CN107827108A - A kind of pole micro-pore carbon material and preparation method thereof - Google Patents
A kind of pole micro-pore carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of preparation method of pole micro-pore carbon material, and monose, unsaturated organic acid and water are mixed into laggard water-filling thermal response, obtain hydro-thermal carbon material；Then laggard line replacement reaction is mixed with alkali metal hydroxide and water, obtains replacing carbon material；Activated again, obtain pole micro-pore carbon material.The present invention during hydrothermal carbonization by mixing unsaturated organic acid, the functional group of alkali metal ion displacement can be carried out by being formed in carbon material surface, ion exchange site is provided for subsequent ion type chemical activation method, finally realize that the atom level of alkali metal ion is disperseed, and the dosage of activator can be effectively reduced, 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 0.3 of carbon matrix precursor quality, the pole micro-pore carbon material being prepared is 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 pole micro-pore carbon material and its preparation side
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 pole micro-pore carbon material and preparation method thereof.Preparation method provided by the invention
Activator level is few, and the pole micro-pore carbon material being prepared is rich in the atomic hole that aperture is below 0.7nm.
The invention provides a kind of preparation method of pole micro-pore carbon material, comprise the following steps：
(1) monose, unsaturated organic acid and water are mixed into laggard water-filling thermal response, obtains hydro-thermal carbon material；
(2) that the hydro-thermal carbon material that the step (1) obtains is mixed into laggard line replacement with alkali metal hydroxide and water is anti-
Should, obtain replacing carbon material；
(3) the displacement carbon material that the step (2) obtains is activated, obtains pole micro-pore carbon material.
Preferably, the monose in the step (1) includes one in glucose, fructose, galactolipin, ribose and deoxyribose
Kind is a variety of.
Preferably, the unsaturated organic acid in the step (1) includes organic containing unsaturated double-bond and/or three keys
Acid.
Preferably, the unsaturated organic acid includes one kind or more in acrylic acid, crotonic acid, acetylenedicarboxylic acid and maleic acid
Kind.
Preferably, the mass ratio of unsaturated organic acid and monose is (0.01~1) in the step (1):1.
Preferably, the temperature of hydro-thermal reaction is 160~200 DEG C in the step (1), time of hydro-thermal reaction for 10~
24h。
Preferably, in the step (2) in alkali metal hydroxide and step (1) material of unsaturated organic acid amount it
Than >=1.
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.
Present invention also offers pole micro-pore carbon material prepared by preparation method described in above-mentioned technical proposal, the pole microporous carbon
The aperture in the atomic hole in material is below 0.7nm.
The invention provides a kind of preparation method of pole micro-pore carbon material, comprise the following steps：Monose, unsaturation is organic
Acid and water mix laggard water-filling thermal response, obtain hydro-thermal carbon material；By the hydro-thermal carbon material and alkali metal hydroxide and water
Laggard line replacement reaction is mixed, obtains replacing carbon material；The displacement carbon material is activated, obtains pole micro-pore carbon material.
For the present invention by mixing unsaturated organic acid in hydrothermal carbonization process, alkali metal ion displacement can be carried out by being formed in carbon material surface
Functional group, provide ion exchange site for subsequent ion type chemical activation method, finally realize the atom fraction of alkali metal ion
Dissipate, so that alkali metal ion substitutes conventional physical mixing KOH components as activator, reduce the dosage of activator, most
Porous carbon materials of the synthesis rich in atomic hole eventually.Test result indicates that preparation method activator level (conversion provided by the invention
Into industrial KOH chemical activation methods dosage) it is about the 0.3 of carbon matrix precursor quality, the pole micro-pore carbon material being prepared is rich in mesopore
Footpath is below 0.7nm atomic hole.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the hydro-thermal carbon sample obtained in embodiment 3；
Fig. 2 is the transmission electron microscope picture of the hydro-thermal carbon sample obtained in embodiment 3；
Fig. 3 is the scanning electron microscope (SEM) photograph of the AcA3 samples obtained in embodiment 3；
Fig. 4 is the transmission electron microscope picture of the AcA3 samples obtained in embodiment 3；
Fig. 5 is the N of the AcA1~AcA6 samples obtained in embodiment 1~62Adsorption and desorption isotherms；
Fig. 6 is the graph of pore diameter distribution of the AcA1~AcA6 samples obtained in embodiment 1~6.
