CN103332688B - A kind of method by metal salts of organic acids synthesizing graphite alkene - Google Patents
A kind of method by metal salts of organic acids synthesizing graphite alkene Download PDFInfo
- Publication number
- CN103332688B CN103332688B CN201310296522.6A CN201310296522A CN103332688B CN 103332688 B CN103332688 B CN 103332688B CN 201310296522 A CN201310296522 A CN 201310296522A CN 103332688 B CN103332688 B CN 103332688B
- Authority
- CN
- China
- Prior art keywords
- metal salts
- organic acids
- graphene
- product
- tube furnace
- 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
Links
Abstract
A kind of method by metal salts of organic acids synthesizing graphite alkene is that tube furnace is warmed up to 700-1300 DEG C in advance, and logical inert atmosphere protection; Metal salts of organic acids is placed in the tube furnace with nitrogen protection, heating 0.5-120min, to be cooled to room temperature, obtain solid product.Above-mentioned solid product washing, filtration, drying are obtained graphene product.The present invention has without in template situation, and simple to operate, cost is low, has advantage prepared by mass-producing simultaneously.
Description
Technical field
The invention belongs to a kind of method of synthesizing graphite alkene, be specifically related to a kind of method of metal salts of organic acids pyrolysis synthesizing graphite alkene.
Background technology
Graphene be discovered in recent years by individual layer sp
2the two-dimentional carbonaceous crystal that hydridization carbon is formed, have excellent electroconductibility, mechanical property, superelevation specific surface area and to guest molecule/ion good by and transporting etc., at numerous areas, there is potential using value.Along with going deep into of research, the demand that magnanimity obtains Graphene is day by day strong.Therefore, how to realize mass-producing preparation become restriction Graphene obtain one of problem demanding prompt solution of further investigation and application.
At present, the method preparing Graphene developed can be divided into two kinds of approach: " top-down " and " bottom-up " approach.Graphite oxide stripping method wherein in " top-down " approach is considered to the current effective ways that can obtain Graphene in a large number, but due to the use havoc conjugated structure of Graphene of strong oxidizer, cause its intrinsic electrical property loss of energy, need to carry out follow-up reduction treatment to repair its electric property.[atom economy synthesizing graphite alkene/trimanganese tetroxide mixture is used for electric chemical super capacitor research, " nanoscale ", the 5th volume, the 2999th page of (Highly Atom-Economic ~ Synthesis of Graphene/Mn in 2013
3o
4hybrid Composites for Electrochemical Supercapacitors. Nanoscale, 2013, Vol.5,2999)].And preparation process is loaded down with trivial details, consume a large amount of energy, the use of a large amount of strong oxidizer simultaneously causes very large harm to environment.In " bottom-up " approach, [chemical Vapor deposition process prepares the Graphene network structure that three-dimension flexible is communicated with the inside of conduction to chemical Vapor deposition process (CVD), " nature material ", 2011, 10th volume, 424th page of (Three-dimensional Flexible and Conductive Interconnected Graphene Networks Grown by Chemical Vapour Deposition, Nat. Mater., 2011, Vol. 10, 424) high-quality minority layer even single-layer graphene can] be obtained, but requirement for experiment condition is harsh, and need in aftertreatment, use strong acid etc. to remove template, advantage is not had in magnanimity synthesis.Therefore, for breaking through the bottleneck of Graphene magnanimity synthesis, new building-up process must be researched and developed, when not using template, making the directed autonomous growth of carbon atom two dimension, and adopting intrinsic technological method to suppress the accumulation of Graphene.Stride etc. are with ethanol and sodium for raw material is through solution heat pre-treatment, and then incomplete combustion in air atmosphere, obtains Graphene through supersound process.[based on solvent thermal and ultrasonic procedure synthesis gram quantity level Graphene, " natural nanotechnology ", 2009, Volume Four, the 30th page, (Gram-Scale Production of Graphene Based on Solvothermal Synthesis and Sonication, Nat. Nanotechnol, 2009, Vol. 4,30)].Sodium and excess ethyl alcohol are then obtained by reacting sodium ethylate/ethanolic soln by Christopher etc., then obtain Graphene 900 DEG C of process.[utilize the easy synthesis minority layer graphene of approach mass-producing from bottom to top and graphene film, " materials chemistry magazine ", 2011, 21st volume, 3378th page, (Simple and Scalable Route for the ' Bottom-Up ' Synthesis of Few-Layer Graphene Platelets and Thin Films, J. Mater. Chem, 2011, Vol.21, 3378)] although. these methods can obtain Graphene when not using template, but all need that pre-treatment is carried out to reactant and obtain intermediate, add operating unit and preparation cost etc., advantage is not had in prepared by mass-producing.
