CN102942179B - Preparation method of partially reduced network structure oxidized graphene - Google Patents

Preparation method of partially reduced network structure oxidized graphene Download PDF

Info

Publication number
CN102942179B
CN102942179B CN201210487679.2A CN201210487679A CN102942179B CN 102942179 B CN102942179 B CN 102942179B CN 201210487679 A CN201210487679 A CN 201210487679A CN 102942179 B CN102942179 B CN 102942179B
Authority
CN
China
Prior art keywords
network structure
graphene
graphite oxide
preparation
solution
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.)
Active
Application number
CN201210487679.2A
Other languages
Chinese (zh)
Other versions
CN102942179A (en
Inventor
朱珍平
孟新
郑剑锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Institute of Coal Chemistry of CAS
Original Assignee
Shanxi Institute of Coal Chemistry of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shanxi Institute of Coal Chemistry of CAS filed Critical Shanxi Institute of Coal Chemistry of CAS
Priority to CN201210487679.2A priority Critical patent/CN102942179B/en
Publication of CN102942179A publication Critical patent/CN102942179A/en
Application granted granted Critical
Publication of CN102942179B publication Critical patent/CN102942179B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

A kind of preparation method of network structure graphene oxide of partial reduction
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 forms, has that excellent electricity is led, a specific surface area of mechanical property, superelevation and to good the passing through and transporting etc. of guest molecule/ion, has potential using value at numerous areas.Because stronger π-π interacts, can there is serious stacking in single-layer graphene, had a strong impact on its performance in actual applications.The material with nanostructure is assembled into the committed step that block materials is Application of micron, is also the important channel of nano material large-scale application.Nano material is in the time being assembled into block structure material, and the peculiar character under its nanostructure is delivered in be assembled into block materials, and therefore the three-dimensional structure macroscopic material of Graphene is one of target of paying close attention to of investigator always.
The method of preparing graphene three-dimensional structure of having developed is at present also few, mainly contain following several: [chemical Vapor deposition process is prepared 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 part peels off and reduction method [microwave-assisted is peeled off with reduction-oxidation graphite-made for electrode material for super capacitor, " 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 graphene-structured π-π in following process accumulation causing that interacts simultaneously, be conducive to the specific surface area that keeps Graphene higher; The reduction of oxygen level after partial reduction, than network structure graphene oxide, its electroconductibility is obviously promoted, all significant in theoretical and practical application.
Summary of the invention
The object of this invention is to provide one, can effectively to suppress 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) the standby graphite oxide [preparation of graphite oxide of Hummers legal system of improvement will be adopted, " 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 placement 5-7 days, obtain mixture of viscous form and collect;
(2) tube furnace is warmed up to 900-1200 ℃ in advance, and logical protection of inert gas;
(3) mixture of viscous form is placed in to 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.
Rare gas element as above is nitrogen.
Tool of the present invention has the following advantages:
(1) raw material such as natural graphite used is cheap and easy to get, without pre-treatment, is conducive to reduce costs.
(2) the Hummers legal system of improvement, can preparation in macroscopic quantity for graphite oxide technical maturity.
(3) synthesis technique flow process is simple, 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 preparing 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 partial reduction is prepared in mass-producing in a large number.
Accompanying drawing explanation
Fig. 1 is graphene oxide network structure scanning electron microscope (SEM) figure of embodiment of the present invention partial reduction.
Embodiment
Embodiment 1
Adopt the Hummers legal system of improvement for graphite oxide, concrete steps are as follows: the sulfuric acid that is 98wt% by concentration is placed under condition of ice bath and stirs, and first add Graphite Powder 99 and NaNO 3, more slowly add KMnO 4, Graphite Powder 99, NaNO 3and KMnO 4mass ratio be 2:1:6, control fluid temperature be no more than 20 ℃.Reaction was carried out after for some time, and beaker is transferred to continuation reaction 0.5h in 35 ℃ of waters bath with thermostatic control.Distilled water is slowly added in solution, make temperature rise to 98 ℃, continue to stir 0.5h.By 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 filtrate sulfate radical-free be detected.The loft drier that finally filter cake is placed in to 60 ℃ is dry, grinds (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 is placed in and is warmed up in advance 900 ℃ and have nitrogen purging 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 16%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～5 nm.
