath carry out, reaction temperature Control reduces the speed of oxidation polymerization at 0-5 DEG C.
Step 2：The condition that product is carbonized is：In box atmosphere furnace, under nitrogen atmosphere, with 3 DEG C/min heating Speed is heated to 500 DEG C, and keeps 4h at 500 DEG C, then natural cooling.The particle diameter of product after charing is 60 ± 20nm.Production The BET specific surface areas of product, pore volume, the analysis result of aperture and nitrogen element content are shown in Table 1.
Embodiment 6
Step one：The method for preparing PPy nano particles is same as Example 2, simply replaces 0.1M p-methyl benzenesulfonic acid For 0.15M HCl, other reaction conditions are identical, and washing and the process dried are also same as Example 1.Characterized by SEM The size of obtained polypyrrole nano particle is 60 ± 20nm.
Step 2：The condition of PPy nano particles charing is same as Example 1.The particle diameter of product after charing be 60 ± 20nm.The BET specific surface area of product, pore volume, the analysis result of aperture and nitrogen element content are shown in Table 1.
Embodiment 7
Step one：Polyaniline (PANI) nano particle is prepared, preparation method is specially：Equipped with the anti-of mechanical stirring device Answer and aniline, PVP (K30, molecular weight 10,000, Xilong Chemical Co., Ltd), hydrochloric acid and deionized water are added in container, stir Mix it is uniform after, add ammonium persulfate (APS) aqueous solution, make the aniline in final system, PVP, HCl, APS concentration be respectively 0.21M, 0.018M, 0.21M and 0.21M.Reaction is carried out in ice-water bath at 0-5 DEG C, is stopped after reaction 24h.Product separation is washed The method washed is same as Example 1.
Step 2：The charing method of PANI particles is same as Example 1.The BET specific surface area of product, pore volume and aperture Analysis result is shown in Table 1.
Table 1
Wherein：SBETFor the specific surface area calculated by Brunauer-Emmett-Teller (BET) method；
SmicroFor the micropore specific area obtained by t-plot；
VmicroTo analyze obtained Micropore volume by t-plot；
VtotFor P/P0The single-point for being less than 70nm for hole size at 0.97 adsorbs total pore volume；
DmesoFor the mesoporous average pore size calculated by Barrett-Joyner-Halenda (BJH) method；
DmicroFor the micropore size calculated by Horvath-Kawazoe (HK) method；
CNFor the N element content in the product ontology that is obtained by elementary analysis.

Claims (59)

1. a kind of carbon nano-particle of Heteroatom doping, it is characterised in that there is the carbon nano-particle aperture to be less than the micro- of 2nm Hole, aperture are more than 50nm macropore for 2-50nm mesoporous and aperture, and the BET specific surface area of the carbon nano-particle is 300- 1500m2Content of heteroatoms in/g, the carbon nano-particle is 2-25wt%, and the hetero atom is in nitrogen phosphate and sulfur and boron At least one.
2. carbon nano-particle according to claim 1, it is characterised in that the carbon nano-particle is in P/P0At=0.97 The single-point absorption total pore volume in the hole that aperture is below 70nm is 0.2-0.7cm3g-1, the pore volume of the micropore is 0.1-0.4cm3g-1, the total pore volume of mesoporous and macropore is 0.2-0.8cm3g-1。
3. carbon nano-particle according to claim 1 or 2, it is characterised in that the BET specific surface area of the nano particle is 400-1000m2/g。
4. carbon nano-particle according to claim 1 or 2, it is characterised in that the particle diameter of the nano particle is 10- 500nm。
5. carbon nano-particle according to claim 4, it is characterised in that the particle diameter of the nano particle is 20-300nm.
6. carbon nano-particle according to claim 4, it is characterised in that the particle diameter of the nano particle is 30-100nm.
7. carbon nano-particle according to claim 1 or 2, it is characterised in that the hetero atom is nitrogen-atoms, and the nitrogen The content of atom is 2-23%.
8. carbon nano-particle according to claim 7, it is characterised in that the hetero atom is nitrogen-atoms, and the nitrogen is former The content of son is 3-20%.
9. carbon nano-particle according to claim 7, it is characterised in that the hetero atom is nitrogen-atoms, and the nitrogen is former The content of son is 4-15%.
10. carbon nano-particle according to claim 1 or 2, it is characterised in that the hetero atom is sulphur atom, and described The content of sulphur atom is 2-25%.
11. carbon nano-particle according to claim 10, it is characterised in that the hetero atom is sulphur atom, and the sulphur The content of atom is 3-22%.
12. carbon nano-particle according to claim 10, it is characterised in that the hetero atom is sulphur atom, and the sulphur The content of atom is 4-17%.
