CN108298517A - A kind of method and its product preparing porous carbon materials using halogenated polyolefin hydrocarbon-based polymeric object as presoma - Google Patents
A kind of method and its product preparing porous carbon materials using halogenated polyolefin hydrocarbon-based polymeric object as presoma Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods and its product preparing porous carbon materials using halogenated polyolefin hydrocarbon-based polymeric object as presoma, the method is to use halogenated polyolefin hydrocarbon-based polymeric object for raw material, under air and/or inert atmosphere, removing halogen and carbonization treatment are carried out to it；Since the raw material of the present invention has anti-flammability, and the carburizing temperature used is low so that the halogenated polyolefin hydrocarbon-based polymeric object will not aoxidize in air；The use cost for greatly reducing inert gas simplifies into carbon condition.The method preparation process is simple, easy to operate, and reaction temperature is low, low for equipment requirements, in air atmosphere it is achieved that saving the energy, the application prospect with industrialized production.Activation process is needed not move through using the porous carbon materials that this method is prepared, and carburizing temperature is low；The specific surface area of the carbon material is 200~2000m20.2~1.0cm of/g, Kong Rongwei3/g；Degree of graphitization is higher, and ID/IG is 0.3~1.5.
Description
Technical field
The invention belongs to porous carbon materials technical fields, and in particular to one kind is using halogenated polyolefin hydrocarbon-based polymeric object as presoma
The porous carbon materials for preparing the method for porous carbon materials and its being prepared.
Background technology
Porous carbon materials are because with high-specific surface area, high porosity, good electric conductivity and thermal conductivity, regulatable aperture
And surface property, it is widely used in fields such as catalyst carrier, super capacitor, catalyst, adsorbent and gas storages.
There are two types of the customary preparation methods of porous carbon materials：Activation method and template.Wherein, activation method includes mainly following
Two steps：1) it is carbonized under an inert atmosphere to presoma, obtains carbonized product；2) it is lived to carbonized product with activator
Change.Activation process is selectively to be handled the active site of carbon material to obtain porous structure using oxidant.It is living
Change method is to prepare the conventional method of porous carbon materials, using the method be prepared it is mostly be disordered structure porous carbon materials.
The porous carbon materials of Template synthesis have good structural controllability, but building-up process complexity is cumbersome, are unsuitable for extensive
Industrial production.
The raw material sources for preparing porous carbon materials are extensive, as polyimides, poly furfuryl alcohol, polyethylene terephthalate,
The high molecular polymers such as phenolic resin and polyvinyl chloride, various coals and coal radical derivative, biomass, petroleum by-products etc. are former
The technique that the difference of material prepares porous carbon materials accordingly is also different, and the performance of obtained porous carbon materials is also different.Wherein, hole
Gap rate is to evaluate an important indicator of porous carbon materials performance quality, and the increase of porous carbon materials porosity depends on
The processes such as activation process (such as physically activated, chemical activation, catalytic activation).It is reported in Chinese patent CN105293473A, with
Kynoar is the porous carbon materials that raw material is prepared, after Kynoar is first is dissolved by the preparation process, then
High temperature cabonization is carried out at 500~1000 DEG C, so that it may obtain that aperture is uniform, specific surface area is more than 1000m2The microporous carbon of/g.
Invention content
In order to solve the deficiencies in the prior art, an object of the present invention is intended to provide one kind with halogenated polyolefin hydrocarbon-based polymeric
Object is the method that presoma prepares porous carbon materials, and the method operating process is easy, and the porous carbon materials being prepared are not necessarily to
High temperature and subsequent activation processing, in this embodiment it is not even necessary to achieve that carbonization under an inert atmosphere.
The second object of the present invention is intended to provide the porous carbon materials that the above method is prepared, the porous carbon materials tool
It is 200~2000m to have porous structure, specific surface area20.2~1.0cm of/g, Kong Rongwei3/g。
Purpose of the present invention is to what is be achieved through the following technical solutions：
A method of preparing porous carbon materials, the preparation method packet by presoma of halogenated polyolefin hydrocarbon-based polymeric object
It includes：
A) presoma halogenated polyolefin hydrocarbon-based polymeric object is placed in tube furnace, in air atmosphere, slowly heating carries out halogen
Element removing, is prepared the porous carbon materials；Alternatively,
B) presoma halogenated polyolefin hydrocarbon-based polymeric object is placed in tube furnace, under an inert atmosphere, slowly heating carries out carbon
Change is handled, and the porous carbon materials are prepared；Alternatively,
C) presoma halogenated polyolefin hydrocarbon-based polymeric object is placed in tube furnace, in air atmosphere, slowly heating carries out halogen
Element removing, then passes to inert atmosphere, and heating carries out carbonization treatment, the porous carbon materials are prepared.
