CN105858642A - Porous graphene material, and preparation method and application thereof - Google Patents
Porous graphene material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN105858642A CN105858642A CN201510031488.9A CN201510031488A CN105858642A CN 105858642 A CN105858642 A CN 105858642A CN 201510031488 A CN201510031488 A CN 201510031488A CN 105858642 A CN105858642 A CN 105858642A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- porous
- thermal expansion
- porous graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The present invention discloses a porous graphene material, preparation method and application thereof. The present invention provides a preparation method of a porous graphene material. The method comprises the steps of: conducting thermal expansion on a graphene substrate stacked body to obtain a porous graphene material. The preparation method has universal applicability, uses easily available raw materials, and directly acquires the porous graphene material by a one-step thermal expansion treatment method. The method has the advantages of simple operation, quick preparation and low production cost, and is conducive to large-scale preparation. The prepared porous graphene has the characteristics of broad pore size distribution, high porosity and large surface area, and can be used for the adsorptive separation of metal ions, adsorption of organic solvent, and catalyst carriers, and has great application value.
Description
Technical field
The present invention relates to a kind of porous graphene material, its preparation method and application.
Background technology
Graphene (Graphene) has real monoatomic layer thickness and strict two-dimensional structure, has very
High mechanical strength, elastic, heat conductivity, electric conductivity, and quantum hall effect etc., cause in recent years
The extensive concern of academia and industrial quarters.Consider from reality application angle, by nano-graphene lamellar material
Material is changed into macroporous structure material and is undoubtedly the most valuable research direction.Because grapheme material
Porous can give its more applicability, had substantial amounts of research for macroscopic view graphene-structured
The preparation of material.The method preparing this macroporous graphene aerogel material at present passes through self assembly more
More harsh and that the time the is longer method of the method in addition condition such as supercritical drying or freeze-drying obtains
Arrive, or relatively costly by physical chemistry sedimentation etc. on catalysts template, and the method for condition harshness obtains
Arrive, therefore in application, have the biggest difficulty.
A kind of method preparing porous graphene material of unification and simplicity has to be developed, in order to more
Good large-scale application.
The method preparing graphene-based accumulation body is then varied, and simplicity is easy to get.Such as, oxidation stone
Ink alkene is collapsed method [patent of invention, application publication number CN103966699A] or wet spinning by reduction self assembly
The sedimentation method [patent of invention, application publication number CN102586946A] can obtain one-dimensional graphene fiber shape
Accumulation body；By sucking filtration construction from part [Dikin DA, etal.Nature, 2007,448,457-460] or interface mould
Plate construction from part [Chen C, etal.Advanced Materials, 2009,21,3007-3011] and by certain
Electronation auxiliary law [Pei S, etal.Carbon, 2010,48,4466-4474] obtain two-dimensional graphene film
Shape accumulation body；Collapsed method [Tao Y, etal.Scientific Reports, 2013,3,2975] by templating self-assembly
Three-dimensional grapheme block accumulation body etc. can be obtained.
To sum up, the preparation side of porous graphene material that find a kind of simplicity, that be suitable for industrialized production
Method, and the graphite that prepared pore-size distribution width, porosity are high, specific surface area is big, industrial application value is high
Alkene, is to be badly in need of at present solving the technical problem that.
Summary of the invention
The technical problem to be solved is to overcome porous graphene material in prior art
Complicated process of preparation and post processing are difficult to the defect of scale, it is provided that a kind of porous graphene material,
Its preparation method and application.The preparation method of the present invention is simple to operate, practical, has the most general
Adaptive.Utilize the porous graphene material that method of the present invention prepares, for loose structure, with
Time pore-size distribution width, porosity is high, specific surface area big, has good using value.
The invention provides the preparation method of a kind of porous graphene material, it comprises the following steps: by stone
Mertenyl accumulation body carries out thermal expansion, obtains porous graphene material.
In the present invention, described graphene-based accumulation body can be graphene oxide heap conventional in the art
Long-pending body or redox graphene accumulation body, it is respectively by graphene oxide lamella or reduction-oxidation graphite
Alkene lamella dense packing forms.Described graphene-based accumulation body can be one-dimensional graphene-based threadiness heap
Long-pending body, two-dimensional graphene basement membrane shape accumulation body or three-dimensional grapheme matrix body accumulation body.
