CN104108707B - A kind of sulfur doping Graphene and preparation method thereof - Google Patents
A kind of sulfur doping Graphene and preparation method thereof Download PDFInfo
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- CN104108707B CN104108707B CN201410360674.2A CN201410360674A CN104108707B CN 104108707 B CN104108707 B CN 104108707B CN 201410360674 A CN201410360674 A CN 201410360674A CN 104108707 B CN104108707 B CN 104108707B
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Abstract
The present invention relates to a kind of sulfur doping Graphene and preparation method thereof, described preparation method comprises: by sulphur source and organic salt or be heated to 300-1600 DEG C with the mixture of organic acid and salt under non-oxidizing atmosphere, obtains the mixture of sulfur doping Graphene and metal oxide; Remove the metal oxide in mixture, obtain sulfur doping Graphene.The present invention, by heating sulphur source and organic salt or the mixture with organic acid and salt in non-oxidizing atmosphere, utilizes the theory of organic salt carbonized graphite alkene, inorganic oxide nucleation and sulphur source pyrolysis generation active sulphur, prepares sulfur doping Graphene.The method have technique simple, with short production cycle, can be in-situ doped etc. advantage, and the sulfur doping Graphene prepared has the advantages that porousness, specific surface area greatly, are not reunited, and can be widely used in the every field such as lithium ion battery, ultracapacitor, lead-acid cell, water treatment, electrocatalysis, photochemical catalysis.
Description
Technical field
The present invention relates to carbon material technical field, is a kind of sulfur doping Graphene and preparation method thereof specifically.
Background technology
Since the people such as Geim in 2004 successfully prepare mono-layer graphite, Graphene is with the two dimension of its uniqueness (2D) honeycomb carbon structure and excellent physics, chemistry, mechanical property, and the research of Graphene is a current study hotspot.But energy gap is too small in grapheme material electronic spectrum, can not be controlled completely as traditional semi-conductor, large switch signal ratio etc. may be stoped.Hetero atom is incorporated into the sp of Graphene
2hybrid structure is proved to be a kind of and effectively opens Graphene band gap and one of method improving its chemical reactivity, has great significance for its application.
Sulfur doping Graphene is a kind of important Graphene derivative, in alkaline medium, have more excellent catalytic activity than commercial platinum/carbon.Have graphene oxide to heat in hydrogen sulfide atmosphere about the method preparing sulfur doping Graphene in prior art to mix sulphur, anneal oxidation Graphene and Benzyl disulfide, thermal annealing sulfonated polystyrene film etc. in argon hydrogen atmosphere in argon gas.There is the shortcomings such as non-uniform doping, complicated building-up process and poisonous presoma in first two method.Last method relates to the preparation of sulfonated polystyrene, the spin coating of polymeric film, high-temperature heat treatment and multiple step such as follow-up.
Summary of the invention
In order to make up above-mentioned the deficiencies in the prior art, technical problem to be solved by this invention be to provide a kind of technique simple, can the sulfur doping graphene preparation method of in-situ doped sulphur.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of sulfur doping graphene preparation method, comprising:
By sulphur source and organic salt or be heated to 300-1600 DEG C with the mixture of organic acid and salt under non-oxidizing atmosphere, obtain the mixture of sulfur doping Graphene and metal oxide;
Remove the metal oxide in mixture, obtain sulfur doping Graphene;
Wherein, described sulphur source is selected from one or more in di-n-octyl thioether, dodecyl thioether, tetramethylene sulfone, 4-propylthio vinyl acetate, sulfuric acid vinyl ester, propylene sulfite, sulfuric acid propylene, 4-methyl ethylene sulfite and butylene sulfite;
Wherein, one or more in the alkyl soap that described organic salt is selected from the Citrate trianion of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth, gluconate, tartrate, D-VB5 salt, threose acid salt, carbonatoms are 8-24 and oleate;
Wherein, one or more in the alkyl lipid acid that described organic acid is selected from citric acid, gluconic acid, tartrate, D-VB5, threonic acid, carbonatoms are 8-24 and oleic acid;
Wherein, described salt is selected from one or more in the acetate of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth, nitrate, chlorate, Bromide and iodized salt.
Beneficial effect of the present invention is: technique is simple, with short production cycle, can in-situ doped sulphur, obtained sulfur doping Graphene has porousness, feature that specific surface area is large, can be applicable to the every field such as lithium ion battery, ultracapacitor, lead-acid cell, water treatment, electrocatalysis, photochemical catalysis.