Embodiment
The invention provides a kind of preparation method of pole micro-pore carbon material, comprise the following steps：
(1) monose, unsaturated organic acid and water are mixed into laggard water-filling thermal response, obtains hydro-thermal carbon material；
(2) that the hydro-thermal carbon material that the step (1) obtains is mixed into laggard line replacement with alkali metal hydroxide and water is anti-
Should, obtain replacing carbon material；
(3) the displacement carbon material that the step (2) obtains is activated, obtains pole micro-pore carbon material.
Monose, unsaturated organic acid and water are mixed laggard water-filling thermal response by the present invention, obtain hydro-thermal carbon material.In this hair
In bright, the monose preferably includes the one or more in glucose, fructose, galactolipin, ribose and deoxyribose.The present invention is right
The source of the monose does not have special restriction, 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 atom, carbon source can be used as to provide matrix.
In the present invention, the unsaturated organic acid preferably includes the organic acid containing unsaturated double-bond and/or three keys, more
Preferably include the one or more in acrylic acid, crotonic acid, acetylenedicarboxylic acid and maleic acid.In the present invention, when the unsaturation
Organic acid is that the present invention does not have special restriction to the ratio of each component in the composition when including a variety of sour compositions,
Mixed with arbitrary proportion.In the present invention, unsaturated double-bond or three keys are contained in the unsaturated organic acid, can be in list
Sugared surface forms carboxyl functional group, is easy to follow-up ion exchange.
In the present invention, the mass ratio of the unsaturated organic acid and monose is preferably (0.01~1):1, more preferably
(0.02~0.05):1.The present invention does not have special restriction to the dosage of the water, using water well known to those skilled in the art
The dosage of thermal response.In the present invention, the mass ratio of the volume of the water and monose is preferably (8~12) mL:1g, it is more excellent
Elect 10mL as:1g.
The no special restriction of operation of mixing of the present invention to the monose, unsaturated organic acid and water, using ability
The technical scheme of mixed material is prepared known to field technique personnel.In the present invention, the monose, unsaturated organic acid and
The mixing of water is preferably carried out under agitation.
In the present invention, the temperature of the hydro-thermal reaction is preferably 160~200 DEG C, more preferably 170~190 DEG C, optimal
Elect 180 DEG C as；The time of the hydro-thermal reaction is preferably 10~24h, more preferably 12~20h, most preferably 14~16h.
In the present invention, in the hydrothermal reaction process, unsaturated organic acid is doped into monose, forms the carbon materials that surface carries carboxyl
Material, reaction site is provided for follow-up displacement reaction.
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 hydro-thermal carbon 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 hydro-thermal carbon material, the present invention is carried out after the hydro-thermal carbon material is mixed with alkali metal hydroxide and water
Displacement reaction, obtain replacing carbon material.In the present invention, the alkali metal hydroxide preferably includes potassium hydroxide and/or hydrogen
Sodium oxide molybdena.In the present invention, the ratio between amount of material of the alkali metal hydroxide and unsaturated organic acid is preferably >=1, more excellent
Elect 1.1~1.5 as.
The no special restriction of operation that the present invention mixes to the hydro-thermal carbon material with alkali metal hydroxide and water, is adopted
With the technical scheme of reaction raw material well known to those skilled in the art.The present invention preferably by the hydro-thermal carbon material with
The aqueous solution mixing of alkali metal hydroxide.It is special that the present invention does not have to the concentration of the aqueous solution of the alkali metal hydroxide
Limit, 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 carboxyl of alkali metal ion and hydro-thermal carbon material surface in alkali metal hydroxide
Or phenolic hydroxyl group etc.) replace, alkali metal ion is realized that atom level is disperseed, formed in final product be evenly distributed it is atomic
Hole.
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 pole micro-pore carbon material.At this
In invention, the temperature of the activation is preferably 600~800 DEG C, more preferably 620~680 DEG C, most preferably 640~660 DEG C；
The time of the activation is preferably 2~8h, more preferably 4~6h, most preferably 5h.In the present invention, the activation preferably exists
Carried out under vacuum or inert gas shielding；The inert gas is preferably nitrogen.In the present invention, the scattered alkali metal of atom level
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 aperture
For 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, obtains pole microporous carbon
Material.The present invention is to the pickling and the no special restriction of operation dried, using pickling well known to those skilled in the art
With dry technical scheme.In the present invention, the detergent of the pickling is preferably watery hydrochloric acid；The quality of the watery hydrochloric acid
Concentration is preferably 5~15%, and more preferably 10%.
