CN109012580A - A kind of preparation method of the multi-layer porous material of graphene-active carbon - Google Patents
A kind of preparation method of the multi-layer porous material of graphene-active carbon Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of multi-layer porous material of graphene-active carbon, belong to adsorbent material technical field, it is characterised in that it includes the activation of active carbon comminution pretreatment, active carbon alkali, fireworks graphene package active carbon, be blended with sodium alginate cladding, high-temperature process, drying etc. operating procedures;Active carbon, graphene and cheap marine organism material sodium alginate are combined, material is carried out pore-creating from inside to outside, is prepared for the carbon material with abundant pore structure, specific surface area is high, and adsorption capacity is high, is easily recycled and reuses.
Description
Technical field
The present invention relates to water-treatment technology fields, and in particular to a kind of preparation of the multi-layer porous material of graphene-active carbon
Method.
Background technique
With the acceleration of countries in the world process of industrialization, economy is developed, and people's lives level has very big
It improves.But the environmental pollution that course of industrialization bring is got worse becomes the unavoidable major issue of people.A large amount of industry
Waste water is unprocessed to be directly or indirectly discharged into water body, causes water quality condition serious, ecological environment is destroyed.As country is to dirt
Water discharge standard is increasingly stringenter, such as based on traditional sewage water treatment method based on high concentration, additional metering reaction reagent
Electrolysis method, chemical precipitation method, ion-exchange, catalytic degradation etc. have been difficult that processing water is made to reach standard.Therefore, how effectively
Processing water pollution problem has become the hot research problem of water treatment field.
Absorption method is by adsorbent own characteristic (large specific surface area and porous structure) or adsorbent surface active group
Group and the bonding action of adsorbate, the selective method for treating water for making micropollutants concentration and separation, be it is a kind of simply, have before
Scape and also be the purifying water process technique being widely used.When porous solid (such as active carbon, absorption resin) with
When waste water, Cucumber colliding solid surface in dyestuff, substance rests on suction because of the attraction by unbalanced power
Attached dose of surface, to achieve the purpose that purify waste water.The active charcoal of common adsorbent, coke, fiber series, sawdust, silicon
Diatomaceous earth, coal ash etc..
The two scientist An Deliegaimu and Constantine Nuo Woxiaoluofuyin of Univ Manchester UK are two
Since the pionerring research of dimension space material graphene obtains Nobel Prize in physics in 2010, this novel carbon materials of graphene
Material has become the research hotspot of materials science field.Graphene because its special two-dimensional structure make its contained it is abundant due to it is novel
Physical chemical phenomenon shows excellent electric property, mechanical property and heating conduction, it is contemplated that in following computer chip material
Material, solar battery, capacitor, nano functional device etc. have broad application prospects.Two wiener of single layer of graphene
Rice structure also gives its good Molecular Adsorption performance.Preliminary Results discovery, graphene is to CH4、H2、NH3、NO2、Xe、
CO2Equal gas molecules all have good adsorption capacity, and graphene also has good adsorption capacity to heavy metal ion.Stone
The research work that black alkene is used as micropollutants in adsorbent removal sewage is at the early-stage, has in terms of water environment adsorbent material huge
Big application potential.
It is mostly to be passed through physically or chemically to activate for raw material by coal, shell or sawdust etc. for the active carbon of water process at present
It is made, but asks there are still specific surface area is relatively low, adsorption capacity is small, be not easily recycled, polluted-water, recycling rate of waterused are low etc.
Topic.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of graphene-active carbon
The preparation method of multi-layer porous material combines active carbon, graphene and cheap marine organism material sodium alginate, than
Surface area is high, and adsorption capacity is high, is easily recycled and reuses.
The technical scheme to solve the above technical problems is that
A kind of preparation method of the multi-layer porous material of graphene-active carbon, which comprises the steps of:
A) absorbent charcoal material Activated Carbon Pretreatment: is crushed to partial size less than 5 μm;
Ball-milling method or comminution by gas stream can be used in the breaking method of active carbon, and wherein the concrete operations of ball-milling method are by active raw material of wood-charcoal
Material is added to ball milling 10h-48h in ball grinder;
The purpose of crushing is the partial size of reduction active carbon, first is that increasing activation point, two are easy for graphene oxide to activity
The package of charcoal;
B) active carbon activates: the active carbon after ball milling being added in the potassium hydroxide solution that concentration is 10%-40%, impregnates 1h-
For 24 hours, filtering drying;
The porous structure having using active carbon itself, after impregnating in potassium hydroxide solution, active carbon can inhale potassium hydroxide
It receives in its hole internal structure, it is therefore intended that activation can be played convenient for potassium hydroxide when subsequent high temperature processing;
C) graphene oxide wraps up active carbon: the active carbon after drying is added to the oxidation stone that concentration is 1mg/ml-5mg/ml
In black aqueous solution, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Its
In, the mass ratio of the solid content of graphene oxide and active carbon is 1:1-5 in graphene oxide water solution.
By spray drying treatment, the presence of active carbon can prevent graphene oxide from occurring reuniting now in spray process
As increasing the specific surface area of graphene, simultaneous oxidation graphene can also carry out package molding, the composite material of formation to active carbon
Particle is uniform;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) calcium chloride for mixed system obtained by step d) being added dropwise to 5%-10% by syringe needle using peristaltic pump is molten
In liquid, ball-type gel-like product is obtained, stands 2h-10h;After ball-type gel-like product is cleaned with deionized water again, freezed
Dry 5h-48h;
By the way that graphene oxide-absorbent charcoal composite material is wrapped up with the method for collosol and gel, foring outer layer is seaweed
The composite material of sour calcium cladding.The step for further increase the partial size of composite material, convenient for material in water process return
It receives and recycles, ultimately form and be followed successively by active carbon-graphene oxide-calcium alginate multilayer chondritic from inside to outside
Composite material;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process under the conditions of 500 DEG C -800 DEG C
0.5h-4h;
By high-temperature process, the calcium alginate in composite material is carbonized, graphene oxide is restored;At the same time,
The potassium hydroxide that active carbon internal pore structure absorbs at high temperature to the calcium alginate of the graphene of active carbon, reduction, carbonization into
The activation of row from inside to outside, considerably increases the pore structure of composite material;
G) more up to graphene-active carbon multilayer after dry after the hydrochloric acid of the product after high-temperature process and deionized water being cleaned
Porous materials, up to the multi-layer porous material of graphene-active carbon after drying;Wherein, the washing of hydrochloric acid and deionized water is to go
Except the impurity in composite porous.
The beneficial effects of the present invention are: the side combined using spray drying, collosol and gel, alkali activation and high-temperature process
Then method successively carries out graphene oxide cladding active carbon, calcium alginate coats oxygen first with activated carbon adsorption potassium hydroxide
Graphite alkene-active carbon, formation are followed successively by active carbon-graphene oxide-calcium alginate multilayered structure carbon materials from inside to outside
Calcium alginate, is finally carbonized under high-temperature process, graphene oxide restores by material, while active carbon internal pore structure
The potassium hydroxide of absorption carries out activation from inside to outside to the graphene of active carbon, reduction, the calcium alginate of carbonization at high temperature,
Material is carried out pore-creating from inside to outside, is prepared for ultimately forming multilayer porous structure, particularly with the carbon material of abundant pore structure
Composite material considerably increases the pore structure of composite material, improves its specific surface area and methylene blue decoloring ability, can be used in
The absorption of heavy metal, the processing of colorful wastewater and air cleaning etc.;Material structure prepared by the present invention is stablized, and is carrying out
It is easy to collect and post-process during water process, is convenient for reusing.
Specific embodiment
Embodiment 1
The present embodiment graphene-active carbon multi-layer porous material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: being added to ball milling 30h in ball grinder for absorbent charcoal material, it is made to be crushed to partial size less than 5 μm;
B) active carbon and potassium hydroxide mixing: the active carbon after ball milling is added in the potassium hydroxide solution that concentration is 25%, leaching
Steep 12h, filtering drying;
C) graphene oxide wraps up active carbon: it is water-soluble that the active carbon after drying is added to the graphene oxide that concentration is 3mg/ml
In liquid, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Wherein, stone is aoxidized
The mass ratio of the solid content of graphene oxide and active carbon is 1:3 in black aqueous solution;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) mixed system obtained by step d) is added dropwise in 7% calcium chloride solution by syringe needle using peristaltic pump,
Ball-type gel-like product is obtained, 6h is stood;After ball-type gel-like product is cleaned with deionized water again, freeze-drying 25h is carried out;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process 2h under the conditions of 650 DEG C;
G) after the hydrochloric acid of the product after high-temperature process and deionized water being cleaned, the dry 8h of blast drier is put into get graphite
The multi-layer porous material of alkene-active carbon, up to the multi-layer porous material of graphene-active carbon after drying.
