CN106672935B - A kind of preparation method of the hollow porous carbon materials of N doping - Google Patents
A kind of preparation method of the hollow porous carbon materials of N doping Download PDFInfo
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- CN106672935B CN106672935B CN201611213497.0A CN201611213497A CN106672935B CN 106672935 B CN106672935 B CN 106672935B CN 201611213497 A CN201611213497 A CN 201611213497A CN 106672935 B CN106672935 B CN 106672935B
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Abstract
The present invention relates to a kind of preparation methods of N doping porous carbon; specific step is as follows: preparing manganese dioxide presoma first; configure the mixed solution containing certain proportion aniline and pyrrole monomer; it disperses manganese dioxide powder in above-mentioned solution; by dispersion liquid temperature be cooled to 10 DEG C hereinafter, and be added into above-mentioned dispersion liquid acid solution, low-temp reaction separating obtained product after a certain period of time; the finally high temperature cabonization under protective atmosphere obtains the hollow porous carbon materials of N doping.The present invention has synthesis technology simple, synthesis process safe green is pollution-free, and byproduct recoverable is suitble to the features such as industrialized production, gained N doping porous carbon function admirable, specific surface area is higher, can be widely applied to the fields such as the energy storage such as supercapacitor, catalysis and absorption.
Description
Technical field
The invention belongs to porous material preparation fields, and in particular to a kind of preparation side of the hollow porous carbon materials of N doping
Method.
Background technique
Recent years, porous carbon materials are because have such as high electric conductivity, big specific surface area, and cheap price etc. is excellent
Point has attracted the attention of more and more researchers, has obtained more and more extensive research, has been widely used as supercapacitor
Electrode material, negative electrode material, gas adsorption material and the catalyst carrier material of lithium ion battery etc., and there is hollow structure
Nitrogen-doped porous carbon material because with macropore (>50nm), mesoporous (2-50nm), micropore (<2nm) complete pore system,
The needs that can be competent under different application field, while the presence of nitrogen-atoms can significantly improve the electrochemistry of material after N doping
Performance and hydrophily, therefore have a vast market foreground.As the hollow N doping porous carbon that can be used with industrialization promotion
Material first has to guarantee that prepared porous carbon materials have suitable pore-size distribution and higher specific surface area, secondly ask a price
Lattice are cheap, and synthesis process is pollution-free, environmentally friendly, it is therefore desirable to accomplish that synthesising by-product can be with recycling.
Some porous carbon materials of commercial applications at present, because of itself unreasonable pore-size distribution and complicated tediously long and right
The disagreeableness synthesis process of environment, has not been reached yet above-mentioned requirements.Such as electrode material for super capacitor, for supercapacitor
For, existing electrode material needs special reaction raw materials as not yet realized industry such as Chinese patent 201610272051.9
Change the graphene oxide and ionic liquid of volume production, and needs to activate and could use, other some patents, such as Chinese patent
201410705947.2, it is also desirable to porous structure can just be obtained by activated material under alkaline matter high temperature, but alkaline matter
High temperature etching can damage reaction vessel, and synthesis process can also impact environment.Almost without the China of this field
Patent is related to the recycling of synthetic product byproduct.Therefore, it finds one kind and has both suitable pore-size distribution and higher
Specific surface area and and, synthesising by-product recoverable pollution-free at process and cheap porous carbon materials synthetic method
With very great meaning.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of preparation side of hollow porous carbon materials of N doping
Method does not need interminable activation and template removal step, it is hollow that the higher N doping of specific surface area can be obtained by direct carbonization
Porous carbon materials, and this method is raw materials used cheap, and easily prepared, synthesis process is environmentally friendly.
Technical solution
A kind of preparation method of the hollow porous carbon materials of N doping, it is characterised in that steps are as follows:
Step 1: dispersing manganese dioxide precursor powder in the mixed solution of aniline and pyrrole monomer, dispersed
Liquid；The molar ratio of the aniline and pyrrole monomer is 0.5:1-2:1；The molar ratio of the manganese dioxide and aniline and pyrrole monomer
Example is 0.01:1-2000:1；
Step 2: dispersion liquid being cooled to 10 DEG C hereinafter, adding acid solution, in a low temperature of 0-10 DEG C, reaction 1-24 is small
When after separating obtained product；The acid solution of the addition makes the molar ratio of hydrogen ion and manganese dioxide in solution be 0.5:100-
4:100；
Step 3: the high temperature cabonization under protective atmosphere obtains the hollow porous carbon materials of N doping；The pyrocarbon chemical industry
Heating rate is 0.1-20 DEG C/min in skill, and temperature is 600-1200 DEG C, and carbonization time is 2-20 hours；The protective atmosphere
For nitrogen, argon gas or helium.