Preparation method provided by the invention in hydrothermal carbonization process by mixing unsaturated organic acid, in carbon material surface shape
Into the functional group that can carry out alkali metal ion displacement, ion exchange site is provided for subsequent ion type chemical activation method；Using from
The inorganic base metal ion for undertaking activation is incorporated into predecessor by the mode that son exchanges, and is reducing activator consumption
Meanwhile its decentralization and coverage on the surface of carbonized product is improved, finally realize that the atom level of alkali metal ion is disperseed, from
And make it that alkali metal ion substitutes conventional physical and mixes KOH components as activator, reduces activator level, reduces raw material
Cost, the corrosion of equipment is avoided, and the porous carbon materials rich in atomic hole can be synthesized.
Present invention also offers pole micro-pore carbon material prepared by preparation method described in above-mentioned technical proposal, the pole microporous carbon
The aperture in the atomic hole in material is below 0.7nm.
In order to further illustrate the present invention, the preparation side with reference to embodiment to pole micro-pore carbon material provided by the invention
Method is described in detail, but they can not be interpreted as into limiting the scope of the present invention.
Embodiment 1:
6g glucose is added in the 60mL aqueous solution, stirs to clarify liquid, adds 0.06g (the 1% of glucose quality)
Acrylic acid stir, polytetrafluoroethylene (PTFE) is put into reactor, in 200 DEG C of hydro-thermal process 12h, the solution that will finally obtain
Filtered, washed, 10h is then dried at 80 DEG C, obtains hydro-thermal carbon material.
KOH is configured to the aqueous solution 30mL that concentration is 0.03mol/L, above-mentioned hydro-thermal carbon material is added, then in 70 DEG C
Stirring 10h in water-bath, centrifuge to cleaning solution in neutrality, afterwards by solid in 80 DEG C of drying in oven.
Solid is placed in tube type resistance furnace afterwards and activated, is warming up to 600 DEG C, constant temperature 8h in a nitrogen atmosphere, finally
It is placed in sample in 10% watery hydrochloric acid and stirs 1h, dried, you can obtains AcA1 samples.
Embodiment 2:
6g glucose is added in the 60mL aqueous solution, stirs to clarify liquid, adds 0.12g (the 2% of glucose quality)
Acrylic acid stir, polytetrafluoroethylene (PTFE) is put into reactor, in 180 DEG C of hydro-thermal process 16h, the solution that will finally obtain
Filtered, washed, 10h is then dried at 80 DEG C, obtains hydro-thermal carbon material.
KOH is configured to the aqueous solution 30mL that concentration is 0.06mol/L, above-mentioned hydro-thermal carbon material is added, then in 80 DEG C
Stirring 8h in water-bath, centrifuge to cleaning solution in neutrality, afterwards by solid in 80 DEG C of drying in oven.
Solid is placed in tube type resistance furnace afterwards and activated, is warming up to 700 DEG C, constant temperature 6h in a nitrogen atmosphere, finally
It is placed in sample in 10% watery hydrochloric acid and stirs 1h, dried, you can obtains AcA2 samples.
Embodiment 3:
6g glucose is added in the 60mL aqueous solution, stirs to clarify liquid, adds 0.3g's (the 5% of glucose quality)
Acrylic acid stirs, and is put into polytetrafluoroethylene (PTFE) in reactor, in 160 DEG C of hydro-thermal process 18h, finally enters obtained solution
Row filtering, washing, 10h is then dried at 80 DEG C, obtains hydro-thermal carbon material.
KOH is configured to the aqueous solution 30mL that concentration is 0.15mol/L, above-mentioned hydro-thermal carbon material is added, then in 80 DEG C
Stirring 8h in water-bath, centrifuge to cleaning solution in neutrality, afterwards by solid in 80 DEG C of drying in oven.
Solid is placed in tube type resistance furnace afterwards and activated, is warming up to 800 DEG C, constant temperature 4h in a nitrogen atmosphere, finally
It is placed in sample in 10% watery hydrochloric acid and stirs 1h, dried, you can obtains AcA3 samples.
Embodiment 4:
6g glucose is added in the 60mL aqueous solution, stirs to clarify liquid, adds 0.6g (the 10% of glucose quality)
Acrylic acid stir, polytetrafluoroethylene (PTFE) is put into reactor, in 160 DEG C of hydro-thermal process 24h, the solution that will finally obtain
Filtered, washed, 10h is then dried at 80 DEG C, obtains hydro-thermal carbon material.
KOH is configured to the aqueous solution 30mL that concentration is 0.3mol/L, above-mentioned hydro-thermal carbon material is added, then in 60 DEG C of water
Stirring 8h in bath, centrifuge to cleaning solution in neutrality, afterwards by solid in 80 DEG C of drying in oven.