In the present invention, described Graphene accumulation body can use the routine of Graphene accumulation body in this area
Prepared by preparation method, can be wet spinning, the sedimentation method, sucking filtration or filter press technique, interface concentrate construction from part,
One or more in reduction construction from part and template.
In the present invention, the temperature of described thermal expansion preferably 220 DEG C～1100 DEG C, further preferably
300 DEG C～1100 DEG C, the most preferably 600 DEG C～1100 DEG C, most preferably 800 DEG C～1100 DEG C.
In the present invention, time preferred 0.5s～1800s, further preferred 1s～600s of described thermal expansion.
In the present invention, the processing mode of described thermal expansion can be microwave high-temperature heating, high-temperature heating or
Flame heats.Described microwave high-temperature heating can use the conventional method of microwave high-temperature heating in this area
And condition, preferably carry out in microwave applicator.Described high-temperature heating can use high temperature in this area
The conventional method of heating and condition, described high-temperature heating is preferably carried out in Muffle furnace.Described flame
Heating can use conventional method and the condition of this area Flame heating.
The bar that the preparation method of porous graphene material of the present invention can also exist at protective gas
Carry out under part.Described protective gas can be protective gas conventional in the art, preferably nitrogen, argon
One or more in gas, helium and neon, further preferred nitrogen.
Present invention also offers the porous stone that the preparation method of described a kind of porous graphene material prepares
Ink alkene material.
In the present invention, the pore-size distribution of described porous graphene material is in 2nm～100 μm；Porosity
It is 30%～96%；Phosphorus content is more than or equal to 50%, and generally 50%～80%, described phosphorus content is
Refer to that the quality of carbon accounts for the percentage ratio of porous graphite material gross mass；Single-point BET specific surface area is 1000
m2/ g～2000m2/g。
Present invention also offers the application as carrier of the described porous graphene material.Described carrier can
Think carrier, the absorption carrier of organic solvent or the carrier of catalyst that metal biosorption separates.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can combination in any, obtain this
Invent each preferred embodiments.
Agents useful for same of the present invention and raw material are the most commercially.
The most progressive effect of the present invention is:
1. the preparation method of the present invention has general applicability, with graphene oxide accumulation body or reduction-oxidation
Graphene accumulation body can directly obtain porous graphene material by a step thermal expansion processing method, operation
Succinctly (a step thermal expansion), preparation quickly, is conducive to extensive preparation.
2. the initial raw material that the present invention utilizes is graphene oxide, originates widely, low cost.
3. the graphene-based accumulation body that the present invention utilizes, wide variety, preparation method is various.
4. utilize method of the present invention can prepare porous graphene material aperture to be distributed in
2nm～100 μ m, have pore-size distribution width, porosity is high, specific surface area is a big feature.
5. the method for the invention can be for difform graphene oxide accumulation body or oxygen reduction fossil
Ink alkene accumulation body obtains difform porous graphene material.
The porous graphene material that method the most of the present invention prepares have bigger specific surface area and
Wider pore-size distribution, can be used for metal biosorption separation, the absorption of organic solvent, catalyst
Carriers etc., have great using value.
Accompanying drawing explanation
Fig. 1 is graphene oxide accumulation body (two dimension membrane structure) section obtained in the embodiment of the present invention 1
Stereoscan photograph.
Fig. 2 is the two dimension membranaceous porous graphene material after the thermal expansion obtained in the embodiment of the present invention 1 processes
The profile scanning electromicroscopic photograph of material.
Fig. 3 is redox graphene accumulation body (the one dimension fibre shape knot obtained in the embodiment of the present invention 2
Structure) profile scanning electromicroscopic photograph.
Fig. 4 is the one dimension fibre shape porous graphene after the thermal expansion obtained in the embodiment of the present invention 2 processes
The profile scanning electromicroscopic photograph of material.
Detailed description of the invention
Further illustrate the present invention below by the mode of embodiment, but the most therefore limit the present invention to
Among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to often
Rule method and condition, or select according to catalogue.