According to the present invention, in the halogenated polyolefin hydrocarbon-based polymeric object, carbon, three kinds of elements of hydrogen and halogen quality and be not less than
The 90wt% of the halogenated polyolefin hydrocarbon-based polymeric amount of substance；The quality of halogens is not less than the halogenated polyolefin hydrocarbon-based polymeric amount of substance
40wt%, preferably not less than 45wt%, be not higher than the halogenated polyolefin hydrocarbon-based polymeric amount of substance 85wt%, preferably no greater than
80wt%；Halogens is selected from F, Cl, one or more, preferably Cl or Br in Br and I；The molar ratio of halogen and carbon is
(0.5~2.0):1, preferably (0.5~1.8):1.
Preferably, the halogenated polyolefin hydrocarbon-based polymeric object includes but not limited to halogenated polyolefin, the poly- halogen alkene of halogenation.It is preferred that
Ground, the polyolefin in the halogenated polyolefin are poly alpha olefin, for example, polyethylene, polypropylene, poly 1-butene, poly- 1- amylenes,
Poly- 1- hexenes, poly- 1- heptene, poly- 1- octenes, poly- 1- nonenes, poly- 1- decene, poly- 1- hendecenes or its copolymer, it is also preferably poly-
Ethylene, polypropylene, poly 1-butene or its copolymer.Preferably, the halogen choosing in the poly- halogen alkene in the poly- halogen alkene of the halogenation
From chlorine or bromine, the poly- halogen alkene for example selected from polyvinyl chloride, polyvinyl bromide, poly- vinylidene chloride, poly- 1,2-dichloroethene,
Poly- 1,1,2- trichloro ethylenes, poly- chlorallylene, poly- 3- bromopropenes, polychloroprene, poly- bromobutene etc..
It is further preferred that the halogenated polyolefin hydrocarbon-based polymeric object includes but not limited to halogenated polyethylene, halogenated polypropylene, halogenation
Poly 1-butene, halogenation polyvinyl chloride, the poly- 1,1- dichloroethylene of halogenation, the poly- 1,2- dichloroethylene of halogenation, the poly- 1,1,2- trichlorines of halogenation
In ethylene, the poly- chlorallylene of halogenation, halogenation polychloroprene, halogenation polyvinyl bromide, the poly- 3- bromopropenes of halogenation, the poly- bromobutene of halogenation
It is one or more of.
It is highly preferred that the halogenated polyolefin hydrocarbon-based polymeric object includes but not limited to haloflex, chlorinated polypropylene, chlorination
Poly 1-butene, chliorinated polyvinyl chloride, the poly- vinylidene chloride of chlorination, the poly- 1,2-dichloroethene of chlorination, chlorination poly- 1,1,2- trichlorine
Ethylene, the poly- chlorallylene of chlorination, chlorinated polychloroprene, chlorination polyvinyl bromide, the poly- 3- bromopropenes of chlorination, the poly- bromobutene of chlorination, bromine
Change polyethylene, bromination polypropylene, poly- 1, the 2- of bromination poly 1-butene, bromination polyvinyl chloride, the poly- vinylidene chloride of bromination, bromination bis-
The poly- 1,1,2- trichloro ethylenes of vinyl chloride, bromination, the poly- chlorallylene of bromination, bromination polychloroprene, bromination polyvinyl bromide, the poly- 3- of bromination
One or more of poly- bromobutene of bromopropene, bromination.
According to the present invention, the halogenated polyolefin hydrocarbon-based polymeric object can be powdered, voluminous powder shape, threadiness or block
Shape.
According to the present invention, in air atmosphere, the heating rate is 1~20 DEG C/min, preferably 1~10 DEG C/min；
The removing halogen temperature is 150~450 DEG C, preferably 200~400 DEG C；The removing halogen time is 0.5-5 hours, excellent
It is selected as 0.5-3 hours.
According to the present invention, under an inert atmosphere, the heating rate is 1~20 DEG C/min, preferably 1~10 DEG C/min；
The carburizing temperature is 200~1000 DEG C, preferably 250~800 DEG C；The carbonization time is 1-10 hours, and preferably 2-7 is small
When.
According to the present invention, the flow of the inert gas is 1-100mL/min.
According to the present invention, the inert gas is one or more of nitrogen, argon gas, helium.
The present invention also provides the porous carbon materials that method described above is prepared, the specific surface area of the porous carbon materials is
200~2000m2/ g, it is therefore preferable to 500~1900m2/g；0.2~1.0cm of Kong Rongwei3/ g, it is therefore preferable to 0.3~0.9cm3/g。
According to the present invention, also contain graphite-structure in the porous carbon materials in addition to agraphitic carbon, degree of graphitization (by
The relative intensity ID/IG at the peaks D and the peaks G is detected in Raman spectrum) ID/IG is 0.3~1.5, it is therefore preferable to 0.4~0.9, it is also excellent
It is selected as 0.4~0.8.
Beneficial effects of the present invention：
1. the present invention provides a kind of preparation method preparing porous carbon materials using halogenated polyolefin hydrocarbon-based polymeric object as presoma,
The method is to use halogenated polyolefin hydrocarbon-based polymeric object for raw material, and under air and/or inert atmosphere, removing halogen is carried out to it
And/or carbonization treatment；Most of existing carbon matrix precursors (including polyvinyl chloride etc.) can aoxidize under oxygen, Wu Facheng
Carbon, and it is characteristic of the invention that will not be aoxidized in air；This is mainly due to carburizing temperatures of the present invention
It is low, and presoma of the present invention has anti-flammability；Carbonization greatly reduces the use cost of inert gas in air, i.e.,
It can also be substantially reduced using the flow of inert atmosphere, its inert gas, simplify into carbon condition.The method preparation process
Simply, easy to operate, reaction temperature is low, low for equipment requirements, in air atmosphere it is achieved that saving the energy, has work
The application prospect of industry metaplasia production.
2. the present invention also provides the porous carbon materials that the above method is prepared, the porous carbon that is prepared using this method
Material needs not move through activation process, and carburizing temperature is low；The specific surface area of the carbon material is 200~2000m2/ g, Kong Rong
For 0.2~1.0cm3/g；And also contain graphite-structure in the porous carbon materials in addition to agraphitic carbon, degree of graphitization compared with
Height, ID/IG are 0.3~1.5.
Description of the drawings
Fig. 1 is the N2 adsorption desorption curve of porous carbon materials prepared by embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of porous carbon materials prepared by embodiment 1.
Fig. 3 is the Raman figure of porous carbon materials prepared by embodiment 1.
Specific embodiment
The following is specific embodiments of the present invention, is further described to the present invention, it should be noted that following implementations
Example cannot function as limiting the scope of the invention, any protection improved all in the present invention made on the basis of the present invention
Within the scope of.
Embodiment 1
By 10g chlorinated polypropylenes raw material, (mass content of chlorine element is 70wt%, and Cl/C molar ratios are 0.92:1) it is put into
In the quartz ampoule of tube furnace, to system inflated with nitrogen, make the active gas such as no oxygen in quartz ampoule.With the rate of 10 DEG C/min to chlorine
Change polypropylene to be heated, is warming up to 400 DEG C of final carburizing temperature, and constant temperature 2 hours at such a temperature.It slowly drops under a nitrogen
Temperature obtains porous carbon materials.
Fig. 1 is the N2 adsorption desorption curve that embodiment 1 prepares porous carbon materials.Fig. 2 is that embodiment 1 prepares porous carbon materials
Scanning electron microscope (SEM) photograph.Fig. 3 is the Raman figure that embodiment 1 prepares porous carbon materials.
By that can be obtained in Fig. 1-3, the specific surface area for the porous carbon materials that the present embodiment is prepared is 1200m2/ g, hole
It is 0.55cm to hold3/ g, ID/IG 0.6.
Embodiment 2
By 10g chlorinated polypropylenes raw material, (mass content of chlorine element is 61wt%, and Cl/C molar ratios are 0.62:1) it is put into
In the quartz ampoule of tube furnace, air is passed through to system, chlorinated polypropylene is heated with the rate of 10 DEG C/min, is warming up to most
300 DEG C of whole carburizing temperature, and constant temperature 2 hours at such a temperature.Slow cooling under air obtains porous carbon materials.
The specific surface area for the porous carbon materials that the present embodiment is prepared is 1070m2/ g, Kong Rongwei 0.49cm3/ g, ID/IG
It is 0.51.
Embodiment 3
By 10g chliorinated polyvinyl chlorides raw material, (mass content of chlorine element is 68.5wt%, and Cl/C molar ratios are 0.83:1)
It is put into the quartz ampoule of tube furnace, air is passed through to system, chlorinated polypropylene is heated with the rate of 10 DEG C/min, heat up
To 400 DEG C of final carburizing temperature, and constant temperature 2 hours at such a temperature.Slow cooling under air obtains porous carbon materials.
The specific surface area for the porous carbon materials that the present embodiment is prepared is 546m2/ g, Kong Rongwei 0.31cm3/ g, ID/IG
It is 0.7.
Embodiment 4
By 10g haloflexes raw material, (mass content of chlorine element is 60wt%, and Cl/C molar ratios are 0.6:1) it is put into pipe
In the quartz ampoule of formula stove, to system inflated with nitrogen, make the active gas such as no oxygen in quartz ampoule.With the rate of 10 DEG C/min to chlorination
Polypropylene is heated, and 450 DEG C of final carburizing temperature, and constant temperature 2 hours at such a temperature are warming up to.It slowly drops under a nitrogen
Temperature obtains porous carbon materials.
The specific surface area for the porous carbon materials that the present embodiment is prepared is 700m2/ g, Kong Rongwei 0.38cm3/ g, ID/IG
It is 0.68.
Embodiment 5
By 10g chlorinated polypropylenes raw material, (mass content of chlorine element is 75wt%, and Cl/C molar ratios are 1.13:1) it is put into
In the quartz ampoule of tube furnace, air is passed through to system, chlorinated polypropylene is heated with the rate of 10 DEG C/min, is warming up to most
300 DEG C of whole carburizing temperature, and constant temperature 1 hour at such a temperature, are slowly dropped to room temperature.To system inflated with nitrogen, make nothing in quartz ampoule
The active gas such as oxygen.Chlorinated polypropylene is heated with the rate of 5 DEG C/min, is warming up to 600 DEG C of final carburizing temperature, and
Constant temperature 2 hours at such a temperature.Slow cooling under a nitrogen obtains porous carbon materials.
The specific surface area for the porous carbon materials that the present embodiment is prepared is 1500m2/ g, Kong Rongwei 0.63cm3/ g, ID/IG
It is 0.48.
Embodiment 6
By 10g haloflexes raw material, (mass content of chlorine element is 67wt%, and Cl/C molar ratios are 0.8:1) it is put into pipe
In the quartz ampoule of formula stove, air is passed through to system, chlorinated polypropylene is heated with the rate of 10 DEG C/min, is warming up to final
300 DEG C of carburizing temperature, and constant temperature 1 hour at such a temperature, are slowly dropped to room temperature.To system inflated with nitrogen, make anaerobic in quartz ampoule
The active gas such as gas.Chlorinated polypropylene is heated with the rate of 10 DEG C/min, is warming up to 600 DEG C of final carburizing temperature, and
Constant temperature 2 hours at such a temperature.Slow cooling under a nitrogen obtains porous carbon materials.
The specific surface area for the porous carbon materials that the present embodiment is prepared is 800m2/ g, Kong Rongwei 0.43cm3/ g, ID/IG
It is 0.62.
It can be in inert atmosphere and/or air atmosphere from can be seen that halogenated polyolefin hydrocarbon-based polymeric object in embodiment 1-6
Porous carbon materials are prepared, the halogenated polyolefin hydrocarbon-based polymeric object is first handled through air atmosphere, halogen can be removed, obtained porous
Carbon material, and continue to heat up under inert atmosphere conditions, the porous carbon materials being prepared are more only in air atmosphere or only lazy
Property atmosphere under porous carbon materials its performance for being prepared significantly improve, its can be improved and be graphitized content, that is, reduce ID/IG
Value makes its ordering degree increase.
