CN107416812B - A method of graphene oxide is prepared by carbon source of walnut shell - Google Patents

A method of graphene oxide is prepared by carbon source of walnut shell Download PDF

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CN107416812B
CN107416812B CN201710667426.6A CN201710667426A CN107416812B CN 107416812 B CN107416812 B CN 107416812B CN 201710667426 A CN201710667426 A CN 201710667426A CN 107416812 B CN107416812 B CN 107416812B
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walnut shell
graphene oxide
powder
temperature
high temperature
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CN107416812A (en
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张丽园
姜菲
盛蒂
王传虎
樊万鑫
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Bengbu College
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

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Abstract

The invention discloses a kind of methods for preparing graphene oxide as carbon source using walnut shell, mainly comprise the steps that the pretreatment of 1) walnut shell；2) carbonization treatment；3) catalyzed graphitization；4) it is acidified and removes.The present invention solves the problems, such as high production cost present in previous graphene oxide preparation process, is limited by carbon source, gained graphene oxide size is lesser, have the characteristics that raw material sources are abundant, production cost is low, reproducible, product quality is high, has broad application prospects.

Description

A method of graphene oxide is prepared by carbon source of walnut shell
Technical field
The present invention relates to a kind of preparation methods of graphene oxide, and in particular to using walnut shell as raw material, preparation oxidation The method of graphene.
Background technique
Graphene oxide is the important growth of graphene, it is considered to be the strategic starting point of extensive synthesizing graphite alkene.Oxygen Graphite alkene be in structure by hydrophobic not oxidized aromatic region and hydrophilic oxygen-containing group (such as: carboxyl, hydroxyl Base, epoxy group) composition, as the important presoma for preparing graphene, while with some peculiar properties of itself (as having parents Performance can reduce the energy between interface, play the role of interfacial agent etc.), and receive the extensive concern of people.It is answered With mainly energy industry is covered, such as: energy storage, biological medicine and building fire protection fire proofing of electric energy etc..
Currently, the method that the preparation of graphene oxide mainly uses chemical oxidation, specific mainly to use three kinds of oxygen in fact Change method: Brodie method, Staudenmair method and three kinds of Hummers method.Those methods are all with natural crystal resource: graphite The surface of graphite flake layer and edge is set to contain great amount of hydroxy group, carboxyl and epoxy etc. oxygen-containing after chemical oxidation treatment for raw material Group finally obtains graphene oxide then using removing.
It is worth noting that, being usually to be deposited using natural flake graphite as raw material in above-mentioned graphene oxide preparation process Limited by carbon source, the problem that high production cost, gained graphene oxide size are smaller etc..
Summary of the invention
The present invention proposes a kind of method for preparing graphene oxide as carbon source using walnut shell regarding to the issue above.
The present invention adopts the following technical scheme:
A method of graphene oxide is prepared by carbon source of walnut shell, which comprises the steps of:
(1) pretreatment of walnut shell: walnut shell is polished into powder with crusher, is sieved to obtain walnut shell with 180 mesh sieve Powder is washed with deionized to neutrality, is dried for standby then with after 10% salt acid soak 12 ~ for 24 hours；
(2) it is carbonized: the walnut shell powder and activator Fe that step (1) is obtained2O3After being mixed in a certain ratio uniformly, use Mortar grinder is uniform, is subsequently placed in high temperature process furnances, and is continually fed into protective gas and carries out carbonization heat treatment；Wherein, at heat Manage bar part are as follows: in high temperature furnace, rise to 600 DEG C with the heating rate of 2.5-20 DEG C/min, and keep the temperature 1-2 h, obtain biology Matter charcoal；