Wherein the graphene oxide water solution in embodiment 1～9 is peeled off by the hummers oxidation improved
Graphite method prepares: 10g graphite, pre-oxidation: by the concentrated sulphuric acid 150mL that mass percent is 98%
(described mass percent refers to that the quality of sulphuric acid accounts for the percentage ratio of concentrated sulphuric acid gross mass), percent mass
Than the concentrated nitric acid 30mL being 65%, (described mass percent refers to that the quality of nitric acid accounts for the total matter of concentrated nitric acid
The percentage ratio of amount), join in 500mL conical flask and 24h is stirred at room temperature, slowly pour in 1L water and filter
Collect solid, wash 3 times, dry 4 hours for 80 DEG C, obtain pre-oxidizing graphite.Repeat preoxidation process
Twice.Dried pre-oxidation graphite is put into 1100 DEG C of thermal expansion 20s in batch-type furnace and obtains thermal expansion oxygen
Graphite.By 5g thermal expansion graphite oxide and 300mL mass percent in 500mL wide mouthed Erlenmeyer bottle
Be 98% concentrated sulphuric acid (described mass percent refers to that the quality of sulphuric acid accounts for the percentage of concentrated sulphuric acid gross mass
Than), 5g K2S2O8, latter 80 DEG C of 7g phosphorus pentoxide mixing is heated 4 hours, dilutes with 2L water, mistake
Filter washing, air drying obtains pre-oxidizing thermal expansion graphite for 3 days.By dry pre-oxidation thermal expansion stone
It is black that (described mass percent refers to the matter of sulphuric acid with the concentrated sulphuric acid that 200mL mass percent is 98%
Amount accounts for the percentage ratio of concentrated sulphuric acid gross mass) mix at low temperature 0～5 DEG C, add 20g potassium permanganate, slowly
Slow addition, 35 DEG C of stirring 1h, adding and adding 10mL mass percent after the dilution of 2L water stands 1h is 30%
Hydrogen peroxide (described mass percent refers to that the quality of hydrogen peroxide accounts for the percentage of hydrogen peroxide gross mass
Than), standing 2 days, outwell supernatant, centrifuge washing, gentle agitation obtains homodisperse oxidation stone
Ink aqueous solution.
Embodiment 1
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Dikin DA, etal. through document
Nature, 2007,448,457-460] sucking filtration method obtains the membranaceous accumulation body of two dimensional oxidation Graphene, its section
Microscopic appearance is as shown in Figure 1.
(3) the two dimensional oxidation Graphene film material that step (2) obtains is put into the high temperature of nitrogen protection
In Muffle furnace, setting the internal heating-up temperature of Muffle furnace furnace chamber as 800 DEG C, the response time is 180s, obtains
Expanded porous graphene material.
After testing, the aperture of the porous graphene material obtained and distribution (2nm～170nm,
1 μm～30 μm) relative to the pore diameter range of the two dimensional oxidation Graphene dense film without high-temperature heat treatment
(2nm～5nm) significantly increases, through microcosmic scanning electron microscope characterize be shown as loose structure (as
Shown in accompanying drawing 2).Testing through specific surface area, its single-point BET specific surface area is 1750m2/g.Pass through
BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos are distributed in 2nm～170nm,
1 μm～30 μm.Porosity ranges is 65%～70%.Gained porous graphene material purity is higher, carbon
Content is 60%～70%.Described carbon content refers to that the quality of carbon accounts for the hundred of porous graphite material gross mass
Proportion by subtraction.Having light weight, density is low, the feature that specific surface area is high.
Embodiment 2
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Chen C, etal. in document
Advanced Materials, 2009,21,3007-3011] interfacial assembly method obtains two dimensional oxidation graphene film
Shape accumulation body.
(3) the two dimensional oxidation Graphene film material that step (2) obtains is put in high temperature Muffle furnace,
Setting the internal heating-up temperature of Muffle furnace furnace chamber as 800 DEG C, the response time is 5s, obtains expanded porous stone
Ink alkene material.
