CN107043101B - A kind of three-dimensional porous grapheme foam material and its preparation method and application - Google Patents
A kind of three-dimensional porous grapheme foam material and its preparation method and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
The present invention relates to a kind of three-dimensional porous grapheme foam materials and its preparation method and application, the described method includes: Polymeric Industry product is heat-treated in an inert atmosphere, then it is graphitized 1~5 hour at 900~2500 DEG C in an inert atmosphere again, obtains the three-dimensional porous graphene block；The organic polymer industrial products are ultralight clay or/and paper clay.The three-dimensional porous graphene block that the method obtains according to the present invention has good hydrophobicity, higher pore volume, and certain mechanical strength can be good at being applied to greasy dirt adsorbing domain.
Description
Technical field
The present invention relates to a kind of cheap and simple preparation methods of three-dimensional porous grapheme foam block, and in particular to Yi Zhonggao
The method that temperature graphitization prepares three-dimensional porous grapheme foam block.
Background technique
With global industry fast development, the discharge of oil-polluted water is also increasing, causes to water quality and soil huge
Pollution, seriously affect the health and sustainable development of the mankind.In addition, along with being made in a large amount of recovery process of fossil feedstock
At greasy dirt leakage event it is also more and more, to environment and ecology cause the destruction that can not be retrieved.Therefore, design and develop green wood
Material and new process are to cope with the oil pollution problem got worse with very great meaning.Graphene is a kind of height sp2
The material of hydridization has outstanding physicochemical properties, for example has good conductive property, and carrier rate at room temperature may be used
Reach 1.5 × 104cm2/ (VS), stretch modulus and intrinsic strength are respectively 1000GPa and 130GPa；Thermal conductivity is fabulous, heat
Conductance reaches 5000W/ (mK).Due to these excellent physicochemical properties, grapheme material is in the energy, environment, sensing and meter
The fields such as machine core piece are calculated to be widely used prospect[1],[2].Particularly, due to its preferable hydrophobic performance and higher
The grapheme material of specific surface area, high quality shows excellent performance in terms of greasy dirt absorption[3].Importantly, graphene
Material has lower density, therefore compared with traditional adsorbent material, and grapheme material adsorbs quality required for greasy dirt more
It is few.But graphene, as a kind of planar material, very easy stacking between lamella causes specific surface area and pore volume
Greatly reduce, so that it is directly used in greasy dirt adsorbent material, there are many difficult.This just needs us that can start with from structure, and construction is suitable
The three-dimensional grapheme material of conjunction.Recently, having researcher with nickel foam is substrate, three-dimensional grapheme material is prepared, but steeped
The restriction of foam nickel substrate, aperture is larger, reaches several hundred microns, it is difficult to be utilized.In addition, the three-dimensional stone of this method preparation
Black alkene mechanical strength is very poor, also limits its application in terms of greasy dirt absorption.It can be seen that grapheme material is used for oil
Dirty adsorbing domain needs to be prepared large specific surface area and pore volume, the three-dimensional grapheme material of higher-strength.
Start with from the construction of three-dimensional grapheme, people have studied a variety of methods, mainly have redox graphene (RGO) certainly
Graphene etc. is grown by chemical vapor deposition (CVD) in assembling, three-dimensional substrate.RGO self-assembling method can be prepared compared with
The three-dimensional grapheme material of high pore volume also shows preferable performance in terms of greasy dirt absorption, however prepared by this method
The mechanical property of materials arrived it is poor, it is difficult to adapt to greasy dirt absorption present in mal-condition.In addition, since this method obtains
Graphene contain very high oxygen-containing functional group, hydrophobicity and lipophilic be also restricted.In three-dimensional substrate (such as SiO2)
The three-dimensional grapheme of high quality, high-mechanical property and high hydrophobicity can be prepared by CVD growth graphene[4], but due to
This method is related to the etching of CVD process and template, thus cost is very high, is difficult to promote in practical application.To sum up, low
Cost preparation high quality three-dimensional grapheme material still suffers from more problem, but the exploitation of this material has environmental improvement
Very great meaning；
Bibliography:
[1]X.Cao,Z.Yin and H.Zhang,Energy&Environmental Science,2014,7,1850-
1865.