Comparative example 1
By 10g chlorinated polypropylenes raw material, (mass content of chlorine element is 10wt%, and Cl/C molar ratios are 0.05:1) it is put into
In the quartz ampoule of tube furnace, system is vacuumized and inflated with nitrogen, makes the active gas such as no oxygen in quartz ampoule.With 10 DEG C/
The rate of min heats chlorinated polypropylene, is warming up to 400 DEG C of final carburizing temperature, and constant temperature 2 hours at such a temperature.
Slow cooling under a nitrogen does not obtain porous carbon materials.
By comparative example 1 as can be seen that (not protected in this patent when content of halogen is low in halogenated polyolefin hydrocarbon-based polymeric object
In content of halogen) when, porous carbon materials can not be prepared using preparation method of the present invention.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to the above embodiments.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of method preparing porous carbon materials as presoma using halogenated polyolefin hydrocarbon-based polymeric object, which is characterized in that the system
Preparation Method includes：
A) presoma halogenated polyolefin hydrocarbon-based polymeric object is placed in tube furnace, in air atmosphere, it is de- to carry out halogen for slowly heating
It removes, the porous carbon materials is prepared；Alternatively,
B) presoma halogenated polyolefin hydrocarbon-based polymeric object is placed in tube furnace, under an inert atmosphere, slowly heating carries out at carbonization
Reason, is prepared the porous carbon materials；Alternatively,
C) presoma halogenated polyolefin hydrocarbon-based polymeric object is placed in tube furnace, in air atmosphere, it is de- to carry out halogen for slowly heating
It removes, then passes to inert atmosphere, heating carries out carbonization treatment, the porous carbon materials are prepared.
2. preparation method according to claim 1, which is characterized in that in the halogenated polyolefin hydrocarbon-based polymeric object, carbon, hydrogen and
The quality of three kinds of elements of halogen and 90wt% not less than the halogenated polyolefin hydrocarbon-based polymeric amount of substance；The quality of halogens is not small
In the 40wt% of the halogenated polyolefin hydrocarbon-based polymeric amount of substance, preferably not less than 45wt%, it is not higher than the halogenated polyolefin hydrocarbon-based polymeric
The 85wt% of amount of substance, preferably no greater than 80wt%；Halogens is selected from F, Cl, one or more, the preferably Cl in Br and I
Or Br；The molar ratio of halogen and carbon is (0.5~2.0):1, preferably (0.5~1.8):1.
3. preparation method according to claim 1 or 2, which is characterized in that the halogenated polyolefin hydrocarbon-based polymeric object include but
It is not limited to halogenated polyolefin, the poly- halogen alkene of halogenation.
Preferably, the polyolefin in the halogenated polyolefin is poly alpha olefin, for example, polyethylene, polypropylene, poly 1-butene, poly-
1- amylenes, poly- 1- hexenes, poly- 1- heptene, poly- 1- octenes, poly- 1- nonenes, poly- 1- decene, poly- 1- hendecenes or its copolymer, it is also excellent
It is selected as polyethylene, polypropylene, poly 1-butene or its copolymer.
Preferably, the halogen in the poly- halogen alkene in the poly- halogen alkene of the halogenation is selected from chlorine or bromine, and the poly- halogen alkene for example selects
From polyvinyl chloride, polyvinyl bromide, poly- 1,1- dichloroethylene, poly- 1,2- dichloroethylene, poly- 1,1,2- trichloro ethylenes, poly- 3- chlorine third
Alkene, poly- 3- bromopropenes, polychloroprene, poly- bromobutene etc..
It is further preferred that the halogenated polyolefin hydrocarbon-based polymeric object includes but not limited to halogenated polyethylene, and halogenated polypropylene, the poly- 1- of halogenation
Butylene, halogenation polyvinyl chloride, the poly- 1,1- dichloroethylene of halogenation, the poly- 1,2- dichloroethylene of halogenation, the poly- 1,1,2- trichloro ethylenes of halogenation,
One kind in the poly- chlorallylene of halogenation, halogenation polychloroprene, halogenation polyvinyl bromide, the poly- 3- bromopropenes of halogenation, the poly- bromobutene of halogenation
Or it is several.