Summary of the invention
The object of this invention is to provide a kind of without in template situation, simple to operate, cost is low, have prepared by mass-producing simultaneously by the method for metal salts of organic acids synthesizing graphite alkene.
Synthetic method of the present invention for raw material, does not use template with the organic acid salt containing metal, without the need to carrying out pre-treatment to raw material, and one-step synthesis Graphene.Gained Graphene is three-dimensional net structure, while effectively suppressing Graphene to be reunited, maintains the performance of its excellence.In prepared by mass-producing, there is clear superiority simultaneously.
Preparation method of the present invention is as follows:
(1) tube furnace is warmed up to 700-1300 DEG C in advance, and logical inert atmosphere protection;
(2) metal salts of organic acids is placed in the tube furnace with nitrogen protection, heating 0.5-120min, to be cooled to room temperature, obtain solid product.
(3) above-mentioned solid product washing, filtration, drying are obtained graphene product.
Described metal salts of organic acids comprises sodium acetate, Sodium Propionate, Sodium propanecarboxylate and Soduxin and potassium acetate, magnesium acetate, zinc acetate or venus crystals etc.
Described inert atmosphere is argon gas or nitrogen etc.
Described tube furnace is horizontal pipe furnace.
Tool of the present invention has the following advantages:
(1) raw material such as metal salts of organic acids used is cheap and easy to get, without the need to pre-treatment, is conducive to reducing costs.
(2) synthesis technique flow process is simple, and easy and simple to handle, influence factor is few, is convenient to control, favorable reproducibility.
(3) Graphene synthesized can keep its pattern and not reunite.
(4) do not need additionally to introduce metal as substrate or template.
(5) a large amount of synthesizing graphite alkene of mass-producing is convenient to.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of the Graphene of the embodiment of the present invention 3 metal salts of organic acids pyrolysis synthesis.
Fig. 2 is Raman (Raman) spectrogram of the Graphene of the embodiment of the present invention 3 metal salts of organic acids pyrolysis synthesis.
Fig. 3 is scanning electron microscope (SEM) photo of the Graphene of the embodiment of the present invention 8 metal salts of organic acids pyrolysis synthesis.
Fig. 4 is Raman (Raman) spectrogram of the Graphene of the embodiment of the present invention 8 metal salts of organic acids pyrolysis synthesis.
Fig. 5 is scanning electron microscope (SEM) photo of the Graphene of the embodiment of the present invention 11 metal salts of organic acids pyrolysis synthesis.
Fig. 6 is Raman (Raman) spectrogram of the Graphene of the embodiment of the present invention 11 metal salts of organic acids pyrolysis synthesis.
Embodiment
Embodiment 1
2g sodium acetate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of nitrogen atmosphere protection.After tube furnace is warmed up to 700 DEG C, porcelain boat is pushed flat-temperature zone, reaction 120min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), scanning electron microscope result show sample is laminated structure, graphene-based lamellar spacing ~ 4 nm.
Embodiment 2
2g sodium acetate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of nitrogen atmosphere protection.After tube furnace is warmed up to 1300 DEG C, porcelain boat is pushed flat-temperature zone, reaction 0.5min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7%(atomic percent), scanning electron microscope result show sample is network structure, graphene-based lamellar spacing ~ 2.2 nm
Embodiment 3
1.5g potassium acetate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 1000 DEG C, porcelain boat is pushed flat-temperature zone, reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7.0%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene-based lamellar spacing ~ 4.5 nm.
Embodiment 4
2g Sodium propanecarboxylate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 800 DEG C, porcelain boat is pushed flat-temperature zone, reaction 30min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 10%(atomic percent), scanning electron microscope result show sample is laminar structured, graphene-based lamellar spacing ~ 5 nm.
Embodiment 5
2g Sodium Propionate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 800 DEG C, porcelain boat is pushed flat-temperature zone, reaction 100min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 9.5%(atomic percent), scanning electron microscope result show sample is laminar structured, graphene-based lamellar spacing ~ 4.5 nm.
Embodiment 6
2g venus crystals solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 1150 DEG C, porcelain boat is pushed flat-temperature zone, reaction 5min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 6.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene-based lamellar spacing ~ 4.0 nm.
Embodiment 7
2g Soduxin solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 700 DEG C, porcelain boat is pushed flat-temperature zone, reaction 50min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), scanning electron microscope result show sample is laminar structured, graphene-based lamellar spacing ~ 3.5 nm.
