CN107840334A - A kind of atomic hole porous carbon materials and preparation method thereof - Google Patents
A kind of atomic hole porous carbon materials and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of preparation method of atomic hole porous carbon materials, the present invention is handled monose or hydro-thermal carbon material by air oxidation process, to realize the modulation to carbon material surface oxygen-containing functional group, dramatically increase the content of the ion-exchangeable functional group of hydro-thermal carbon surface (such as carboxyl, phenolic hydroxyl group), ion exchange site is provided for subsequent ion type chemical activation process, and then realize that the atom level of alkali metal ion is disperseed by ion-exchange, effectively reduce the dosage of activator, final porous carbon materials of the synthesis rich in atomic hole.Test result indicates that, preparation method activator level (being converted to industrial KOH chemical activation methods dosage) provided by the invention is about the 0.1~0.3 of carbon matrix precursor quality, and the atomic hole porous carbon materials being prepared are rich in the atomic hole that middle aperture is below 0.7nm.
Description
Technical field
The present invention relates to porous carbon materials preparing technical field, more particularly to a kind of atomic hole porous carbon materials and its preparation
Method.
Background technology
CO2As most important greenhouse gases, content nowadays in an atmosphere is growing day by day, result in global warming etc. one
Serial environmental problem, serious threat have arrived the survival and development of the mankind, therefore to CO2Trapping become particularly important with sealing up for safekeeping.Mesh
Before, CO2Trapping technique mainly has absorption process, membrane separation process and absorption method etc..Absorption process is big to equipment corrosion, regeneration energy consumption
Height, while restricted by temperature；The universal cost of membrane separation process is higher, limits its application；And absorption method shows big advantage,
Enjoy the favor of researcher.The core of absorption law technology is porosu solid adsorbent, at present applied to CO2The solid of absorption is inhaled
Attached dose mainly has metal-organic framework material (MOFs), molecular sieve, porous carbon materials and high temperature alkali metal or alkaline-earth metal compound
Oxide.By contrast, porous carbon materials are due to its outstanding CO2Absorption property, flourishing pore structure, it is relatively low it is economical into
Originally, the advantage such as abundant raw material sources, good chemically and thermally stability, relatively low regeneration energy consumption and structural controllability, into
For the CO of most prospects for commercial application2Solid absorbent.
By way of hydrothermal carbonization biomass resource, carbon materials can be converted biomass under gentle reaction condition
Material and high value chemicals, cause the extensive concern of researcher in the industry in recent years.First, raw material sources are extensive, various each
Biomass, the raw material of industry or the waste of sample are all used as the synthetic microporous carbon material of carbon precursor；Secondly, equipment is simply easily grasped
Make, reaction condition is gently easy to control, and energy consumption is low, easily makes production extension and industrialization；Finally, reaction medium is made using water, it is whole
Individual building-up process is carried out in enclosed system, the generation of contamination-free, and production technology is green.However, pass through Hydrothermal Synthesiss
The carbon material that method obtains typically has relatively low ratio surface.If applied to gas absorption field, then need further structure hair
Atomic pore size distribution up to pore structure, particularly aperture size less than 0.7nm is to CO2Adsorbing and trapping material have it is decisive because
Element.
In general, the carbon material of high-specific surface area is industrially mainly prepared by chemical activation method, wherein mainly with KOH
For chemical activating agent.Although this method can produce the pore structure of prosperity, activation effect is preferable, traditional activation process meeting
Consume substantial amounts of KOH, physical grinding is typically carried out with the mass ratio of 3~4 times of carbon matrix precursor so that prepare cost increase, together
Shi Zaocheng equipment corrosions, larger pollution is produced to environment, and the micropore canals built are concentrated mainly on 1~2nm, pore structure
It is still not flourishing enough.
The content of the invention
It is an object of the invention to provide a kind of atomic hole porous carbon materials and preparation method thereof.Preparation provided by the invention
Method activator level is few, and the atomic hole porous carbon materials being prepared are rich in the atomic hole that aperture is below 0.7nm.