The manganese dioxide precursor construction is one-dimensional nano line, nanotube, nanometer rods, two-dimensional nano piece, three-dimensional manometer
Colored or sea urchin shape nanosphere pattern.
The manganese dioxide presoma is prepared by hydro-thermal method, chemical precipitation method or electrochemical deposition method.
The molar ratio of the aniline and pyrrole monomer is 1:1.
The molar ratio of the manganese dioxide and aniline and pyrrole monomer is 1000:1-600:1.
The acid solution is sulfuric acid, hydrochloric acid, nitric acid or acetic acid etc., solution concentration 0.01-5mol/L.
The step 2 dispersion liquid cooling is added after acid solution in a low temperature of 0-5 DEG C, reacts 6-8 hours.
Beneficial effect
A kind of preparation method of the hollow porous carbon materials of N doping proposed by the present invention, principle are as follows.Aniline and pyrroles are complete
After fully dissolved, because pyrroles is hydrophobic and aniline is hydrophilic, pyrroles can be gathered in around manganese dioxide surface, and aniline then disperses in water
It opens.After acid is added, under acid effect, manganese dioxide is reacted with aniline, pyrroles, and aniline and pyrroles are copolymerized, in dioxy
Change and form copolymer around manganese, the aniline and pyrrole concentrations near manganese dioxide in solution reduce, unreacted aniline in solution
It can diffuse through to come with pyrroles, make to react lasting progress.Manganese dioxide is consumed as oxidant simultaneously, generates divalent manganesetion,
Aniline and pyrroles ultimately form hollow copolymer.Since the copolymer has solid carbon skeleton network, therefore in higher temperature
Degree still can keep pore structure without collapsing with carbonization under harsher Carbonization Conditions, it is possible to directly be obtained by carbonization
Porous structure.
Beneficial effects of the present invention are as follows.Firstly, raw material used in the present invention is all common and cheap raw material,
Mature production technology.Secondly, entire synthesis technology of the invention is not huge using having to hydrofluoric acid, surfactant etc. to environment
Big harm or the reagent for having serious harm to the person, equipment.Again, step of the invention (2) resulting filtrate obtains after being evaporated
Manganese sulfate can be used for step (1) synthesis manganese dioxide just, can be recycled, can also be applied to other field, meet current
The theme to economize on resources with protection environment, and harm of the metal ion to environment is eliminated, it does not need with other means back and forth
Purification waste liquid is received, environmental benefit is obvious.In addition to this, pass through the pattern of control manganese dioxide presoma, thus it is possible to vary final to produce
The pattern of object porous carbon materials.Last synthesis technology of the present invention is simple, and prepared porous carbon is had excellent performance, and is suitble to industry metaplasia
It produces.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph of manganese dioxide nano pipe prepared by embodiment 1.
Fig. 2 is the electron scanning micrograph of intermediate product prepared by embodiment 1.
Fig. 3 is the electron scanning micrograph of final product N doping porous carbon prepared by embodiment 1.
Fig. 4 is the nitrogen adsorption desorption test curve of N doping porous carbon prepared by embodiment 1.
Fig. 5 is the electron scanning micrograph of three-dimensional manganese dioxide prepared by embodiment 2.
Fig. 6 is the electron scanning micrograph of three-dimensional nitrogen-doped porous carbon material prepared by embodiment 2.
Fig. 7 is for nitrogen-doped porous carbon material prepared by embodiment 4 not when as electrode material for super capacitor
With the cyclic voltammetry curve under sweep speed.
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
Embodiment 1
Take 0.7g KMnO4, 1.4g MnSO4, it is dissolved in 70ml water.Solution is poured into water heating kettle, keeps the temperature 12 at 150 DEG C
Hour, after it is cooled to room temperature, filtering and washing products therefrom and the desciccate at 60 DEG C.The brown ceramic powder obtained at this time is i.e.
