CN105439115A - Heteroatom doping carbon nanoparticle and production method thereof - Google Patents
Heteroatom doping carbon nanoparticle and production method thereof Download PDFInfo
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- CN105439115A CN105439115A CN201410390123.0A CN201410390123A CN105439115A CN 105439115 A CN105439115 A CN 105439115A CN 201410390123 A CN201410390123 A CN 201410390123A CN 105439115 A CN105439115 A CN 105439115A
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Abstract
The present invention relates to a heteroatom doping carbon nanoparticle, wherein the carbon nanoparticle has micropores with the pore size less than 1nm, mesopores with the pore size of 2-50nm and macropores with the pore size greater than 50nm, the BET specific surface area of the carbon nanoparticle is 300-1500m<2> / g, the hetero atom content of the carbon nanoparticle is 2-25wt%, and the heteroatom is selected from at least one of nitrogen, phosphorus, sulfur and boron. The present invention also relates to a production method of the carbon nanoparticle.
Description
Technical field
The invention belongs to the preparation field of carbon material, further, relate to a kind of to there is carbon nano-particle of hierarchical porous structure and bigger serface and preparation method thereof.
Background technology
Porous carbon materials has that specific surface area is large usually, the character of thermostability and the excellence such as chemical stability is good, resistance is low, surface hydrophobicity is good, at poison gas absorption, wastewater treatment, lithium ion battery, ultracapacitor, CO
2there is good application prospect the aspects such as seizure, catalyzer and support of the catalyst.Nearest investigator finds that the electronic structure of carbon material, crystalline texture and wetting ability can be changed by Heteroatom doping.The ratio capacitance of the carbon material compared with unadulterated carbon material after chemical doping can improve usually.Recent years, the elements such as phosphorus, sulphur, boron, nitrogen are all used to doping carbon material to improve its chemical property.Such as, the electronegativity (3.0) of nitrogen element is higher than carbon (2.5), and atomic diameter is less, therefore, interaction through the carbon material of nitrogen-doping and lithium ion is stronger, is more conducive to the insertion of lithium ion, in addition, nitrogen-doping can improve the wetting ability of carbon material, therefore also receives much concern in numerous doped element.The carbon material of N doping can be rich in presoma or the polymkeric substance of nitrogen by direct thermo-cracking, as vinyl cyanide, trimeric cyanamide, gelatin, but the product porosity that By Direct Pyrolysis obtains is lower, therefore usually need to introduce extra sacrificial template (as Nano-meter CaCO3
3and SiO
2) improve porosity (EnergyEnviron.Sci.2012, the 5:7950-7955 of product; Electrochim.Acta.2012,78:147-153; Micropor.Mesopor.Mat.2012,163:140-146), cause preparation process complicated, consuming time.Do not use the template of sacrificial, the product after charing just needs just can obtain porous carbon materials through high-temperature activation.The method of activation has physically activated and chemical activation.Physically activated usual use CO
2, air or water vapour is activator, and chemical activation uses KOH, ZnCl usually
2, K
2cO
3, H
3pO
4deng being activator.As LongQie (Adv.Mater.2012,24:2047-2050) etc. have studied with polypyrrole nano line is presoma, by using KOH to be activator, high-temperature activation obtains the porous carbon fiber material of N doping, and the electrode materials that this material is used as lithium ion battery has very high electric capacity and good large current discharging capability.But a large amount of highly basic KOH adds, need during aftertreatment, to use a large amount of acid to carry out neutralization washing, make preparation process become complicated.Visible, the porous carbon materials using simple method to prepare Heteroatom doping remains a challenge.Structural conductive macromolecular is owing to its molecular backbone chain having usually large conjugatedπbond structure and the ring texture such as five-ring, six-ring, and intermolecular π-π interacts large, therefore under an inert atmosphere, when high temperature pyrolysis, easily carbonizes.In addition, structural conductive macromolecular, comprise polypyrrole (PPy), polyaniline (PANI) and Polythiophene (PTh) etc., all containing the heteroatomss such as N, S in molecule, is the presoma of the excellence preparing Heteroatom doping carbon material.We have prepared the Heteroatom doping carbon nano-particle with hierarchical porous structure first for presoma to use structural conductive macromolecular.
Summary of the invention
The preparation method of carbon nano-particle about the Heteroatom doping with hierarchical porous structure in prior art is less, and existing preparation method needs the template of sacrificial or the physics in later stage or chemical activating process usually, and preparation process is lengthy and tedious.The present invention prepares the Heteroatom doping carbon nano-particle with hierarchical porous structure to provide a kind of method simple to operation.