The invention provides a kind of preparation method of atomic hole porous carbon materials, comprise the following steps：
(1) monose is subjected to high temperature oxygen processing in atmosphere, obtains oxygen processing carbon material；
(2) the oxygen processing carbon material that the step (1) obtains is mixed into laggard line replacement with alkali metal hydroxide and water
Reaction, obtain replacing carbon material；
(3) the displacement carbon material that the step (2) obtains is activated, obtains atomic hole porous carbon materials.
Preferably, the step (1) replaces with：
The aqueous solution of monose is subjected to hydro-thermal reaction in closed container, obtains pre- char-forming material；
The pre- char-forming material is subjected to high temperature oxygen processing in atmosphere, obtains oxygen processing carbon material.
Preferably, the temperature of the hydro-thermal reaction is 160~200 DEG C, and the time of hydro-thermal reaction is 10~24h.
Preferably, the monose includes the one or more in glucose, fructose, galactolipin, ribose and deoxyribose.
Preferably, the temperature of step (1) the high temperature oxygen processing is 200~400 DEG C, and the time of high temperature oxygen processing is 2
~12h.
Preferably, the air in the step (1) is still air or dynamic air.
Preferably, in the step (2) mass ratio of alkali metal hydroxide and oxygen processing carbon material be preferably 1.0~
2.0。
Preferably, the temperature of displacement reaction is 60~80 DEG C in the step (2), and the time for replacing reaction is 8~12h.
Preferably, the temperature of activation is 600~800 DEG C in the step (3), and the time of activation is 2~8h.
It is described atomic present invention also offers atomic hole porous carbon materials prepared by preparation method described in above-mentioned technical proposal
The aperture in the atomic hole in the porous carbon materials of hole is below 0.7nm.
The invention provides a kind of preparation method of atomic hole porous carbon materials, comprise the following steps：By monose or monose
The pre- char-forming material obtained through hydro-thermal reaction carries out high temperature oxygen processing in atmosphere, obtains oxygen processing carbon material；At the oxygen
Reason carbon material mixes laggard line replacement reaction with alkali metal hydroxide and water, obtains replacing carbon material；By the displacement carbon materials
Material is activated, and obtains atomic hole porous carbon materials.The present invention by air oxidation process to monose or hydro-thermal carbon material at
Reason, to realize the modulation to carbon material surface oxygen-containing functional group, dramatically increase the ion-exchangeable function of hydro-thermal carbon surface
The content of group's (such as carboxyl, phenolic hydroxyl group), provides ion exchange site, and then pass through for subsequent ion type chemical activation process
Ion-exchange realizes that the atom level of alkali metal ion is disperseed, and effectively reduces the dosage of activator, and final synthesis is rich in atomic hole
Porous carbon materials.Test result indicates that preparation method activator level provided by the invention (it is living to be converted to industrial KOH chemistry
Change method dosage) it is about the 0.1~0.3 of carbon matrix precursor quality, the atomic hole porous carbon materials being prepared are rich in middle aperture
Below 0.7nm atomic hole.
Brief description of the drawings
Fig. 1 is the N of the sample obtained in embodiment 1~42Adsorption and desorption isotherms；
Fig. 2 is the graph of pore diameter distribution of the sample obtained in embodiment 1~4.
Embodiment
The invention provides a kind of preparation method of atomic hole porous carbon materials, comprise the following steps：
(1) monose is subjected to high temperature oxygen processing in atmosphere, obtains oxygen processing carbon material；
(2) the oxygen processing carbon material that the step (1) obtains is mixed into laggard line replacement with alkali metal hydroxide and water
Reaction, obtain replacing carbon material；
(3) the displacement carbon material that the step (2) obtains is activated, obtains atomic hole porous carbon materials.
In the technical scheme of the present invention, monose is carried out high temperature oxygen processing by the present invention in atmosphere, is obtained at oxygen
Manage carbon material.In the present invention, the monose preferably includes one kind in glucose, fructose, galactolipin, ribose and deoxyribose
It is or a variety of.The present invention does not have special restriction to the source of the monose, using commercially available prod well known to those skilled in the art
.In the present invention, the monose is preferably polyhydroxy aldehyde or polyhydroxyketone containing 3~6 carbon atoms, can be used as carbon
Source provides matrix.
In the present invention, the air is preferably still air or dynamic air.Stream of the present invention to the dynamic air
Speed can ensure the oxygen-supplying amount of oxidation reaction without special restriction.
