CN108615899A - A kind of Heteroatom doping porous carbon materials and preparation method thereof and the application in zinc and air cell - Google Patents
A kind of Heteroatom doping porous carbon materials and preparation method thereof and the application in zinc and air cell Download PDFInfo
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Abstract
The present invention discloses a kind of Heteroatom doping porous carbon materials and preparation method thereof and the application in zinc and air cell.By biological material by being self-assembly of three-dimensional net structure self-assembly in alkaline solution, the three-dimensional net structure self-assembly is placed in protective atmosphere after freeze-drying, is carbonized to get Heteroatom doping porous carbon materials.Heteroatom doping porous carbon materials catalytic activity is high, and stability is good, can substitute existing Pt/C and use, and is applied to zinc and air cell as oxygen reduction catalyst, can obtain the zinc and air cell that discharge voltage is stable, capacity is big.And the preparation process of Heteroatom doping porous carbon materials is simple, and it is at low cost, it is expected to be applied in industrial production.
Description
Technical field
The present invention relates to a kind of porous carbon materials and its preparation method and application, and in particular to one kind is existed by biological material
By being self-assembly of three-dimensional net structure self-assembly in alkaline solution, miscellaneous original is prepared using freeze-drying and high temperature cabonization
The method of sub- doped porous carbon material, further relate to Heteroatom doping porous carbon materials as oxygen reduction catalyst zinc and air cell just
Application in the material of pole belongs to electro-catalysis energy storage material field.
Background technology
As global energy requirements are continuously increased, to a large amount of profits of traditional fossil fuel (such as coal, oil, natural gas)
With not only causing the variation for being difficult to reverse, the even more excessive use of these primary energy in terms of amblent air temperature, cause serious
Energy crisis.In face of the increasingly exhausted energy, on the one hand it is energy saving and taps a new source of energy, while improves the use of the energy
Efficiency, but the service efficiency of current primary energy only has 40% or so.Fuel cell is as a kind of novel energy conversion
The utilization rate of the energy can be increased to 70% or so by device.Oxygen reduction catalyst is the key that fuel cell and metal-air portion
Part (positive electrode of battery), which determine the performances of fuel cell and metal zinc and air cell.In recent years, the anode of fuel cell
Material is the research hotspot of energy and material.Platinum-base material has been commercialized be applied on fuel cell at present, but because it is expensive
Its application is limited with scarcity of resources.Currently, various base metals, transition metal and its compound and the carbon such as including Fe, Co
Composite material base catalyst receives extensive attention, its catalytic efficiency of some of materials can be equal to Pt base catalyst performances
U.S., especially in terms of the toxicity such as the stability of catalyst and methanol tolerance, CO, even better than Pt bases catalyst.But in acidity
Under the conditions of stability it is poor the problems such as, fail to obtain effective solution always.
The carbon material of nonmetal doping is applied to the positive electrode of fuel cell as ORR catalyst, steady with height
Qualitative and good electric conductivity is in recent years by the common concern of people [Gong K, Du F, Xia Z, et
al.Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity
for oxygen reduction[J].Science,2009,323(5915):760-764].People synthesize a variety of non-gold at present
Belong to carbon material and be applied to oxygen reduction catalyst, includes mainly that nitrogen phosphate and sulfur, boron etc. is atom doped and its dual element doping, multielement
Carbon material [Zhang J, Qu L, Shi G, et al.N, the P-Codoped Carbon Networks as of doping
Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen
Evolution Reactions[J].Angew Chem Int Ed Engl,2016,55(6):2230].Preparation traditional at present
Method is to obtain the carbon material of Heteroatom doping by carbon source presoma and containing heteroatomic presoma after high temperature cabonization.At present
Common nitrogen source material has urea, melamine, ammonia etc. to be doped at high temperature, and this doped forms need additional nitrogen
Source.And the preparation method of existing porous material mainly passes through template and its post-processing, complex technical process is of high cost.
Invention content
It is low and material source is limited for the catalytic activity of existing fuel cell and metal-air battery positive electrode, system
The defects of standby of high cost, of the invention first purpose are to be to provide a kind of suitable with Pt/C electro-chemical activities, and stability
And the performances such as anti methanol toxication are better than the Heteroatom doping porous carbon materials of Pt/C.
