CN102942179A - Preparation method of partially reduced network structure oxidized graphene - Google Patents
Preparation method of partially reduced network structure oxidized graphene Download PDFInfo
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- CN102942179A CN102942179A CN2012104876792A CN201210487679A CN102942179A CN 102942179 A CN102942179 A CN 102942179A CN 2012104876792 A CN2012104876792 A CN 2012104876792A CN 201210487679 A CN201210487679 A CN 201210487679A CN 102942179 A CN102942179 A CN 102942179A
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Abstract
The invention provides a preparation method of partially reduced network structure oxidized graphene. The preparation method includes that graphite oxide prepared through a Hummers method is soaked in an aqueous hydrogen peroxide solution or carbon acid aqueous solution to obtain a viscous mixture, and the viscous mixture is collected; a tube furnace is preheated up to 900-1200 DEG C and protected through inert gas; and the viscous mixture is arranged in the tube furnace protected by the inert gas, heated for 10-50s and cooled to the room temperature to obtain the partially reduced network structure oxidized graphene. The preparation method of the partially reduced network structure oxidized graphene has the advantages of being capable of effectively restraining graphene sheet layers from being stacked and being reduced to a network structure partially.
Description
Technical field
The present invention relates to a kind of preparation method of network structure graphene oxide of partial reduction.
Background technology
Graphene be discovered in recent years by individual layer sp
2The two-dimentional carbonaceous crystal that hydridization carbon consists of has that excellent electricity is led, a specific surface area of mechanical property, superelevation and to good the passing through and the property transmitted etc. of guest molecule/ion, has potential using value at numerous areas.Because stronger π-π interacts, serious stacking can occur in single-layer graphene in actual applications, has had a strong impact on its performance.The material that will have nanostructure is assembled into the committed step that block materials is Application of micron, also is the important channel of nano material large-scale application.Nano material is when being assembled into the block structure material, and the peculiar character under its nanostructure is delivered in the block materials that is assembled into, so the three-dimensional structure macroscopic material of Graphene is one of target of paying close attention to of investigator always.
The method for preparing graphene three-dimensional structure of having developed at present is also few, mainly contain following several: [chemical Vapor deposition process prepares the Graphene network structure of the internal communication of three-dimension flexible and conduction to chemical Vapor deposition process, " nature material ", 2011, the 10th volume, the 424th page of (Three-dimensional Flexible and Conductive Interconnected Graphene Networks Grown by Chemical Vapour Deposition, Nat. Mater., 2011, Vol.10,424); The preparation of novel three-dimensional Graphene network structure and the application in ultracapacitor thereof, " micro-nano ", 2011, the 7th volume, the 3163rd page of (Preparation of Novel 3D Graphene Networks for Supercapacitor Applications, Small, 2011, Vol. 7,3163)], microwave-assisted partly peels off and reduction method [microwave-assisted is peeled off and the standby electrode material for super capacitor of reduction-oxidation graphite-made, " carbon ", 2010, the 48th volume, the 2118th page of (Microwave Assisted Exfoliation and Reduction of Graphite Oxide for Ultracapacitors, Carbon, 2010, Vol.48,2118)], hydrothermal method [the Graphene hydrogel of water-heat process one-step synthesis self-assembly, " American Chemical Society's nanometer periodical ", 2010, the 4th volume, the 4324th page of (Self-Assembled Graphene Hydrogel via a One-Step Hydrothermal Process, ACS Nano, 2010, Vol.4,4324)], fast vacuum method of enrichment [a kind of controlled self-assembling method macroscopic preparation of graphene sponge and graphene film, " advanced function material ", 2010, the 20th volume, the 1930th page of (A Controllable Self-Assembly Method for Large-Scale Synthesis of Graphene Sponges and Free-Standing Graphene Films, Adv. Funct. Mater., 2010, Vol. 20,1930)], negative pressure cryochemistry method [the negative pressure low temperature of the Graphene standby and electrochemical energy storage character of legal system of dissociating of dissociating, " American Chemical Society's nanometer periodical ", 2009, the 3rd volume, the 3730th page of (Low-Temperature Exfoliated Graphenes:Vacuum-Promoted Exfoliation and Electrochemical Energy Storage, ACS Nano, 2009, Vol.3,3730)] etc.And constructing for the network structure graphene oxide of partial reduction, because oxygen-containing functional group wherein can play the effect of bonding graphene sheet layer, can also effectively avoid simultaneously the graphene-structured accumulation that π-π interacts and causes in following process, be conducive to the specific surface area that keeps Graphene higher; The reduction of oxygen level after the partial reduction, than the network structure graphene oxide, its electroconductibility is obviously promoted, and is all significant in theoretical and practical application.