Accompanying drawing explanation
Figure 1 shows that the scanning electron microscope (SEM) photograph of sulfur doping Graphene prepared by the embodiment of the present invention 1.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, realized object and effect, accompanying drawing is coordinated to be explained in detail below in conjunction with embodiment.
The design of most critical of the present invention is: by heating sulphur source and organic salt or the mixture with organic acid and salt in non-oxidizing atmosphere; organic salt carbonized graphite alkene, inorganic oxide nucleation and the pyrolysis of sulphur source is utilized to produce the theory of active sulphur; prepare the original position sulfur doping Graphene with advantages such as porousness, specific surface area are large; the method technique is simple, with short production cycle, be produced on a large scale, and the sulfur doping Graphene prepared can be applicable to the every field such as lithium ion battery, ultracapacitor, lead-acid cell, water treatment, electrocatalysis, photochemical catalysis.
Sulfur doping graphene preparation method provided by the invention, comprising:
By sulphur source and organic salt or be heated to 300-1600 DEG C with the mixture of organic acid and salt under non-oxidizing atmosphere, obtain the mixture of sulfur doping Graphene and metal oxide;
Remove the metal oxide in mixture, obtain sulfur doping Graphene;
Wherein, described sulphur source is selected from one or more in di-n-octyl thioether, dodecyl thioether, tetramethylene sulfone, 4-propylthio vinyl acetate, sulfuric acid vinyl ester, propylene sulfite, sulfuric acid propylene, 4-methyl ethylene sulfite and butylene sulfite;
Wherein, one or more in the alkyl soap that described organic salt is selected from the Citrate trianion of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth, gluconate, tartrate, D-VB5 salt, threose acid salt, carbonatoms are 8-24 and oleate;
Wherein, one or more in the alkyl lipid acid that described organic acid is selected from citric acid, gluconic acid, tartrate, D-VB5, threonic acid, carbonatoms are 8-24 and oleic acid;
Wherein, described salt is selected from one or more in the acetate of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth, nitrate, chlorate, Bromide and iodized salt.
The mechanism that the present invention prepares sulfur doping Graphene is as follows:
In the mixed system of sulphur source and rich carbon organic salt or rich carbon organic acid and salt, rich carbon organic acid or rich carbon organic salt as carbon source in high temperature non-oxygenated property atmosphere, through pyrolysis, the metal oxide surface that carbon atom grows in position becomes nuclear rearrangement, reset the growth presenting two-dimensional directional according to oxide surface template, and continuity is good, thus obtain the mixture of porous graphene and metal oxide.Meanwhile, after the pyrolysis of sulphur source, produce active sulphur, take part in the rearrangement process of carbon atom, realize the growth of the in-situ doped Graphene of sulphur; And not only provide active sulphur for organosulfur compound, part carbon is also provided, realizes the growth of the in-situ doped Graphene of sulphur.Metal oxide has the advantages that to be dissolved in acid, and therefore mixture is after cleanup acid treatment, can obtain pure sulfur doping porous graphene.
From foregoing description, beneficial effect of the present invention is:
Because the present invention only needs by heating sulphur source and organic salt or the mixture with organic acid and salt in non-oxidizing atmosphere, the mixture of sulfur doping Graphene and metal oxide can be prepared, follow-uply can remove metal oxide in mixture to obtain the higher sulfur doping Graphene of purity by conventional impurity removal process such as wash liquid, therefore compared to existing technologies, it is simple that the present invention has technique, with short production cycle, can be in-situ doped etc. advantage, and the sulfur doping Graphene prepared has porousness, the feature that specific surface area is large, lithium ion battery can be widely used in, ultracapacitor, lead-acid cell, water treatment, electrocatalysis, the every field such as photochemical catalysis.
Preferably, the weight ratio of described organic acid and salt is organic acid: salt=1: 9-9: 1.
Preferably, the weight ratio of described sulphur source and organic salt is sulphur source: organic salt=0.1: 100-1: 10.
Preferably, the weight ratio of the mixture of described sulphur source and organic acid and salt is sulphur source: mixture=0.1 of organic acid and salt: 100-1: 10.
Preferably, described non-oxidizing atmosphere is made up of one or more in nitrogen, argon gas, hydrogen and ammonia.