Embodiment 2
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improveing with the carboxamide aqueous solution dipping of 7.5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:40; leave standstill 6 days; getting 350mg is placed in and is warmed up in advance 1000 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; heating 30s, collects after being cooled to room temperature.XPS analysis result shows that oxygen level is 16%(atomic percent), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4 nm.
Embodiment 3
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improvement will be adopted; be impregnated in the aqueous hydrogen peroxide solution of 9 wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:50; leave standstill 7 days; getting 350mg is placed in and is warmed up in advance 1200 ℃ and have nitrogen purging 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 13%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4.5 nm.
Embodiment 4
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improveing with the carboxamide aqueous solution dipping of 10wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:45; leave standstill 6 days; getting 300mg is placed in and is warmed up in advance 1150 ℃ and have nitrogen purging 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 14%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～5.5nm.
Embodiment 5
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improvement will be adopted; be impregnated in the aqueous hydrogen peroxide solution of 10wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:40; leave standstill 6 days; getting 350mg is placed in and is warmed up in advance 1050 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; heating 25s, is cooled to room temperature and collects.XPS analysis result shows that oxygen level is reduced to 15%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4 nm.
Embodiment 6
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improveing with the carboxamide aqueous solution dipping of 5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:35; leave standstill 5 days; getting 300mg is placed in and is warmed up in advance 1100 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; heating 15s, is cooled to room temperature and collects.XPS analysis result shows that oxygen level is reduced to 13%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4 nm.
Embodiment 7
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improvement will be adopted; be impregnated in the aqueous hydrogen peroxide solution of 8wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:40; leave standstill 5.5 days; getting 350mg is placed in and is warmed up in advance 950 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; heating 50s, is cooled to room temperature and collects.XPS analysis result shows that oxygen level is reduced to 16%(atomic percent by 36% of graphite oxide), the network-like result of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4 nm.
Embodiment 8
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improveing with the carboxamide aqueous solution dipping of 7wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:45; leave standstill 6.5 days; getting 300mg is placed in and is warmed up in advance 1000 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; heating 40s, is cooled to room temperature and collects.XPS analysis result shows that oxygen level is reduced to 15%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4.5 nm.
Embodiment 9
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improvement will be adopted; be impregnated in the aqueous hydrogen peroxide solution of 6.5wt%; the volume ratio of graphite oxide and hydrogen peroxide solution is 1:40; leave standstill 6 days; getting 350mg is placed in and is warmed up in advance 1050 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; heating 30s, is cooled to room temperature and collects.XPS analysis result shows that oxygen level is reduced to 14%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4 nm.
Embodiment 10
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improveing with the carboxamide aqueous solution dipping of 5.5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:35; leave standstill 5 days; getting 300mg is placed in and is warmed up in advance 950 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; heating 45s, is cooled to room temperature and collects.XPS analysis result shows that oxygen level is reduced to 16%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4 nm.
Embodiment 11
The standby graphite oxide (prepared by embodiment 1) of Hummers legal system of improvement will be adopted; be impregnated in the carboxamide aqueous solution of 8.5wt%; the volume ratio of graphite oxide and the carboxamide aqueous solution is 1:45; leave standstill 5.5 days; getting 350mg is placed in and is warmed up in advance 1150 ℃ and have nitrogen purging and the horizontal pipe furnace of protection; regulating carrier gas flux control heat-up time is 15s, is cooled to room temperature and collects.XPS analysis result shows that oxygen level is reduced to 13%(atomic percent by 36% of graphite oxide), the network-like structure of scanning electron microscope (SEM) result show sample, graphene-based lamellar spacing～4 nm.

Claims (2)