In the present invention, the temperature of the high temperature oxygen processing is preferably 200~400 DEG C, more preferably 250~350 DEG C, most
Preferably 300 DEG C；The time of the high temperature oxygen processing is preferably 2~12h, more preferably 5~10h, most preferably 6~8h.
In the present invention, in the high temperature oxygen processing, monose carries out partial oxidation reaction with oxygen, so as to be constructed in hydro-thermal carbon material surface
Oxygen-containing functional group, some of which oxygen-containing functional group has carries out ion-exchange performance with alkali metal ion, is subsequent ion type
Chemical activation process provides ion exchange site.
In another technical scheme of the present invention, it is anti-that the aqueous solution of monose is carried out hydro-thermal by the present invention in closed container
Should, obtain pre- char-forming material；The pre- char-forming material is subjected to high temperature oxygen processing in atmosphere, obtains oxygen processing carbon material.
The aqueous solution of monose is carried out hydro-thermal reaction by the present invention in closed container, obtains pre- char-forming material.In the present invention
In, the temperature of the hydro-thermal reaction is preferably 160~200 DEG C, more preferably 170~190 DEG C, most preferably 180 DEG C；The water
The time of thermal response is preferably 10~24h, more preferably 12~20h, most preferably 14~16h.In the present invention, the hydro-thermal
Reaction without extra pressurization or decompression, the pressure of the hydro-thermal reaction be preferably the hydro-thermal reaction at a temperature of spontaneous pressure
Power.In the present invention, the hydro-thermal reaction can synthesize a certain amount of ion-exchangeable oxygen-containing functional group site, enter one
Step improves the reaction site in follow-up displacement reaction, makes the ratio surface of the porous carbon materials of preparation higher.
The present invention does not have special restriction to the device of the hydro-thermal reaction, using hydro-thermal well known to those skilled in the art
Reactor.
After the completion of hydro-thermal reaction, the product of the hydro-thermal reaction is preferably filtered, washed and dried by the present invention successively,
Obtain pre- char-forming material.The present invention is to the no special restriction of operation being filtered, washed and dried, using art technology
The technical scheme being filtered, washed and dried known to personnel.In the present invention, the temperature of the drying is preferably 70~90
DEG C, more preferably 80 DEG C；The time of the drying is preferably 8~12h, more preferably 10h.
After obtaining pre- char-forming material, the pre- char-forming material is carried out high temperature oxygen processing by the present invention in atmosphere, obtains oxygen
Handle carbon material.In the present invention, the pre- char-forming material high temperature oxygen processing operation preferably with described in above-mentioned technical proposal
The technical scheme of high temperature oxidation process is identical, will not be repeated here.In the present invention, in the high temperature oxygen processing procedure, pre- carbon
Change material and carry out partial oxidation reaction with oxygen, so as to construct oxygen-containing functional group in hydro-thermal carbon material surface, some of which contains
Oxygen functional group has carries out ion-exchange performance with alkali metal ion, and providing ion for subsequent ion type chemical activation process hands over
Exchange point.
After obtaining oxygen processing carbon material, after the present invention mixes oxygen processing carbon material with alkali metal hydroxide and water
Enter line replacement reaction, obtain replacing carbon material.In the present invention, the alkali metal hydroxide preferably include potassium hydroxide and/
Or sodium hydroxide.In the present invention, the mass ratio of the alkali metal hydroxide and oxygen processing carbon material is preferably 1.0~2.0,
More preferably 1.1~1.5.
The no special restriction of operation that the present invention mixes to oxygen processing carbon material with alkali metal hydroxide and water,
Using the technical scheme of reaction raw material well known to those skilled in the art.The oxygen is preferably handled carbon materials by the present invention
Material mixes with the aqueous solution of alkali metal hydroxide.The present invention is to the concentration of the aqueous solution of the alkali metal hydroxide without spy
Different restriction, any concentration.In the present invention, the concentration of the aqueous solution of the alkali metal hydroxide be preferably 0.01~
1mol/L, more preferably 0.03~0.3mol/L.