Second object of the present invention is to be to provide that a kind of cost of material is low, simple for process to prepare Heteroatom doping more
The method of hole carbon material；The relatively existing preparation method of this method, without template or pore creating material, post-processing is simple, letter
The processing step of porous carbon materials preparation is changed.
Third object of the present invention is to be to provide a kind of Heteroatom doping porous carbon materials in metal-air battery
Application, porous carbon materials show higher catalytic activity, the zinc air of preparation as zinc-air battery cell positive material
Battery has many advantages, such as that discharge voltage stabilization, capacity are big.
In order to achieve the above technical purposes, the present invention provides a kind of preparation method of Heteroatom doping porous carbon materials,
This method be by biological material in alkaline solution by being self-assembly of three-dimensional net structure self-assembly, the three dimensional network
Network structure self-assembly is placed in after freeze-drying in protective atmosphere, is carbonized to get Heteroatom doping porous carbon
Material.
Preferred scheme, biological material is soluble in water, add alkaline matter, at 0~60 DEG C stir 5~
300min obtains three-dimensional net structure self-assembly.More preferably reaction temperature is room temperature.More preferably the reaction time is
30min。
More preferably scheme, the biological material include at least one in protein, carbohydrate, natural lipid class compound
Kind.Preferably protein bovine serum albumin (BSA).
More preferably scheme, the alkaline matter include at least one of alkali metal hydroxide and ammonium hydroxide.Alkali metal hydrogen
Oxide is preferably sodium hydroxide and/or potassium hydroxide.
More preferably scheme, concentration range of the biological material in alkaline solution are 1.0mg/mL~100mg/
mL；A concentration of 0.01~1.0M of the alkaline solution neutral and alkali substance.Most preferred biological material is BSA, in alkalinity
A concentration of 75mg/mL in solution, a concentration of 0.4M of the sodium hydroxide of relative usage.
The ratio of biological material and sodium hydroxide is directly related to the performance of material, hydroxide in technical solution of the present invention
The amount of sodium is very few, can influence the specific surface area of material, keeps the exposure of its active site less, electro-chemical activity reduces, sodium hydroxide
Amount it is excessive, a large amount of carbon material can be caused to be corroded, obtained carbon material yield largely declines, or even is etched
It cannot get carbon material entirely.
The temperature of preferred scheme, the carbonization is 500~1200 DEG C.Carburizing temperature is to more in technical scheme of the present invention
Also there is Porous materials larger impact, alkaloid substance sodium hydroxide to be performed etching to material in different temperatures, and temperature is higher, reaction interval
Degree is bigger, and carbon material, in carbonisation, temperature is higher, and the crystallinity of material is better, and the performance of material is also better.It is more excellent
The high temperature cabonization temperature of choosing is 700~900 DEG C.
Protective atmosphere is the mixed atmosphere of nitrogen or inert atmosphere, or both, indifferent gas in technical scheme of the present invention
Atmosphere such as argon gas.
The present invention provides a kind of Heteroatom doping porous carbon materials, are obtained by above-mentioned preparation method.
The pore size distribution range of preferred scheme, the Heteroatom doping porous carbon materials is 0.4~110nm.
Preferred scheme, the Heteroatom doping porous carbon materials are the porous carbon materials that hetero atom adulterates in situ.
Preferred scheme, the porous carbon materials carry out the electro-catalysis test of hydrogen reduction, hydrogen reduction electrocatalysis characteristic with it is existing
Some platinum catalysts are suitable.
The present invention also provides a kind of applications of porous carbon materials, are applied to zinc and air cell as ORR catalyst.
As oxygen reduction catalyst during hydrogen reduction, take-off potential exists the Heteroatom doping porous carbon materials of the present invention
It is (0.93V v/s RHE) under alkaline condition, half wave potential has quite between (0.83~0.84v/s RHE) compared to Pt/C
Catalytic activity.