[2]S.Nardecchia,D.Carriazo,M.L.Ferrer,M.C.Gutiérrez and F.del Monte,
Chemical Society Reviews,2013,42,794-830.
[3]W.Wan,Y.Lin,A.Prakash and Y.Zhou,Journal of Materials Chemistry A,
2016,4,18687-18705.
[4]H.Bi,I.W.Chen,T.Lin and F.Huang,Advanced materials,2015,27,5943-
5949.。
Summary of the invention
In face of problem of the existing technology, in order to prepare the three-dimensional grapheme material of high quality, mesh of the invention
Be provide it is a kind of can the low cost method that prepare three-dimensional porous grapheme foam material, and the three-dimensional porous stone prepared
Black alkene foamed material and its application.
On the one hand, the present invention provides a kind of methods for preparing three-dimensional porous grapheme foam material, comprising:
Polymeric Industry product is heat-treated in an inert atmosphere, then again in an inert atmosphere 900~2500
It is graphitized 1~5 hour at DEG C, obtains the three-dimensional porous graphene block；
The organic polymer industrial products are ultralight clay or/and paper clay.
The present invention utilize for the first time Polymeric Industry product (such as ultralight clay or/and paper clay) in an inert atmosphere into
Row heat treatment is allowed to sufficiently be carbonized, and the high temperature graphitization at 900~2500 DEG C in an inert atmosphere, final preparation high quality
Three-dimensional grapheme block.The macromolecule product is cheap, has excellent plasticity, it is thus possible to various differences be prepared
The block materials of shape and size.The three-dimensional porous graphene block that the method obtains according to the present invention has good hydrophobic
Property, higher pore volume, certain mechanical strength can be good at being applied to greasy dirt adsorbing domain.
Preferably, the heat treatment is to keep the temperature 1~5 hour at 300~600 DEG C.The present invention is first at 300~600 DEG C
After heat preservation 1~5 hour, high molecular material is made to lose part H and O element, avoids the quick generation and abjection pair of gas under high temperature
Material, which is constituted, to be destroyed.Be graphitized 1~5 hour at 900~2500 DEG C, material made to lose most O elements, and obtain compared with
Crystallization in big degree.
Preferably, the inert atmosphere is the gaseous mixture of inert gas or inert gas and hydrogen, the inert gas is
At least one of nitrogen, argon gas and helium.
Also, the flow of the hydrogen is 1~100sccm preferably, the flow of the inert gas is 1~800sccm.
Preferably, the graphited temperature is 900~2500 DEG C, the time is 1~5 hour.
Preferably, the Polymeric Industry product is pre-processed, it is heat-treated again after making its abundant drying and dehydrating.
Preferably, the mode of the drying and dehydrating is drying at room temperature or/and oven drying.The drying at room temperature be 0~
It is 1 day~15 days dry at 30 DEG C.The oven drying is 1~15 day dry at 40~120 DEG C.
On the other hand, the present invention also provides a kind of three-dimensional porous grapheme foam materials prepared according to above-mentioned method
Material, the micromorphology of the three-dimensional porous graphene block are the macroporous structure of three-dimensional communication, and macropore diameter is 10~100 μm.
In another aspect, the present invention also provides a kind of three-dimensional porous grapheme foam materials according to above method preparation to exist
Application in greasy dirt absorption.
The present invention is by selecting suitable high molecular material that regular shape block and good aperture can be prepared
Grapheme material.Further, grapheme material (three-dimensional grapheme block or the three-dimensional graphite being prepared in such processes
Alkene foamed material) there is good hydrophobicity and lipophilicity, macroporous structure abundant, certain mechanical strength and heat resistance are to meet
The needs of greasy dirt adsorbing domain.