In the present invention, the temperature of the displacement reaction is preferably 60~80 DEG C, more preferably 65~75 DEG C, is most preferably
70℃；The time of the displacement reaction is preferably 8~12h, more preferably 9~11h, most preferably 10h.In the present invention, institute
State in displacement course of reaction, functional group's (such as carboxylic of the alkali metal ion in alkali metal hydroxide and oxygen processing carbon material surface
Base or phenolic hydroxyl group etc.) replace, alkali metal ion is realized that atom level is disperseed, the pole being evenly distributed is formed in final product
Micropore.
The present invention does not have special restriction to the temperature control mode of the displacement reaction, ripe using those skilled in the art
The water bath heating known.In the present invention, the displacement reaction is preferably carried out under agitation.The present invention is stirred described
The speed mixed does not have special restriction, using the speed of the conventional stirring in this area.
After the completion of displacement reaction, product of the present invention preferably by the displacement reaction is centrifuged, washed and dried successively.
The present invention to the centrifugation, washing and the no special restriction of operation dried, using centrifugation well known to those skilled in the art,
Washing and the technical scheme dried.In the present invention, the washing is preferably to wash；The number of the washing is with detergent
Untill neutrality.
Obtain after replacing carbon material, the present invention is activated the displacement carbon material, obtains atomic hole porous carbon materials.
In the present invention, the temperature of the activation is preferably 600~800 DEG C, more preferably 620~680 DEG C, most preferably 640~660
℃；The time of the activation is preferably 2~8h, more preferably 4~6h, most preferably 5h.In the present invention, the activation is preferred
Carried out under vacuum or inert gas shielding；The inert gas is preferably nitrogen.In the present invention, the scattered alkali gold of atom level
Category ion is decomposed at high temperature in activation process with the oxygen-containing functional group of hydro-thermal carbon material surface reacts and then is formed hole
Footpath is below 0.7nm atomic hole.
The present invention does not have special restriction to the device of the activation, is heated using tubular type well known to those skilled in the art
Stove.
After the completion of activation, the product of the activation is preferably carried out pickling and drying by the present invention successively, and it is more to obtain atomic hole
Hole carbon material.The present invention is well known to those skilled in the art to the pickling and the no special restriction of operation dried, use
Pickling and the technical scheme dried.In the present invention, the detergent of the pickling is preferably watery hydrochloric acid；The watery hydrochloric acid
Mass concentration is preferably 5~15%, and more preferably 10%.
The present invention is handled monose or hydro-thermal carbon material by air oxidation process, oxygen-containing to carbon material surface to realize
The modulation of functional group, the content of the ion-exchangeable functional group of hydro-thermal carbon surface (such as carboxyl, phenolic hydroxyl group) is dramatically increased,
Ion exchange site is provided for subsequent ion type chemical activation process, and then alkali metal ion is realized by ion-exchange
Atom level is disperseed, and effectively reduces the dosage of activator, final porous carbon materials of the synthesis rich in atomic hole.Test result indicates that
Preparation method activator level (being converted to industrial KOH chemical activation methods dosage) provided by the invention is about carbon matrix precursor quality
0.1~0.3, the atomic hole porous carbon materials being prepared are rich in the atomic hole that middle aperture is below 0.7nm.
It is described atomic present invention also offers atomic hole porous carbon materials prepared by preparation method described in above-mentioned technical proposal
The aperture in the atomic hole in the porous carbon materials of hole is below 0.7nm.
In order to further illustrate the present invention, the system with reference to embodiment to atomic hole porous carbon materials provided by the invention
Preparation Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1:
8g glucose is placed directly within the Muffle furnace of static atmosphere of air the processing 5h at 300 DEG C and obtains oxygen processing carbon materials
Material.
1.1 times of KOH of oxygen processing carbon material quality is configured to the aqueous solution that concentration is 30mL, adds above-mentioned oxygen processing carbon
Material, then in stirring 10h in 70 DEG C of water-baths, centrifuge to cleaning solution in neutrality, afterwards by solid in 80 DEG C of baking ovens
Drying obtains alkali metal displacement carbon material.
Above-mentioned alkali metal displacement carbon material is placed in tube type resistance furnace and activated, is warming up to 800 DEG C in a nitrogen atmosphere,
Constant temperature 2h, finally obtain sample and be placed in 10% watery hydrochloric acid and stir 1h, dry, you can sample CA-G-300.