(3) it catalyzed graphitization: after the biomass carbon grinding uniformly that step (2) is obtained, is replaced in high temperature process furnances Secondary heat treatment is carried out, and is continually fed into protective gas, and rise to 960 DEG C with the heating rate of 2.5-20 DEG C/min, and protect Warm 5-6 h obtains charing iron powder after furnace cooling, then charing iron powder is fitted into the small crucible of 100ml, then by small earthenware Crucible is put into the big crucible of 250ml, is packed into uniformly mixed Al2O3With the mixed-powder of active carbon, Al2O3With the matter of active carbon Amount is than being 1:1, until burying small crucible completely, after closeing the lid, it is placed it in again in high temperature furnace, and with 2.5-20 DEG C/heating rate of min rises to 1200 DEG C, and keeps the temperature 2-3 h, obtain biomass graphite；
(4) be acidified and remove: take 23 mL concentration be 98% sulfuric acid solution and 0.5 g sodium nitrate after mixing, ice water The lower cooling of bath makes system temperature lower than 5 DEG C, is stirred continuously 1.0 g of biomass graphite that lower addition step (3) obtains, and mixing is equal 0.3 g potassium permanganate of addition after even, control reaction temperature are 10-15 DEG C, and 35 DEG C are warming up to after reaction 1-2 h and continues stirring instead After answering 0.5-1 h, 46 mL of deionized water is added, controls reacting liquid temperature at 98 DEG C, continues to stir 15 min, is then added 140 ML deionized water terminate reaction, add the hydrogen peroxide of 3 mL mass concentrations 30%, filter while hot, and with hydrochloric acid solution wash to Without SO in filtrate4 2-, then be washed with deionized to neutrality；Resulting filter cake is re-dispersed into water, is formed uniform molten Liquid, ultrasonic lift-off processing 30-120 min；Again with centrifuge to be centrifuged 3-5 min, gained under conditions of 4000-6000 r/min Supernatant is the aqueous solution of graphene oxide.
The present invention also has following technical characteristic:
Walnut shell powder and activator Fe in aforesaid operations step (2)2O3Mass ratio are as follows: 17:3~4:1.
Protection gas described in aforesaid operations step (2) and step (3) is nitrogen, argon gas, one kind of helium or wherein The gas that several arbitrary proportions mix.
Ultrasound 30-120 min described in aforesaid operations step (4), is in supersonic frequency 30-50KHz, ultrasonic power is It is carried out under the conditions of 100-150 W.
The utility model has the advantages that the present invention using walnut shell be raw material ideal graphene oxide has been prepared, solve with Toward limited present in graphene oxide preparation process by carbon source, high production cost, gained graphene oxide size is lesser asks Topic has the characteristics that raw material sources are abundant, production cost is low, reproducible, product quality is high, has broad application prospects.
Detailed description of the invention
Fig. 1 is walnut shell of the present invention and its carbonization, graphitized products photo, and as can be seen from Figure 1 walnut shell passes through carbon After change and graphitization processing, available ideal graphite powder；
Fig. 2 is the dispersion liquid photo of graphene oxide of the present invention in water, as can be seen from Figure 2 preparation-obtained oxygen Graphite alkene is in water in a highly dispersed state；
Fig. 3 is the FT-IR figure of graphene oxide of the present invention, can be seen that graphene oxide on piece is living from the curve in Fig. 3 The infrared signature absorption peak of property functional group, stretching vibration (1729 cm of C=O-1), bending vibration (1387 cm of O-H-1), ring C-O stretching vibration (1122 cm in oxygroup-1), not oxidized sp2C=C stretching vibration (1625 cm between the carbon atom of hydridization-1), in 3422 cm-1Place is spy caused by the-OH group stretching vibration in stannic oxide/graphene nano on piece and its adsorbed water Levy absorption peak.FTIR figure is strong to be demonstrated after oxidation processes, and the functional groups such as hydroxyl, epoxy group, carboxyl are grafted to On graphene film；