Embodiment 2
The present embodiment graphene-active carbon multi-layer porous material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: being added to ball milling 10h in ball grinder for absorbent charcoal material, it is made to be crushed to partial size less than 5 μm;
B) active carbon and potassium hydroxide mixing: the active carbon after ball milling is added in the potassium hydroxide solution that concentration is 10%, leaching
Steep 1h, filtering drying;
C) graphene oxide wraps up active carbon: it is water-soluble that the active carbon after drying is added to the graphene oxide that concentration is 1mg/ml
In liquid, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Wherein, stone is aoxidized
The mass ratio of the solid content of graphene oxide and active carbon is 1:1 in black aqueous solution;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) mixed system obtained by step d) is added dropwise in 5% calcium chloride solution by syringe needle using peristaltic pump,
Ball-type gel-like product is obtained, 2h is stood;After ball-type gel-like product is cleaned with deionized water again, freeze-drying 5h is carried out;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process 4h under the conditions of 500 DEG C;
G) after the hydrochloric acid of the product after high-temperature process and deionized water being cleaned, the dry 5h of blast drier is put into get graphite
The multi-layer porous material of alkene-active carbon, up to the multi-layer porous material of graphene-active carbon after drying.
Embodiment 3
The present embodiment graphene-active carbon multi-layer porous material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: being added to ball milling 48h in ball grinder for absorbent charcoal material, it is made to be crushed to partial size less than 5 μm;
B) active carbon and potassium hydroxide mixing: the active carbon after ball milling is added in the potassium hydroxide solution that concentration is 40%, leaching
It steeps for 24 hours, filtering drying;
C) graphene oxide wraps up active carbon: it is water-soluble that the active carbon after drying is added to the graphene oxide that concentration is 5mg/ml
In liquid, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Wherein, stone is aoxidized
The mass ratio of the solid content of graphene oxide and active carbon is 1:5 in black aqueous solution;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) mixed system obtained by step d) is added dropwise to 10% calcium chloride solution using peristaltic pump by syringe needle
In, ball-type gel-like product is obtained, 10h is stood;After ball-type gel-like product is cleaned with deionized water again, it is freeze-dried
48h;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process 0.5h under the conditions of 800 DEG C;
G) after the hydrochloric acid of the product after high-temperature process and deionized water being cleaned, the dry 12h of blast drier is put into get graphite
The multi-layer porous material of alkene-active carbon, up to the multi-layer porous material of graphene-active carbon after drying.
Embodiment 4
The present embodiment graphene-active carbon multi-layer porous material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: absorbent charcoal material is crushed to less than 5 μm by partial size using comminution by gas stream, device therefor is air-flow
Pulverizer;
B) active carbon and potassium hydroxide mixing: the active carbon after ball milling is added in the potassium hydroxide solution that concentration is 25%, leaching
Steep 12h, filtering drying;
C) graphene oxide wraps up active carbon: it is water-soluble that the active carbon after drying is added to the graphene oxide that concentration is 3mg/ml
In liquid, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Wherein, stone is aoxidized
The mass ratio of the solid content of graphene oxide and active carbon is 1:3 in black aqueous solution;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) mixed system obtained by step d) is added dropwise in 7% calcium chloride solution by syringe needle using peristaltic pump,
Ball-type gel-like product is obtained, 6h is stood;After ball-type gel-like product is cleaned with deionized water again, freeze-drying 25h is carried out;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process 2h under the conditions of 650 DEG C;
G) after the hydrochloric acid of the product after high-temperature process and deionized water being cleaned, the dry 8h of blast drier is put into get graphite
The multi-layer porous material of alkene-active carbon, up to the multi-layer porous material of graphene-active carbon after drying.
Comparative example 1
Graphene-absorbent charcoal composite material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: being added to ball milling 30h in ball grinder for absorbent charcoal material, it is made to be crushed to partial size less than 5 μm;
B) graphene oxide wraps up active carbon: it is water-soluble that smashed active carbon is added to the graphene oxide that concentration is 3mg/ml
In liquid, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Wherein, stone is aoxidized
The mass ratio of the solid content of graphene oxide and active carbon is 1:3 in black aqueous solution;
C) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
D) mixed system obtained by step d) is added dropwise in 7% calcium chloride solution by syringe needle using peristaltic pump,
Ball-type gel-like product is obtained, 6h is stood;After ball-type gel-like product is cleaned with deionized water again, freeze-drying 25h is carried out;
E) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process 2h under the conditions of 650 DEG C;
F) after the product after high-temperature process being cleaned with deionized water, the dry 8h of blast drier is put into get graphene-activity
The multi-layer porous material of charcoal, up to the multi-layer porous material of graphene-active carbon after drying.
Comparative example 2
Graphene-absorbent charcoal composite material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: being added to ball milling 30h in ball grinder for absorbent charcoal material, it is made to be crushed to partial size less than 5 μm;
B) active carbon and potassium hydroxide mixing: the active carbon after ball milling is added in the potassium hydroxide solution that concentration is 25%, leaching
Steep 12h, filtering drying;
C) active carbon after drying graphene oxide and active carbon mixing: is added to the graphene oxide water that concentration is 3mg/ml
In solution, it is uniformly mixed;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the graphene oxide and absorbent charcoal material mixed solution of step c) is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) mixed system obtained by step d) is added dropwise in 7% calcium chloride solution by syringe needle using peristaltic pump,
Ball-type gel-like product is obtained, 6h is stood;After ball-type gel-like product is cleaned with deionized water again, freeze-drying 25h is carried out;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process 2h under the conditions of 650 DEG C;
G) after the hydrochloric acid of the product after high-temperature process and deionized water being cleaned, the dry 8h of blast drier is put into get graphite
The multi-layer porous material of alkene-active carbon, up to the multi-layer porous material of graphene-active carbon after drying.
Comparative example 3
Graphene-absorbent charcoal composite material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: being added to ball milling 30h in ball grinder for absorbent charcoal material, it is made to be crushed to partial size less than 5 μm;
B) active carbon and potassium hydroxide mixing: the active carbon after ball milling is added in the potassium hydroxide solution that concentration is 25%, leaching
Steep 12h, filtering drying;
C) graphene oxide wraps up active carbon: it is water-soluble that the active carbon after drying is added to the graphene oxide that concentration is 3mg/ml
In liquid, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Wherein, stone is aoxidized
The mass ratio of the solid content of graphene oxide and active carbon is 1:3 in black aqueous solution;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) mixed system obtained by step d) is added dropwise in 7% calcium chloride solution by syringe needle using peristaltic pump,
Ball-type gel-like product is obtained, 6h is stood;After ball-type gel-like product is cleaned with deionized water again, freeze-drying 25h is carried out;
F) after the product after freeze-drying being cleaned with deionized water, it is put into the dry 8h of blast drier.
Comparative example 4
Graphene-absorbent charcoal composite material preparation method, includes the following steps:
A) Activated Carbon Pretreatment: being added to ball milling 30h in ball grinder for absorbent charcoal material, it is made to be crushed to partial size less than 5 μm;
B) graphene oxide wraps up active carbon: it is water-soluble that smashed active carbon is added to the graphene oxide that concentration is 3mg/ml
In liquid, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;Wherein, stone is aoxidized
The mass ratio of the solid content of graphene oxide and active carbon is 1:3 in black aqueous solution;
C) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
D) mixed system obtained by step d) is added dropwise in 7% calcium chloride solution by syringe needle using peristaltic pump,
Ball-type gel-like product is obtained, 6h is stood;After ball-type gel-like product is cleaned with deionized water again, freeze-drying 25h is carried out;
E) compound for obtaining step d) is added in the potassium hydroxide solution that concentration is 25%, impregnates 12h, filtering drying;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process 2h under the conditions of 650 DEG C;
G) after the hydrochloric acid of the product after high-temperature process and deionized water being cleaned, the dry 8h of blast drier is put into get graphite
The multi-layer porous material of alkene-active carbon, up to the multi-layer porous material of graphene-active carbon after drying.
BET method and absorption are respectively adopted to graphene-absorbent charcoal composite material obtained by above-described embodiment and comparative example
Method carries out the test of specific surface area and Methylene blue adsorption, and test result is shown in Table 1.
The test result of 1 embodiment and comparative example of table
Test item | Specific surface area (m2/ g) | Methylene blue adsorption (mL/g) |
Embodiment 1 | 3043 | 761 |
Embodiment 2 | 2671 | 703 |
Embodiment 3 | 3720 | 886 |
Embodiment 4 | 2925 | 790 |
Comparative example 1 | 1460 | 356 |
Comparative example 2 | 2133 | 561 |
Comparative example 3 | 893 | 235 |
Comparative example 4 | 1677 | 417 |
From the data in table 1, it can be seen that as the concentration of potassium hydroxide in step b) is high in embodiment 1-4, the specific surface area of final product
Decolorizing ability with methylene blue can be high, the reason is that the concentration of hydrogen-oxygen potassium is high, activation degree is high, caused by pore-creating more, embodiment 3
In, the concentration of step b) potassium hydroxide is high, and step f) high-temperature process temperature is high, and the pore structure of formation is most abundant, specific surface area and
The color ability of methylene blue is all highest.Active carbon does not impregnate potassium hydroxide solution, the ratio table of final product in comparative example 1
Area is low, the reason is that the activation of potassium hydroxide, pore structure do not cause less;In comparative example 2, not over graphene oxide
Graphene oxide and active carbon is caused not to be wrapped up not over spray drying step with active carbon, and then high-temperature activation
During, the potassium hydroxide inside active carbon cannot be activated from inside to outside, lead to the de- of specific surface area and methylene blue
Color ability is low;In comparative example 3, does not pass through high temperature processing step, graphene oxide is caused not to be reduced (graphene oxide
Specific surface area is very low), potassium hydroxide does not play activation, and the outermost layer calcium alginate of composite material is not also carbonized,
Cause the decoloring ability of specific surface area and methylene blue very low;In comparative example 4, using first prepare covering material, again activated,
Final high temperature processing process sequence, product specific surface area obtained is relatively small, and methylene blue decoloring ability is lower, this be because
To activate the activation only carried out in material surface, the pore structure of formation is smaller.It is found that the embodiment of the present invention is adopted compared with comparative example
Active carbon, calcium alginate cladding oxidation are coated with graphene oxide first with activated carbon adsorption potassium hydroxide, is then successively carried out
Graphene-active carbon, formation is followed successively by active carbon-graphene oxide-calcium alginate multilayered structure from inside to outside, finally in height
Calcium alginate is carbonized by temperature under handling, graphene oxide restores, while the hydrogen-oxygen that active carbon internal pore structure absorbs
Change potassium carries out activation from inside to outside to the graphene of active carbon, reduction, the calcium alginate of carbonization at high temperature, ultimately forms more
The composite material of layer porous structure, considerably increases the pore structure of composite material, improves its specific surface area and methylene blue decoloration
Ability.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (9)
1. a kind of preparation method of the multi-layer porous material of graphene-active carbon, which comprises the steps of:
A) absorbent charcoal material Activated Carbon Pretreatment: is crushed to partial size less than 5 μm;
B) active carbon activates: the active carbon after ball milling being added in the potassium hydroxide solution that concentration is 10%-40%, impregnates 1h-
For 24 hours, filtering drying;
C) graphene oxide wraps up active carbon: the active carbon after drying is added to the oxidation stone that concentration is 1mg/ml-5mg/ml
In black aqueous solution, it is uniformly mixed;Then spray drying treatment is carried out, the absorbent charcoal material of graphene oxide package is made;
D) absorbent charcoal material of graphene oxide package is blended with sodium alginate: sodium alginate is add to deionized water, and
It is stirred continuously to being completely dissolved, the absorbent charcoal material that graphene oxide made from step c) wraps up is added to sodium alginate soln
In be sufficiently stirred, obtain mixed system;
E) mixed system obtained by step d) is added dropwise in calcium chloride solution, obtains ball-type gel-like product, stood;Again by ball
After type gel-like product is cleaned with deionized water, it is freeze-dried;
F) the dry material completed is added in tube furnace, under nitrogen protection, high-temperature process under the conditions of 500 DEG C -800 DEG C
0.5h-4h;
G) after the product after high-temperature process being cleaned with deionized water, up to the multi-layer porous material of graphene-active carbon after drying.
2. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 1, which is characterized in that described
The breaking method of active carbon uses ball-milling method or comminution by gas stream in step a).
3. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 2, which is characterized in that described
Ball-milling method is that absorbent charcoal material is added in ball grinder, ball milling 10h-48h.
4. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 1, which is characterized in that described
The mass ratio of the solid content of graphene oxide and active carbon is 1:1-5 in graphene oxide water solution in step c).
5. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 1, which is characterized in that described
Mixed system is added dropwise in calcium chloride solution by syringe needle using peristaltic pump in step e).
6. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 1 or 5, which is characterized in that institute
Stating the calcium chloride solution concentration in step e) is 5%-10%.
7. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 1, which is characterized in that described
Time of repose in step e) is 2h-10h.
8. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 1, which is characterized in that described
Sublimation drying is 5h-48h in step e).
9. the preparation method of the multi-layer porous material of graphene-active carbon according to claim 1, which is characterized in that described
The dry 5h-12h of blast drier is put into after the product after high-temperature process is cleaned with deionized water in step g).
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