CN102206388B - Preparation method of graphene composite by industrialized electrolytic stripping - Google Patents
Preparation method of graphene composite by industrialized electrolytic stripping Download PDFInfo
- Publication number
- CN102206388B CN102206388B CN2011101216870A CN201110121687A CN102206388B CN 102206388 B CN102206388 B CN 102206388B CN 2011101216870 A CN2011101216870 A CN 2011101216870A CN 201110121687 A CN201110121687 A CN 201110121687A CN 102206388 B CN102206388 B CN 102206388B
- Authority
- CN
- China
- Prior art keywords
- graphene
- graphene composite
- electrolytic stripping
- electrolytic
- preparation
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene composite by industrialized electrolytic stripping, belonging to the field of electrochemistry. In the method, an electrolytic stripping technology is adopted, a high-purity graphite rod is used as an electrolytic anode/cathode, polymers or biomolecules are used as electrolyte, and meanwhile, the high-purity graphite rod is electrolytically stripped for 10minutes to 24hours under the action of an electrolytic assistant by rapidly stirring at constant direct current voltage of below 4-16V to obtain a high-quality graphene composite which can be used for modifying electrodes to be used as a biosensor and the like. The method has the advantages of only need of one direct current constant potential rectifier, small investment, simplicity, easily controlled reaction process, low cost and no pollution. The prepared graphene composite has high quality and favorable popularization and application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of graphene composite material, relate in particular to a kind of novel method of utilizing electrolytic stripping technique to high-efficiency, the low defective graphene composite material of mass preparation, belong to electrochemical field.
Background technology
Graphene is a kind of nanometer novel material by the tightly packed one-tenth individual layer of carbon atom bi-dimensional cellular shape crystalline network.Graphene becomes the nano material new lover who attracts tremendous attention in recent years in the world as a kind of two-dimentional carbon material truly with its unique physics-chem characteristic (as high surface area, high thermal conductivity, high conductivity, high mechanical strength and easy functionalization etc.).At present, Graphene is all used to some extent at numerous areas such as electronics, energy storage and conversion, biotechnologys.
Most of grapheme materials all are to be that raw material makes with graphite, and these class methods not only raw material are very cheap, and can obtain to have the grapheme material of big two dimensional structure.Mainly contain about in this respect Graphene synthetic method at present: micromechanics is peeled off method, SiC pyrolysis method, chemical vapour deposition (Chemical Vapor Deposition, CVD) method, oxidation-dispersion-reduction method etc.In aforesaid method, it is a kind of simple and direct method that micromechanics is peeled off method, and this method is utilized mechanical force from graphite crystal sur-face peeling Graphene lamella and transferred on the carrier surface such as silicon oxide.Novoselov etc. utilize this method to prepare single-layer graphene the earliest, and have verified that it independently exists, but this method gained grapheme material is big or small wayward, can't produce the graphite flake material of size foot supply usefulness reliably.The SiC pyrolysis method is to be that raw material removes Si by pyrolysis and prepares grapheme material with SiC, this method can obtain individual layer and double-layer graphite alkene, but adopts this method to be difficult to realize the preparation of big area grapheme material, and it is inhomogeneous to have the product film forming, the preparation condition harshness, many restrictions such as production cost height.Chemical Vapor deposition process is that reactive material issues biochemical reaction in quite high temperature, gaseous state condition, and the solid matter of generation is deposited on the solid matrix surface of heating, and then makes the Technology of solid material.Adopt this technology effectively also controllably to prepare into big area, high-quality graphene platelet material by the selection of substrate, the temperature of growth, the growth parameter(s)s such as exposed amount of precursor, its preparation difficulty is big, cost is high, is not suitable for large-scale application demand.Oxidation-dispersion-reduction method is the synthetic method that is most widely used at present.It at first utilizes strong protonic acid to handle graphite, forms compound between graphite layers, and the Graphene precursor that graphite oxidation is obtained disperseing in the solution with strong oxidizer obtains the single or multiple lift grapheme material with the reductive agent reduction at last again.Common method for oxidation has Brodie method, Hummer method and Staudenmaier method at present, adopts hydrazine class compound redox graphene precursor preparation Graphene most investigator aspect the use of reductive agent, because hydrazine is utmost point toxic agent, is unfavorable for using.In addition, still contain the part oxygen-containing functional group and have the certain structure defective by the Graphene that obtains after the graphite oxide reduction, thereby greatly reduce the specific conductivity of grapheme material, limit its further application.