Embodiment 2:
8g glucose is added in the 60mL aqueous solution, stirs to clarify liquid, is put into polytetrafluoroethylene (PTFE) in reactor, in
160 DEG C of hydro-thermal process 12h, obtained solid mixture is finally filtered, washed, and 10h is then dried at 80 DEG C, is obtained
The pre- char-forming material of hydro-thermal.
Above-mentioned pre- char-forming material is placed in air atmosphere Muffle furnace the processing 20h at 200 DEG C and obtains oxygen processing carbon material.
1.5 times of KOH of oxygen processing carbon material quality is configured to the 30mL aqueous solution, adds above-mentioned oxygen processing carbon material, so
After stirring 10h in 70 DEG C of water-baths, centrifuge to cleaning solution in neutrality, afterwards obtain solid in 80 DEG C of drying in oven
Alkali metal replaces carbon material.
Above-mentioned alkali metal displacement carbon material is placed in tube type resistance furnace and activated, is warming up to 600 DEG C in a nitrogen atmosphere,
Constant temperature 8h, finally obtain sample and be placed in 10% watery hydrochloric acid and stir 1h, dry, you can sample CA-HTC-200.
Embodiment 3:
8g glucose is added in the 60mL aqueous solution, stirs to clarify liquid, is put into polytetrafluoroethylene (PTFE) in reactor, in
180 DEG C of hydro-thermal process 12h, obtained solid mixture is finally filtered, washed, and 10h is then dried at 80 DEG C, is obtained
The pre- char-forming material of hydro-thermal.
Above-mentioned pre- char-forming material is placed in air atmosphere Muffle furnace the processing 10h at 250 DEG C and obtains oxygen processing carbon material.
1.5 times of KOH of oxygen processing carbon material quality is configured to the 30mL aqueous solution, adds above-mentioned oxygen processing carbon material, so
After stirring 10h in 70 DEG C of water-baths, centrifuge to cleaning solution in neutrality, afterwards obtain solid in 80 DEG C of drying in oven
Alkali metal replaces carbon material.
Above-mentioned alkali metal displacement carbon material is placed in tube type resistance furnace and activated, is warming up to 700 DEG C in a nitrogen atmosphere,
Constant temperature 4h, finally obtain sample and be placed in 10% watery hydrochloric acid and stir 1h, dry, you can sample CA-HTC-250.
Embodiment 4:
8g glucose is added in the 60mL aqueous solution, stirs to clarify liquid, is put into polytetrafluoroethylene (PTFE) in reactor, in
200 DEG C of hydro-thermal process 12h, obtained solid mixture is finally filtered, washed, and 10h is then dried at 80 DEG C, is obtained
The pre- char-forming material of hydro-thermal.
Above-mentioned pre- char-forming material is placed in air atmosphere Muffle furnace the processing 5h at 300 DEG C and obtains oxygen processing carbon material.
1.5 times of KOH of oxygen processing carbon material quality is configured to the 30mL aqueous solution, adds above-mentioned oxygen processing carbon material, so
After stirring 10h in 70 DEG C of water-baths, centrifuge to cleaning solution in neutrality, afterwards obtain solid in 80 DEG C of drying in oven
Alkali metal replaces carbon material.
Above-mentioned alkali metal displacement carbon material is placed in tube type resistance furnace and activated, is warming up to 800 DEG C in a nitrogen atmosphere,
Constant temperature 2h, finally obtain sample and be placed in 10% watery hydrochloric acid and stir 1h, dry, you can sample CA-HTC-300.