13. a kind of production method of nano particle according to any one of claim 1-12, including：
1) reaction solution containing decentralized medium, oxidant, dopant, stabilizer and conductive high polymer monomer is carried out into oxidation to gather Close, the speed that control reaction is carried out, it is ensured that obtained conducting polymer particle is dispersed spherical spherical particle；
2) high temperature carbonization of conducting polymer nano particle is directly carried out in an inert atmosphere, is obtained the Heteroatom doping carbon and is received Rice grain；
The conducting polymer is selected from the conducting polymer being made up of at least one of following monomer：Pyrroles, thiophene, 3,4- Ethene dioxythiophene, indoles, carbazole, the derivative of furans and these monomers；
The dopant is selected from least one of following material：
Inorganic acid, lewis acid, organic acid, the derivative of organic acid, iron (III) salt, tetracyanoethylene and the fluoroform of organic acid Sulfonic acid.
14. method according to claim 13, it is characterised in that the conducting polymer is selected from following monomer The conducting polymer of at least one composition：In pyrroles, aniline and its derivatives, thiophene and 3,4- ethene dioxythiophenes and carbazole It is at least one.
15. method according to claim 13, it is characterised in that the conducting polymer is selected from following monomer The conducting polymer of at least one composition：Pyrroles, aniline, thiophene and one kind in 3,4- ethene dioxythiophenes and its derivative or It is several.
16. method according to claim 13, it is characterised in that the pyrroles, the structure such as Formulas I of thiophene and derivatives It is shown：
Wherein, X is N-R2Or S；R2For C1-C20Alkyl, aryl either replace aryl；
4 R existed1It may be the same or different, H, alkyl, alkenyl, aryl, hydroxyl, alkoxy, halogen can be each independently selected from Element or nitro, wherein at least two R1Selected from H, halogen or alkoxy.
17. method according to claim 16, it is characterised in that the R2For H or C1-C12- alkyl.
18. method according to claim 16, it is characterised in that the R2For H or C1-C8- alkyl.
19. method according to claim 16, it is characterised in that the R2For H.
20. method according to claim 16, it is characterised in that each R1It is each independently selected from H, C1-C20Alkyl, Hydroxyl, C1-C4Alkoxy, chlorine or nitro, wherein, at least two R at X ortho positions1Must separately be selected from H, halogen or Person's alkoxy.
21. method according to claim 16, it is characterised in that each R1Can be respectively H, methyl, hydroxyl, chlorine or Person's nitro, wherein, at least two R at X ortho positions1It is H.
22. method according to claim 14, it is characterised in that the structural formula of the aniline and its derivatives such as Formula II institute Show：
Wherein, R3For H, C1-C20- alkyl, aryl or substituted aryl；
4 R existed4It may be the same or different, be each independently selected from H, alkyl, alkenyl, aryl, hydroxyl, alkoxy, halogen Or nitro, wherein at least one R4It is necessary for H, halogen or alkoxy.
23. method according to claim 22, it is characterised in that the R3For H or C3-C12Alkyl.
24. method according to claim 22, it is characterised in that the R3For H or C4-C8Alkyl.
25. method according to claim 22, it is characterised in that the R3For H.
26. method according to claim 22, it is characterised in that 4 R existed4Can be independently selected from H, C1-C4- Alkyl, hydroxyl, C1-C4- alkoxy, chlorine or nitro, and at least in NHR3The R of contraposition4It is H, halogen or alkoxy.
27. method according to claim 22, it is characterised in that 4 R existed4Can independently selected from H, methyl, Ethyl, hydroxyl, chlorine, bromine or nitro, and NHR3The R of contraposition4For H.
28. method according to claim 22, it is characterised in that all R4All it is H.
29. method according to claim 13, it is characterised in that the conductive high polymer monomer is in step 1) in reactant Mass concentration in system is 0.1-30%.
30. method according to claim 29, it is characterised in that the conductive high polymer monomer is in step 1) in reactant Mass concentration in system is 0.5-20%.
31. method according to claim 29, it is characterised in that the conductive high polymer monomer is in step 1) in reactant Mass concentration in system is 1-10%.
32. method according to claim 29, it is characterised in that the conductive high polymer monomer is in step 1) in reactant Mass concentration in system is 1-5%.
33. method according to claim 13, it is characterised in that the decentralized medium be selected from water, organic solvent or its At least one of mixed solvent.
34. method according to claim 33, it is characterised in that the organic solvent in following compound at least It is a kind of：Ethanol, acetone, 1-METHYLPYRROLIDONE, tetrahydrofuran, sulfolane, acetonitrile, toluene, propene carbonate, ethylene carbonate And chloroform.
35. method according to claim 33, it is characterised in that the organic solvent is selected from ethanol and/or acetonitrile.
36. method according to claim 33, it is characterised in that the decentralized medium is water.