After testing, the aperture of the porous graphene material obtained and distribution (2nm～158nm, 1 μm～
40 μm) relative to the pore diameter range (2nm～5nm) of the two dimensional oxidation graphene film without high-temperature heat treatment
Significantly increase, characterize through microcosmic scanning electron microscope and be shown as loose structure.Survey through specific surface area
Examination, its single-point BET specific surface area is 1605m2/g.Through BJH-absorption-pore size distribution data and surface sweeping
Its pore diameter range of electronic microscope photos is distributed in 2nm～158nm, 1 μm～40 μm.Porosity ranges be 70%～
75%.Gained porous graphene material purity is higher, and carbon content is 50%～60%.Described carbon content
Refer to that the quality of carbon accounts for the percentage ratio of porous graphite material gross mass.Having light weight, density is low, compares table
The feature that area is high.
Embodiment 3
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Dong Z, etal.Adv. through document
Mater.2012,24,1856 1861] reduction self-assembling method obtain one-dimensional redox graphene fiber stack
Long-pending body, its section microscopic appearance is as shown in Figure 3.
(3) step (2) is obtained one-dimensional redox graphene fiber accumulations body, put into nitrogen protection
High temperature Muffle furnace in, set the internal heating-up temperature of Muffle furnace furnace chamber as 800 DEG C, the response time is 15s,
Obtain expanded porous graphene material.
After testing, the aperture of the porous graphene material obtained and distribution (2nm～185nm,
1 μm～50 μm) relative to the pore diameter range of the one-dimensional graphene oxide accumulation body without high-temperature heat treatment
(5nm～40nm) compares and significantly increases, and characterizes through microcosmic scanning electron microscope and is shown as porous knot
Structure (as shown in Figure 4).Testing through specific surface area, its single-point BET specific surface area is 1755m2/g。
Through BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos be distributed in 2nm～
185nm, 1 μm～50 μm.Porosity ranges is 50%～60%.Gained porous graphene material purity
Higher, carbon content is 55%～65%.It is total that described carbon content refers to that the quality of carbon accounts for porous graphite material
The percentage ratio of quality.Having light weight, density is low, the feature that specific surface area is high.
Embodiment 4
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Li J, etal. through document
J.Mater.Chem.A, 2014,2,6359 6362] electronation self assembly is dried method of collapsing and obtains one-dimensional
Redox graphene fiber accumulations body.
(3) step (2) is obtained one-dimensional redox graphene fiber accumulations body at flame heating
Reason, selecting Flame Heating Temperature is 600 DEG C, and the response time is 0.5s, obtains expanded porous graphene
Material.
After testing, the aperture of the porous graphene material obtained and distribution (2nm～174nm,
1 μm～50 μm) relative to the pore diameter range of the one-dimensional graphene oxide accumulation body without high-temperature heat treatment
(5nm～30nm) compares and significantly increases, and characterizes through microcosmic scanning electron microscope and is shown as porous knot
Structure (as shown in Figure 4).Testing through specific surface area, its single-point BET specific surface area is 1655m2/g。
Through BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos be distributed in 2nm～
174nm, 1 μm～50 μm.Porosity ranges is 55%～60%.Gained porous graphene material purity
Higher, carbon content is 55%～65%.It is total that described carbon content refers to that the quality of carbon accounts for porous graphite material
The percentage ratio of quality.Having light weight, density is low, the feature that specific surface area is high.
Embodiment 5
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Rodolfo C S, etal. through document
ACS Nano, 2014,8 (6), pp 5,959 5967] method, pass through by graphene oxide being made thin film
Roll spinning method and obtain one-dimensional graphene oxide fiber accumulations body.
(3) step (2) is obtained one-dimensional graphene oxide fiber accumulations body and puts in microwave applicator,
Setting the internal heating-up temperature of microwave applicator furnace chamber as 800 DEG C, the response time is 180s, obtains expanded
Porous graphene material.
After testing, the aperture of the porous graphene material obtained and distribution (2nm～174nm,
1 μm～50 μm) relative to the pore diameter range of the one-dimensional graphene oxide accumulation body without high-temperature heat treatment
(2nm～5nm, 1 μm～5 μm) are compared and are significantly increased, and characterize aobvious through microcosmic scanning electron microscope
It is shown as loose structure (as shown in Figure 4).Test through specific surface area, its single-point BET specific surface area
For 1655m2/g.It is distributed through BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos
At 2nm～174nm, 1 μm～50 μm.Porosity ranges is 80%～96%.Gained porous graphene
Material purity is higher, and carbon content is 65%～75%.Described carbon content refers to that the quality of carbon accounts for porous stone
The percentage ratio of ink material gross mass.Having light weight, density is low, the feature that specific surface area is high.