As can be seen, have following deficiency in the existing graphene preparation method: the preparation difficulty is big, cost is high or use the high toxicity chemical reagent, oxygen-containing functional group is many or have technical problem such as more textural defect.
Summary of the invention
In order to overcome the prior art deficiency, but the object of the invention is to propose the novel method that a kind of low cost, green, efficient, oxygen-free functional group and large-scale industrialization prepare the high quality graphene composite material.
For realizing the object of the invention, the present invention is based on the electrolytic stripping technology, realize efficient, the extensive electrolytic stripping preparation of Graphene by following steps: with two high purity graphite rods (99.999%) respectively as negative electrode and the anode of electrolysis electrode, be ionogen with polymkeric substance or biomolecules, simultaneously, under electrolysis auxiliary agent, the agitation condition, under constant 4 ~ 16V volts DS, electrolytic stripping high purity graphite rod 10min ~ 24h can obtain the high quality graphene composite material.
But described negative electrode and anode be mutual alternative after electrolysis for some time, to guarantee effective utilization of electrode materials, also can effectively increase electrolytic efficiency simultaneously.
Described polymkeric substance or biomolecules ionogen are polymer ions liquid (as 1-hydroxyethyl-3-Methylimidazole polyethylene benzene sulfonic acid sodium salt etc.), the PVP(Polyvinylpyrolidone (PVP)), beta-cyclodextrin, chitosan, DNA, RNA, polypeptide and protein etc. are wherein a kind of.
Add the electrolysis auxiliary agent in the described electrolyte solution, can be acid, alkali, salt and tensio-active agent such as sulfuric acid, Glacial acetic acid, sodium hydroxide, potassium hydroxide, soluble sulphate, soluble phosphate, muriate, nitrate, SDS(sodium lauryl sulphate), the SDBS(Sodium dodecylbenzene sulfonate) or the CTAB(cetyl trimethylammonium bromide) etc.
The pH value of described electrolyte solution is 0 ~ 12.
Described electrolysis temperature scope is 10 ~ 60 ℃.
In electrolytic process, the present invention changes kind, performance and the productive rate of Graphene and matrix material thereof by the proportioning situation of regulation and control external electric field and electrolytic solution.
The present invention utilizes on the high purity graphite electrode single or multiple lift Graphene under the electric field activation and electrolytical π-π piles up and peels off graphite electrode surface under the effect and make the high quality graphene composite material.This method only needs a direct current potentiostat, does not need other specific equipment, and its preparation method is simple, reaction process is easy to control, and cost is low, pollution-free, prepared graphene quality height, the preparation method is convenient to industrial application, can prepare the rare matrix material of high-quality graphite in a large number.Rare and the matrix material of graphite can be widely used in fields such as biosensor, electrocatalysis, bioanalysis.
Description of drawings
Fig. 1 is the Graphene/DNA (a) and afm scan figure and the altitude profile figure (rap pattern) of Graphene/chitosan (b) on sheet mica of the preparation of electrolytic stripping method;
Fig. 2 is the infrared spectrogram of Graphene/DNA (a) with the Graphene/chitosan (b) of the preparation of electrolytic stripping method.1 is the Graphene infrared spectrogram among Fig. 2-a, and 2 is Graphene/DNA infrared spectrogram; 1 is the Graphene infrared spectrogram among Fig. 2-b, and 2 is Graphene/chitosan infrared spectrogram;
Fig. 3 is the cyclic voltammogram of 5mg/mL oxyphorase on Graphene/DNA mixture modified electrode, sweeps speed and is 50mV/s; Wherein 1 is the cyclic voltammetry curve of Graphene/DNA/ oxyphorase, and 2 is the cyclic voltammetry curve of oxyphorase, and 3 is the cyclic voltammetry curve of Graphene/DNA;
Fig. 4 is naked glass-carbon electrode, Nafion modified glassy carbon electrode, Graphene/chitosan complexes/Nafion modified electrode and the Graphene/Nafion modified electrode cyclic voltammogram in 1 mmol/L, six ammino ruthenium solutions, sweeps speed and is 100mV/s; Wherein 1 is the circulation volt curve of Graphene/chitosan/Nafion/ glass carbon, and 2 is the circulation volt curve of Graphene/Nafion/ glass carbon, and 3 circulations that follow for glass carbon lie prostrate curve, and 4 is the circulation volt curve of Nafion/ glass carbon.