For manganese dioxide nano pipe shown in attached drawing 1.
Prepared manganese dioxide nano pipe 400mg, aniline 0.152ml, pyrroles 0.116ml are taken, is added in 180ml water,
After stirring 20min, solution is put into refrigerator (3-5 DEG C) and freezes 30min, 1mlH is added after taking-up2SO4, 0.5min is stirred, is put
Enter in refrigerator (3-5 DEG C) reaction 8h, product is filtered to filtrate and is in neutrality, it is dry at 60 DEG C.The black product obtained at this time
As attached intermediate product shown in Fig. 2.
Intermediate product 400mg is taken, is placed in tube furnace, in a nitrogen atmosphere, 900 DEG C is warming up to 5 DEG C/min rate, protects
Warm 7h, later cooled to room temperature.The product obtained at this time is attached nitrogen-doped porous carbon material shown in Fig. 3.
It is tested through nitrogen adsorption desorption, the specific surface area of products therefrom is 538m2/ g, pore volume 1.2cm3/g.
Embodiment 2
Take 0.7g KMnO4, 1.5g MnSO4, it is dissolved in 70ml water.Solution is poured into water heating kettle, it is small that 5 are kept the temperature at 120 DEG C
When, after it is cooled to room temperature, filtering and washing products therefrom and the desciccate at 60 DEG C.Three-dimensional shown in attached drawing 5 is obtained at this time
Manganese dioxide.
Prepared manganese dioxide 200mg, aniline 0.38ml, pyrroles 0.29ml are taken, is added in 60ml water, 20min is stirred
Afterwards, solution is put into refrigerator (3-5 DEG C) and freezes 30min, the 15ml freezed in advance is added after taking-up and contains the dense H of 1ml2SO4's
Aqueous solution stirs 0.5min, is put into refrigerator (3-5 DEG C) reaction 8h, product is filtered to filtrate and is in neutrality, and does at 60 DEG C
It is dry, obtain intermediate product.
Intermediate product 200mg is taken, is placed in tube furnace, in a nitrogen atmosphere, 900 DEG C is warming up to 5 DEG C/min rate, protects
Warm 7h, later cooled to room temperature.The product obtained at this time is attached nitrogen-doped porous carbon material shown in fig. 6.
Embodiment 3
Take 0.7g KMnO4, 1.5g MnSO4, it is dissolved in 70ml water.Solution is poured into water heating kettle, keeps the temperature 12 at 160 DEG C
Hour, after it is cooled to room temperature, filtering and washing products therefrom and the desciccate at 60 DEG C.1-dimention nano threadiness is obtained at this time
Manganese dioxide.
Prepared manganese dioxide 400mg, aniline 0.38ml, pyrroles 0.29ml are taken, is added in 60ml water, 20min is stirred
Afterwards, solution is put into refrigerator (3-5 DEG C) and freezes 30min, the 15ml freezed in advance is added after taking-up and contains 2ml H2SO4's
Aqueous solution stirs 0.5min, is put into refrigerator (3-5 DEG C) reaction 8h, product is filtered to filtrate and is in neutrality, and does at 60 DEG C
It is dry, obtain intermediate product.
Intermediate product 200mg is taken, is placed in tube furnace, in a nitrogen atmosphere, 900 DEG C is warming up to 5 DEG C/min rate, protects
Warm 15h, later cooled to room temperature.One-dimensional nitrogen-doped porous carbon material is obtained at this time.Its nitrogen adsorption desorption test result is such as
Shown in attached drawing 4, specific surface area 720m2/g。
Embodiment 4
Take 0.7g KMnO4, 1.5g MnSO4, it is dissolved in 70ml water.Solution is poured into water heating kettle, keeps the temperature 10 at 150 DEG C
Hour, after it is cooled to room temperature, filtering and washing products therefrom and the desciccate at 60 DEG C.
Prepared manganese dioxide nano pipe 400mg, aniline 0.38ml, pyrroles 0.29ml are taken, is added in 60ml water, stirring
After 20min, solution is put into refrigerator (3-5 DEG C) and freezes 30min, 1ml H is added after taking-up2SO4, 0.5min is stirred, ice is put into
(3-5 DEG C) reaction 8h, product is filtered to filtrate and is in neutrality in case, dry at 60 DEG C.