It is highly preferred that the halogenated polyolefin hydrocarbon-based polymeric object includes but not limited to haloflex, and chlorinated polypropylene, the poly- 1- of chlorination
Butylene, chliorinated polyvinyl chloride, the poly- vinylidene chloride of chlorination, the poly- 1,2-dichloroethene of chlorination, chlorination poly- 1,1,2- trichloro ethylene,
The poly- chlorallylene of chlorination, chlorinated polychloroprene, chlorination polyvinyl bromide, the poly- 3- bromopropenes of chlorination, the poly- bromobutene of chlorination, the poly- second of bromination
Alkene, bromination polypropylene, poly- 1,2-, bis- chloroethenes of bromination poly 1-butene, bromination polyvinyl chloride, the poly- vinylidene chloride of bromination, bromination
The poly- 3- bromines of the poly- 1,1,2- trichloro ethylenes of alkene, bromination, the poly- chlorallylene of bromination, bromination polychloroprene, bromination polyvinyl bromide, bromination third
One or more of poly- bromobutene of alkene, bromination.
4. preparation method according to any one of claim 1-3, which is characterized in that the halogenated polyolefin hydrocarbon-based polymeric object
Can be powdered, voluminous powder shape, threadiness or blocky.
5. according to the preparation method described in any one of claim 1-4, which is characterized in that in air atmosphere, the heating
Rate is 1~20 DEG C/min, preferably 1~10 DEG C/min；The removing halogen temperature be 150~450 DEG C, preferably 200~
400℃；The removing halogen time is 0.5-5 hours, preferably 0.5-3 hours.
6. preparation method according to any one of claims 1-5, which is characterized in that under an inert atmosphere, the heating
Rate is 1~20 DEG C/min, preferably 1~10 DEG C/min；The carburizing temperature be 200~1000 DEG C, preferably 250~800
℃；The carbonization time is 1-10 hours, preferably 2-7 hours.
Preferably, the inert gas is one or more of nitrogen, argon gas, helium.
It is further preferred that the flow of the inert gas is 1-100mL/min.
7. the porous carbon materials that the method described in any one of claim 1-6 is prepared, which is characterized in that the porous carbon
The specific surface area of material is 200~2000m20.2~1.0cm of/g, Kong Rongwei3/g。
8. porous carbon materials according to claim 7, which is characterized in that the specific surface area of the porous carbon materials is 500
~1900m2/g；0.3~0.9cm of Kong Rongwei3/g。
9. porous carbon materials according to claim 7 or 8, which is characterized in that remove agraphitic carbon in the porous carbon materials
Outer also to contain graphite-structure, degree of graphitization (is detected) ID/IG by the relative intensity ID/IG at the peaks D in Raman spectrum and the peaks G and is
0.3~1.5.
10. porous carbon materials according to claim 9, which is characterized in that in the porous carbon materials in addition to agraphitic carbon
Also contain graphite-structure, degree of graphitization (is detected) ID/IG by the relative intensity ID/IG at the peaks D in Raman spectrum and the peaks G and is
0.4~0.9, also preferably 0.4~0.8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108947533A (en) * | 2018-08-31 | 2018-12-07 | 上海万华科聚化工科技发展有限公司 | A kind of preparation method of porous carbon material and the purposes of obtained porous carbon material |
| CN111439739A (en) * | 2019-01-17 | 2020-07-24 | 中国科学院化学研究所 | Nitrogen-doped porous carbon material and preparation method and application thereof |
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| CN105217627A (en) * | 2015-10-13 | 2016-01-06 | 福州大学 | A kind of preparation method of coconut husk greying gac |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108947533A (en) * | 2018-08-31 | 2018-12-07 | 上海万华科聚化工科技发展有限公司 | A kind of preparation method of porous carbon material and the purposes of obtained porous carbon material |
| CN108947533B (en) * | 2018-08-31 | 2022-02-15 | 万华化学集团股份有限公司 | Preparation method of porous carbon material and application of obtained porous carbon material |
| CN111439739A (en) * | 2019-01-17 | 2020-07-24 | 中国科学院化学研究所 | Nitrogen-doped porous carbon material and preparation method and application thereof |
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