Detailed description of the invention
Fig. 1 shows the macromolecule raw material material object photo after drying used in the embodiment of the present invention 1；
Fig. 2 shows the three-dimensional porous graphene block material object photos being prepared through the embodiment of the present invention 1；
Fig. 3 shows the three-dimensional porous graphene block stereoscan photograph being prepared through the embodiment of the present invention 1, can observe
To being wherein the aperture structure of 10 μm to 100 μm sizes；
Fig. 4 shows the three-dimensional porous graphene block high power stereoscan photograph being prepared through the embodiment of the present invention 1, can
With the aperture structure of three-dimensional communication；
The high-resolution-ration transmission electric-lens that Fig. 5 shows the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1 shine
Piece, therefrom it can be seen that graphene number of plies is about 8 layers or so；
Fig. 6 shows the Raman spectrogram for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1, can be with
Seeing has three characteristic peaks possessed by typical graphene in map；
Fig. 7 shows the XRD spectrum for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1, it can be seen that
Nearby there is stronger diffraction maximum at 26 °, show that carbon material is high-graphitized；
The contact angle test result that Fig. 8 shows the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1 is shone
Piece, three-dimensional grapheme block are 140 ° to the contact angle of water；
Fig. 9 shows the photograph in kind on the three-dimensional porous graphene block load water surface being prepared through the embodiment of the present invention 1
Piece；
The performance that Figure 10 shows the three-dimensional porous graphene block absorption organic matter being prepared through the embodiment of the present invention 1 is shone
Piece, abscissa value indicates the quality of absorption organic matter and the ratio of three-dimensional grapheme block quality in figure；
Figure 11 shows the three-dimensional porous graphene pictorial diagram being prepared through the embodiment of the present invention 2 and SEM figure；
Figure 12 shows the three-dimensional porous graphene pictorial diagram being prepared through the embodiment of the present invention 3 and SEM figure；
Figure 13 shows the three-dimensional porous graphene pictorial diagram being prepared through the embodiment of the present invention 4 and SEM figure；
Figure 14 shows the three-dimensional porous graphene pictorial diagram being prepared through the embodiment of the present invention 5 and SEM figure；
Figure 15 show the three-dimensional porous graphene block that is prepared through the embodiment of the present invention 1 bear own wt~
10000 times of counterweight.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention utilizes Polymeric Industry product high temperature cabonization for the first time and is graphitized the three-dimensional grapheme of preparation high quality
Block.Specifically, then the product abundant drying and dehydrating at a lower temperature is heat-treated one section under inert gas protection
Time (such as being carbonized in tube furnace).Finally (such as utilizing high temperature nitrogen steam stove) is sufficiently graphitized in an inert atmosphere.This hair
Bright obtained three-dimensional porous graphene block has good hydrophobicity, and higher pore volume, certain mechanical strength can be very
Good is applied to greasy dirt adsorbing domain.Illustrate to following exemplary provided by the invention to prepare three-dimensional porous grapheme foam material
Method.
In the present invention, Polymeric Industry product includes but is not limited to paper clay, ultralight clay etc..Wherein Polymeric Industry produces
Product paper clay, ultralight clay are purchased from commercialization.In addition, containing a large amount of 20~100 μm of sizes in macromolecule product microstructure
Hole, so that it can swimmingly decomposite to come from material in the carbon nitrogen oxide gas etc. that carbonisation generates, thus to system
Standby carbon material will not constitute structure destruction.It should be pointed out that three can not be obtained through this macromolecule product direct carbonization
Macroscopical block is tieed up, but needs to be dehydrated it sufficiently by certain drying means, is shaped.On this basis, the heat under low temperature
Processing keeps gas slowly abjection very crucial to the density and block structure of material, belongs to pith of the invention.It is specific and
Speech, by the first abundant drying and dehydrating of the Polymeric Industry product, then carrying out heat treatment makes its carbonization, finally carries out graphite again
Change, finally obtains three-dimensional porous grapheme foam material.
Polymeric Industry product is pre-processed, its abundant drying and dehydrating is made.Specifically, by a kind of Polymeric Industry
Product places certain time dehydration and drying (drying at room temperature) at room temperature, is then placed within dry one in the baking oven of certain temperature
It fixes time (oven drying).The mode of the drying and dehydrating can be drying at room temperature or/and oven drying.The drying at room temperature can be
It is 1 day~15 days dry at 0~30 DEG C.The oven drying can be 1~15 day dry at 40~120 DEG C.Show as one
Polymeric Industry product (for example, paper clay, ultralight clay and ultralight soil etc.) is sufficiently placed certain time by example at room temperature,
The temperature of room temperature can be 0 DEG C~30 DEG C, preferably 10 DEG C~20 DEG C, standing time can be 1 day~15 days, preferably 7 days~12
It.It is subsequently placed in baking oven, oven temperature can be 40 DEG C~120 DEG C, and preferably 60 DEG C~80 DEG C, standing time can be 1 day
~15 days, preferably 5 days~10 days.