First embodiment of the present invention is the carbon nano-particle providing a kind of Heteroatom doping, described carbon nano-particle has that aperture is less than the micropore of 2nm, aperture is the macropore that the mesoporous of 2-50nm and aperture are greater than 50nm, and the BET specific surface area of described carbon nano-particle is 300-1500m
2/ g, the content of heteroatoms in described carbon nano-particle is 2-25wt%, and described heteroatoms is selected from least middle one in nitrogen phosphate and sulfur and boron.
In a preferred embodiment of the present invention, described carbon nano-particle is at P/P
0the aperture at=0.97 place is that to adsorb total pore volume be 0.2-0.7cm to the single-point in the hole of below 70nm
3g
-1, wherein, the pore volume of micropore is 0.1-0.4cm
3g
-1, mesoporous and total pore volume that is macropore is 0.2-0.8cm
3g
-1.
In another preferred embodiment of the present invention, the BET specific surface area of described nano particle is 400-1000m
2/ g.
In a preferred embodiment of the present invention, the particle diameter of described nano particle is 10-500nm, preferred 20-300nm, more preferably 30-100nm.
In preferred implementations more of the present invention, the heteroatoms in the carbon nano-particle of described Heteroatom doping is nitrogen-atoms, and the content of described nitrogen-atoms is 2-23%, preferred 3-20%, more preferably 4-15%.
In other preferred implementations of the present invention, the heteroatoms in the carbon nano-particle of described Heteroatom doping is sulphur atom, and the content of described sulphur atom is 2-25%, preferred 3-22%, more preferably 4-17%.
Second embodiment of the present invention relates to a kind of production method of carbon nano-particle of described Heteroatom doping, comprising:
1) reaction soln containing dispersion medium, oxygenant, doping agent, stablizer and conductive high polymer monomer is carried out oxypolymerization, control to react the speed of carrying out, ensure that the conducting polymer particle obtained is homodisperse spherical and/or spherical particle;
2) directly carry out the high temperature carbonization of structural conductive macromolecular nano particle in an inert atmosphere, obtain the Heteroatom doping carbon nano-particle with hierarchical porous structure.
The method that speed is carried out in described control reaction comprises the condition etc. adopting different raw material addition manners, select suitable oxidation system, select the consumption of suitable stabilising system and stablizer and control reaction to carry out.
Research before shows that structural conductive macromolecular is dissolved in all solvents hardly, namely allows to dissolve, and its solubleness is also low-down.Therefore, structural conductive macromolecular can not be swelling by monomer whose as common polymkeric substance, and nucleation mode is nonhomogen-ous nucleation mainly, and particle is combined by collision and increases.Therefore, well to control rate of polymerization in reaction process, avoid too fast speed of reaction.It is serious that the too fast meeting of speed of reaction causes product to be reunited, and cannot obtain spherical or class spherical nanoparticle.
Further, to preparation method of the present invention, details are as follows:
In a preferred embodiment of the present invention, described structural conductive macromolecular is be selected from the conducting polymer be made up of at least one in following monomer: the derivative of pyrroles, thiophene, 3,4-rthylene dioxythiophene, indoles, carbazole, aniline etc. and these monomers; The mixture of when structural conductive macromolecular monomer uses can be a kind of also can be several monomer.Preferred pyrroles, aniline, thiophene, 3, one or more in 4-ethene dioxythiophene, carbazole and in derivative, consider the stability of monomer and polymkeric substance, one or more more preferably in pyrroles, aniline, thiophene and 3,4-rthylene dioxythiophene and derivative thereof.
In a preferred embodiment of the present invention, the structure of described pyrroles, thiophene and their derivative is such as formula shown in I:
Wherein, X is N-R
2or S; R
2for C
1-C
20alkyl, aryl or replacement aryl, be preferably H or C
1-C
12-alkyl; Be more preferably H or C
1-C
8-alkyl, most preferably H;
4 R existed
1may be the same or different, H, alkyl, cycloalkyl, alkenyl, aryl, alkylaryl, hydroxyl, alkoxyl group, halogen, nitro can be selected from independently of one another, it should be noted that wherein have two R at least
1be necessary for H, halogen or alkoxyl group, these two R
1can be identical, also can be different; Preferably, 4 R of existence
1h, C can be selected from independently of one another
1-C
20alkyl, hydroxyl, C
1-C
4alkoxyl group, chlorine or nitro, it should be noted that four R
1in, at least at two R at X ortho position
1must be H, halogen or alkoxyl group respectively, but two R
1can be identical, also can be different; More preferably, 4 R of existence
1h, methyl, hydroxyl, chlorine or nitro can be selected from independently of one another, it should be noted that four R
1in, at least at two R at X ortho position
1must be H.