Embodiment
For the present invention is illustrated better, as follows for embodiment:
With 10mg/mL herring sperm dna solution in 90
oCultivate 1h under the C water-bath so that the DNA uncoiling becomes single stranded DNA.
2. will add the KNO of 0.1M at the dna solution of separating supination
3Make Graphene electrolytic solution.
3. respectively two high purity graphite rods (99.999%) are connected on the direct current potentiostat as negative electrode and anode, under quick agitation condition (450r/min), in the above-mentioned electrolytic solution of 100mL, 20 ℃ of electrolysis temperatures, 4V DC potential electrolytic stripping high purity graphite 8h with constant namely obtains finely dispersed black Graphene/DNA matrix material solution.
4. with solution centrifugal 30min under the 13000r/min rotating speed of Graphene/DNA matrix material, remove the deionized water wash that adds equivalent after the supernatant liquor, afterwards repeated centrifugation 30min and remove supernatant liquor under the 13000r/min rotating speed.
5. after the washing process in the step 4 being repeated 3 times, the centrifugal product of gained black is weighed after lyophilize, finally obtain Graphene/DNA matrix material 15g.
Fig. 1 a is afm scan figure and the altitude profile figure (rapping pattern) of the Graphene/DNA matrix material of electrolytic stripping method preparation.As known in the figure, the thickness of gained Graphene/DNA matrix material is about 1nm, shows that Graphene in the matrix material is based on individual layer.As shown in Figure 3, utilize Graphene/DNA matrix material fixedly behind the oxyphorase, the electrochemical signals of oxyphorase shows that than obviously strengthening this matrix material has good katalysis to the electrochemical redox of oxyphorase on bare electrode, be a kind of good biological sensing material.
1. 1g chitosan and 1g SDBS are dissolved in the Glacial acetic acid of 100mL 5%, are made into 1% chitosan electrolytic solution.
2. respectively two high purity graphite rods (99.999%) are connected on the direct current potentiostat as negative electrode and anode, under quick agitation condition (450r/min), in the above-mentioned electrolytic solution of 100mL, 40 ℃ of electrolysis temperatures, 10V DC potential electrolytic stripping high purity graphite 6h with constant namely obtains finely dispersed black Graphene/chitosan matrix material solution.
4. with solution centrifugal 30min under the 13000r/min rotating speed of Graphene/polymer ions liquid composite, remove the deionized water wash that adds equivalent after the supernatant liquor, afterwards repeated centrifugation 30min and remove supernatant liquor under the 13000r/min rotating speed.
5. after the washing process in the step 4 being repeated 3 times, the centrifugal product of gained black is weighed after lyophilize, finally obtain Graphene/chitosan matrix material 8g.
Fig. 1 b is afm scan figure and the altitude profile figure (rapping pattern) of the Graphene/chitosan matrix material of electrolytic stripping method preparation.As known in the figure, the thickness of gained Graphene/chitosan matrix material is about 1～3nm, and mainly by due to the bigger molecular structure of chitosan itself, the graphene-based end of this moment is still based on individual layer for the thickness of increase.As shown in Figure 4, Graphene/chitosan matrix material can effectively promote six ammino rutheniums and interelectrode transfer transport, has played significant signal enhancement, utilizes this matrix material will be expected to develop novel high sensitive electrochemical senser element.
1. 10g 1-hydroxyethyl-3-Methylimidazole polyethylene benzene sulfonic acid sodium salt is dissolved in the 100mL deionized water, is made into 10% polymer ions liquid ions liquid electrolyte.
2. respectively two high purity graphite rods (99.999%) are connected on the direct current potentiostat as negative electrode and anode, under quick agitation condition (450r/min), in above-mentioned 100mL electrolytic solution, 60 ℃ of electrolysis temperatures, 16V DC potential electrolytic stripping high purity graphite 12h with constant namely obtains finely dispersed black Graphene/polymer ions liquid composite solution.
4. with solution centrifugal 30min under the 13000r/min rotating speed of Graphene/polymer ions liquid composite, remove the deionized water wash that adds equivalent after the supernatant liquor, afterwards repeated centrifugation 30min and remove supernatant liquor under the 13000r/min rotating speed.
5. after the washing process in the step 4 being repeated 3 times, the centrifugal product of gained black is weighed after lyophilize, finally obtain Graphene/polymer ions liquid composite 22g.