Summary of the invention
The purpose of this invention is to provide a kind of can the establishment graphene sheet layer stacking, the method for the network structure graphene oxide of preparation partial reduction.
Preparation method of the present invention is as follows:
(1) will adopt the standby graphite oxide [preparation of graphite oxide of Hummers legal system that improves, " JACS ", 1958, the 80th volume: the 1339th page of (Preparation of Graphitic Oxide, J. Am. Chem. Soc., 1958, Vol.80,1339)] be immersed in the aqueous hydrogen peroxide solution or the carboxamide aqueous solution of 5-10wt% concentration, the volume ratio of graphite oxide and aqueous hydrogen peroxide solution or the carboxamide aqueous solution is 1:35-1:50, and room temperature placed 5-7 days, obtained mixture of viscous form and collected;
(2) tube furnace is warmed up to 900-1200 ℃ in advance, and logical protection of inert gas;
(3) mixture of viscous form is placed the tube furnace of blanketing with inert gas, heating 10-50s, to be cooled to room temperature, obtain the network structure graphene oxide of partial reduction.
Aforesaid rare gas element is nitrogen.
The present invention has following advantage:
(1) raw material such as used natural graphite is cheap and easy to get, need not pre-treatment, is conducive to reduce cost.
(2) the standby graphite oxide technical maturity of the Hummers legal system of improvement can preparation in macroscopic quantity.
(3) the synthesis technique flow process is simple, and is easy and simple to handle, and influence factor is few, is convenient to control, favorable reproducibility.
(4) the network structure graphene oxide of the partial reduction of preparation can keep in a long time its pattern and not reunite.
(5) do not need additionally to introduce metal as masterplate.
(6) be convenient to the network structure graphene oxide that mass-producing prepares partial reduction in a large number.
Description of drawings
Fig. 1 is graphene oxide network structure scanning electron microscope (SEM) figure of embodiment of the invention partial reduction.
Embodiment
Adopt the standby graphite oxide of Hummers legal system of improvement, concrete steps are as follows: be that the sulfuric acid of 98wt% is placed under the condition of ice bath and stirs with concentration, add first Graphite Powder 99 and NaNO
3, slowly add again KMnO
4, Graphite Powder 99, NaNO
3And KMnO
4Mass ratio be 2:1:6, control fluid temperature be no more than 20 ℃.After for some time is carried out in reaction, beaker is transferred to continuation reaction 0.5h in 35 ℃ of waters bath with thermostatic control.Distilled water is slowly added in the solution, make temperature rise to 98 ℃, continue to stir 0.5h.With solution dilution, add the H of 30wt% with distilled water
2O
2Solution reduces residual oxygenant.Filtered while hot, and with distilled water and 5wt% dilute hydrochloric acid fully wash until in the filtrate sulfate radical-free be detected.At last filter cake is placed 60 ℃ loft drier dry, grind (lower same) for subsequent use.Graphite oxide is impregnated in the aqueous hydrogen peroxide solution of 5wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:35, leaves standstill 5 days, gets 300mg and places and be warmed up in advance 900 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 45s collects after being cooled to room temperature.XPS analysis result shows that oxygen level is reduced to the 16%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～5 nm.
Embodiment 2
Flood the standby graphite oxide (embodiment 1 preparation) of Hummers legal system of improvement with the carboxamide aqueous solution of 7.5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:40; left standstill 6 days; getting 350mg places and is warmed up in advance 1000 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 30s collects after being cooled to room temperature.XPS analysis result shows that oxygen level is the 16%(atomic percent), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4 nm.
Embodiment 3
The graphite oxide that the Hummers legal system that adopts improvement is standby (embodiment 1 preparation); be impregnated in the aqueous hydrogen peroxide solution of 9 wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:50; left standstill 7 days; getting 350mg places and is warmed up in advance 1200 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 10s collects after being cooled to room temperature.XPS analysis result shows that oxygen level is reduced to the 13%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4.5 nm.
Embodiment 4
Flood the standby graphite oxide (embodiment 1 preparation) of Hummers legal system of improvement with the carboxamide aqueous solution of 10wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:45; left standstill 6 days; getting 300mg places and is warmed up in advance 1150 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 15s collects after being cooled to room temperature.XPS analysis result shows that oxygen level is reduced to the 14%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～5.5nm.