The Polymeric Industry product (for example, paper clay, ultralight clay) that drying finishes is subjected to hot place under an inert atmosphere
It manages (carbonization treatment).Specifically, then sample is heat-treated under certain atmospheric condition: is warming up to certain temperature, protected
Warm a period of time, the holding temperature can be 300 DEG C~600 DEG C, preferably 370 DEG C~430 DEG C.Soaking time can be 1 hour~5
Hour, preferably 2 hours~3 hours.The wherein gas of Polymeric Industry product (for example, paper clay, ultralight clay etc.) heat treatment
Atmosphere is the mixed gas of inert gas or inert gas and hydrogen.Inert gas can in nitrogen, argon gas and helium at least
It is a kind of.Inert gas flow is 1sccm~800sccm, and hydrogen gas flow is 1sccm~100sccm.
The sample obtained after heat treatment is further graphitized in inert atmosphere (such as high temperature inert atmosphere furnace), that is, is made
It is standby to obtain three-dimensional porous graphene block.Treatment temperature can be 900 DEG C~2500 DEG C, preferably 1500 DEG C~2300 DEG C.Graphite
Changing the time can be 1 hour~5 hours, preferably 2 hours~3 hours.The graphited atmosphere can be inert atmosphere, preferably
At least one of argon gas, nitrogen and helium.
In addition, the present invention only needs normal atmosphere furnace (high temperature inert atmosphere furnace) that three-dimensional porous graphene block can be realized
Large scale preparation, it is at low cost, it is easy to operate, it is very suitable for industrialized production.
Three-dimensional porous graphene block prepared according to the methods of the invention, micromorphology are the macropore knot of three-dimensional communication
Structure, macropore diameter is between 10 μm~100 μm.Three-dimensional porous graphene block even aperture distribution of the invention, pore volume compared with
Greatly, there is very excellent hydrophobic performance, biggish pore volume and certain mechanical strength, be the suitable material of greasy dirt absorption,
It can be applied to greasy dirt adsorbing domain.
In an example of the invention, preparation flow is as follows:
(1) using ultralight clay as raw material, certain time is placed at room temperature, with appropriate dehydration and drying.It is then placed into 60
DEG C~80 DEG C of baking ovens in, place certain time；
(2) the ultralight clay after drying is warming up to 370 DEG C~430 DEG C under the protection of argon gas and hydrogen, heat preservation 2~3
A hour；
(3) then obtained sample is warming up in high temperature nitrogen steam stove to 900 DEG C~2500 DEG C, keep the temperature 2~3 hours, i.e.,
Three-dimensional porous graphene block materials are prepared；
(4) the three-dimensional porous graphene block materials being prepared have very excellent absorption property to organic matter, inhale
Attached organic matter includes but is not limited to methanol, ethyl alcohol, acetone, butanone, chloroform, dichloroethanes, tetrachloro-ethylene, four chlorinations
Carbon, decahydronaphthalene, hexamethylene, carbon disulfide etc..
The present invention is carbonized using ultralight clay by inert gas and high temperature graphitization prepares three-dimensional porous graphene block
Body.This three-dimensional porous graphene block have excellent hydrophobicity, biggish pore volume and certain mechanical strength, thus
Greasy dirt absorption aspect has preferable application.
Referring to Fig. 1, the macromolecule raw material material object photo after drying used in the present invention is shown；
Referring to fig. 2, the three-dimensional porous graphene block material object photo being prepared through the embodiment of the present invention 1 is shown；
Referring to Figure 15, shows and be able to bear certainly through the three-dimensional porous graphene block that the embodiment of the present invention 1 is prepared
The counterweight of body weight~10000 times；
Referring to Fig. 3, the three-dimensional porous graphene block scanning electron microscope being prepared through the embodiment of the present invention 1 is shown and is shone
Piece, it can be observed that being wherein the aperture structure of 10 μm to 100 μm sizes；
Referring to fig. 4, the three-dimensional porous graphene block high power scanning electron microscope being prepared through the embodiment of the present invention 1 is shown
Photo, can be with the aperture structure of three-dimensional communication；
Referring to Fig. 5, the high-resolution transmission for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1 is shown
Electromicroscopic photograph, therefrom it can be seen that graphene number of plies is about 8 layers or so；
Referring to Fig. 6, the Raman spectrum for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1 is shown
Figure, it can be seen that there are three characteristic peaks possessed by typical graphene in map；
Referring to Fig. 7, the XRD spectrum for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1 is shown, it can
Nearby there is stronger diffraction maximum at 26 ° to see, show that carbon material is high-graphitized；
Referring to Fig. 8, the contact angle test for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1 is shown
As a result photo, three-dimensional grapheme block are 140 ° to the contact angle of water；
Referring to Fig. 9, show on the three-dimensional porous graphene block load water surface being prepared through the embodiment of the present invention 1
Photo in kind；
Referring to Figure 10, the three-dimensional porous graphene block absorption organic matter being prepared through the embodiment of the present invention 1 is shown
Performance photo, abscissa value indicates the quality of absorption organic matter and the ratio of three-dimensional grapheme block quality in figure；
Referring to Figure 11, the three-dimensional porous graphene pictorial diagram being prepared through the embodiment of the present invention 2 and SEM figure are shown；
Referring to Figure 12, the three-dimensional porous graphene pictorial diagram being prepared through the embodiment of the present invention 3 and SEM figure are shown；
Referring to Figure 13, the three-dimensional porous graphene pictorial diagram being prepared through the embodiment of the present invention 4 and SEM figure are shown.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
Using the ultralight clay of the BM24-100 model of Quzhou Bei Meng school supply and stationery Manufacturing Co., Ltd production as raw material, in room
Temperature is lower to place 7 days, with appropriate dehydration and drying.It is then placed into 60 DEG C of baking ovens, places 7 days.By the ultralight clay after drying
It is warming up to 400 DEG C, argon flow 300sccm, hydrogen flowing quantity 30sccm under the protection of argon gas and hydrogen, keeps the temperature 2 small
When.Then obtained sample is warming up in high temperature nitrogen steam stove 2200 DEG C, keeps the temperature 2 hours, that is, three-dimensional porous stone is prepared
Black alkene block materials.
The three-dimensional porous graphene block materials density being prepared is 20mg/cm3, it is 2.6g/cm according to graphite density3
Be calculated the block materials porosity be 99.24%, to organic matter have very excellent absorption property, absorption it is organic
Object includes but is not limited to methanol, ethyl alcohol, acetone, butanone, chloroform, dichloroethanes, tetrachloro-ethylene, carbon tetrachloride, decahydro
Naphthalene, hexamethylene, carbon disulfide etc..It is as shown in Figure 1 through the dry macromolecule raw material material object photo of the embodiment of the present invention 1.Through
The three-dimensional porous graphene block material object photo that the embodiment of the present invention 1 is prepared is as shown in Figure 2.As shown in figure 15, the block
With good compression strength, area 0.8cm*0.8cm, with a thickness of 2.8mm, a block of weight 18.2mg can be born
The counterweight of 200g weight can bear weight of 10000 times more than itself.
The stereoscan photograph such as Fig. 3 and Fig. 4 institute for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1
Show, it can be seen that the three-dimensional porous graphene block of the method for the present invention preparation has the aperture of 10 μm to 100 μm sizes abundant
Structure, and interconnected between aperture.The height for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1
Resolved transmittance electromicroscopic photograph is as shown in Figure 5, it can be seen that graphene number of plies is probably at 8 layers or so.It is prepared through the embodiment of the present invention 1
The Raman map of obtained three-dimensional porous graphene block is as shown in fig. 6, there are typical three peaks of graphene, respectively in figure
For the peak D, the peak G and the peak 2D.
The XRD spectrum for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1 is as shown in fig. 7, can see
Nearby there is stronger diffraction maximum at 26 °, show that carbon material is high-graphitized.
The contact angle test result photo for the three-dimensional porous graphene block being prepared through the embodiment of the present invention 1, it is three-dimensional
Graphene block is 140 ° to the contact angle of water, as shown in Figure 8.The three-dimensional porous graphite being prepared through the embodiment of the present invention 1
Alkene block loads the photo in kind on the water surface, as shown in figure 9, therefrom it can be seen that, three-dimensional porous graphene block has very
Excellent hydrophobic performance.The performance for the three-dimensional porous graphene block absorption organic matter being prepared through the embodiment of the present invention 1 is shone
Piece is as shown in Figure 10, and abscissa value indicates the quality of absorption organic matter and the ratio of three-dimensional grapheme block quality in figure.Through this
The three-dimensional porous graphene block highest that the method for invention is prepared can adsorb 60 times of own wt of tetrachloro-ethylene.
Embodiment 2
Using the ultralight clay of the BM24-100 model of Quzhou Bei Meng school supply and stationery Manufacturing Co., Ltd production as raw material, in room
Temperature is lower to place 7 days, with appropriate dehydration and drying.It is then placed into 60 DEG C of baking ovens, places 1 day.By the ultralight clay after drying
It is warming up to 400 DEG C, argon flow 300sccm, hydrogen flowing quantity 30sccm under the protection of argon gas and hydrogen, keeps the temperature 2 small
When.Then obtained sample is warming up in high temperature nitrogen steam stove 2200 DEG C, keeps the temperature 2 hours, that is, three-dimensional porous stone is prepared
Black alkene block materials.
The three-dimensional porous graphene block materials density being prepared is 0.1g/cm3Left and right, porosity reach 96.2%,
To organic matter have very excellent absorption property, the organic matter of absorption include but be not limited to methanol, ethyl alcohol, acetone, butanone,
Chloroform, dichloroethanes, tetrachloro-ethylene, carbon tetrachloride, decahydronaphthalene, hexamethylene, carbon disulfide etc..Figure 11 is embodiment 2
The three-dimensional porous graphene pictorial diagram and its SEM being prepared are schemed, as can be observed from Figure the aperture of 10 μm to 100 μm sizes
Structure interconnects between hole, forms 3 D pore canal network.The block has good compression strength, and being able to bear is more than certainly
The weight that 10000 times of body.
Embodiment 3
Using the ultralight clay of the BM24-100 model of Quzhou Bei Meng school supply and stationery Manufacturing Co., Ltd production as raw material, in room
Temperature is lower to place 7 days, with appropriate dehydration and drying.It is then placed into 60 DEG C of baking ovens, places 7 days.By the ultralight clay after drying
It is warming up to 500 DEG C, argon flow 300sccm, hydrogen flowing quantity 30sccm under the protection of argon gas and hydrogen, keeps the temperature 2 small
When.Then obtained sample is warming up in high temperature nitrogen steam stove 2200 DEG C, keeps the temperature 2 hours, that is, three-dimensional porous stone is prepared
Black alkene block materials.
The three-dimensional porous graphene block materials density being prepared is 0.08g/cm3Left and right, porosity reach 97.0%,
To organic matter have very excellent absorption property, the organic matter of absorption include but be not limited to methanol, ethyl alcohol, acetone, butanone,
Chloroform, dichloroethanes, tetrachloro-ethylene, carbon tetrachloride, decahydronaphthalene, hexamethylene, carbon disulfide etc..Figure 12 is embodiment 3
The three-dimensional porous graphene pictorial diagram and its SEM being prepared are schemed, as can be observed from Figure the aperture of 10 μm to 100 μm sizes
Structure interconnects between hole, forms 3 D pore canal network.The block has good compression strength, and being able to bear is more than certainly
The weight that 10000 times of body.
Embodiment 4
Using the ultralight clay of the BM24-100 model of Quzhou Bei Meng school supply and stationery Manufacturing Co., Ltd production as raw material, in room
Temperature is lower to place 7 days, with appropriate dehydration and drying.It is then placed into 60 DEG C of baking ovens, places 7 days.By the ultralight clay after drying
It is warming up to 300 DEG C, argon flow 300sccm, hydrogen flowing quantity 30sccm under the protection of argon gas and hydrogen, keeps the temperature 2 small
When.Then obtained sample is warming up in high temperature nitrogen steam stove 2200 DEG C, keeps the temperature 2 hours, that is, three-dimensional porous stone is prepared
Black alkene block materials.