Embodiment 6
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) by step (1) prepare graphene oxide solution through document report [Rouhollah Jalili,
Etal.Adv.Funct.Mater.2013,23,5345 5354] wet spinning intermediate processing obtains one-dimensional graphite oxide
Alkene fiber accumulations body.
(3) step (2) is obtained one-dimensional graphene oxide fiber accumulations body and puts in high temperature Muffle furnace,
Setting the internal heating-up temperature of Muffle furnace furnace chamber as 300 DEG C, the response time is 600s, obtains expanded porous
Grapheme material.
After testing, the aperture of the porous graphene material obtained and distribution (2nm～100nm,
1 μm～50 μm) relative to the pore diameter range of the one-dimensional graphene oxide accumulation body without high-temperature heat treatment
(5nm～100nm) compares and significantly increases, and characterizes through microcosmic scanning electron microscope and is shown as porous
Structure (as shown in Figure 4).Testing through specific surface area, its single-point BET specific surface area is 1295m2/g。
Through BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos be distributed in 2nm～
100nm, 1 μm～50 μm.Porosity ranges is 30%～50%.Gained porous graphene material purity
Higher, carbon content is 50%～55%.It is total that described carbon content refers to that the quality of carbon accounts for porous graphite material
The percentage ratio of quality.Having light weight, density is low, the feature that specific surface area is high.
Embodiment 7
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Tao Y, etal. through document
Scientific Reports, 2013,3,2975] template reduction self assembly is dried the method for collapsing and obtains three-dimensional reduction-oxidation
Graphene block accumulation body.
(3) step (2) is obtained three-dimensional graphene oxide block accumulation body through microwave heating reactor
Heat treated, selects reactor interior if heating-up temperature is 1100 DEG C, and the response time is 30s, obtains expanded
Porous graphene material.
After testing, the aperture of the porous graphene material obtained and distribution (2nm～150nm,
1 μm～100 μm) relative to the hole of the three-dimensional graphene oxide block accumulation body without high-temperature heat treatment
Footpath scope (5nm～100nm) is compared and is significantly increased, and characterizes display through microcosmic scanning electron microscope
For loose structure.Testing through specific surface area, its single-point BET specific surface area is 1855m2/g.Pass through
BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos are distributed in 2nm～150nm,
1 μm～100 μm.Porosity ranges is 60%～65%.Gained porous graphene material purity is higher,
Carbon content is 60%～70%.Described carbon content refers to that the quality of carbon accounts for porous graphite material gross mass
Percentage ratio.Having light weight, density is low, the feature that specific surface area is high.
Embodiment 8
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Bi H, etal. through document
Advanced.Materials.2012,24,5124 5129] the template reduction self assembly method of collapsing obtains three-dimensional circle
Cylindricality redox graphene block accumulation body.
(3) three-dimensional cylinder redox graphene block accumulation body step (2) obtained is through micro-
Wave heating reactor heat treated, selects if heating-up temperature is 1100 DEG C in reactor, and the response time is
5s, obtains expanded porous graphene material.
After testing, the aperture, inside of the porous graphene material obtained and distribution (2nm～160nm,
1 μm～30 μm), pile up relative to the three-dimensional cylinder graphene oxide block without high-temperature heat treatment
The pore diameter range (5nm～100nm) of body is compared and is significantly increased, through microcosmic scanning electron microscope table
Levy and be shown as loose structure.Testing through specific surface area, its single-point BET specific surface area is 1525m2/g。
Through BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos be distributed in 2nm～
160nm, 1 μm～30 μm.Porosity ranges is 50%～55%.Gained porous graphene material purity
Higher, carbon content is 60%～75%.It is total that described carbon content refers to that the quality of carbon accounts for porous graphite material
The percentage ratio of quality.Having light weight, density is low, the feature that specific surface area is high.