Preferably, be easy to oxidized because sulfur doping Graphene at high temperature contacts with air, the problems such as the product purity caused in order to avoid oxidation and Quality Down, the present invention is when removing the metal oxide in mixture, preferably in the following ways: under the condition of isolated air and/or mixture temperature remove metal oxide in mixture lower than adopting the mode of wash liquid under the condition of 100 DEG C, described washing lotion be selected from hydrochloric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid one or more.Preferred, adopt in 37% concentrated hydrochloric acid and 30% acetic acid one or both, pickling 4-8 hour under the temperature condition of 40-60 DEG C.After having washed, can further suction filtration to dry to obtain highly purified sulfur doping Graphene.
Preferably, the speed of described heating is 0.5-15 DEG C/min.When heating rate is too fast, the productive rate of sulfur doping Graphene is lower, and excessively slow heating rate, greatly can extend again the production cycle of product.Preferred, the speed of described heating is 2-10 DEG C/min.
Preferably, in order to improve the quality product of sulfur doping Graphene, described sulphur source and organic salt or be incubated 1-6h after being heated to 400-1600 DEG C with the mixture of organic acid and salt under non-oxidizing atmosphere.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, take 2 grams of citrate of lime and 0.2 gram of dodecyl thioether, put it in magnetic boat, then with tube furnace ramp to 600 DEG C by 2 DEG C/min in nitrogen, 600 DEG C of heating 2 hours, obtain sulfur doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acids of 10 milliliters at 50 DEG C, wash 4 hours, suction filtration, to dry, obtains sulfur doping Graphene.Through ultimate analysis, the sulphur content of this sulfur doping Graphene is 5.1%.
Embodiment 2, take 2 grams of Zinc Gluconates and 0.5 gram of tetramethylene sulfone, put it in magnetic boat, then with tube furnace ramp to 600 DEG C by 2 DEG C/min in argon gas, 600 DEG C of heating 2 hours, obtain sulfur doping Graphene and zinc oxide mix, with 37% concentrated hydrochloric acids of 10 milliliters at 50 DEG C, wash 4 hours, suction filtration, to dry, obtains sulfur doping Graphene.Through ultimate analysis, the sulphur content of this sulfur doping Graphene is 4.5%.
Embodiment 3, take 2 grams of Eighteen alkyl acid calcium and 0.9 gram of propylene sulfite, put it in magnetic boat, then with tube furnace ramp to 600 DEG C by 10 DEG C/min in nitrogen, 600 DEG C of heating 2 hours, obtain sulfur doping Graphene and calcium oxide mixture, with 30% acetic acid of 10 milliliters at 50 DEG C, wash 4 hours, suction filtration, to dry, obtains sulfur doping Graphene.Through ultimate analysis, the sulphur content of this sulfur doping Graphene is 4.1%.
Embodiment 4, take 1 gram of zinc oleate and 0.4 gram of ethylene sulfite, put it in magnetic boat, then with tube furnace ramp to 800 DEG C by 5 DEG C/min in argon gas and hydrogen mixed gas, 800 DEG C of heating 2 hours, obtain sulfur doping Graphene and zinc oxide mix, with 37% concentrated hydrochloric acids of 10 milliliters at 50 DEG C, wash 4 hours, suction filtration, to dry, can obtain sulfur doping Graphene.Through ultimate analysis, the sulphur content of this sulfur doping Graphene is 3.5%.
Embodiment 5, take 1 gram of oleic acid, 1 gram of zinc acetate and 0.5 gram of ethylene sulfite, put it in magnetic boat, then with tube furnace ramp to 800 DEG C by 5 DEG C/min in nitrogen, 800 DEG C of heating 2 hours, obtain sulfur doping Graphene and zinc oxide mix, with 37% concentrated hydrochloric acids of 10 milliliters at 50 DEG C, wash 4 hours, suction filtration, to dry, can obtain sulfur doping Graphene.Through ultimate analysis, the sulphur content of this sulfur doping Graphene is 2.7%.
Embodiment 6, take 2 grams of citrate of lime, 1 gram of calcium tartrate and 0.3 gram of dodecyl thioether, put it in magnetic boat, then with tube furnace ramp to 900 DEG C by 2 DEG C/min in nitrogen, 900 DEG C of heating 2 hours, obtain sulfur doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acids of 10 milliliters at 50 DEG C, wash 4 hours, suction filtration, to dry, can obtain sulfur doping Graphene.Through ultimate analysis, the sulphur content of this sulfur doping Graphene is 3.6%.