Embodiment 5:
Using K in thermogravimetric analysis (TGA) measure alkali metal displacement carbon material+Content, specific method of testing is as follows：By one
Quantitative alkali metal displacement carbon material is placed in thermogravimetric analysis sample cell, permanent after being warming up to 900 DEG C with 5 DEG C/min of heating rate
It is warm 2 hours, the weight change situation of sample in determination sample pond.According to the weight remained after weightlessness, with K2K is calculated exemplified by O+Contain
Amount, equivalent KOH amounts are calculated based on this, calculate KOH/ hydro-thermal carbon mass ratioes, its result is listed in table 1：
The pore structure data of synthetic sample in the embodiment 1~4 of table 1
| Embodiment | Residual content (%) | Equivalent K+(mmol) | KOH/ hydro-thermal carbon |
| Embodiment 1 | 11 | 1.17 | 0.14 |
| Embodiment 2 | 16 | 1.70 | 0.22 |
| Embodiment 3 | 19 | 2.02 | 0.27 |
| Embodiment 4 | 21 | 2.23 | 0.30 |
It can see by table 1：For embodiment 1, can also be synthesized rich in ion-exchange sites only with air oxidation process
Point, but measure relatively fewer.For embodiment 2~4, combine air oxidation process to hydro-thermal carbon material using gentle hydrothermal condition
Carry out handling the modulation that can successfully realize to the functional group of carbon material surface, ion is provided for subsequent ion type chemical activation method
Site is exchanged, finally realizes K+Displacement, replace K+Amount convert into after KOH with the mass ratio of hydro-thermal carbon material between 0.1~0.3, it is living
Agent dosage is much smaller than conventional KOH physical mixeds chemical activation method.
Embodiment 6:
Using low temperature N2Adsorption-desorption method carries out pore structure study to the representative sample synthesized in embodiment 3.
N2For adsorption-desorption curve using liquid nitrogen as cold-trap, High Purity Nitrogen determines pore structure as adsorbate by static volumetric method
And specific surface area.Before sample test, at a temperature of 300 DEG C, vacuum outgas 3h, so as to deviate from the hydrone adsorbed in sample with
And other pass through the impurity of physical absorption.According to N2The pressure-dependent characteristic of adsorbance in material surface under 77K makes sample
The adsorption-desorption isothermal of product.The specific surface area of material, root are calculated by Brunauer-Emmett-Teller methods (BET method)
Micro pore surface area, Micropore volume are calculated according to t-plot methods.The micropore distribution of material is using the nitrogen adsorption number under low relative pressure
According to being calculated by DFT method.
Table 2 is the pore structure data of synthetic sample in embodiment 1~4.
Fig. 1 is the N of the sample of embodiment 1~42Adsorption and desorption isotherms.
Fig. 2 is the graph of pore diameter distribution of the sample of embodiment 1~4.
Pass through the pore structure data of table 2 and Fig. 1 N2Adsorption desorption data can see, air oxidation process synthesis provided by the invention
Biomass-based porous carbon materials there is flourishing microcellular structure.And Fig. 2 pore-size distribution can see, the present invention synthesizes more
The aperture of hole carbon material more concentrates on the pole range of micropores less than 0.7nm.
The pore structure data of synthetic sample in the embodiment 1~4 of table 2
Embodiment 7:
CO is carried out to sample AcA1, AcA2, AcA5, AcA10 for preparing using static adsorptive method2Absorption property survey
Examination.Before absorption test, adsorbent is deaerated 4h under the conditions of 300 DEG C, vacuum reaches 1 μm of mHg, removes moisture and impurity.It is de-
Adsorbent is tested after gas in 0 DEG C and 25 DEG C of CO2Absorption property.Test result such as table 3：
Pass through table 3CO2Absorption property test result can see：Sky is directly carried out in embodiment 1 to biological material
The porous carbon materials that gas oxidative treatment obtains can equally have considerable amount of CO2Adsorption capacity.To water in embodiment 2~4
Hot carbon material, which carries out the carbon material that airoxidation obtains, can significantly improve CO2Adsorption capacity.
CO under the conditions of 30 DEG C and 25 DEG C of table2Absorption property result
As can be seen from the above embodiments, preparation method activator level provided by the invention is few, and what is be prepared is atomic
The atomic hole rich in aperture for below 0.7nm of hole porous carbon materials, specific surface area is big, to CO2Absorption property it is good.
Described above is only the preferred embodiment of the present invention, not makees any formal limitation to the present invention.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of atomic hole porous carbon materials, comprises the following steps：
(1) monose is subjected to high temperature oxygen processing in atmosphere, obtains oxygen processing carbon material；
(2) oxygen that the step (1) obtains is handled into carbon material and laggard line replacement reaction is mixed with alkali metal hydroxide and water,
Obtain replacing carbon material；
(3) the displacement carbon material that the step (2) obtains is activated, obtains atomic hole porous carbon materials.