Embodiment 5
The graphite oxide that the Hummers legal system that adopts improvement is standby (embodiment 1 preparation); be impregnated in the aqueous hydrogen peroxide solution of 10wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:40; left standstill 6 days; getting 350mg places and is warmed up in advance 1050 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 25s is cooled to room temperature and collection.XPS analysis result shows that oxygen level is reduced to the 15%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4 nm.
Embodiment 6
Flood the standby graphite oxide (embodiment 1 preparation) of Hummers legal system of improvement with the carboxamide aqueous solution of 5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:35; left standstill 5 days; getting 300mg places and is warmed up in advance 1100 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 15s is cooled to room temperature and collection.XPS analysis result shows that oxygen level is reduced to the 13%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4 nm.
Embodiment 7
The graphite oxide that the Hummers legal system that adopts improvement is standby (embodiment 1 preparation); be impregnated in the aqueous hydrogen peroxide solution of 8wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:40; left standstill 5.5 days; getting 350mg places and is warmed up in advance 950 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 50s is cooled to room temperature and collection.XPS analysis result shows that oxygen level is reduced to the 16%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like result of show sample as a result, graphene-based lamellar spacing～4 nm.
Embodiment 8
Flood the standby graphite oxide (embodiment 1 preparation) of Hummers legal system of improvement with the carboxamide aqueous solution of 7wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:45; left standstill 6.5 days; getting 300mg places and is warmed up in advance 1000 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 40s is cooled to room temperature and collection.XPS analysis result shows that oxygen level is reduced to the 15%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4.5 nm.
Embodiment 9
The graphite oxide that the Hummers legal system that adopts improvement is standby (embodiment 1 preparation); be impregnated in the aqueous hydrogen peroxide solution of 6.5wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:40; left standstill 6 days; getting 350mg places and is warmed up in advance 1050 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 30s is cooled to room temperature and collection.XPS analysis result shows that oxygen level is reduced to the 14%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4 nm.
Embodiment 10
Flood the standby graphite oxide (embodiment 1 preparation) of Hummers legal system of improvement with the carboxamide aqueous solution of 5.5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:35; left standstill 5 days; getting 300mg places and is warmed up in advance 950 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; heating 45s is cooled to room temperature and collection.XPS analysis result shows that oxygen level is reduced to the 16%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4 nm.
Embodiment 11
The graphite oxide that the Hummers legal system that adopts improvement is standby (embodiment 1 preparation); be impregnated in the carboxamide aqueous solution of 8.5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:45; left standstill 5.5 days; getting 350mg places and is warmed up in advance 1150 ℃ and nitrogen purging is arranged and the horizontal pipe furnace of protection; it is 15s that the adjusting carrier gas flux is controlled heat-up time, is cooled to room temperature and collection.XPS analysis result shows that oxygen level is reduced to the 13%(atomic percent by 36% of graphite oxide), scanning electron microscope (SEM) is the network-like structure of show sample as a result, graphene-based lamellar spacing～4 nm.
Claims (2)
1. the preparation method of the network structure graphene oxide of a partial reduction is characterized in that comprising the steps:
(1) will adopt the standby graphite oxide of Hummers legal system of improvement to be immersed in the aqueous hydrogen peroxide solution or the carboxamide aqueous solution of 5-10wt% concentration, the volume ratio of graphite oxide and aqueous hydrogen peroxide solution or the carboxamide aqueous solution is 1:35-1:50, and room temperature placed 5-7 days, obtained mixture of viscous form and collected;
(2) tube furnace is warmed up to 900-1200 ℃ in advance, and logical protection of inert gas;
(3) mixture of viscous form is placed the tube furnace of blanketing with inert gas, heating 10-50s, to be cooled to room temperature, obtain the network structure graphene oxide of partial reduction.
2. the preparation method of the network structure graphene oxide of a kind of partial reduction as claimed in claim 1 is characterized in that described rare gas element is nitrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110186789A1 (en) * | 2008-05-22 | 2011-08-04 | The University Of North Carolina At Chapel Hill | Synthesis of graphene sheets and nanoparticle composites comprising same |
| CN102583339A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Method for preparing graphene from three-dimensional porous carbon material and three-dimensional porous graphene |
| CN102760866A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110186789A1 (en) * | 2008-05-22 | 2011-08-04 | The University Of North Carolina At Chapel Hill | Synthesis of graphene sheets and nanoparticle composites comprising same |
| CN102760866A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of nitrogen-doped graphene |
| CN102583339A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Method for preparing graphene from three-dimensional porous carbon material and three-dimensional porous graphene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
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