In a preferred embodiment of the present invention, the derivative of pyrroles and thiophene is selected from least one in following compound: N-methylpyrrole, N-N-ethyl pyrrole N-, N-n-propyl pyrroles, N-normal-butyl pyrroles, N-phenylpyrrole, N-phenmethyl pyrroles, N-naphthylpyrrole, N-carboxy pyrrole, 3-methylpyrrole, 3-carboxy pyrrole, 3,4-dimethyl pyrrole, 3-N-ethyl pyrrole N-, 3-n-propyl pyrroles, 3-normal-butyl pyrroles, 3-phenylpyrrole, 3-phenmethyl pyrroles, 3-naphthylpyrrole, 3-methoxypyrrole, 3-oxyethyl group pyrroles, 3-propoxy-pyrroles, 3-phenoxy group pyrroles, 3,4-dimethoxy pyrroles, 3-methyl-N-methyl pyrroles, 3-methoxy-. N-methyl pyrroles, 3-chlorine pyrroles, 3-bromine pyrroles, 3-alkylthrophene (3 methyl thiophene, 3-ethylthiophene, 3-propyl group thiophene, 3-hexyl thiophene etc.), 2,2 '-two thiophene, 3-methyl-2,2 '-two thiophene, 3,3 '-dimethyl-2,2 '-two thiophene, 3,4-dimethyl-2,2 '-two thiophene, 3,4-dimethyl-3 ', 4 '-dimethyl-2,2 '-two thiophene, 3-methoxyl group-2,2 '-two thiophene, 3,3 '-dimethoxy-2,2 '-two thiophene, 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, in the present invention the structural formula of aniline and its derivatives such as formula shown in II:
Wherein, R
3can be H, C
1-C
20the aryl of-alkyl, aryl or replacement; Be preferably H or C
3-C
12alkyl; Be more preferably H or C
4-C
8alkyl; Most preferably be H;
4 R existed
4may be the same or different, be selected from H, alkyl, cycloalkyl, alkenyl, aryl, alkyl substituting aromatic base, hydroxyl, alkoxyl group, halogen or nitro independently of one another, it should be noted that to have a R at least
4be necessary for H, halogen or alkoxyl group.4 R existed
4can independently selected from H, C
1-C
4alkyl, hydroxyl, C
1-C
4alkoxyl group, chlorine or nitro, and at least at NHR
3the R of contraposition
4h, halogen or alkoxyl group.More preferably, 4 R of existence
4can independently selected from H, methyl, ethyl, hydroxyl, chlorine, bromine or nitro, and NHR
3the R of contraposition
4for H.Most preferably, all R
4be all H.
In a preferred embodiment of the present invention, the monomer of anils can be selected from least one in following material: aniline, 2-aminotoluene, 2-ethylaniline, 2-propyl group aniline, 2-anisidine, 2-phenetidine, 3-monomethylaniline, 3-ethylaniline, 3-propyl group aniline, 3-anisidine, 3-phenetidine, 3-hexyl aniline, methylphenylamine, N propyl aniline, N-butylaniline; Preferred aniline.
In a preferred embodiment of the present invention, in the present invention, conductive high polymer monomer is in step 1) in mass concentration in reaction system be 0.1-30%, preferred concentration is 0.5-20%, and more preferably concentration is 1-10%, and most preferable concentrations is 1-5%.
In a preferred embodiment of the present invention, the reaction medium used in the present invention, i.e. solvent, the oxidizing any solvent used when being and can not being oxidizedly polymerized can be water, organic solvent or mixed solvent.Preferred reaction medium is water.
In further preferred implementation, the organic solvent in the present invention comprises ethanol, acetone, tetrahydrofuran (THF), tetramethylene sulfone, acetonitrile, toluene, propylene carbonate, NSC 11801, chloroform etc., preferred alcohol, acetonitrile.
There is no particular limitation for the oxygenant used in the present invention, can use iron (III) salt of mineral acid, copper (II) salt of mineral acid, persulphate, periodate, hydrogen peroxide, ozone, six cyanogen close iron (III) potassium, two hydrated sulfuric acid four ammoniums cerium (IV), bromine, iodine, organic acid iron (III) salt, and one or more in metal ion and the composite oxidation system of hydrogen peroxide.One or more in preferred mineral acid or organic acid iron (III) salt, persulphate and metal ion and the composite oxidation system of hydrogen peroxide.More preferably one or more in metal ion and the composite oxidation system of hydrogen peroxide.