37. method according to claim 13, it is characterised in that the oxidant in following material at least one Kind：Iron (III) salt of inorganic acid, copper (II) salt of inorganic acid, persulfate, periodate, hydrogen peroxide, ozone, six cyanogen are closed Iron (III) potassium, the ammonium cerium (IV) of two hydrated sulfuric acid four, bromine, iodine, iron (III) salt of organic acid, and metal ion and hydrogen peroxide Compound oxidation system.
38. the method according to claim 37, it is characterised in that the oxidant uses inorganic acid or the iron of organic acid (III) one or more in salt and persulfate.
39. the method according to claim 37, it is characterised in that the oxidant is persulfate.
40. method according to claim 13, it is characterised in that the molar ratio range of the oxidant and polymer monomer For 0.1-10.
41. method according to claim 40, it is characterised in that the molar ratio range of the oxidant and polymer monomer For 0.3-5.
42. method according to claim 40, it is characterised in that the molar ratio range of the oxidant and polymer monomer For 0.5-2.
43. method according to claim 13, it is characterised in that the stabilizer in following material at least one Kind：Anionic emulsifier, nonionic emulsifier, macromolecular stabilizer agent and polyanion.
44. method according to claim 43, it is characterised in that the stabilizer be selected from anionic emulsifier and/or At least one of macromolecular stabilizer agent.
45. method according to claim 43, it is characterised in that the stabilizer in macromolecular stabilizer agent at least It is a kind of.
46. method according to claim 43, it is characterised in that the molecular weight of the macromolecular stabilizer agent is 5000- 5000000。
47. method according to claim 43, it is characterised in that the molecular weight of the macromolecular stabilizer agent is 10000- 2500000。
48. method according to claim 43, it is characterised in that the molecular weight of the macromolecular stabilizer agent is 10000- 1000000。
49. method according to claim 13, it is characterised in that the organic acid includes alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulphur Acid, anthraquinone sulfonic acid, one kind in inorganic acid, lewis acid, alkyl sulfonic acid, benzene sulfonic acid and its derivative of the dopant or It is several.
50. method according to claim 49, it is characterised in that the dopant is selected from HCl, p-methyl benzenesulfonic acid, camphor At least one of sulfonic acid and DBSA.
51. method according to claim 49, it is characterised in that the dopant is selected from p-methyl benzenesulfonic acid.
52. method according to claim 13, it is characterised in that the mol ratio of the Can Za Ji ︰ polymer monomers is 0.05-10。
53. method according to claim 52, it is characterised in that the mol ratio of the Can Za Ji ︰ polymer monomers is 0.1-5。
54. method according to claim 52, it is characterised in that the mol ratio of the Can Za Ji ︰ polymer monomers is 0.2-2。
55. method according to claim 13, it is characterised in that the temperature range of the reaction is -10 DEG C -70 DEG C.
56. method according to claim 55, it is characterised in that the temperature range of the reaction is 0-50 DEG C.
57. method according to claim 13, it is characterised in that the temperature range of charing is 400-2300 DEG C.
58. method according to claim 57, it is characterised in that the temperature range of charing is 500-1500 DEG C.
59. method according to claim 57, it is characterised in that the temperature range of charing is 500-1000 DEG C.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101054171A (en) * 2006-04-12 2007-10-17 中国科学院金属研究所 Layer combination controllable carbon material with nano pole of different scale, preparation method and application
WO2009149540A1 (en) * 2008-06-10 2009-12-17 National Research Council Of Canada Controllable synthesis of porous carbon spheres, and electrochemical applications thereof
CN102718205A (en) * 2012-06-27 2012-10-10 北京科技大学 Method for preparing three-dimensional hierarchical porous carbon
CN103420353A (en) * 2012-05-15 2013-12-04 北京化工大学 Porous carbon material and preparation method and application thereof
CN103482601A (en) * 2013-09-06 2014-01-01 浙江大学 Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer
CN103964412A (en) * 2013-01-30 2014-08-06 北京化工大学 Preparation method of nitrogen-doped porous-structure carbon material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101054171A (en) * 2006-04-12 2007-10-17 中国科学院金属研究所 Layer combination controllable carbon material with nano pole of different scale, preparation method and application
WO2009149540A1 (en) * 2008-06-10 2009-12-17 National Research Council Of Canada Controllable synthesis of porous carbon spheres, and electrochemical applications thereof
CN103420353A (en) * 2012-05-15 2013-12-04 北京化工大学 Porous carbon material and preparation method and application thereof
CN102718205A (en) * 2012-06-27 2012-10-10 北京科技大学 Method for preparing three-dimensional hierarchical porous carbon
CN103964412A (en) * 2013-01-30 2014-08-06 北京化工大学 Preparation method of nitrogen-doped porous-structure carbon material
CN103482601A (en) * 2013-09-06 2014-01-01 浙江大学 Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer

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