Embodiment 9
A kind of preparation method of porous graphene material, it comprises the following steps:
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) graphene oxide solution that step (1) prepares is reported [Bi H, etal. through document
Advanced.Materials.2012,24,5124 5129] the template reduction self assembly method of collapsing obtains three-dimensional circle
Cylindricality redox graphene block accumulation body.
(3) three-dimensional cylinder redox graphene block accumulation body step (2) obtained puts into nitrogen
In the high temperature Muffle furnace of gas shielded, set the internal heating-up temperature of Muffle furnace furnace chamber as 800 DEG C, the response time
For 30s, obtain expanded porous graphene material.
After testing, the aperture, inside of the porous graphene material obtained and distribution (2nm～140nm,
1 μm～30 μm) relative to the three-dimensional cylinder graphene oxide block accumulation body without high-temperature heat treatment
Pore diameter range (5nm～100nm) compare and significantly increase, characterize through microcosmic scanning electron microscope
It is shown as loose structure.Testing through specific surface area, its single-point BET specific surface area is 1825m2/g。
Through BJH-absorption-pore size distribution data and its pore diameter range of surface sweeping electronic microscope photos be distributed in 2nm～
140nm, 1 μm～30 μm.Porosity ranges is 45%～50%.Gained porous graphene material purity
Higher, carbon content is 60%～70%.It is total that described carbon content refers to that the quality of carbon accounts for porous graphite material
The percentage ratio of quality.Having light weight, density is low, the feature that specific surface area is high.
Comparative example 1
Repeating embodiment 4, in addition to having following difference, other conditions are the most identical.
(2) graphene oxide solution that step (1) prepares is reported [Li J, etal. through document
J.Mater.Chem.A, 2014,2,6359 6362] by frozen drying side after electronation self assembly
Method obtains porous graphene aerogel material after being dried 72h.
After testing, the pore size distribution range of the porous graphene material obtained at 10nm～100nm,
10 μm～50 μm, relative to the porous graphene material pore size distribution range obtained through high-temperature heat treatment
Narrow.Testing through specific surface area, its single-point BET specific surface area is 65m2/ g, much smaller than embodiment 4
Specific surface area 1655m of the porous graphene material obtained is processed by high-temperature heat expansion2/g.Obviously pass through
It is the longest that freeze-drying prepares porous graphene material, and specific surface area is relatively low, and pore-size distribution narrows.
Comparative example 2
(1) utilize the Hummers oxidation improved to peel off graphite method and prepare graphene oxide solution.
(2) by step (1) prepare graphene oxide solution through document report [Nanoscale, 2013,
5,5462 5467] porous graphene aeroge is obtained by after frozen drying 72h after reduction self assembly
Material.
Testing through specific surface area, its single-point BET specific surface area is 300m2/ g～350m2/ g is the least
Specific surface area 1855m of the porous graphene material obtained is processed by high-temperature heat expansion in embodiment 72/g。
Obviously preparing porous graphene material through freeze-drying the longest, specific surface area is relatively low.
Claims (10)
1. the preparation method of a porous graphene material, it is characterised in that it comprises the following steps: will
Graphene-based accumulation body carries out thermal expansion, obtains porous graphene material.
2. preparation method as claimed in claim 1, it is characterised in that: described graphene-based accumulation
Body is graphene oxide accumulation body or redox graphene accumulation body, and it is respectively by graphene oxide sheet
Layer or redox graphene lamella dense packing form；
And/or,
Described graphene-based accumulation body is one-dimensional graphene-based threadiness accumulation body, two-dimensional graphene basement membrane
Shape accumulation body or three-dimensional grapheme matrix body accumulation body；
And/or,
The preparation method of described Graphene accumulation body is wet spinning, the sedimentation method, sucking filtration or filter press technique, boundary
Face concentrates one or more in construction from part, reduction construction from part and template.
3. preparation method as claimed in claim 1, it is characterised in that:
The temperature of described thermal expansion is 220 DEG C～1100 DEG C；
And/or,
The time of described thermal expansion is 0.5s～1800s；
And/or,
The processing mode of described thermal expansion is microwave high-temperature heating, high-temperature heating or flame heating；
And/or,
The preparation method of described porous graphene material is carried out under conditions of protective gas exists.