Embodiment 7, take 2 grams of citrate of lime, 0.2 gram of dodecyl thioether and 0.1 gram of tetramethylene sulfone, put it in magnetic boat, then with tube furnace ramp to 1000 DEG C by 2 DEG C/min in nitrogen, 1000 DEG C of heating 2 hours, obtain sulfur doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acids of 10 milliliters at 50 DEG C, wash 4 hours, suction filtration, to dry, can obtain sulfur doping Graphene.Through ultimate analysis, the sulphur content of this sulfur doping Graphene is 4.8%.
The sulfur doping Graphene prepared by above-described embodiment 1-7, carries out electron-microscope scanning, and the scanning electron microscope (SEM) photograph obtained can refer to shown in Fig. 1.Known as shown in Figure 1, the sulfur doping Graphene that the present invention finally prepares is made up of flaky texture and presents cell texture.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (5)
1. a sulfur doping graphene preparation method, is characterized in that, comprising:
Be incubated 1-6h by sulphur source and organic salt or after being heated to 400-1600 DEG C with the mixture of organic acid and salt under non-oxidizing atmosphere, obtain the mixture of sulfur doping Graphene and metal oxide;
Remove the metal oxide in mixture, obtain sulfur doping Graphene;
Wherein, described sulphur source is selected from one or more in di-n-octyl thioether, dodecyl thioether, tetramethylene sulfone, 4-propylthio vinyl acetate, sulfuric acid vinyl ester, propylene sulfite, sulfuric acid propylene, 4-methyl ethylene sulfite and butylene sulfite;
Wherein, one or more in the alkyl soap that described organic salt is selected from the Citrate trianion of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth, gluconate, tartrate, D-VB5 salt, threose acid salt, carbonatoms are 8-24 and oleate;
Wherein, one or more in the alkyl lipid acid that described organic acid is selected from citric acid, gluconic acid, tartrate, D-VB5, threonic acid, carbonatoms are 8-24 and oleic acid;
Wherein, described salt is selected from one or more in the acetate of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth, nitrate, chlorate, Bromide and iodized salt;
The speed of described heating is 0.5-15 DEG C/min;
The weight ratio of described organic acid and salt is organic acid: salt=1: 9-9: 1; The weight ratio of described sulphur source and organic salt is sulphur source: organic salt=0.1: 100-1: 10; The weight ratio of the mixture of described sulphur source and organic acid and salt is sulphur source: mixture=0.1 of organic acid and salt: 100-1: 10.
2. sulfur doping graphene preparation method according to claim 1, it is characterized in that: under the condition of isolated air and/or mixture temperature remove metal oxide in mixture lower than adopting the mode of wash liquid under the condition of 100 DEG C, described washing lotion be selected from hydrochloric acid, nitric acid, acetic acid and oxalic acid one or more.
3. sulfur doping graphene preparation method according to claim 1, is characterized in that: described non-oxidizing atmosphere is made up of one or more in nitrogen, argon gas, hydrogen and ammonia.
4. sulfur doping graphene preparation method according to claim 1, is characterized in that: the speed of described heating is 2-10 DEG C/min.
5. the sulfur doping Graphene prepared by the preparation method described in Claims 1-4 any one.
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| CN105731428B (en) * | 2014-12-12 | 2018-06-01 | 中国科学院过程工程研究所 | A kind of graphene of sulfur doping and its preparation method of derivative and purposes |
| CN107221652A (en) * | 2017-03-28 | 2017-09-29 | 深圳新宙邦科技股份有限公司 | A kind of sulfur doping carbon material and preparation method thereof |
| CN107973289B (en) * | 2017-11-08 | 2021-08-03 | 华侨大学 | Sulfur-doped graphene catalytic material and preparation method thereof |
| JP7338993B2 (en) * | 2019-03-06 | 2023-09-05 | 株式会社クラレ | Porous carbon and method for producing porous carbon |
| CN111547705B (en) * | 2020-05-12 | 2022-03-29 | 中国计量大学 | Preparation method of porous carbon electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| CN103395767A (en) * | 2013-07-25 | 2013-11-20 | 中国石油大学(北京) | Preparation method of sulfur-containing carbon material as well as sulfur-containing carbon material prepared by using same |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| CN103395767A (en) * | 2013-07-25 | 2013-11-20 | 中国石油大学(北京) | Preparation method of sulfur-containing carbon material as well as sulfur-containing carbon material prepared by using same |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Single Source Precursor-based Solvothermal Synthesis of Heteroatom-doped Graphene and Its Energy Storage and Conversion Applications;Bo Quan et al.;《Scientific Reports》;20140710;第4卷(第5369期);第2页左栏第1-21行，第5页左栏第4-11行 * |
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