Iron (III) salt of mineral acid described in the present invention comprises Anhydrous Ferric Chloride (III), ferric chloride hexahydrate (III), nine water iron nitrates (III), anhydrous nitric acid iron (III), n ferric sulfate hydrate (III) (n=3 to 12), 12 hydrated sulfuric acid ammonium iron (III), n perchloric acid hydrate iron (III) (n=1,6), Tetrafluoroboric acid iron etc., more preferably ferric chloride hexahydrate (III); Copper (II) salt of described mineral acid comprises cupric chloride (II), copper sulfate (II), cupric nitrate (II), neutralized verdigris (II), Tetrafluoroboric acid copper (II) etc., more preferably cupric chloride (II); Described persulphate comprises ammonium persulphate, Potassium Persulphate and Sodium Persulfate etc., more preferably ammonium persulphate; Described periodate comprises potassium periodate etc.; Described organic acid iron (III) salt comprises tosic acid iron (III) etc.; Described metal ion and the composite oxidation system of hydrogen peroxide comprise Fe
2+-H
2o
2, Fe
3+-H
2o
2, Cu
2+-H
2o
2deng, more preferably Fe
3+-H
2o
2.
Oxygenant/the monomer mole ratio used in the present invention is 0.1-10, and preferred molar ratio is 0.2-5, and more preferably mol ratio is 0.5-2.
The doping agent used in the present invention can be mineral acid, Lewis acid, organic acid and their derivative or iron (III) salt, alkylsulphonic acid, Phenylsulfonic acid, naphthene sulfonic acid, anthraquinone sulfonic acid and derivative thereof, tetracyanoethylene, one or more in trifluoromethanesulfonic acid.One or more in preferred mineral acid and alkylsulphonic acid, Phenylsulfonic acid and derivative thereof.
The mineral acid used in the present invention comprises HCl, H
2sO
4, HNO
3, HClO
4, chlorsulfonic acid etc.; Lewis acid comprises BF
3, PCl
5, AlCl
3, SnCl
4, WCl
6, MoCl
5deng; Organic acid comprises alkylsulphonic acid, Phenylsulfonic acid, anthraquinone sulfonic acid, camphorsulfonic acid and their derivative or their iron (III) salt; Sulfonic acid comprises single sulfonic acid, disulfonic acid or trisulfonic acid; The derivative of alkylsulphonic acid comprises 2-acrylamide-2-methyl propane sulfonic etc.; The derivative of Phenylsulfonic acid comprise sulfocarbolic acid, styrene sulfonic acid, tosic acid, to ethyl phenenyl azochlorosulfonate acid, Witco 1298 Soft Acid etc.; The derivative of naphthene sulfonic acid comprises 1-naphthalene sulfonic aicd, 2-naphthene sulfonic acid, 1,3-naphthalene disulfonic acid, 1,3,6-naphthalene trisulfonic acid and 6-ethyl-1-naphthalene sulfonic aicd etc.; The example of the derivative of anthraquinone sulfonic acid comprises anthraquinone-1-sulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-2,6-disulfonic acid and 2-methylanthraquinone-6-sulfonic acid etc.One or more in preferred HCl, tosic acid, camphorsulfonic acid, Witco 1298 Soft Acid.More preferably tosic acid.
In the present invention, doping agent/monomer mole ratio is 0.05-10, and preferred molar ratio is 0.1-5, and more preferably mol ratio is 0.2-2.
There is no particular limitation for the stablizer used in the present invention, can use all stablizers disclosed in prior art, comprises one or more in anionic emulsifier, nonionic emulsifier and various macromolecular stabilizer agent and polyanion.One or more in preferred anionic type emulsifying agent and macromolecular stabilizer agent.More preferably one or more in macromolecular stabilizer agent.
The anionic emulsifier used in the present invention comprises sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Witco 1298 Soft Acid, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate etc.Cationic emulsifier comprises Trimethyllaurylammonium bromide, cetyl trimethylammonium bromide etc.Nonionic emulsifier has OP series, NP is serial, Trixon is serial, Span series and TWEEN Series etc.Macromolecular stabilizer agent comprises polyoxyethylene (PEO), Polyvinylpyrolidone (PVP) (PVP), polyvinyl acetate (PVA) (PVAc, degree of hydrolysis: 70-99%), poly 4 vinyl pyridine, poly 2 vinyl pyridine, poly-(4-vinylpridine-co-butyl methacrylate), polyacrylamide, methylcellulose gum, cyclodextrin etc.Polyanion comprises sodium polyacrylate, poly (sodium 4-styrenesulfonate) etc.One or more wherein preferably in Sodium dodecylbenzene sulfonate, Witco 1298 Soft Acid, PVP, PVAc, methylcellulose gum and poly (sodium 4-styrenesulfonate).More preferably one or more in Witco 1298 Soft Acid, PVP and PVAc.
The molecular weight of the macromolecular stabilizer agent that the present invention uses is 5000-5000000.Preferred 10000-2500000; More preferably 10000-1000000.
The concentration of the stablizer used in the present invention is 0.1%-30%, and optimization concentration is 0.2%-20%, and more optimizing concentration is 0.2%-10%.
The temperature of reaction used in the present invention is-20 DEG C-150 DEG C, and preferable reaction temperature is-10 DEG C-100 DEG C, and more preferably temperature of reaction is-5 DEG C-50 DEG C.
Reaction times of using in the present invention needs the reaction conditions that carries out according to oxypolymerization and determine, the condition difference of polyreaction, and corresponding change also can occur the speed of polyreaction, generally between several hours to several days.
Structural conductive macromolecular nano particle in the present invention is spherical or class is spherical.
The size range of the structural conductive macromolecular nano particle prepared in the present invention is 10-500nm, and the size range of optimization is 20-300nm, and the size range more optimized is 30-100nm.
The inert atmosphere carrying out structural conductive macromolecular high temperature carbonization in the present invention comprises nitrogen and argon gas etc., and the purity of argon gas is higher by contrast, foreign matter content is few, therefore preferred argon gas, but argon gas cost is higher, uses nitrogen also passable.
The temperature range of carrying out structural conductive macromolecular charing in the present invention is 400-2300 DEG C, considers that heteroatomic content can reduce with the rising of carbonization temperature, and preferred temperature range is 500-1500 DEG C, and preferred carbonization temperature is 500-1000 DEG C.If carbonization temperature is too low, the pore structure in product still can not well be formed.
Beneficial effect of the present invention:
The carbon nano-particle of Heteroatom doping provided by the invention has hierarchical porous structure, and have micropore, mesoporous even macroporous structure, Heteroatom doping amount is high simultaneously, does not need activation just can obtain higher specific surface area, at CO
2there is application prospect the aspects such as trapping, battery, ultracapacitor, catalyzer, support of the catalyst.
The method of described carbon nano-particle provided by the invention has the features such as technique is simple, easy handling, direct charing just can obtain the porous carbon nano particle of Heteroatom doping, avoid in art methods and use the wasting shortcoming of a large amount of template, it also avoid the process that materials such as using alkali carries out activating, simplify preparation process, and obtained carbon nano-particle performance and structure all very stable.
Accompanying drawing explanation
Scanning electronic microscope (SEM) photo of porous carbon nano particle prepared by Fig. 1 embodiment 1.
Embodiment
Describe embodiments of the present invention in detail below with reference to embodiment, to the present invention, how utilisation technology means solve technical problem whereby, and the implementation procedure reaching technique effect can fully understand and implement according to this.It should be noted that; following examples are only for illustration of the present invention; any restriction can not be formed to scope of the present invention; only otherwise form conflict; each embodiment in the present invention and each feature in each embodiment can be combined with each other, and the technical scheme formed is all within protection scope of the present invention.
Testing method
Scanning electronic microscope (SEM): the shape of product and surface topography are by S-4800 type field emission scanning electron microscope (Hitachi, Japan) directly observe under 1kV voltage, the electroconductibility of product itself is better, does not need metal spraying directly to observe.
N2 adsorption desorption isothermal curve: on MicrometriticsASAP2020 adsorption unit, carries out the test of N2 adsorption desorption isothermal curve under-196 DEG C of conditions.Before test, first 180 DEG C, degassed process at least 6h is carried out to sample under high vacuum condition.
The specific surface area of product is calculated by the method for Brunauer-Emmett-Teller (BET).
Micropore size and distribution are obtained by Horvath-Kawazoe (HK) computing method.
Mesoporous pore size and distribution are obtained by Barrett-Joyner-Halenda (BJH) computing method.
Total pore volume is by relative pressure P/P
0be that the adsorptive capacity at 0.97 place calculates.
Micropore volume is then calculated by t-plot model.
Ultimate analysis: analyzed by the content of EA1112 instrument to the nitrogen element in product and element sulphur of Thermo company of the U.S..
In the present invention, described conducting polymer refers to the conducting polymer of structural conductive macromolecular or other types, and under the preferred conditions, it refers to structural conductive macromolecular or intrinsically conducting polymer.
Embodiment 1
Step one: first prepare polypyrrole (PPy) nano particle, preparation method is specially: add pyrroles, Polyvinylpyrolidone (PVP) (PVP being equipped with in the reaction vessel of mechanical stirring device of 500ml, molecular weight 220,000), tosic acid and deionized water, after stirring, add ferric chloride hexahydrate (III) (FeCl successively
36H
2the hydrogen peroxide solution of O) and 30%, make pyrroles in end reaction solution, PVP, tosic acid, ferric chloride hexahydrate (III) and hydrogen peroxide concentration be respectively 0.3M, 0.018M, 0.3M, 0.001M and 0.36M (wherein the concentration of PVP is the concentration of repeating unit in molecule).Reaction process uses ferric chloride hexahydrate (III) and the composite oxidation system of hydrogen peroxide, the speed of reduction oxypolymerization.Reaction is carried out at 23 DEG C, stops after reaction 24h.By the method for centrifugation, centrifugal 15min under 4000rpm speed, by PPy nanoparticle deposition, and uses deionized water wash 2-3 time, the salt in product, residual monomer and other impurity is washed off.And in the vacuum drying oven of 60 DEG C vacuum-drying 24h.The size being characterized the polypyrrole nano particle obtained by SEM is about 70 ± 30nm.