Intermediate product 400mg is taken, is placed in tube furnace, in a nitrogen atmosphere, 900 DEG C is warming up to 5 DEG C/min rate, protects
Warm 10h, later cooled to room temperature.
Using the potassium hydroxide solution of 6M as electrolyte, capacitive property survey is carried out to the material more prepared using three-electrode system
Examination.Cyclic voltammetry curve of the products therefrom under different scanning rates shows that the high rate performance of product is excellent, and products therefrom is in 1A/
Capacity is 209F/g under the current density of g, and capacity retention ratio is 100% after 5000 circulations at 50A/g, electrochemical impedance
Spectrum shows the resistance very little of material, simultaneously as material has excellent multiplying power property, so material can carry out high-power fill
Electric discharge, is suitable as the electrode material of supercapacitor.
Claims (3)
1. a kind of preparation method of the hollow porous carbon materials of N doping, it is characterised in that steps are as follows:
Step 1: dispersing manganese dioxide precursor powder in the mixed solution of aniline and pyrrole monomer, obtain dispersion liquid；Institute
The molar ratio for stating aniline and pyrrole monomer is 0.5:1-2:1；The molar ratio of the manganese dioxide and aniline and pyrrole monomer is
0.01:1-2000:1；
Step 2: dispersion liquid is cooled to 10 DEG C hereinafter, acid solution is added, in a low temperature of 0-10 DEG C, after reaction 1-24 hours
Separating obtained product；The acid solution of the addition makes the molar ratio of hydrogen ion and manganese dioxide in solution be 0.5:100-4:
100；
Step 3: the high temperature cabonization under protective atmosphere obtains the hollow porous carbon materials of N doping；In the high temperature cabonization technique
Heating rate is 0.1-20 DEG C/min, and temperature is 600-1200 DEG C, and carbonization time is 2-20 hours；The protective atmosphere is nitrogen
Gas, argon gas or helium；
The manganese dioxide precursor construction be one-dimensional nano line, nanotube, nanometer rods, two-dimensional nano piece, three-dimensional manometer flower or
Sea urchin shape nanosphere pattern；
The manganese dioxide presoma is prepared by hydro-thermal method, chemical precipitation method or electrochemical deposition method；
The acid solution is sulfuric acid, hydrochloric acid, nitric acid or acetic acid, solution concentration 0.01-5mol/L.
2. the preparation method of the hollow porous carbon materials of N doping according to claim 1, it is characterised in that: the manganese dioxide
It is 1000:1-600:1 with the molar ratio of aniline and pyrrole monomer.
3. the preparation method of the hollow porous carbon materials of N doping according to claim 1, it is characterised in that: the step 2 is divided
Dispersion liquid is added after acid solution in a low temperature of 0-5 DEG C, reacts 6-8 hours.
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| CN107706405A (en) * | 2017-11-23 | 2018-02-16 | 齐鲁工业大学 | A kind of method for preparing nitrogen or the bar-shaped Zinc ion battery positive electrode of nitrogen sulfur doping carbon coating manganese dioxide composite Nano |
| CN109167074A (en) * | 2018-08-08 | 2019-01-08 | 东华大学 | The nitrogen-doped carbon nanocomposite of hollow additive Mn cobalt oxide nickel coated and preparation |
| CN110534716B (en) * | 2019-08-30 | 2020-08-14 | 华北电力大学 | Porous manganese oxide micro-sphere and preparation method and application thereof |
| CN110451465B (en) * | 2019-09-09 | 2022-08-16 | 吉林大学 | Sea urchin-shaped boron nitride nanosphere-nanotube hierarchical structure and preparation method thereof |
| CN111268668B (en) * | 2020-02-17 | 2021-11-19 | 西安交通大学 | Nitrogen-doped porous nano carbon material, preparation method and application of nitrogen-doped porous nano carbon material as negative electrode material of lithium ion battery |
| CN111547705B (en) * | 2020-05-12 | 2022-03-29 | 中国计量大学 | Preparation method of porous carbon electrode material |
| CN114068935B (en) * | 2021-11-15 | 2023-01-24 | 大连理工大学 | High-activity Mn/Co-N dual-site doped carbon material catalyst, preparation method and application thereof in lithium-sulfur battery |
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