1. a preparation method for the network structure graphene oxide of partial reduction, is characterized in that comprising the steps:
(1) the standby graphite oxide of Hummers legal system that adopts improvement is 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 placement 5-7 days, obtain mixture of viscous form and collect;
(2) tube furnace is warmed up to 900-1200 ℃ in advance, and logical protection of inert gas;
(3) mixture of viscous form is placed in to 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;
The Hummers legal system of described employing improvement is for graphite oxide, and concrete steps are as follows:
The sulfuric acid that is 98wt% by concentration is placed under condition of ice bath and stirs, and first adds Graphite Powder 99 and NaNO 3, more slowly add KMnO 4, Graphite Powder 99, NaNO 3and KMnO 4mass ratio be 2:1:6, control fluid temperature and be no more than 20 ℃, reaction was carried out after for some time, beaker is transferred to continuation reaction 0.5h in 35 ℃ of waters bath with thermostatic control, distilled water is slowly added in solution, make temperature rise to 98 ℃, continue to stir 0.5h, by 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 filtrate sulfate radical-free be detected, the loft drier that finally filter cake is placed in to 60 ℃ is dry, grinds for subsequent use.
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.
CN201210487679.2A 2012-11-27 2012-11-27 Preparation method of partially reduced network structure oxidized graphene Active CN102942179B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210487679.2A CN102942179B (en) 2012-11-27 2012-11-27 Preparation method of partially reduced network structure oxidized graphene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210487679.2A CN102942179B (en) 2012-11-27 2012-11-27 Preparation method of partially reduced network structure oxidized graphene

Publications (2)

Publication Number Publication Date
CN102942179A CN102942179A (en) 2013-02-27
CN102942179B true CN102942179B (en) 2014-07-09

Family

ID=47725203

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210487679.2A Active CN102942179B (en) 2012-11-27 2012-11-27 Preparation method of partially reduced network structure oxidized graphene

Country Status (1)

Country Link
CN (1) CN102942179B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103601177B (en) * 2013-11-19 2015-04-29 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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
CN102942179A (en) 2013-02-27

Similar Documents

Publication Publication Date Title
Chen et al. Mxene (Ti3C2Tx)/cellulose nanofiber/porous carbon film as free-standing electrode for ultrathin and flexible supercapacitors
Xuan et al. In-situ growth of hollow NiCo layered double hydroxide on carbon substrate for flexible supercapacitor
Ye et al. Deposition of three-dimensional graphene aerogel on nickel foam as a binder-free supercapacitor electrode
Patil et al. Nanostructured pseudocapacitive materials decorated 3D graphene foam electrodes for next generation supercapacitors
Yang et al. Direct reduction of graphene oxide by Ni foam as a high-capacitance supercapacitor electrode
Lai et al. Preparation of supercapacitor electrodes through selection of graphene surface functionalities
Gong et al. Vertically aligned bismuthene nanosheets on MXene for high-performance capacitive deionization
Dong et al. Synthesis of a MnO2–graphene foam hybrid with controlled MnO2 particle shape and its use as a supercapacitor electrode
Zhang et al. Growth of manganese oxide nanoflowers on vertically-aligned carbon nanotube arrays for high-rate electrochemical capacitive energy storage
CN108117065B (en) Method for preparing graphene by adopting alternate current stripping
CN101654245B (en) Solid-liquid interface self-assembly preparation method for graphene oxide film
Pham et al. Reduced graphene oxide hydrogels deposited in nickel foam for supercapacitor applications: toward high volumetric capacitance
Ye et al. Producing large-area, foldable graphene paper from graphite oxide suspensions by in-situ chemical reduction process
CN105322146B (en) A kind of selenizing molybdenum/carbon nano-fiber/graphene composite material and preparation method thereof
CN102417176A (en) Preparation method of graphene-carbon nanotube compound film based on three-dimensional network appearance
CN103833008A (en) Method for preparing graphene at normal temperature
CN106698430A (en) Titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as transition layer and preparation method thereof
WO2018120601A1 (en) Preparation method for self-supporting thin film of graphene-enhanced three-dimensional porous carbon
CN105217616A (en) Porous graphene load carbon nano-onions three-dimensional composite material preparation method
CN110517900B (en) Preparation method of nitrogen-doped low-temperature carbon nanofiber electrode material for supercapacitor
Wu et al. Chitosan assisted MXene decoration onto polymer fabric for high efficiency solar driven interfacial evaporation of oil contaminated seawater
Chang et al. like N-doped graphene films prepared by hydroxylamine diffusion induced assembly and their ultrahigh-rate capacitive properties
Gu et al. Producing “symbiotic” reduced graphene oxide/Mn3O4 nanocomposites directly from converting graphite for high-performance supercapacitor electrodes
CN107697905A (en) A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge
CN110148524A (en) A kind of nested type CeO2/ GO/AAO nano-array electrode material for super capacitor and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant