CN103613097A - Environment-friendly method for preparing sulfonated graphene - Google Patents
Environment-friendly method for preparing sulfonated graphene Download PDFInfo
- Publication number
- CN103613097A CN103613097A CN201310652941.9A CN201310652941A CN103613097A CN 103613097 A CN103613097 A CN 103613097A CN 201310652941 A CN201310652941 A CN 201310652941A CN 103613097 A CN103613097 A CN 103613097A
- Authority
- CN
- China
- Prior art keywords
- graphene
- dispersion liquid
- sulfonated
- preparing
- 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.)
- Pending
Links
Images
Abstract
The invention discloses an environment-friendly method for preparing sulfonated graphene. The method comprises the following steps: preparing an oxidized graphene dispersion liquid by using a Hummers method; regulating the pH value of the dispersion liquid to 9-10; then performing pre-reduction on the oxidized graphene dispersion liquid through ascorbic acid; sulfonating the oxidized graphene dispersion liquid with an aromatic diazonium salt; and finally, performing complete reduction on the oxidized graphene dispersion liquid through sodium citrate, thereby preparing the sulfonated graphene. As the method is used, the defects that the industrialization is difficult to realize and the environment is polluted due to the reasons that an existing synthetic method needs to be carried out under specific conditions or a toxic reducing reagent is adopted are overcome. The method is simple in whole preparation process, low in cost and easy to industrialize, and has no special requirement on environment conditions and no pollution on environments; the sulfonated graphene with high quality is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of functionalization graphene, be specifically related to a kind of method of preparing sulfonated graphene of environmental protection.
Background technology
Graphene is a kind of by the tightly packed one-tenth Colloidal particles of monolayer carbon atom.Because it has large specific surface area, good conductivity and the easy characteristics such as surface chemistry of modification, be just widely used in nano composite material, field emmision material, sensing and energy storage material Applied research fields.In recent years, Chinese scholars has been carried out large quantity research with regard to the functionalization on Graphene surface, and dispersiveness and the deliquescent while of improving Graphene do not affect himself character.Due to the high-hydrophilic of sulfonic acid group, Graphene is carried out, after sulfonation processing, not only can improving its dispersiveness, can also retain its unique character, so sulfonation has become one of study hotspot of Graphene modification.As employing benzoyl peroxide, the vitriol oils etc. such as Liang carry out sulfonation to carbon nanotube, obtained the higher Sulfonated carbon nanotube of quality, the stability of its aqueous solution can reach some months.Mukherjee etc. adopt identical method, obtain the sulfonation Nano graphite material of individual layer and a small amount of multilayer.Si etc. first use after sodium borohydride prereduction sulfonated graphene, introduce Phenylsulfonic acid group, finally with hydrazine hydrate, go to reduce completely, have obtained good dispersity and have conducted electricity good sulfonated graphene.But, synthetic method in the past need to be carried out mostly under special conditions, or adopt the poisonous original reagent of going back, be difficult to industrialization and to environment, so the high quality sulfonated graphene of preparing how simple, cheap environmental protection is one of current required difficult point overcoming.
Summary of the invention
For above-mentioned prior art, the invention provides a kind of method of preparing sulfonated graphene of environmental protection, take graphite as raw material, adopt improved Hummers method to make graphite oxide (GO), by xitix prereduction, sulfonation reaction, Trisodium Citrate, reduce prepare high-quality sulfonated graphene completely, its preparation process environmental protection.