The three-dimensional porous graphene block materials density being prepared is 0.026g/cm3, porosity reaches 99.0%, right
Organic matter has very excellent absorption property, and the organic matter of absorption includes but is not limited to methanol, ethyl alcohol, acetone, butanone, three
Chloromethanes, dichloroethanes, tetrachloro-ethylene, carbon tetrachloride, decahydronaphthalene, hexamethylene, carbon disulfide etc..Figure 13 is the system of embodiment 4
Standby obtained three-dimensional porous graphene pictorial diagram and its SEM figure, the aperture of 10 μm to 100 μm sizes is tied as can be observed from Figure
Structure interconnects between hole, forms 3 D pore canal network.The block has good compression strength, is able to bear more than itself
10000 times of weight.
Embodiment 5
Using the ultralight clay of the BM24-100 model of Quzhou Bei Meng school supply and stationery Manufacturing Co., Ltd production as raw material, in room
Temperature is lower to place 7 days, with appropriate dehydration and drying.It is then placed into 60 DEG C of baking ovens, places 7 days.By the ultralight clay after drying
It is warming up to 400 DEG C, argon flow 300sccm, hydrogen flowing quantity 30sccm under the protection of argon gas and hydrogen, keeps the temperature 2 small
When.Then obtained sample is warming up in high temperature nitrogen steam stove 1800 DEG C, keeps the temperature 2 hours, that is, three-dimensional porous stone is prepared
Black alkene block materials.
The three-dimensional porous graphene block materials density being prepared is 0.026g/cm3, porosity reaches 99.0%, right
Organic matter has very excellent absorption property, and the organic matter of absorption includes but is not limited to methanol, ethyl alcohol, acetone, butanone, three
Chloromethanes, dichloroethanes, tetrachloro-ethylene, carbon tetrachloride, decahydronaphthalene, hexamethylene, carbon disulfide etc..Figure 14 is the system of embodiment 5
Standby obtained three-dimensional porous graphene pictorial diagram and its SEM figure, the aperture of 10 μm to 100 μm sizes is tied as can be observed from Figure
Structure interconnects between hole, forms 3 D pore canal network.The block has good compression strength, is able to bear more than itself
10000 times of weight.
Industrial applicability
This method is low for equipment requirements, short preparation period, magnanimity preparation may be implemented, it is big that preparative-scale is limited to stove
It is small.The three-dimensional porous graphene block hydrophobic oleophilic oil performance being prepared is good, possesses cellular structure abundant, greasy dirt absorption property
It is excellent.The three-dimensional porous graphene block that the present invention is prepared has broad application prospects in greasy dirt adsorbing domain.
Claims (7)
1. a kind of method for preparing three-dimensional porous grapheme foam material characterized by comprising
Polymeric Industry product is heat-treated in an inert atmosphere, then again in an inert atmosphere at 900~2500 DEG C
Graphitization 1~5 hour, obtains the three-dimensional porous graphene block；Wherein the Polymeric Industry product is pre-processed,
It is heat-treated again after making its abundant drying and dehydrating；
The Polymeric Industry product is ultralight clay or/and paper clay.
2. the method according to claim 1, wherein the heat treatment is small to keep the temperature 1~5 at 300~600 DEG C
When.
3. the method according to claim 1, wherein the inert atmosphere be nitrogen, argon gas and helium in extremely
The gaseous mixture of at least one of a kind of few gas or nitrogen, argon gas and helium gas and hydrogen.
4. according to the method described in claim 3, it is characterized in that, at least one of the nitrogen, argon gas and helium gas
Flow be 1~800sccm, the flow of the hydrogen is 1~100sccm.
5. method according to any of claims 1-4, which is characterized in that the mode of the drying and dehydrating is dry for room temperature
Dry or/and oven drying；The drying at room temperature is drying 1 day~15 days at 0~30 DEG C, and oven drying is at 40~120 DEG C
Lower drying 1~15 day.
6. a kind of three-dimensional porous grapheme foam material of method preparation according to any one of claims 1-5, special
Sign is that the micromorphology of the three-dimensional porous graphene block is the macroporous structure of three-dimensional communication, and macropore diameter is 10~100
μm。
7. a kind of application of three-dimensional porous grapheme foam material as claimed in claim 6 in greasy dirt absorption.
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| CN110775966B (en) * | 2019-11-21 | 2021-07-27 | 秦皇岛中科瀚祺科技有限公司 | Flexible graphene film and application thereof |
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