Step 2: be put in crucible by dried PPy powder of nanometric particles, carbonize in box atmosphere furnace, carbonization condition is: in a nitrogen atmosphere, is raised to 800 DEG C with the temperature rise rate of 3 DEG C/min, and keep 3h, then naturally cooling at 800 DEG C.Finally obtain the carbon nano-particle with hierarchical porous structure of N doping.The SEM of product characterizes as shown in Figure 1.Therefrom we can measure the particle diameter of the product after charing, with the adjoining dimensions of the polypyrrole nano particle before charing, are 70 ± 30nm.The analytical results of the BET specific surface area of product, pore volume, aperture and nitrogen element content is in table 1.
Embodiment 2
Step one: preparation PPy nano particle, preparation method is identical with embodiment 1, be just 220 by molecular weight, the PVP of 000 replace with domestic PVP (K30, molecular weight is about 10,000, Xilong Chemical Co., Ltd), and the concentration improving PVP is to 0.036M, reacts and carries out at 23 DEG C, stop after reaction 24h.In reaction process, monomer is slowly added drop-wise in reaction soln in form of an aqueous solutions, reduces rate of polymerization.Product washing methods is identical with embodiment 1 with drying means.Characterize by SEM the PPy nano particle obtained and be of a size of 60 ± 20nm.
Step 2: the condition that product carries out carbonizing is identical with embodiment 1.The particle diameter of the product after charing is 60 ± 20nm.The analytical results of the BET specific surface area of product, pore volume, aperture and nitrogen element content is in table 1.
Embodiment 3
Step one: the preparation method of PPy nano particle is identical with embodiment 2, but the concentration of pyrroles in end reaction solution, PVP, tosic acid, ferric chloride hexahydrate (III) and hydrogen peroxide is respectively 0.3M, 0.036M, 0.06M, 0.001M and 0.36M (wherein the concentration of PVP is the concentration of repeating unit in molecule).
Step 2: the condition that product carries out carbonizing is: in box atmosphere furnace, under nitrogen atmosphere, is heated to 700 DEG C with the temperature rise rate of 3 DEG C/min, and keep 3h, then naturally cooling at 700 DEG C.The particle diameter of the product after charing is 60 ± 20nm.The analytical results of the BET specific surface area of product, pore volume, aperture and nitrogen element content is in table 1.
Embodiment 4
Step one: the preparation method of PPy nano particle is identical with embodiment 2, but the concentration of pyrroles in end reaction solution, PVP, tosic acid, ferric chloride hexahydrate (III) and hydrogen peroxide is respectively 0.3M, 0.036M, 0.3M, 0.001M and 3.0M (wherein the concentration of PVP is the concentration of repeating unit in molecule), and oxidants hydrogen peroxide is slowly added drop-wise in reaction soln after dilution, and controlled oxidization rate of polymerization is slower.
Step 2: the condition that product carries out carbonizing is: in box atmosphere furnace, under nitrogen atmosphere, is heated to 600 DEG C with the temperature rise rate of 3 DEG C/min, and keep 3h, then naturally cooling at 600 DEG C.The particle diameter of the product after charing is 60 ± 20nm.The analytical results of the BET specific surface area of product, pore volume, aperture and nitrogen element content is in table 1.
Embodiment 5
Step one: the preparation method of PPy nano particle is identical with embodiment 2, but the concentration of pyrroles in end reaction solution, PVP, tosic acid, ferric chloride hexahydrate (III) and hydrogen peroxide is respectively 0.3M, 0.036M, 0.15M, 0.001M and 0.45M (wherein the concentration of PVP is the concentration of repeating unit in molecule), and reaction carries out in ice-water bath, temperature of reaction controls at 0-5 DEG C, reduces the speed of oxypolymerization.
Step 2: the condition that product carries out carbonizing is: in box atmosphere furnace, under nitrogen atmosphere, is heated to 500 DEG C with the temperature rise rate of 3 DEG C/min, and keep 4h, then naturally cooling at 500 DEG C.The particle diameter of the product after charing is 60 ± 20nm.The analytical results of the BET specific surface area of product, pore volume, aperture and nitrogen element content is in table 1.
Embodiment 6
Step one: the method preparing PPy nano particle is identical with embodiment 2, just the tosic acid of 0.1M is replaced with the HCl of 0.15M, other reaction conditions is identical, washs also identical with embodiment 1 with dry process.Characterize by SEM the polypyrrole nano particle obtained and be of a size of 60 ± 20nm.