In order to solve the problems of the technologies described above, a kind of method of preparing sulfonated graphene of environmental protection, comprises the following steps:
Step 1, by Hummers legal system, obtaining the graphene oxide dispersion liquid that concentration is 1～2mg/ml, is 8～12:1 according to the mass ratio of solute in xitix and graphene oxide dispersion liquid subsequently, and xitix is joined and uses Na
2cO
3solution is adjusted to pH value in 9～10 graphene oxide dispersion liquid, and is placed in the water-bath of 80 ℃～95 ℃, under the stirring that is 600r/min, reacts 2～4h at revolution, obtains prereduction product solution;
Step 2, according to the volume ratio of diazonium salt solution and prereduction product solution, be 6～8:1, the prereduction product that step 1 is obtained joins in diazonium salt solution, and be placed in ice bath, and under the stirring that is 600r/min at revolution, react 2～4h, obtain sulfonated products solution;
Step 3, according to the mass ratio of solute in Trisodium Citrate and sulfonated products, be 2～4:1, Trisodium Citrate is joined in the resulting sulfonated products solution of step 2, and be placed in 80 ℃～95 ℃ water-baths, under the stirring that is 600r/min at revolution, react 8～10h, so far, prepare sulfonated graphene.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention prepares high-quality sulfonated graphene by xitix prereduction, sulfonation reaction, the complete reduction process of Trisodium Citrate, and in whole preparation process, environmentally safe has been realized environmental protection.
Accompanying drawing explanation
Fig. 1 is the TEM picture of the sulfonated graphene that obtains of the embodiment of the present invention 1;
Fig. 2 is the TEM picture of the sulfonated graphene that obtains of the embodiment of the present invention 2;
Fig. 3 is the TEM picture of the sulfonated graphene that obtains of the embodiment of the present invention 3;
Fig. 4 is the infrared spectrum of the sulfonated graphene that obtains of the embodiment of the present invention 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, the method for preparing sulfonated graphene of a kind of environmental protection of the present invention is described further.It is the convenience in order to understand that embodiment is provided, and is never restriction the present invention.
Embodiment 1:
1. get the 1mg/ml graphene oxide dispersion liquid that 80ml makes by Hummers method, subsequently 0.64g xitix is joined and uses Na
2cO
3solution is adjusted to pH value in 9 dispersion liquid, mixture is placed in to the water-bath of 80 ℃, under the stirring that is 600r/min, reacts 2h at revolution, and this is prereduction process, obtains prereduction product solution;
2. the above-mentioned prereduction product solution preparing is joined in 10ml diazonium salt solution, and be placed in ice bath, under the stirring that is 600r/min, react 2h at revolution, this is sulfonation process, obtains sulfonated products solution;
3. 1.6g Trisodium Citrate is joined in the resulting sulfonated products solution of above-mentioned sulfonation process, be placed in 80 ℃ of water-baths, under the stirring that is 600r/min, react 8h at revolution, this is complete reduction process, so far, prepares sulfonated graphene.
Fig. 1 is the TEM picture of the sulfonated graphene that obtains of the embodiment of the present invention 1, that can obviously to observe sulfonation graphite that the inventive method prepares be individual layer and pure transparent; Fig. 4 is the infrared spectrum of the sulfonated graphene that obtains of the embodiment of the present invention 1,1161cm in this infrared spectrum
-1, 1118cm
-1to be produced by the stretching vibration of S-O, 1037cm
-1it is the stretching vibration charateristic avsorption band of S-phenyl; The existence of these two absorption peaks shows successfully to have introduced sulfonic group.
Embodiment 2:
1. get the 1.5mg/ml graphene oxide dispersion liquid that 60ml makes by Hummers method, subsequently 0.63g xitix is joined and uses Na
2cO
3solution is adjusted to pH value in 9 dispersion liquid, mixture is placed in to the water-bath of 90 ℃, under the stirring that is 600r/min, reacts 3h at revolution, and this is prereduction process, obtains prereduction product solution;
2. prereduction product being joined in 7.5ml diazonium salt solution, and be placed in ice bath, is 600r/min at revolution
Stir lower reaction 3h.This is sulfonation process, obtains sulfonated products solution;
3. 2g Trisodium Citrate is joined in the resulting sulfonated products solution of sulfonation process, be placed in 90 ℃ of water-baths, under the stirring that is 600r/min, react 9h at revolution, this is complete reduction process, so far prepares sulfonated graphene.
Fig. 2 is the TEM picture of the sulfonated graphene that obtains of the embodiment of the present invention 2, that can obviously to observe sulfonation graphite that embodiment 2 prepares be individual layer and pure transparent.
Embodiment 3:
1. get the 2mg/ml graphene oxide dispersion liquid that 100ml makes by Hummers method, subsequently 4g xitix is joined and uses Na
2cO
3solution is adjusted to pH value in 10 dispersion liquid, mixture is placed in to the water-bath of 95 ℃, under the stirring that is 600r/min, reacts 4h at revolution, and this is prereduction process, obtains prereduction product solution;
2. prereduction product solution is joined in 12.5ml diazonium salt solution, and be placed in ice bath, under the stirring that is 600r/min at revolution, react 4h.This is sulfonation process, obtains sulfonated products solution;
3. 8g Trisodium Citrate is joined in the resulting solution of sulfonation process, be placed in 95 ℃ of water-baths, under the stirring that is 600r/min, react 10h at revolution, this is complete reduction process, so far prepares sulfonated graphene.
Fig. 3 is the TEM picture of the sulfonated graphene that obtains of the embodiment of the present invention 3, that can obviously to observe sulfonation graphite prepared by this law be individual layer and pure transparent.
Preparation method of the present invention has overcome synthetic method in the past and need under special conditions, carry out, or adopt the poisonous original reagent of going back, be difficult to industrialization and the defect to environment, not only whole preparation process is simple, envrionment conditions is not had to particular requirement, with low cost, easily industrialization, and environment is not polluted, and obtained high-quality sulfonated graphene.
Although in conjunction with figure, invention has been described above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; rather than restrictive; those of ordinary skill in the art is under enlightenment of the present invention; in the situation that not departing from aim of the present invention, can also make a lot of distortion, within these all belong to protection of the present invention.
Claims (4)
1. a method of preparing sulfonated graphene for environmental protection, is characterized in that, comprises the following steps:
Step 1, by Hummers legal system, obtaining the graphene oxide dispersion liquid that concentration is 1～2mg/ml, is 8～12:1 according to the mass ratio of solute in xitix and graphene oxide dispersion liquid subsequently, and xitix is added and uses Na
2cO
3solution is adjusted to pH value in 9～10 graphene oxide dispersion liquid, and is placed in the water-bath of 80 ℃～95 ℃, under the stirring that is 600r/min, reacts 2～4h at revolution, obtains prereduction product solution;
Step 2, according to the volume ratio of diazonium salt solution and prereduction product solution, be 6～8:1, the prereduction product that step 1 is obtained joins in diazonium salt solution, and be placed in ice bath, and under the stirring that is 600r/min at revolution, react 2～4h, obtain sulfonated products solution;
Step 3, according to the mass ratio of solute in Trisodium Citrate and sulfonated products, be 2～4:1, Trisodium Citrate is joined in the resulting sulfonated products solution of step 2, and be placed in 80 ℃～95 ℃ water-baths, under the stirring that is 600r/min at revolution, react 8～10h, so far, prepare sulfonated graphene.
2. the method for preparing sulfonated graphene of environmental protection according to claim 1, wherein, the bath temperature in step 1 and step 3 is 80 ℃.
3. the method for preparing sulfonated graphene of environmental protection according to claim 1, wherein, the bath temperature in step 1 and step 3 is 90 ℃.
4. the method for preparing sulfonated graphene of environmental protection according to claim 1, wherein, the bath temperature in step 1 and step 3 is 95 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652941.9A CN103613097A (en) | 2013-12-04 | 2013-12-04 | Environment-friendly method for preparing sulfonated graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652941.9A CN103613097A (en) | 2013-12-04 | 2013-12-04 | Environment-friendly method for preparing sulfonated graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103613097A true CN103613097A (en) | 2014-03-05 |
Family
ID=50163827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652941.9A Pending CN103613097A (en) | 2013-12-04 | 2013-12-04 | Environment-friendly method for preparing sulfonated graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103613097A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497565A (en) * | 2015-01-14 | 2015-04-08 | 苏州高通新材料科技有限公司 | Nylon material having ultra-strong liquidity and preparation method thereof |
| CN104690290A (en) * | 2015-01-12 | 2015-06-10 | 冯丹 | Preparation method of wave-absorbing composite material with graphene loaded with nano nickel |
| CN104815616A (en) * | 2015-05-05 | 2015-08-05 | 河海大学 | Preparation method of layered sulfonated graphene/titanium dioxide composite material and application of the material in the field of sewage treatment |
| CN104844794A (en) * | 2015-05-20 | 2015-08-19 | 苏州高通新材料科技有限公司 | Heat conducting nylon material based on sulfonated graphene and preparation method thereof |
| CN104993142A (en) * | 2015-05-25 | 2015-10-21 | 苏州高通新材料科技有限公司 | Sulfonated graphene lithium battery positive electrode additive and application thereof |
| CN105061763A (en) * | 2015-07-31 | 2015-11-18 | 苏州高通新材料科技有限公司 | Sulfonated graphene-containing high heat conduction and high barrier polyimide film and production method thereof |
| CN105314626A (en) * | 2014-06-03 | 2016-02-10 | 伊思幕有限公司 | Methods of manufacturing graphene and conductor |
| CN107366040A (en) * | 2017-08-11 | 2017-11-21 | 广东富琳健康产业有限公司 | A kind of fiber for graphene far-infrared magnet therapeutic knee-pad and preparation method thereof |
| CN107555566A (en) * | 2017-08-31 | 2018-01-09 | 华南理工大学 | The method that sulfonated graphene cooperates with treatment of heavy metal polluted water with cation polypropylene acyl emulsion amine |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050064539A (en) * | 2003-12-24 | 2005-06-29 | 재단법인 포항산업과학연구원 | Manufacturing method of exfoliated graphite from surface-treated graphite |
| CN101728534A (en) * | 2009-12-24 | 2010-06-09 | 华东理工大学 | Method for preparing poly organic polysulfide/sulfonated graphene conductive composite material |
| CN102659099A (en) * | 2012-05-29 | 2012-09-12 | 上海第二工业大学 | Preparation method of anisotropic graphene foam |
| CN103012819A (en) * | 2012-12-26 | 2013-04-03 | 复旦大学 | Method for preparing acetylacetone polyvinyl alcohol/graphene nanocomposite |
| CN103342355A (en) * | 2013-07-09 | 2013-10-09 | 北京化工大学 | Method for preparing graphene and composite material thereof |
-
2013
- 2013-12-04 CN CN201310652941.9A patent/CN103613097A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050064539A (en) * | 2003-12-24 | 2005-06-29 | 재단법인 포항산업과학연구원 | Manufacturing method of exfoliated graphite from surface-treated graphite |
| CN101728534A (en) * | 2009-12-24 | 2010-06-09 | 华东理工大学 | Method for preparing poly organic polysulfide/sulfonated graphene conductive composite material |
| CN102659099A (en) * | 2012-05-29 | 2012-09-12 | 上海第二工业大学 | Preparation method of anisotropic graphene foam |
| CN103012819A (en) * | 2012-12-26 | 2013-04-03 | 复旦大学 | Method for preparing acetylacetone polyvinyl alcohol/graphene nanocomposite |
| CN103342355A (en) * | 2013-07-09 | 2013-10-09 | 北京化工大学 | Method for preparing graphene and composite material thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105314626A (en) * | 2014-06-03 | 2016-02-10 | 伊思幕有限公司 | Methods of manufacturing graphene and conductor |
| CN104690290A (en) * | 2015-01-12 | 2015-06-10 | 冯丹 | Preparation method of wave-absorbing composite material with graphene loaded with nano nickel |