Solid is placed in tube type resistance furnace afterwards and activated, is warming up to 800 DEG C, constant temperature 2h in a nitrogen atmosphere, finally
It is placed in sample in 10% watery hydrochloric acid and stirs 1h, dried, you can obtains AcA4 samples.
Embodiment 5:
6g fructose is added in the 60mL aqueous solution, stirs to clarify liquid, adds 0.3g (the 5% of fructose quality) Malaysia
Acid stirs, and is put into polytetrafluoroethylene (PTFE) in reactor, in 160 DEG C of hydro-thermal process 18h, finally carries out obtained solution
Filter, washing, 10h is then dried at 80 DEG C, obtains hydro-thermal carbon material.
KOH is configured to the aqueous solution 30mL that concentration is 0.3mol/L, above-mentioned hydro-thermal carbon material is added, then in 80 DEG C of water
Stirring 8h in bath, centrifuge to cleaning solution in neutrality, afterwards by solid in 80 DEG C of drying in oven.
Solid is placed in tube type resistance furnace afterwards and activated, is warming up to 800 DEG C, constant temperature 4h in a nitrogen atmosphere, finally
It is placed in sample in 10% watery hydrochloric acid and stirs 1h, dried, you can obtains AcA5 samples.
Embodiment 6:
6g glucose sugar is added in the 60mL aqueous solution, stirs to clarify liquid, adds 0.3g (the 5% of fructose quality) fourth
Alkynes diacid stirs, and is put into polytetrafluoroethylene (PTFE) in reactor, in 160 DEG C of hydro-thermal process 18h, finally enters obtained solution
Row filtering, washing, 10h is then dried at 80 DEG C, obtains hydro-thermal carbon material.
KOH is configured to the aqueous solution 30mL that concentration is 0.3mol/L, above-mentioned hydro-thermal carbon material is added, then in 80 DEG C of water
Stirring 8h in bath, centrifuge to cleaning solution in neutrality, afterwards by solid in 80 DEG C of drying in oven.
Solid is placed in tube type resistance furnace afterwards and activated, is warming up to 800 DEG C, constant temperature 4h in a nitrogen atmosphere, finally
It is placed in sample in 10% watery hydrochloric acid and stirs 1h, dried, you can obtains AcA6 samples.
Embodiment 7:
Observed in embodiment 3 and made using scanning electron microscope analysis (SEM) and high resolution transmission electron microscopy (TEM)
Standby AcA3 samples and the pattern of intermediate product, obtain the scanning nuclear microprobe figure of hydro-thermal carbon material sample respectively such as Fig. 1 and
Shown in Fig. 2, the scanning nuclear microprobe figure difference of AcA3 samples is as shown in Figure 3 and Figure 4.
The accelerating potential that scanning electron microscope analysis (SEM) use is 0.5-30KV, multiplication factor 500-30000
Times.It is first that a little sample is levigate during the pattern of the sample prepared using high resolution transmission electron microscopy (TEM) observation, then
Sample powder is added in ethanol solution.Make sample particle to be measured fully dispersed using the method for supersonic oscillations, then
The suspension of a drop testing sample is taken with rubber head dropper, is dripped on the carbon film of copper mesh support.Copper mesh is dried in ventilation, treats second
After alcohol fully volatilizees, the sample prepared on carbon film is placed under high resolution transmission electron microscopy and is observed.Thoroughly
The microscopical accelerating potential of radio is 200KV.
It can see from Fig. 1~4：For product after hydrothermal carbonization mainly based on spherical deposit, transmission electron microscope shows material
Expect for unformed state of aggregation, in non-porous structure；And pass through K+The state of aggregation pattern and hydro-thermal of AcA3 samples after ion activation
Seemingly, but transmission electron microscope shows that the random graphits structure of a large amount of stackings forms a large amount of vermiform micropores for being less than 1nm to carbons.