Embodiment 8
2g zinc acetate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 900 DEG C, porcelain boat is pushed flat-temperature zone, reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.8%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene-based lamellar spacing ~ 5.5 nm.
Embodiment 9
2g venus crystals solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 1100 DEG C, porcelain boat is pushed flat-temperature zone, reaction 2min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene-based lamellar spacing ~ 5.5 nm.
Embodiment 10
2g Sodium Propionate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 1200 DEG C, porcelain boat is pushed flat-temperature zone, reaction 1.5min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 6.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene-based lamellar spacing ~ 3.0 nm.
Embodiment 11
2g Soduxin solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 1000 DEG C, porcelain boat is pushed flat-temperature zone, reaction 2.5min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 7.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene-based lamellar spacing ~ 4.8nm.
Embodiment 12
2g magnesium acetate solid is positioned in porcelain boat, is placed on the normal temperature district of the horizontal pipe furnace of argon atmospher protection.After tube furnace is warmed up to 1050 DEG C, porcelain boat is pushed flat-temperature zone, reaction 1min.After product cooling, product is taken out, with deionized water wash, filter, dry, collect product.XPS analysis result shows that oxygen level is 8.5%(atomic percent), the network-like structure of scanning electron microscope result show sample, graphene-based lamellar spacing ~ 3.5 nm.
Claims (3)
1., by a method for metal salts of organic acids synthesizing graphite alkene, it is characterized in that comprising the steps:
Tube furnace is warmed up to 700-1300 DEG C in advance, and logical inert atmosphere protection;
(2) metal salts of organic acids is placed in the tube furnace with nitrogen protection, heating 0.5-120min, to be cooled to room temperature, obtain solid product;
(3) above-mentioned solid product washing, filtration, drying are obtained graphene product;
Described metal salts of organic acids is sodium acetate, Sodium Propionate, Sodium propanecarboxylate, Soduxin, potassium acetate, magnesium acetate, zinc acetate or venus crystals.
2. a kind of method by metal salts of organic acids synthesizing graphite alkene as claimed in claim 1, is characterized in that described inert atmosphere is argon gas or nitrogen.
3. a kind of method by metal salts of organic acids synthesizing graphite alkene as claimed in claim 1, is characterized in that described tube furnace is horizontal pipe furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310296522.6A CN103332688B (en) | 2013-07-16 | 2013-07-16 | A kind of method by metal salts of organic acids synthesizing graphite alkene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310296522.6A CN103332688B (en) | 2013-07-16 | 2013-07-16 | A kind of method by metal salts of organic acids synthesizing graphite alkene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103332688A CN103332688A (en) | 2013-10-02 |
| CN103332688B true CN103332688B (en) | 2015-08-19 |
Family
ID=49240917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310296522.6A Active CN103332688B (en) | 2013-07-16 | 2013-07-16 | A kind of method by metal salts of organic acids synthesizing graphite alkene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103332688B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601178B (en) * | 2013-11-19 | 2015-06-17 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene from solid organic acid |
| 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 |
| CN104108707B (en) * | 2014-07-25 | 2016-03-02 | 深圳新宙邦科技股份有限公司 | A kind of sulfur doping Graphene and preparation method thereof |
| CN104108709A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Porous graphene and preparation method thereof |
| CN104108710B (en) * | 2014-07-25 | 2016-01-20 | 深圳新宙邦科技股份有限公司 | A kind of N doping porous graphene and preparation method thereof |
| CN104150475B (en) * | 2014-08-04 | 2016-06-08 | 深圳新宙邦科技股份有限公司 | A kind of binary doped Graphene and preparation method thereof |
| CN104445160B (en) * | 2014-11-07 | 2017-04-12 | 孙旭阳 | Method for preparing graphene through molten inorganic salt reaction bed |
| CN105070892B (en) * | 2015-09-22 | 2018-03-06 | 中国科学院化学研究所 | A kind of preparation method and application of selenium carbon complex |
| US10734638B2 (en) | 2015-09-22 | 2020-08-04 | Ii-Vi Delaware, Inc. | Immobilized selenium, a method of making, and uses of immobilized selenium in a rechargeable battery |