| CN104497565A (en) * | 2015-01-14 | 2015-04-08 | 苏州高通新材料科技有限公司 | Nylon material having ultra-strong liquidity and preparation method thereof |
| CN104815616A (en) * | 2015-05-05 | 2015-08-05 | 河海大学 | Preparation method of layered sulfonated graphene/titanium dioxide composite material and application of the material in the field of sewage treatment |
| CN104844794A (en) * | 2015-05-20 | 2015-08-19 | 苏州高通新材料科技有限公司 | Heat conducting nylon material based on sulfonated graphene and preparation method thereof |
| CN104993142A (en) * | 2015-05-25 | 2015-10-21 | 苏州高通新材料科技有限公司 | Sulfonated graphene lithium battery positive electrode additive and application thereof |
| CN104993142B (en) * | 2015-05-25 | 2017-05-10 | 苏州高通新材料科技有限公司 | Sulfonated graphene lithium battery positive electrode additive and application thereof |
| CN105061763A (en) * | 2015-07-31 | 2015-11-18 | 苏州高通新材料科技有限公司 | Sulfonated graphene-containing high heat conduction and high barrier polyimide film and production method thereof |
| CN107366040A (en) * | 2017-08-11 | 2017-11-21 | 广东富琳健康产业有限公司 | A kind of fiber for graphene far-infrared magnet therapeutic knee-pad and preparation method thereof |
| CN107555566A (en) * | 2017-08-31 | 2018-01-09 | 华南理工大学 | The method that sulfonated graphene cooperates with treatment of heavy metal polluted water with cation polypropylene acyl emulsion amine |
| CN107555566B (en) * | 2017-08-31 | 2020-11-24 | 华南理工大学 | Method for treating heavy metal polluted water by using sulfonated graphene and cationic polyacrylamide emulsion in cooperation mode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103613097A (en) | Environment-friendly method for preparing sulfonated graphene | |
| CN108002374B (en) | Ultrathin two-dimensional layered material nanosheet and preparation method thereof | |
| CN103935998B (en) | A kind of preparation method of graphene aqueous solution | |
| CN103935999B (en) | A kind of preparation method of Graphene | |
| CN101987729B (en) | Method for preparing graphene by reduction of sulfur-contained compound | |
| CN107158964B (en) | Composite membrane material based on metal organic framework nanosheets and graphene oxide, preparation method and application in gas separation | |
| CN105289503B (en) | A kind of application of graphene poly ion liquid composite as orange G adsorbent | |
| CN107301922B (en) | Three-dimensional porous graphene nano material and its preparation method and application | |
| CN103553033B (en) | The preparation method of grapheme material | |
| CN110918075B (en) | Preparation and application of metal organic framework magnetic nano porous carbon material | |
| CN103241727B (en) | Preparation method of graphene | |
| CN104150469B (en) | Method capable of preparing few-layer graphene powder in batches | |
| CN107628597B (en) | By using SiO2Method for preparing biomass carbon material with micropore and mesopore structure by coating method | |
| CN102581297A (en) | Method for preparing controllable green synthetic metallic nano-materials based on graphene oxide | |
| CN102169987B (en) | Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material | |
| CN103058176A (en) | Method for preparing graphene efficiently | |
| CN103641172A (en) | Method for preparing nanometer layered molybdenum disulfide | |
| CN102502610A (en) | Simple method for preparing a large amount of graphene | |
| CN105621406A (en) | Nitrogen-doped porous graphite and preparation method thereof | |
| CN103723773A (en) | Hydrosol of ferroferric oxide nanoparticles and preparation method and application thereof | |
| Chen et al. | Self-catalyzed strategy to form hollow carbon nanospheres for CO2 capture | |
| CN105731444A (en) | Preparation method of graphene easy to disperse | |
| CN105883790A (en) | Low-temperature-stripping modified graphene and preparation method thereof | |
| CN104313055B (en) | Microbial preparation method of strontium carbonate | |
| CN103165866A (en) | Nitrogen doped graphene/metal composite electrode and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140305 |