Step 2: the condition of PPy nano particle charing is identical with embodiment 1.The particle diameter of the product after charing is 60 ± 20nm.The analytical results of the BET specific surface area of product, pore volume, aperture and nitrogen element content is in table 1.
Embodiment 7
Step one: prepare polyaniline (PANI) nano particle, preparation method is specially: in the reaction vessel that mechanical stirring device is housed, add aniline, PVP (K30, molecular weight 10,000, Xilong Chemical Co., Ltd), hydrochloric acid and deionized water, after stirring, add ammonium persulphate (APS) aqueous solution, make the concentration of aniline, PVP, HCl, APS in final system be respectively 0.21M, 0.018M, 0.21M and 0.21M.Reaction, in ice-water bath, is carried out at 0-5 DEG C, stops after reaction 24h.The method of product separation washing is identical with embodiment 1.
Step 2: the charing method of PANI particle is identical with embodiment 1.The analytical results in the BET specific surface area of product, pore volume and aperture is in table 1.
Table 1
Wherein: S
bETfor the specific surface area calculated by Brunauer-Emmett-Teller (BET) method;
S
microfor the micropore specific area obtained by t-plot;
V
microfor being analyzed the Micropore volume obtained by t-plot;
V
totfor P/P
0be that the single-point that 0.97 place's hole dimension is less than 70nm adsorbs total pore volume;
D
mesofor the mesoporous mean pore size calculated by Barrett-Joyner-Halenda (BJH) method;
D
microfor the micropore size calculated by Horvath-Kawazoe (HK) method;
C
nfor the N element content in the product ontology that obtained by ultimate analysis.
Claims (19)
1. a carbon nano-particle for Heteroatom doping, is characterized in that, described carbon nano-particle has that aperture is less than the micropore of 2nm, aperture is the macropore that the mesoporous of 2-50nm and aperture are greater than 50nm, and the BET specific surface area of described carbon nano-particle is 300-1500m
2/ g, the content of heteroatoms in described carbon nano-particle is 2-25wt%, and described heteroatoms is selected from least one in nitrogen phosphate and sulfur and boron.
2. carbon nano-particle according to claim 1, is characterized in that, described carbon nano-particle is at P/P
0the aperture at=0.97 place is that to adsorb total pore volume be 0.2-0.7cm to the single-point in the hole of below 70nm
3g
-1, the pore volume of described micropore is 0.1-0.4cm
3g
-1, mesoporous and total pore volume that is macropore is 0.2-0.8cm
3g
-1.
3. carbon nano-particle according to claim 1 and 2, is characterized in that, the BET specific surface area of described nano particle is 400-1000m
2/ g.
4. the carbon nano-particle according to any one of claim 1-3, is characterized in that, the particle diameter of described nano particle is 10-500nm, preferred 20-300nm, more preferably 30-100nm.
5. the carbon nano-particle according to any one of claim 1-4, is characterized in that, described heteroatoms is nitrogen-atoms, and the content of described nitrogen-atoms is 2-23%, preferred 3-20%, more preferably 4-15%.
6. the carbon nano-particle according to any one of claim 1-5, is characterized in that, described heteroatoms is sulphur atom, and the content of described sulphur atom is 2-25%, preferred 3-22%, more preferably 4-17%.
7. a production method for the nano particle according to any one of claim 1-6, comprising:
1) reaction soln containing dispersion medium, oxygenant, doping agent, stablizer and conductive high polymer monomer is carried out oxypolymerization, control to react the speed of carrying out, ensure that the conducting polymer particle obtained is homodisperse spherical and/or spherical particle;
2) directly carry out the high temperature carbonization of conducting polymer nano particle in an inert atmosphere, obtain described Heteroatom doping carbon nano-particle.
8. method according to claim 7, it is characterized in that, described conducting polymer is be selected from the conducting polymer be made up of at least one in following monomer: the derivative of pyrroles, thiophene, 3,4-rthylene dioxythiophene, indoles, carbazole, furans and these monomers; At least one in preferred pyrroles, aniline and its derivatives, thiophene and 3,4-rthylene dioxythiophene and carbazole; More preferably one or more in pyrroles, aniline, thiophene and 3,4-rthylene dioxythiophene and derivative thereof.
9. method according to claim 8, is characterized in that, the structure of described pyrroles, thiophene and derivatives is such as formula shown in I:
Wherein, X is N-R
2or S; R
2for C
1-C
20alkyl, aryl or replacement aryl, be preferably H or C
1-C
12-alkyl; Be more preferably H or C
1-C
8-alkyl, most preferably H;
4 R existed
1may be the same or different, H, alkyl, cycloalkyl, alkenyl, aryl, alkylaryl, hydroxyl, alkoxyl group, halogen or nitro can be selected from independently of one another, wherein have two R at least
1be selected from H, halogen or alkoxyl group; Preferably, each R
1be selected from H, C independently of one another
1-C
20alkyl, hydroxyl, C
1-C
4alkoxyl group, chlorine or nitro, wherein, at least at two R at X ortho position
1must separately be selected from H, halogen or alkoxyl group; It is further preferred that each R
1h, methyl, hydroxyl, chlorine or nitro can be respectively, wherein, at least at two R at X ortho position
1h.