| US11784303B2 (en) | 2015-09-22 | 2023-10-10 | Ii-Vi Delaware, Inc. | Immobilized chalcogen and use thereof in a rechargeable battery |
| US11588149B2 (en) | 2015-09-22 | 2023-02-21 | Ii-Vi Delaware, Inc. | Immobilized selenium in a porous carbon with the presence of oxygen, a method of making, and uses of immobilized selenium in a rechargeable battery |
| CN105776195B (en) * | 2016-03-14 | 2018-05-04 | 西南大学 | Preparation method and product of a kind of ultracapacitor rich in micro-nano hole superstructure porous graphene |
| US10968105B2 (en) * | 2016-03-28 | 2021-04-06 | Board Of Regents, The University Of Texas System | Low-temperature pyrolysis of organic acid salts providing graphene rich carbons |
| US11870059B2 (en) | 2017-02-16 | 2024-01-09 | Consejo Superior De Investigaciones Cientificas (Csic) | Immobilized selenium in a porous carbon with the presence of oxygen, a method of making, and uses of immobilized selenium in a rechargeable battery |
| CN110422840A (en) * | 2019-09-04 | 2019-11-08 | 河北医科大学 | A kind of method of solid organic acid synthesis azepine graphene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408107A (en) * | 2010-09-26 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene |
| CN102498061A (en) * | 2009-07-27 | 2012-06-13 | 达勒姆大学 | Production of graphene from metal alkoxide |
| FR2983847A1 (en) * | 2011-12-12 | 2013-06-14 | Commissariat Energie Atomique | PROCESS FOR PREPARING GRAPHENE |
-
2013
- 2013-07-16 CN CN201310296522.6A patent/CN103332688B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102498061A (en) * | 2009-07-27 | 2012-06-13 | 达勒姆大学 | Production of graphene from metal alkoxide |
| CN102408107A (en) * | 2010-09-26 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Method for preparing high-quality graphene |
| FR2983847A1 (en) * | 2011-12-12 | 2013-06-14 | Commissariat Energie Atomique | PROCESS FOR PREPARING GRAPHENE |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103332688A (en) | 2013-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103332688B (en) | A kind of method by metal salts of organic acids synthesizing graphite alkene | |
| Vicarelli et al. | Controlling defects in graphene for optimizing the electrical properties of graphene nanodevices | |
| Kairi et al. | Recent trends in graphene materials synthesized by CVD with various carbon precursors | |
| Li et al. | Controllable synthesis of two‐dimensional molybdenum disulfide (MoS2) for energy‐storage applications | |
| CN108117065B (en) | Method for preparing graphene by adopting alternate current stripping | |
| Li et al. | Selective preparation of 1T-and 2H-phase MoS2 nanosheets with abundant monolayer structure and their applications in energy storage devices | |
| CN102092710B (en) | Regular graphene and preparation method thereof | |
| Sirisaksoontorn et al. | Preparation and characterization of a tetrabutylammonium graphite intercalation compound | |
| Chand et al. | Borophene and boron‐based nanosheets: recent advances in synthesis strategies and applications in the field of environment and energy | |
| Gao et al. | Freestanding atomically-thin cuprous oxide sheets for improved visible-light photoelectrochemical water splitting | |
| US20140166496A1 (en) | Method for producing shaped graphene sheets | |
| CN106311282A (en) | Preparing method of porous monocrystal IT MoS2 nanosheet and application thereof | |
| CN104099577B (en) | A kind of preparation method of Graphene | |
| CN103436938B (en) | A kind of preparation method of nano-graphene conductive film | |
| CN102320597B (en) | Preparation method of graphene | |
| Liu et al. | Graphene grown on anatase–TiO2 nanosheets: enhanced photocatalytic activity on basis of a well-controlled interface | |
| Wang et al. | Large-scale synthesis of few-layer graphene from magnesium and different carbon sources and its application in dye-sensitized solar cells | |
| CN102923686A (en) | Graphene/carbon nanotube composite material preparation method | |
| CN106257609A (en) | A kind of method preparing monolayer 1T phase molybdenum bisuphide/graphene composite material | |
| CN103693693A (en) | Preparation method for synthesizing molybdenum sulfide nanospheres by microwave-assisted liquid phase deposition | |
| Zhai et al. | Metal-free synthesis of boron-doped graphene glass by hot-filament chemical vapor deposition for wave energy harvesting | |
| CN102923695A (en) | Graphene preparation method | |
| CN106335925B (en) | A kind of method for preparing individual layer 2H phases molybdenum disulfide/graphene composite material | |
| Xie et al. | In situ formation of indium catalysts to synthesize crystalline silicon nanowires on flexible stainless steel substrates by PECVD | |
| CN106477560A (en) | A kind of preparation method of Graphene |
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 |