Fig. 4 is the TEM figure of graphene oxide of the present invention, and as can be seen from Figure 4 preparation-obtained graphene oxide is in Height exfoliated state；
Fig. 5 is the grain size analysis diagram of graphene oxide of the present invention, as can be seen from Figure 5 preparation-obtained graphite oxide Alkene size is larger, and the partial size of graphene oxide is concentrated mainly on 10 um.
Specific embodiment
Embodiment one:
1, the pretreatment of walnut shell: walnut shell is polished into powder with crusher, is sieved to obtain walnut shell with 180 mesh sieve Powder, then with 10% salt acid soak for 24 hours after, be washed with deionized to neutrality, be dried for standby；
2, it is carbonized: the walnut shell powder and activator Fe that step (1) is obtained2O34:1 in mass ratio after mixing, is used Mortar grinder is uniform, is subsequently placed in high temperature furnace, and is continually fed into nitrogen and carries out carbonization heat treatment；Wherein, heat treatment condition are as follows: In high temperature furnace, 600 DEG C is risen to the heating rate of 20 DEG C/min, and keep the temperature 2h, obtain biomass carbon；
3, catalyzed graphitization: after the biomass carbon grinding uniformly that step (2) is obtained, being replaced in high temperature process furnances, And it is continually fed into protective gas, and rise to 960 DEG C with the heating rate of 20 DEG C/min, and keep the temperature 6 h, after furnace cooling To charing iron powder, then charing iron powder is fitted into the small crucible of 100ml, then small crucible is put into the big crucible of 250ml In, it is packed into uniformly mixed Al2O3With the mixed-powder (Al of active carbon2O3Mass ratio with active carbon is 1:1), until completely Bury small crucible, after closeing the lid, it is placed it in high temperature furnace again, and is risen to the heating rate of 20 DEG C/min 1200 DEG C, and 3 h are kept the temperature, obtain biomass graphite；
4, be acidified and remove: take 23 mL concentration be 98% sulfuric acid solution and 0.5 g sodium nitrate after mixing, ice-water bath Lower cooling makes system temperature lower than 5 DEG C, is stirred continuously 1.0 g of biomass graphite that lower addition step (3) obtains, is uniformly mixed After be added 0.3 g potassium permanganate, control reaction temperature is 15 DEG C, react and be warming up to 35 DEG C after 2 h and continue after being stirred to react 1 h, 46 mL of deionized water is added, controls reacting liquid temperature at 98 DEG C, continues to stir 15 min, 140 mL deionized waters is then added Reaction is terminated, the hydrogen peroxide of 3 mL mass concentrations 30% is added, filters while hot, and wash into filtrate nothing with hydrochloric acid solution SO4 2-, then be washed with deionized to neutrality；Resulting filter cake is re-dispersed into water, uniform solution, ultrasound stripping are formed From handling 120 min；Again with centrifuge to be centrifuged 5 min under conditions of 6000 r/min, gained supernatant is graphene oxide Aqueous solution.As shown in Fig. 2, preparation-obtained graphene oxide is in water in a highly dispersed state；As shown in figure 4, made Standby obtained graphene oxide is in height exfoliated state；As shown in figure 5, preparation-obtained graphene oxide size is larger, oxygen The partial size of graphite alkene is concentrated mainly on 10 um.
Embodiment two:
1, the pretreatment of walnut shell: walnut shell is polished into powder with crusher, is sieved to obtain walnut shell with 180 mesh sieve Powder is washed with deionized to neutrality, is dried for standby then with after 10% salt acid soak 18h；
2, it is carbonized: the walnut shell powder and activator Fe that step (1) is obtained2O382:18 in mass ratio after mixing, It is uniform with mortar grinder, it is subsequently placed in high temperature furnace, and be continually fed into argon gas and carry out carbonization heat treatment；Wherein, heat treatment condition Are as follows: in high temperature furnace, 600 DEG C is risen to the heating rate of 15 DEG C/min, and keep the temperature 1.5 h, obtain biomass carbon；
3, catalyzed graphitization: after the biomass carbon grinding uniformly that step (2) is obtained, be replaced in high temperature process furnances into Row secondary heat treatment, and it is continually fed into protective gas, and rise to 960 DEG C with the heating rate of 15 DEG C/min, and keep the temperature 5.5 H obtains charing iron powder after furnace cooling, then charing iron powder is fitted into the small crucible of 100ml, then small crucible is put into In the big crucible of 250ml, it is packed into uniformly mixed Al2O3With the mixed-powder (Al of active carbon2O3Mass ratio with active carbon is 1:1), until burying small crucible completely, after closeing the lid, it is placed it in high temperature furnace again, and with 15 DEG C/min's Heating rate rises to 1200 DEG C, and keeps the temperature 2.5 h, obtains biomass graphite；
4, be acidified and remove: take 23 mL concentration be 98% sulfuric acid solution and 0.5 g sodium nitrate after mixing, ice-water bath Lower cooling makes system temperature lower than 5 DEG C, is stirred continuously 1.0 g of biomass graphite that lower addition step (3) obtains, is uniformly mixed After be added 0.3 g potassium permanganate, control reaction temperature is 12 DEG C, reacts and is warming up to 35 DEG C after 1.5 h and continues to be stirred to react 1 h Afterwards, 46 mL of deionized water is added, controls reacting liquid temperature at 98 DEG C, continues to stir 15 min, 140 mL deionizations is then added Water terminates reaction, adds the hydrogen peroxide of 3 mL mass concentrations 30%, filters while hot, and washs into filtrate nothing with hydrochloric acid solution SO4 2-, then be washed with deionized to neutrality；Resulting filter cake is re-dispersed into water, uniform solution, ultrasound stripping are formed From handling 60 min；Again with centrifuge to be centrifuged 4 min under conditions of 5000 r/min, gained supernatant is graphene oxide Aqueous solution.
Embodiment three:
1, the pretreatment of walnut shell: walnut shell is polished into powder with crusher, is sieved to obtain walnut shell with 180 mesh sieve Powder is washed with deionized to neutrality, is dried for standby then with after 10% salt acid soak 12h；
2, it is carbonized: the powdered biomass and activator Fe that step (1) is obtained2O317:3 in mass ratio after mixing, is used Mortar grinder is uniform, is subsequently placed in high temperature furnace, and is continually fed into helium and carries out carbonization heat treatment；Wherein, heat treatment condition are as follows: In high temperature furnace, 600 DEG C is risen to the heating rate of 10 DEG C/min, and keep the temperature 1 h, obtain biomass carbon；
3, catalyzed graphitization: after the biomass carbon grinding uniformly that step (2) is obtained, be replaced in high temperature process furnances into Row secondary heat treatment, and it is continually fed into protective gas, and rise to 960 DEG C with the heating rate of 2.5-20 DEG C/min, and keep the temperature 5 h obtain charing iron powder after furnace cooling, then charing iron powder is fitted into the small crucible of 100ml, then small crucible is put Enter in the big crucible of 250ml, is packed into uniformly mixed Al2O3With the mixed-powder (Al of active carbon2O3With the mass ratio of active carbon After closeing the lid, it is placed it in high temperature furnace again, and with 10 DEG C/min for 1:1) until burying small crucible completely Heating rate rise to 1200 DEG C, and keep the temperature 2 h, obtain biomass graphite；
4, be acidified and remove: take 23 mL concentration be 98% sulfuric acid solution and 0.5 g sodium nitrate after mixing, ice-water bath Lower cooling makes system temperature lower than 5 DEG C, is stirred continuously 1.0 g of biomass graphite that lower addition step (3) obtains, is uniformly mixed After be added 0.3 g potassium permanganate, control reaction temperature is 10 DEG C, reacts and is warming up to 35 DEG C after 1 h and continues to be stirred to react 0.5 h Afterwards, 46 mL of deionized water is added, controls reacting liquid temperature at 98 DEG C, continues to stir 15 min, 140 mL deionizations is then added Water terminates reaction, adds the hydrogen peroxide of 3 mL mass concentrations 30%, filters while hot, and washs into filtrate nothing with hydrochloric acid solution SO4 2-, then be washed with deionized to neutrality；Resulting filter cake is re-dispersed into water, uniform solution, ultrasound stripping are formed From handling 30 min；Again with centrifuge to be centrifuged 3 min under conditions of 4000 r/min, gained supernatant is graphene oxide Aqueous solution.