10. the method according to any one of claim 7-9, is characterized in that, the structural formula of described aniline and its derivatives is such as formula shown in II:
Wherein, R
3for H, C
1-C
20the aryl of-alkyl, aryl or replacement; Be preferably H or C
3-C
12alkyl; Be more preferably H or C
4-C
8alkyl; Most preferably be H;
4 R existed
4may be the same or different, be selected from H, alkyl, cycloalkyl, alkenyl, aryl, alkyl substituting aromatic base, hydroxyl, alkoxyl group, halogen or nitro independently of one another, wherein have a R at least
4be necessary for H, halogen or alkoxyl group; Preferably, 4 R of existence
4can independently selected from H, C
1-C
4-alkyl, hydroxyl, C
1-C
4-alkoxyl group, chlorine or nitro, and at least at NHR
3the R of contraposition
4h, halogen or alkoxyl group; More preferably, 4 R of existence
4can independently selected from H, methyl, ethyl, hydroxyl, chlorine, bromine or nitro, and NHR
3the R of contraposition
4for H; Most preferably, all R
4be all H.
11. methods according to any one of claim 7-10, it is characterized in that, described conductive high polymer monomer is in step 1) in mass concentration in reaction system be 0.1-30%, preferred mass concentration is 0.5-20%, more preferably mass concentration is 1-10%, and most preferably mass concentration is 1-5%.
12. methods according to any one of claim 7-11, it is characterized in that, described dispersion medium is selected from least one in water, organic solvent or its mixed solvent; At least one of described organic solvent preferably in following compound: ethanol, acetone, N-Methyl pyrrolidone, tetrahydrofuran (THF), tetramethylene sulfone, acetonitrile, toluene, propylene carbonate, NSC 11801 and chloroform, preferred alcohol and/or acetonitrile;
Preferably, described dispersion medium is water.
13. methods according to any one of claim 7-12, it is characterized in that, described oxygenant is selected from least one in following material: iron (III) salt of mineral acid, copper (II) salt of mineral acid, persulphate, periodate, hydrogen peroxide, ozone, six cyanogen close iron (III) potassium, two hydrated sulfuric acid four ammoniums cerium (IV), bromine, iodine, organic acid iron (III) salt, and metal ion and the composite oxidation system of hydrogen peroxide; One or more in preferred use mineral acid or organic acid iron (III) salt and persulphate; More preferably persulphate.
14. methods according to any one of claim 7-13, it is characterized in that, the molar ratio range of described oxygenant and polymer monomer is 0.1-10, and excellent is 0.3-5, more preferably 0.5-2.
15. methods according to any one of claim 7-14, it is characterized in that, described stablizer is selected from least one in following material: anionic emulsifier, nonionic emulsifier, macromolecular stabilizer agent and polyanion; At least one in preferred anionic type emulsifying agent and/or macromolecular stabilizer agent, at least one more preferably in macromolecular stabilizer agent;
Preferably, the molecular weight of described macromolecular stabilizer agent is 5000-5000000, preferred 10000-2500000, more preferably 10000-1000000.
16. methods according to any one of claim 7-15, it is characterized in that, described doping agent is selected from least one in following material:
Mineral acid, Lewis acid, organic acid and derivative thereof or iron (III) salt, alkylsulphonic acid, Phenylsulfonic acid, naphthene sulfonic acid, anthraquinone sulfonic acid and derivative thereof and tetracyanoethylene and trifluoromethanesulfonic acid; One or more in preferred mineral acid, Lewis acid, alkylsulphonic acid, Phenylsulfonic acid and derivative thereof; Preferred, described doping agent is selected from least one in HCl, tosic acid, camphorsulfonic acid and Witco 1298 Soft Acid, preferred tosic acid.
17. methods according to any one of claim 7-16, it is characterized in that, the mol ratio of described Can Za Ji ︰ polymer monomer is 0.05-10, preferred 0.1-5, more preferably 0.2-2.
18. methods according to any one of claim 7-17, it is characterized in that, the temperature range of described reaction is-10 DEG C-70 DEG C, preferred 0-50 DEG C.
19. methods according to any one of claim 7-18, it is characterized in that, the temperature range of charing is 400-2300 DEG C, is preferably 500-1500 DEG C, is more preferably 500-1000 DEG C.
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