Biological material used in technical solution of the present invention such as protein, carbohydrate etc. can make biomass under alkali effect
Molecular structure change, biomass portion can be degraded and be generated containing bases such as amino, carboxyl, hydroxyls by such as hydrolysis
The small molecule of group, in solution system, due to these group good hydrophilic properties so that hydrolysate can be dispersed in solution system
In, while these groups can generate crosslinking by hydrogen bond or ionic bond effect and carry out self assembly, therefore, entire solution system shape
At the gelinite with three-dimensional net structure, gelinite uses Freeze Drying Technique, can keep its three dimensional network in the liquid phase
Network structure, using high temperature cabonization, obtains porous carbon materials to obtain the self-assembly with three-dimensional porous structure.And it gives birth to
Material itself includes abundant hetero atom, such as P, S, N etc., these hetero atoms adulterate in situ during high temperature cabonization
In porous carbon materials.
Technical solution of the present invention neutral and alkali solution plays an important role in the preparation process of entire porous carbon materials, and one
Aspect can promote biological material to be formed in solution system with three-dimensional as the activator of biological material reaction
The assembly of structure, on the other hand, alkali have the function of activated carbon material, and by freeze-drying, alkali remains in three-dimensional network knot
In structure self-assembly, alkali plays the role of pore creating material during high temperature cabonization, carries out corrosion pore-creating to carbon material, carbon material is made to obtain
To a large amount of microcellular structure, the specific surface area of porous carbon materials is greatly improved, a large amount of active sites is made to expose, to effectively increase
The strong catalytic activity of oxygen reduction catalyst.
Technical solution of the present invention compares day by the natural products porous carbon materials that self assembly, carbonization obtain in alkaline solution
The material that right product direct carbonization obtains has better effect in electrochemical oxygen reduction catalysis.
The currently preferred method for preparing porous carbon materials using biological material self-assembly, what selection manually purified
BSA is dissolved in as biological material in water, after alkali such as sodium hydroxide is added, is stirred continuously, is brought it about self assembly, obtain
To gelatinous assembly, then using the anhydrous assembly of the method for freeze-drying, finally by it in tube furnace, inertia
High temperature cabonization is carried out under atmosphere, obtains the porous carbon materials of Heteroatom doping.
The method that the present invention more preferably prepares porous carbon materials, including step in detail below：
Step (1)：The preparation of biomass self-assembly
Biological material BSA is soluble in water, sodium hydroxide is added, is stirred continuously at room temperature, after 30min, you can
To biomass self-assembly, then water is removed using the method for freeze-drying, you can obtain dry biomass self-assembly.
Step (2)：Obtain the porous carbon materials of Heteroatom doping
The biomass self-assembly of the drying obtained in step 1 is placed in tube furnace, under an inert atmosphere, through pyrocarbon
Change is handled, you can obtains the porous carbon materials of Heteroatom doping.
The present invention Heteroatom doping porous carbon materials carry out hydrogen reduction electro-catalysis test method be：
1, by obtained carbon material with secondary water washing for several times, after vacuum drying, take a small amount of carbon material, be ground into superfine powder
End is dispersed in ethanol solution；
2, Nafion is added to fix on glass-carbon electrode the dispersant liquid drop in step 1, with rotating circular disk and electrochemical operation
It stands and just tests hydrogen reduction potential in alkaline condition and acid condition respectively；
3, by step 1 to dispersant liquid drop on carbon paper, then using carbon paper as positive electrode, zinc metal sheet is as cathode
Material, sodium hydroxide solution assemble zinc and air cell, test its battery performance in blue electrical measurement test system (LAND as electrolyte
CT2001A)。
Compared with the prior art, the advantageous effects that technical scheme of the present invention is brought：
1) present invention is reacted using biological material under alkaline condition for the first time and self assembly obtains has three-dimensional network knot
The self-assembly of structure, using freeze-drying and high temperature cabonization to get Heteroatom doping porous carbon materials.Biological material passes through
Self assembly obtain with three-dimensional net structure self-assembly, eliminate prepare in the prior art porous carbon materials need use mould
The defect of plate agent or pore creating material simplifies pore-creating step.Biological material includes a large amount of hetero atom simultaneously, without in addition addition
Hetero atom source.