Claims (3)

1. a kind of method for preparing graphene oxide as carbon source using walnut shell, which comprises the steps of:
(1) pretreatment of walnut shell: being polished into powder with crusher for walnut shell, is sieved to obtain walnut shell powder with 180 mesh sieve, so Afterwards with after 10% salt acid soak 12-24h, it is washed with deionized to neutrality, is dried for standby；
(2) it is carbonized: the walnut shell powder and activator Fe that step (1) is obtained2O3After being mixed in a certain ratio uniformly, mortar is used Grinding uniformly, is subsequently placed in high temperature process furnances, and be continually fed into protective gas and carry out carbonization heat treatment；Wherein, it is heat-treated item Part are as follows: in high temperature furnace, rise to 600 DEG C with the heating rate of 2 .5-20 DEG C/min, and keep the temperature 1-2h, obtain biomass carbon；
(3) it catalyzed graphitization: after the biomass carbon grinding uniformly that step (2) is obtained, is replaced in high temperature process furnances and carries out Secondary heat treatment, and it is continually fed into protective gas, and rise to 960 DEG C with the heating rate of 2 .5-20 DEG C/min, and keep the temperature 5- 6h obtains charing iron powder after furnace cooling, then charing iron powder is fitted into the small crucible of 100ml, then small crucible is put Enter in the big crucible of 250ml, is packed into uniformly mixed Al2O3With the mixed-powder of active carbon, Al2O3With the mass ratio of active carbon For 1:1, until burying small crucible completely, after closeing the lid, it is placed it in high temperature furnace again, and with 2 .5-20 DEG C/ The heating rate of min rises to 1200 DEG C, and keeps the temperature 2-3h, obtains biomass graphite；
(4) be acidified and remove: take 23mL concentration be 98% sulfuric acid solution and 0 .5g sodium nitrate after mixing, it is cold under ice-water bath But make system temperature lower than 5 DEG C, be stirred continuously 1 .0g of biomass graphite that lower addition step (3) obtains, be added after mixing 0 .3g potassium permanganate, control reaction temperature are 10-15 DEG C, are warming up to 35 DEG C after reaction 1-2h and continue to be stirred to react 0 .5-1h Afterwards, deionized water 46mL is added, controls reacting liquid temperature at 98 DEG C, continues to stir 15min, 140mL deionized water is then added Reaction is terminated, the hydrogen peroxide of 3mL mass concentration 30% is added, filters while hot, and wash into filtrate nothing with hydrochloric acid solution SO4 2-, then be washed with deionized to neutrality；Resulting filter cake is re-dispersed into water, uniform solution, ultrasound stripping are formed From processing 30-120min；Again with centrifuge to be centrifuged 3-5 min under conditions of 4000-6000r/min, gained supernatant is oxygen The aqueous solution of graphite alkene；
(5) walnut shell powder and activator Fe in step (2)2O3Mass ratio are as follows: 17:3~4:1.
2. preparation method according to claim 1, it is characterised in that: protection gas described in step (2) and step (3) is Nitrogen, argon gas, one kind of helium or gas that wherein several arbitrary proportions mix.
3. preparation method according to claim 1, it is characterised in that: ultrasound 30-120min described in step (4), be Supersonic frequency 30-50KHz, ultrasonic power carry out under the conditions of being 100-150W.
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US9359208B2 (en) * 2014-03-20 2016-06-07 Nanotek Instruments, Inc. Production process for highly conductive graphitic films

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