Claims (3)
1. the industrialization electrolytic stripping preparation method of a graphene composite material, it is characterized in that, realize by following steps: with two 99.999% high purity graphite rods respectively as negative electrode and the anode of electrolysis electrode, be ionogen with the biomolecules, simultaneously, in the pH value of adding the electrolysis auxiliary agent is 0 ~ 12 electrolyte solution, under the agitation condition, under 10 ~ 60 ℃ the electrolysis temperature, under constant 4 ~ 16V volts DS, electrolytic stripping high purity graphite rod can obtain the high quality graphene composite material; Described biomolecules ionogen is DNA; Described electrolysis auxiliary agent is sulfuric acid, Glacial acetic acid, sodium hydroxide, potassium hydroxide, soluble sulphate, soluble phosphate, muriate, nitrate, Sodium dodecylbenzene sulfonate or cetyl trimethylammonium bromide.
2. the industrialization electrolytic stripping preparation method of graphene composite material according to claim 1 is characterized in that, electrolytic stripping high purity graphite rod 10min ~ 24h.
3. the industrialization electrolytic stripping preparation method of graphene composite material according to claim 1 and 2 is characterized in that the soluble sulphate preferably sodium dodecyl sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101216870A CN102206388B (en) | 2011-05-12 | 2011-05-12 | Preparation method of graphene composite by industrialized electrolytic stripping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101216870A CN102206388B (en) | 2011-05-12 | 2011-05-12 | Preparation method of graphene composite by industrialized electrolytic stripping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102206388A CN102206388A (en) | 2011-10-05 |
| CN102206388B true CN102206388B (en) | 2013-09-11 |
Family
ID=44695471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101216870A Expired - Fee Related CN102206388B (en) | 2011-05-12 | 2011-05-12 | Preparation method of graphene composite by industrialized electrolytic stripping |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102206388B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515149A (en) * | 2011-11-25 | 2012-06-27 | 黑龙江大学 | Preparation method for high-stability graphene dispersing solution |
| CN102583356B (en) * | 2012-03-20 | 2015-01-21 | 无锡格菲电子薄膜科技有限公司 | Method for transferring and washing graphene film |
| CN102923697B (en) * | 2012-11-19 | 2014-10-01 | 中南大学 | Method for preparing graphene energy storing material through electrochemical cathodic disbonding |
| CN102963887B (en) * | 2012-11-30 | 2015-01-14 | 同济大学 | Electrochemistry stripping and reducing integrated graphene preparation method |
| CN103964418B (en) * | 2013-01-31 | 2016-04-06 | 海洋王照明科技股份有限公司 | Graphene and preparation method thereof |
| CN103112848B (en) * | 2013-03-08 | 2015-01-07 | 厦门大学 | Method for preparing graphene |
| EP3019445A1 (en) * | 2013-07-12 | 2016-05-18 | Danmarks Tekniske Universitet | Electrochemical method for transferring graphene |
| CN104130538B (en) * | 2014-07-14 | 2016-06-15 | 郑州大学 | A kind of method preparing graphene solution based on supercritical carbon dioxide inducing solution phase in version technology |
| CN104674294B (en) * | 2014-12-18 | 2018-02-06 | 南京航空航天大学 | The preparation method and application of graphene-layer/polyaniline conductive compound |
| CN107628609B (en) * | 2016-07-18 | 2020-01-14 | 鸡西市昌隆石墨制品有限公司 | Method for manufacturing graphene with controllable layer number and graphene |
| CN106756165B (en) * | 2016-12-01 | 2018-12-14 | 中国科学院金属研究所 | A kind of preparation method of high structural integrity high dispersive graphene/metallic composite |
| CN107057799B (en) * | 2017-06-08 | 2020-01-31 | 中国科学院过程工程研究所 | Functionalized graphene powder, lubricating oil containing functionalized graphene powder, and preparation method and application of functionalized graphene powder |
| CN107033702B (en) * | 2017-06-09 | 2019-09-13 | 安徽工业大学 | A kind of aqueous metal surface inorganic agent compound based on graphene |
| CN107601488A (en) * | 2017-09-08 | 2018-01-19 | 深圳大学 | A kind of preparation method of graphene oxide |
| CN108455585A (en) * | 2018-04-17 | 2018-08-28 | 刘少华 | A kind of method that electric field-assisted prepares graphene |
| CN108862254A (en) * | 2018-07-12 | 2018-11-23 | 西安交通大学 | A kind of method that the bipolar electrode removing of electrochemistry yin-yang prepares graphene |