2) present invention uses biological material as starting material during preparing Heteroatom doping porous carbon materials, comes
Source is extensive, renewable, environmental-friendly and at low cost, is conducive to carry out large-scale production.
3) Heteroatom doping porous carbon materials of the invention show with the comparable electro-chemical activities of Pt/C, and stability and
The performances such as anti methanol toxication are better than Pt/C.
4) Heteroatom doping porous carbon materials of the invention show height and urge as ORR catalyst application zinc-air batterys
Change activity, and the zinc-air battery prepared has many advantages, such as that discharge voltage is stable, capacity is big.
5) Heteroatom doping porous carbon preparation method for material of the invention is simple, and mild condition meets demand of industrial production.
Description of the drawings
【Fig. 1】The SEM figures of self assembly occur under alkaline condition for biological material in embodiment 1, it can be seen from the figure that
The tridimensional network after gel is formed, and amplifies local observation, has tiny granular substance, which is distributed across biomass
Sodium hydrate solid particle in material；
【Fig. 2】The optical picture, SEM figures and TEM of the porous carbon materials of Heteroatom doping are obtained after the carbonization of 1 high temperature of embodiment
Figure, it can be seen from the figure that fluffy porous structure is presented in macroscopically material, and also has porous structure on a microscopic level
In the presence of；
【Fig. 3】The isothermal nitrogen of three kinds of carbon materials washes desorption curve and graph of pore diameter distribution in embodiment 1,2,3, can see
Go out, with the raising of temperature, specific surface area increases for the amount of identical alkali, and pore size distribution$ is wider；
【Fig. 4】The isothermal nitrogen adsorption desorption curve and graph of pore diameter distribution of three kinds of carbon materials in embodiment 1,4；By regulating and controlling not
The amount of same alkali increases with the amount of alkali, and specific surface area increases, and pore size distribution$ range also expands；
【Fig. 5】A) the oxygen reduction reaction alkaline condition of 4 kinds of different carbon materials and the Pt/C materials of commercialization is surveyed in embodiment
LVS figures are tried, as a result show that the raising with alkali concentration and temperature, the oxygen reduction catalytic activity of carbon material are continuously increased, wherein
The catalytic activity of BSA-8-900 and the Pt/C of commercialization are suitable, b) LSV the and K-L curve graphs of BSA-8-900 in embodiment 1；
【Fig. 6】A) the oxygen reduction reaction acid condition of 4 kinds of different carbon materials and the Pt/C materials of commercialization is surveyed in embodiment
LVS figures are tried, as a result show that the raising with alkali concentration and temperature, the oxygen reduction catalytic activity of carbon material constantly enhance, wherein
The catalytic activity of BSA-8-900 is best, but has some gaps with Pt/C；B) LSV and K-L of BSA-8-900 are bent in embodiment 1
Line chart；
【Fig. 7】Different carbon materials and the Pt/C materials of commercialization are surveyed as the positive electrode of zinc and air cell in 4 in embodiment
Datagram is tried, a) figure is the illustraton of model of zinc and air cell；B) figure is that material is tested as the polarization curve of zinc and air cell positive electrode,
As a result show that the performance of BSA-8-900 is carried out, energy density highest, the Pt/C being slightly above commercialized；C) figure is self-control button zinc
Empty battery lightening LED lamp, curve are the variation of long-time constant-current discharge voltage；D) figure is that the voltage of different current density electric discharges becomes
Change figure.
Specific implementation mode
Following case study on implementation is intended to further illustrate present disclosure, rather than limits the guarantor of the claim of the present invention
Shield.
Embodiment 1
Step (1)：The preparation of biomass self-assembly
Biomass precursor B SA 1.5g are dissolved in 20mL water, sodium hydroxide 8mmol is added, constantly stirs at room temperature
It mixes, after 30min, you can obtain biomass self-assembly.Then water is removed using the method for freeze-drying, you can obtain drying
Biomass self-assembly.
Step (2)：Obtain the porous carbon materials of Heteroatom doping
The biomass self-assembly of the drying obtained in step (1) is placed in tube furnace, under an inert atmosphere, through 900
DEG C carbonization treatment, you can obtain the porous carbon materials of Heteroatom doping, be denoted as BSA-8-900, specific surface area is
1274.1305m2g-1, pore-size distribution is distributed in micropore, mesoporous, macropore, in multistage pore size distribution.
Step (3)：The test of the oxygen reduction reaction of carbon material and zinc and air cell assembling and test：
1, by obtained carbon material with secondary water washing for several times, after vacuum drying, take a small amount of carbon material, be ground into superfine powder
End is dispersed in ethanol solution.
2, Nafion is added to fix on glass-carbon electrode the dispersant liquid drop in step 1, with rotating circular disk and electrochemical operation
It stands and just tests hydrogen reduction potential in alkaline condition and acid condition respectively.
3, by step 1 to dispersant liquid drop on carbon paper, then using carbon paper as positive electrode, zinc metal sheet is as cathode
Material, sodium hydroxide solution assemble zinc and air cell, test its battery performance in blue electrical measurement test system (LAND as electrolyte
CT2001A)。
Embodiment 2
Step (1)：Biomass precursor B SA 1.5g are dissolved in 20mL water, sodium hydroxide 8mmol are added, at room temperature
It is stirred continuously, after 30min, you can obtain biomass self-assembly.Then water is removed using the method for freeze-drying, you can
To dry biomass self-assembly.
Step (2)：Obtain the porous carbon materials of Heteroatom doping
The biomass self-assembly of the drying obtained in step (1) is placed in tube furnace, under an inert atmosphere, through 700
DEG C carbonization treatment, you can obtain the porous carbon materials of Heteroatom doping, be denoted as BSA-8-700, surface area 548.7413m2g-1, pore-size distribution is concentrated mainly on micropore area, and big porose area has a small amount of distribution.
Step (3)：The test of the oxygen reduction reaction of carbon material and zinc and air cell assembling and test：
1, by obtained carbon material with secondary water washing for several times, after vacuum drying, take a small amount of carbon material, be ground into superfine powder
End is dispersed in ethanol solution.
2, Nafion is added to fix on glass-carbon electrode the dispersant liquid drop in step 1, with rotating circular disk and electrochemical operation
It stands and just tests hydrogen reduction potential in alkaline condition and acid condition respectively.
3, by step 1 to dispersant liquid drop on carbon paper, then using carbon paper as positive electrode, zinc metal sheet is as cathode
Material, sodium hydroxide solution assemble zinc and air cell, test its battery performance in blue electrical measurement test system (LAND as electrolyte
CT2001A)。
Embodiment 3
Step (1)：Biomass precursor B SA 1.5g are dissolved in 20mL water, sodium hydroxide 8mmol are added, at room temperature
It is stirred continuously, after 30min, you can obtain biomass self-assembly.Then water is removed using the method for freeze-drying, you can
To dry biomass self-assembly.
Step (2)：Obtain the porous carbon materials of Heteroatom doping
The biomass self-assembly of the drying obtained in step (1) is placed in tube furnace, under an inert atmosphere, through 500
DEG C carbonization treatment, you can obtain the porous carbon materials of Heteroatom doping, be denoted as BSA-8-500, specific surface area is
17.3566m2g-1, pore-size distribution mainly has a small amount of distribution in big porose area.
The test of the oxygen reduction reaction of step (3) carbon material and zinc and air cell assembling and test：
1, by obtained carbon material with secondary water washing for several times, after vacuum drying, take a small amount of carbon material, be ground into superfine powder
End is dispersed in ethanol solution.
2, Nafion is added to fix on glass-carbon electrode the dispersant liquid drop in step 1, with rotating circular disk and electrochemical operation
It stands and just tests hydrogen reduction potential in alkaline condition and acid condition respectively.
3, by step 1 to dispersant liquid drop on carbon paper, then using carbon paper as positive electrode, zinc metal sheet is as cathode
Material, sodium hydroxide solution assemble zinc and air cell, test its battery performance in blue electrical measurement test system (LAND as electrolyte
CT2001A)。
Embodiment 4
Step (1)：Biomass precursor B SA 1.5g are dissolved in 20mL water, sodium hydroxide 2mmol are added, at room temperature
It is stirred continuously, after 30min, you can obtain biomass self-assembly.Then water is removed using the method for freeze-drying, you can
To dry biomass self-assembly.
Step (2)：Obtain the porous carbon materials of Heteroatom doping
The biomass self-assembly of the drying obtained in step (1) is placed in tube furnace, under an inert atmosphere, through 900
DEG C carbonization treatment, you can obtain the porous carbon materials of Heteroatom doping, be denoted as BSA-2-900, specific surface 619.9392m2g-1, pore-size distribution is mainly micropore and mesoporous region.
The test of the oxygen reduction reaction of step (3) carbon material and zinc and air cell assembling and test：
1, by obtained carbon material with secondary water washing for several times, after vacuum drying, take a small amount of carbon material, be ground into superfine powder
End is dispersed in ethanol solution.
2, Nafion is added to fix on glass-carbon electrode the dispersant liquid drop in step 1, with rotating circular disk and electrochemical operation
It stands and just tests hydrogen reduction potential in alkaline condition and acid condition respectively.
3, by step 1 to dispersant liquid drop on carbon paper, then using carbon paper as positive electrode, zinc metal sheet is as cathode
Material, sodium hydroxide solution assemble zinc and air cell, test its battery performance in blue electrical measurement test system (LAND as electrolyte
CT2001A)。
Claims (9)
1. a kind of preparation method of Heteroatom doping porous carbon materials, it is characterised in that：By biological material in alkaline solution
By being self-assembly of three-dimensional net structure self-assembly, the three-dimensional net structure self-assembly is set after freeze-drying
In protective atmosphere, it is carbonized to get Heteroatom doping porous carbon materials.
2. a kind of preparation method of Heteroatom doping porous carbon materials according to claim 1, it is characterised in that：It will be biological
Material is soluble in water, adds alkaline matter, is stirred to react at 0~60 DEG C, obtains three-dimensional net structure self-assembly.
3. a kind of preparation method of Heteroatom doping porous carbon materials according to claim 2, it is characterised in that：The life
Material includes at least one of protein, carbohydrate, natural lipid substance.
4. a kind of preparation method of Heteroatom doping porous carbon materials according to claim 2, it is characterised in that：The alkali
Property substance includes alkali metal hydroxide and/or ammonium hydroxide.
5. a kind of preparation method of Heteroatom doping porous carbon materials according to claim 1, it is characterised in that：The life
Concentration range of the material in alkaline solution is 1.0mg/mL~100mg/mL；The alkaline solution neutral and alkali substance it is dense
Degree is 0.01~1.0M.
6. according to a kind of preparation method of Heteroatom doping porous carbon materials of Claims 1 to 5 any one of them, feature exists
In：The temperature of the carbonization is 500~1200 DEG C.
7. a kind of Heteroatom doping porous carbon materials, it is characterised in that：By claim 1~6 any one of them preparation method
It obtains.
8. a kind of Heteroatom doping porous carbon materials according to claim 7, it is characterised in that：The porous carbon materials
Pore size distribution range is 0.4~110nm.
9. a kind of application of Heteroatom doping porous carbon materials, it is characterised in that：It is applied to zinc and air cell as ORR catalyst.
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| CN110482526A (en) * | 2019-09-17 | 2019-11-22 | 哈尔滨工业大学 | It is a kind of using egg white as the preparation method of the biomass porous carbon electromagnetic-wave absorbent of presoma |
| CN111151283A (en) * | 2020-01-15 | 2020-05-15 | 中南大学 | Nitrogen-cobalt co-doped porous carbon loaded sulfur-zinc-cobalt catalytic material and preparation method and application thereof |
| CN112777583A (en) * | 2021-01-26 | 2021-05-11 | 哈尔滨工业大学 | Preparation method of green heteroatom modified integrated biochar cathode |
| CN113410470A (en) * | 2021-05-21 | 2021-09-17 | 河南师范大学 | Preparation method of 3D cross-linked hierarchical pore heteroatom-doped carbon cathode catalyst |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951636A (en) * | 2012-11-19 | 2013-03-06 | 大连理工大学 | Nitrogen-doped chitosan-based activated carbon and preparation method thereof |
| CN104445195A (en) * | 2014-12-08 | 2015-03-25 | 柳州东侯生物能源科技有限公司 | Preparation method of powdered biomass activated carbon by using longan seeds |
| CN104843668A (en) * | 2015-04-23 | 2015-08-19 | 北京理工大学 | Method for preparing nitrogen doped porous carbon material by using biologic proteins |
| CN105752969A (en) * | 2016-02-29 | 2016-07-13 | 武汉理工大学 | Method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables |
| CN106629655A (en) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | Application and preparation method of biomass-based nitrogen-doped porous carbon |
| CN107159290A (en) * | 2017-04-24 | 2017-09-15 | 长江大学 | Oxygen reduction catalyst based on polyalcohol hydrogel and preparation method thereof |
| CN107331525A (en) * | 2017-07-10 | 2017-11-07 | 北京化工大学 | A kind of porous charcoal nanometer sheet electrode material of polyatom codope and its preparation method and application |
-
2018
- 2018-04-27 CN CN201810390219.5A patent/CN108615899B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102951636A (en) * | 2012-11-19 | 2013-03-06 | 大连理工大学 | Nitrogen-doped chitosan-based activated carbon and preparation method thereof |
| CN104445195A (en) * | 2014-12-08 | 2015-03-25 | 柳州东侯生物能源科技有限公司 | Preparation method of powdered biomass activated carbon by using longan seeds |
| CN104843668A (en) * | 2015-04-23 | 2015-08-19 | 北京理工大学 | Method for preparing nitrogen doped porous carbon material by using biologic proteins |
| CN105752969A (en) * | 2016-02-29 | 2016-07-13 | 武汉理工大学 | Method for preparing polyatomic self-doped graphene by using natural porous and laminated vegetables |
| CN106629655A (en) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | Application and preparation method of biomass-based nitrogen-doped porous carbon |
| CN107159290A (en) * | 2017-04-24 | 2017-09-15 | 长江大学 | Oxygen reduction catalyst based on polyalcohol hydrogel and preparation method thereof |
| CN107331525A (en) * | 2017-07-10 | 2017-11-07 | 北京化工大学 | A kind of porous charcoal nanometer sheet electrode material of polyatom codope and its preparation method and application |
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| CN110054168A (en) * | 2019-04-24 | 2019-07-26 | 中国矿业大学 | A kind of preparation method of full pH value fuel battery negative pole oxygen reduction electro-catalyst |
| CN110482526A (en) * | 2019-09-17 | 2019-11-22 | 哈尔滨工业大学 | It is a kind of using egg white as the preparation method of the biomass porous carbon electromagnetic-wave absorbent of presoma |
| CN110482526B (en) * | 2019-09-17 | 2022-02-08 | 哈尔滨工业大学 | Preparation method of biomass porous carbon electromagnetic wave-absorbing material with egg white as precursor |
| CN111151283A (en) * | 2020-01-15 | 2020-05-15 | 中南大学 | Nitrogen-cobalt co-doped porous carbon loaded sulfur-zinc-cobalt catalytic material and preparation method and application thereof |
| CN112777583A (en) * | 2021-01-26 | 2021-05-11 | 哈尔滨工业大学 | Preparation method of green heteroatom modified integrated biochar cathode |
| CN112777583B (en) * | 2021-01-26 | 2022-07-01 | 哈尔滨工业大学 | Preparation method of green heteroatom modified integrated biochar cathode |
| CN113410470A (en) * | 2021-05-21 | 2021-09-17 | 河南师范大学 | Preparation method of 3D cross-linked hierarchical pore heteroatom-doped carbon cathode catalyst |
| CN113430565A (en) * | 2021-06-16 | 2021-09-24 | 江西师范大学 | Method for preparing carbon-based transition metal nano composite catalyst from tremella |
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