Embodiment 8:
K in the intermediate product alkali metal displacement carbon material prepared in embodiment 3 is determined using thermogravimetric analysis (TGA)+Contain
Amount, specific method of testing are as follows：A certain amount of alkali metal displacement carbon material is placed in thermogravimetric analysis sample cell, with 5 DEG C/min
Constant temperature 2 hours after heating rate is warming up to 900 DEG C, the weight change situation of sample in determination sample pond.According to being remained after weightlessness
Weight, with K2K+ contents are calculated exemplified by O, equivalent KOH amounts is calculated based on this, calculates KOH/ hydro-thermal carbon mass ratioes, it is tied
Fruit is listed in table 1：
The pore structure data of synthetic sample in the embodiment 1- embodiments 6 of table 1
By table 1, it can be seen that, the present invention can be realized successfully by mixing unsaturated organic acid in hydrothermal carbonization process
To the modulation of the functional group of carbon material surface, ion exchange site is provided for subsequent ion type chemical activation method, finally realizes K+
Displacement, replace K+Amount convert into after KOH with the mass ratio of hydro-thermal carbon material between 0.07~0.5, activator level is much smaller than normal
Advise KOH physical mixed chemical activation methods.
Embodiment 9:
Using low temperature N2Adsorption-desorption method carries out pore structure study to the sample synthesized in embodiment 1~6, is implemented
The N of sample in example 1~62Adsorption and desorption isotherms as shown in figure 5, in embodiment 1~6 sample graph of pore diameter distribution as shown in fig. 6,
The pore structure data of synthetic sample are as shown in table 2 in embodiment 1~6.
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.
Pass through the pore structure data of table 2 and Fig. 5 N2Adsorption desorption data can see, micro-pore carbon material tool in pole provided by the invention
There is the microcellular structure of prosperity.And Fig. 6 pore-size distribution can see, the aperture for the pole micro-pore carbon material that the present invention synthesizes is more
Concentrate on the pole range of micropores less than 0.7nm.
The pore structure data of synthetic sample in the embodiment 1~6 of table 2
Embodiment 10:
CO is carried out to sample AcA1, AcA2, AcA3, AcA4 for preparing using static adsorptive method2Absorption property test.
Before absorption test, adsorbent is deaerated 4h under the conditions of 300 DEG C, vacuum reaches 1 μm of mHg, removes moisture and impurity.After degassing
Adsorbent is tested in 0 DEG C and 25 DEG C of CO2Absorption property.Test result such as table 3：
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 carbon material, 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 pole micro-pore carbon material, comprises the following steps：
(1) monose, unsaturated organic acid and water are mixed into laggard water-filling thermal response, obtains hydro-thermal carbon material；
(2) the hydro-thermal carbon material that the step (1) obtains is mixed to laggard line replacement reaction with alkali metal hydroxide and water, obtained
To displacement carbon material；
(3) the displacement carbon material that the step (2) obtains is activated, obtains pole micro-pore carbon material.
2. preparation method according to claim 1, it is characterised in that the monose in the step (1) includes glucose, fruit
One or more in sugar, galactolipin, ribose and deoxyribose.
3. preparation method according to claim 1, it is characterised in that the unsaturated organic acid in the step (1) includes
Organic acid containing unsaturated double-bond and/or three keys.
4. preparation method according to claim 3, it is characterised in that the unsaturated organic acid includes acrylic acid, crotons
One or more in acid, acetylenedicarboxylic acid and maleic acid.
5. according to the preparation method described in Claims 1 to 4 any one, it is characterised in that there is unsaturation in the step (1)
The mass ratio of machine acid and monose is (0.01~1):1.
6. preparation method according to claim 1, it is characterised in that the temperature of hydro-thermal reaction is 160 in the step (1)
~200 DEG C, the time of hydro-thermal reaction is 10~24h.
7. preparation method according to claim 1, it is characterised in that alkali metal hydroxide and step in the step (2)
Suddenly the ratio between amount of material of unsaturated organic acid >=1 in (1).
8. the preparation method according to claim 1 or 7, it is characterised in that the temperature of displacement reaction is in the step (2)
60~80 DEG C, the time for replacing reaction is 8~12h.
9. preparation method according to claim 1, it is characterised in that in the step (3) temperature of activation for 600~
800 DEG C, the time of activation is 2~8h.
10. pole micro-pore carbon material prepared by preparation method described in claim 1~9 any one, in the pole micro-pore carbon material
The aperture in atomic hole be below 0.7nm.
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| CN110436462A (en) * | 2019-07-29 | 2019-11-12 | 华南理工大学 | A kind of micro-pore carbon material and the preparation method and application thereof preparing highly selective separation propylene propane using starch |
| CN112340730A (en) * | 2020-11-24 | 2021-02-09 | 海南大学 | Preparation method of microporous carbon-rich material based on carboxylation anchoring effect |
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| CN117263325B (en) * | 2023-11-21 | 2024-02-09 | 江苏省农业科学院 | Preparation method of modified cathode of MEC-AD system and high-efficiency low-energy-consumption application thereof |
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