| CN109256546A (en) * | 2018-09-03 | 2019-01-22 | 山西煤炭进出口集团科学技术研究院有限公司 | A kind of molybdenum disulfide/graphene composite material and its preparation method and application |
| CN109575370A (en) * | 2019-01-15 | 2019-04-05 | 西北师范大学 | A kind of preparation method of amination β-CD/PTCA functionalization graphene composite material |
| CN111875850B (en) * | 2019-08-27 | 2021-08-24 | 江南大学 | Preparation method and application of water dispersible graphene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214954A (en) * | 2008-01-22 | 2008-07-09 | 东北师范大学 | Method for preparing conductive single-layer graphite sheet modified by ionic liquid cation group |
| CN101509139A (en) * | 2009-04-03 | 2009-08-19 | 西北有色金属研究院 | Method for producing titanium iron alloy with titanic iron ore |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7195701B2 (en) * | 2003-09-30 | 2007-03-27 | The Boeing Company | Electrochemical depositions applied to nanotechnology composites |
-
2011
- 2011-05-12 CN CN2011101216870A patent/CN102206388B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214954A (en) * | 2008-01-22 | 2008-07-09 | 东北师范大学 | Method for preparing conductive single-layer graphite sheet modified by ionic liquid cation group |
| CN101509139A (en) * | 2009-04-03 | 2009-08-19 | 西北有色金属研究院 | Method for producing titanium iron alloy with titanic iron ore |
Non-Patent Citations (1)
| Title |
|---|
| Guoxiu Wang etc.Highly efficient and large-scale synthesis of grapheme by electrolytic exfoliation.《Carbon》.2009,第47卷(第14期),第3243页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102206388A (en) | 2011-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102206388B (en) | Preparation method of graphene composite by industrialized electrolytic stripping | |
| CN106207172B (en) | A kind of preparation method of cobalt sulfide/graphene nanocomposite material, negative electrode of lithium ion battery, lithium ion battery | |
| CN102719877B (en) | Low-cost lossless transfer method of graphene | |
| CN105552399B (en) | A kind of graphene adulterates conducting polymer modified dual polar plates of proton exchange membrane fuel cell and preparation method thereof | |
| CN103903861B (en) | Counter electrode made of metal sulfide and graphene composite materials and preparation method and application of counter electrode | |
| CN106915829B (en) | Carbon fiber electrode, preparation method thereof and bipolar chamber bioelectrochemical device | |
| CN102447064A (en) | Polymer solar cell and preparation method thereof | |
| CN104752070B (en) | A kind of zinc oxide@manganese dioxide@polypyrrole ternary core-shell heterogeneous structural nanos rod array material, preparation method and applications | |
| CN106629676A (en) | Alkaline-electrolyte-based graphene preparation method | |
| CN108831757B (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN110451615B (en) | Preparation method of metal-organic framework carbon nanotube hybrid desalination electrode | |
| CN107235486A (en) | The preparation method of water-soluble graphene | |
| TW201010940A (en) | Mathod for making carbon nanotube/conductive polymer composite | |
| CN103966644A (en) | Preparation method for graphene/macromolecule emulsion composite film material | |
| CN109003826A (en) | N and S codope graphene-graphene nanobelt aeroge preparation method | |
| CN108394895A (en) | A kind of sheet diameter stannic oxide/graphene nano preparation of sections method | |
| CN107641824A (en) | Graphene conductive polymer composites and preparation method thereof | |
| CN106783206A (en) | The preparation method of the graphene oxide polyaniline composite electrode material of three-dimensional structure | |
| CN104091931A (en) | Multi-edge MoS2 nano piece/graphene composite nanomaterial and preparation method thereof | |
| CN111217361B (en) | Method for preparing graphene nanosheet through electrochemical cathode stripping | |
| CN105118686B (en) | The preparation method of graphene/polyaniline/manganese dioxide ternary composite electrode material | |
| CN105789628B (en) | A kind of azepine graphene and manganese dioxide hybrid aerogel and its preparation method and application | |
| CN1378975A (en) | Process for preparing nano graphite carbon sol with dual graphite electrodes | |
| CN102698741B (en) | Method for preparing grapheme platinum nanocomposite material by using argon plasma | |
| CN109368626A (en) | A kind of electrolyte for electrochemical stripping two-dimension nano materials |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130911 Termination date: 20150512 |
|
| EXPY | Termination of patent right or utility model |