4. preparation method as claimed in claim 3, it is characterised in that:
The temperature of described thermal expansion is 300 DEG C～1100 DEG C；
And/or,
The time of described thermal expansion is 1s～600s；
And/or,
Described microwave high-temperature heating is carried out in microwave applicator；
And/or,
Described high-temperature heating is carried out in Muffle furnace；
And/or,
Described protective gas is one or more in nitrogen, argon, helium and neon.
5. preparation method as claimed in claim 4, it is characterised in that:
The temperature of described thermal expansion is 600 DEG C～1100 DEG C.
6. preparation method as claimed in claim 5, it is characterised in that:
The temperature of described thermal expansion is 800 DEG C～1100 DEG C.
7. the porous graphene material that the preparation method as described in any one of claim 1～6 prepares.
8. porous graphene material as claimed in claim 7, it is characterised in that: described porous stone
The pore-size distribution of ink alkene material is 2nm～100 μm, and porosity is 30%～96%, and single-point BET compares table
Area is 1000m2/ g～2000m2/ g, phosphorus content is more than or equal to 50%, and described phosphorus content refers to carbon
Quality account for the percentage ratio of porous graphite material gross mass.
9. porous graphene material as claimed in claim 7 or 8 is as the application of carrier.
Apply the most as claimed in claim 9, it is characterised in that: described carrier is metal ion
The carrier of adsorbing separation, the absorption carrier of organic solvent or the carrier of catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510031488.9A CN105858642A (en) | 2015-01-22 | 2015-01-22 | Porous graphene material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510031488.9A CN105858642A (en) | 2015-01-22 | 2015-01-22 | Porous graphene material, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105858642A true CN105858642A (en) | 2016-08-17 |
Family
ID=56623200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510031488.9A Pending CN105858642A (en) | 2015-01-22 | 2015-01-22 | Porous graphene material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105858642A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698409A (en) * | 2017-01-23 | 2017-05-24 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional graphene foam as well as preparation method and application thereof |
| CN107936480A (en) * | 2017-12-08 | 2018-04-20 | 梁金凤 | A kind of broadband composite wave-suction material containing thermal expansion graphene |
| CN107995831A (en) * | 2017-12-08 | 2018-05-04 | 朱明君 | A kind of mute central control machine case of smart home |
| CN108467026A (en) * | 2018-01-16 | 2018-08-31 | 中国科学院上海应用物理研究所 | Porous graphene material and its preparation method and application |
| CN108530073A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting |
| CN108990187A (en) * | 2018-08-10 | 2018-12-11 | 四川大仁新创科技有限公司 | A kind of radiator that graphene is thermally conductive |
| CN109496119A (en) * | 2017-09-13 | 2019-03-19 | 钰邦科技股份有限公司 | Nanocomposite shielding film and preparation method thereof |
| CN111422856A (en) * | 2020-04-03 | 2020-07-17 | 常州富烯科技股份有限公司 | Method for flame reduction of graphene oxide film and preparation method of graphene film |
| CN111867708A (en) * | 2018-03-13 | 2020-10-30 | 加兹纳特股份公司 | Graphene membrane filter for gas separation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583334A (en) * | 2012-01-19 | 2012-07-18 | 北京理工大学 | Preparation method for graphene fiber |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
-
2015
- 2015-01-22 CN CN201510031488.9A patent/CN105858642A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583334A (en) * | 2012-01-19 | 2012-07-18 | 北京理工大学 | Preparation method for graphene fiber |
| CN103726133A (en) * | 2014-01-02 | 2014-04-16 | 东华大学 | High-strength, compact and ordered porous graphene fiber and continuous preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698409A (en) * | 2017-01-23 | 2017-05-24 | 中国科学院宁波材料技术与工程研究所 | Three-dimensional graphene foam as well as preparation method and application thereof |
| CN106698409B (en) * | 2017-01-23 | 2019-04-16 | 中国科学院宁波材料技术与工程研究所 | A kind of three-dimensional graphene foam and its preparation method and application |
| CN109496119A (en) * | 2017-09-13 | 2019-03-19 | 钰邦科技股份有限公司 | Nanocomposite shielding film and preparation method thereof |
| CN108530073A (en) * | 2017-10-08 | 2018-09-14 | 北京化工大学 | A kind of preparation method of the three-dimensional porous graphene film of flexible self-supporting |
| CN108530073B (en) * | 2017-10-08 | 2020-06-19 | 北京化工大学 | Preparation method of flexible self-supporting three-dimensional porous graphene membrane |
| CN107936480A (en) * | 2017-12-08 | 2018-04-20 | 梁金凤 | A kind of broadband composite wave-suction material containing thermal expansion graphene |
| CN107995831A (en) * | 2017-12-08 | 2018-05-04 | 朱明君 | A kind of mute central control machine case of smart home |
| CN108467026A (en) * | 2018-01-16 | 2018-08-31 | 中国科学院上海应用物理研究所 | Porous graphene material and its preparation method and application |
| CN111867708A (en) * | 2018-03-13 | 2020-10-30 | 加兹纳特股份公司 | Graphene membrane filter for gas separation |
| CN108990187A (en) * | 2018-08-10 | 2018-12-11 | 四川大仁新创科技有限公司 | A kind of radiator that graphene is thermally conductive |
| CN108990187B (en) * | 2018-08-10 | 2021-05-25 | 大连东方腾飞建筑装饰工程有限公司 | Heat radiator with graphene for heat conduction |
| CN111422856A (en) * | 2020-04-03 | 2020-07-17 | 常州富烯科技股份有限公司 | Method for flame reduction of graphene oxide film and preparation method of graphene film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105858642A (en) | Porous graphene material, and preparation method and application thereof | |
| CN105645403B (en) | A kind of preparation method of high-performance N doping three-dimensional grapheme | |
| Shehzad et al. | Three-dimensional macro-structures of two-dimensional nanomaterials | |
| Wang et al. | Hierarchically porous SiC ultrathin fibers mat with enhanced mass transport, amphipathic property and high-temperature erosion resistance | |
| CN103966699B (en) | A kind of preparation method of graphene fiber | |
| Liu et al. | Highly anisotropic graphene aerogels fabricated by calcium ion-assisted unidirectional freezing for highly sensitive sensors and efficient cleanup of crude oil spills | |
| CN104973591B (en) | High-quality graphene and preparation method thereof | |
| CN104045077A (en) | Graphene three-dimensional hierarchical porous carbon material and preparation method thereof | |
| CN104694989B (en) | A kind of preparation method of graphene-based metallic composite | |
| CN103253661B (en) | Method for preparing graphene powder at large scale | |
| CN106032272B (en) | A kind of amido enhancing graphene film, nitrogen-doped graphene film and preparation method thereof | |
| CN106145085A (en) | The graphene aerogel of a kind of crushing resistance high conductivity and low density and the preparation method of doped carbon nanometer pipe composite | |
| CN106927451B (en) | Three-dimensional structure graphene and its carbon source self-template catalytic pyrolysis preparation method | |
| CN106032587A (en) | Amido reinforced graphene fiber and preparation method thereof | |
| CN106082194B (en) | A kind of method for preparing bigger serface and the less graphene of the number of plies | |
| CN106395802B (en) | Preparation method of graphene porous membrane | |
| Guo et al. | Fabricating series of controllable-porosity carbon nanofibers-based palladium nanoparticles catalyst with enhanced performances and reusability | |
| Kim et al. | Activated graphene with fractal structure for the adsorption of malachite green with high removal rate | |
| Chen et al. | Two-step thermal treatment of electrochemical graphene oxide films for high-performance electrical heating and electromagnetic interference shielding | |
| Er et al. | An efficient way to reduce graphene oxide by water elimination using phosphoric acid | |
| Zhang et al. | Modular assembly of MOF-derived carbon nanofibers into macroarchitectures for water treatment | |
| CN108467026A (en) | Porous graphene material and its preparation method and application | |
| CN108144583A (en) | It is a kind of novel except the preparation method of formaldehyde activity charcoal | |
| Liu et al. | New insight of high temperature oxidation on self-exfoliation capability of graphene oxide | |
| CN104466133B (en) | A kind of graphene carbon composite of N doping and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160817 |