2. preparation method according to claim 1, it is characterised in that the step (1) replaces with：
The aqueous solution of monose is subjected to hydro-thermal reaction in closed container, obtains pre- char-forming material；
The pre- char-forming material is subjected to high temperature oxygen processing in atmosphere, obtains oxygen processing carbon material.
3. preparation method according to claim 2, it is characterised in that the temperature of the hydro-thermal reaction is 160~200 DEG C,
The time of hydro-thermal reaction is 10~24h.
4. according to the preparation method described in claims 1 to 3 any one, it is characterised in that the monose includes glucose, fruit
One or more in sugar, galactolipin, ribose and deoxyribose.
5. according to the preparation method described in claims 1 to 3 any one, it is characterised in that at step (1) the high temperature oxygen
The temperature of reason is 200~400 DEG C, and the time of high temperature oxygen processing is 2~12h.
6. preparation method according to claim 5, it is characterised in that air in the step (1) for still air or
Dynamic air.
7. according to the preparation method described in claims 1 to 3 any one, it is characterised in that alkali metal hydrogen in the step (2)
The mass ratio of oxide and oxygen processing carbon material is preferably 1.0~2.0.
8. according to the preparation method described in claims 1 to 3 any one, it is characterised in that displacement reaction in the step (2)
Temperature be 60~80 DEG C, the time for replacing reaction is 8~12h.
9. according to the preparation method described in claims 1 to 3 any one, it is characterised in that the temperature of activation in the step (3)
Spend for 600~800 DEG C, the time of activation is 2~8h.
10. atomic hole porous carbon materials prepared by preparation method described in claim 1~9 any one, the pole microporous
The aperture in the atomic hole in carbon material is below 0.7nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851803A (en) * | 2018-12-27 | 2019-06-07 | 天津理工大学 | A kind of preparation method and application of the metal porous coordination polymer of glycosyl |
| CN112340730A (en) * | 2020-11-24 | 2021-02-09 | 海南大学 | Preparation method of microporous carbon-rich material based on carboxylation anchoring effect |
| CN114195120A (en) * | 2021-12-15 | 2022-03-18 | 株洲科能新材料股份有限公司 | Preparation method of high-purity carbon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948106A (en) * | 2010-09-28 | 2011-01-19 | 华东理工大学 | Preparation method of blocky porous carbon with high specific surface area |
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
| CN103663448A (en) * | 2012-09-19 | 2014-03-26 | 天津普兰纳米科技有限公司 | Preparation method of carbon material, obtained carbon material and application thereof |
| CN106185920A (en) * | 2016-06-27 | 2016-12-07 | 农业部环境保护科研监测所 | A kind of porous carbon materials and its preparation method and application |
-
2017
- 2017-12-19 CN CN201711402101.1A patent/CN107840334A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948106A (en) * | 2010-09-28 | 2011-01-19 | 华东理工大学 | Preparation method of blocky porous carbon with high specific surface area |
| CN102070140A (en) * | 2011-02-28 | 2011-05-25 | 无锡第六元素高科技发展有限公司 | Method for preparing high-specific surface area graphene material by utilizing strong base chemical treatment |
| CN102515145A (en) * | 2011-12-27 | 2012-06-27 | 常州第六元素材料科技股份有限公司 | Preparation process for high specific surface porous carbon material |
| CN103663448A (en) * | 2012-09-19 | 2014-03-26 | 天津普兰纳米科技有限公司 | Preparation method of carbon material, obtained carbon material and application thereof |
| CN106185920A (en) * | 2016-06-27 | 2016-12-07 | 农业部环境保护科研监测所 | A kind of porous carbon materials and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 马萨古托夫 等: "《石油加工和石油化学中催化剂再生》", 31 May 1992 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851803A (en) * | 2018-12-27 | 2019-06-07 | 天津理工大学 | A kind of preparation method and application of the metal porous coordination polymer of glycosyl |
| CN112340730A (en) * | 2020-11-24 | 2021-02-09 | 海南大学 | Preparation method of microporous carbon-rich material based on carboxylation anchoring effect |
| CN112340730B (en) * | 2020-11-24 | 2022-03-29 | 海南大学 | Preparation method of microporous carbon-rich material based on carboxylation anchoring effect |
| CN114195120A (en) * | 2021-12-15 | 2022-03-18 | 株洲科能新材料股份有限公司 | Preparation method of high-purity carbon |
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