CN104556012A - Sulfydryl-modified graphene oxide and preparation method thereof - Google Patents
Sulfydryl-modified graphene oxide and preparation method thereof Download PDFInfo
- Publication number
- CN104556012A CN104556012A CN201510006305.8A CN201510006305A CN104556012A CN 104556012 A CN104556012 A CN 104556012A CN 201510006305 A CN201510006305 A CN 201510006305A CN 104556012 A CN104556012 A CN 104556012A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- acid
- sulfydryl
- deionized water
- modified graphene
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a sulfydryl-modified graphene oxide and a preparation method thereof. According to the sulfydryl-modified graphene oxide, a modified graphene oxide product is obtained by introducing sulfydryl to a graphene oxide lamellar structure. The preparation method comprises the following steps: mixing a graphene oxide solution, a solvent and triethylamine evenly; adding thiocarboxylic acid or sulfo-carboxylate under argon protection and reacting at 10-70 DEG C for 1-7 days to obtain a sulfydryl-modified latent sulfur graphene oxide; centrifugally washing the sulfydryl-modified latent sulfur graphene oxide with deionized water to obtain the sulfydryl-modified graphene oxide; or mixing the sulfydryl-modified latent sulfur graphene oxide with diluted hydrochloric acid evenly, and centrifugally washing with the deionized water to obtain the sulfydryl-modified graphene oxide. The sulfydryl-modified graphene oxide is simple in preparation process, safe, controllable, and low in time consumption and energy consumption; and according to the prepared sulfydryl-modified graphene oxide, the synthesis means and the application field of graphene derived materials and sulfocompounds are further expanded.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly relate to a kind of sulfhydryl modified graphene oxide and preparation method.
Background technology
Since monolithic graphite in 2010 comes out, the performances such as its excellent electricity, mechanics, optics, calorifics obtain the extensive concern of whole world scholar, emerge in a large number based on the material of Graphene and work.Graphene oxide, as the presoma of Graphene, is the most important intermediate that grapheme material realizes macroscopic view assembling and modification.The macroscopical assembled material fiber, film, aerogel etc. that have realized at present are all prepared via graphene oxide intermediate mostly.
Sulfhydryl compound is the compound of a class with one or more SH group, and they occupy critical role in the synthetic of life science and natural product, are important industrial raw material, are employed widely in synthetic pesticide, medicine, plastics and seasonings.Particularly, along with in recent years, the development of sulfydryl click chemistry (thiol-click chemistry), sulfhydryl compound embodies important using value in increasing field.
At present, also fewer about the work containing sulfhydryl oxidase Graphene and preparation thereof.If can prepare sulfhydryl modified graphene oxide, then the synthesizing mean of Graphene derived material and sulfocompound and Application Areas will be widened further.Specifically, sulfhydryl modified graphene oxide can as the successive modified platform of graphene oxide.Due to sulfydryl participate in click chemistry reaction preference high, be swift in response, with sulfhydryl modified graphene oxide for substrate, by the functional group of click-reaction grafting specific function, can molecular designing be realized, obtain the product of estimated performance.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, propose a kind of method that rapid, high volume prepares sulfhydryl modified graphene oxide.
Sulfhydryl modified graphene oxide is that one introduces sulfydryl in graphene oxide laminated structure, thus the modified graphene oxide product obtained, sulfydryl grafts in graphene oxide laminated structure.
A preparation method for sulfhydryl modified graphene oxide, comprises the following steps:
(1) graphene oxide is dissolved in H
2in O, DMF, DMSO, DMAc or NMP, be mixed with the graphene oxide solution that concentration is 5-300 mg/mL;
(2), after the solvent of the graphene oxide solution of 1 volume, 2 ~ 6 volumes, the triethylamine of 0.03 ~ 0.15 volume being mixed, 3 × 10 are added under nitrogen protection
-3~ 3 × 10
-2the thiocarboxylic acid of volume or add and 3 × 10
-3~ 3 × 10
-2the dithionate (concentration of dithionate in mixing solutions is 3-35mg/mL) of the thiocarboxylic acid equivalent of volume; Under 10-70 degree Celsius, react 1-7 days, obtain the latent sulphur graphene oxide of thioesters modification; Described solvent is H
2o, DMF, DMSO, DMAc or NMP;
(3) the latent sulphur graphene oxide deionized water centrifuge washing of thioesters modification step 2 prepared, obtains sulfhydryl modified graphene oxide; Or after the latent sulphur graphene oxide of the thioesters modification prepared by 1 debulking step 2 mixes with the dilute hydrochloric acid (massfraction is 1-5%) of 50-300 volume, then use deionized water centrifuge washing, obtain sulfhydryl modified graphene oxide.
Further, described thiocarboxylic acid is thioacetic acid, propane thioic acid, thio-octanoic acid, 2, 2-dimethyl sulphur-based butyric acid, thiobenzoic acid, 2-furans bamic acid, 3-trifluoromethyl thio phenyl first S-acid, described dithionate is sodium thioglycolate, thioacetic acid potassium, propane thioic acid sodium, propane thioic acid potassium, thio-octanoic acid sodium, thio-octanoic acid potassium, 2, 2-dimethyl sulphur-based Sodium propanecarboxylate, 2, 2-dimethyl sulphur-based potassium butyrate, thiobenzoic acid sodium, thiobenzoic acid potassium, 2-furans bamic acid sodium, 2-furans bamic acid potassium, 3-trifluoromethyl thio phenyl first S-acid sodium or 3-trifluoromethyl thio phenyl first S-acid potassium.
Preparation process of the present invention is simple, safety is controlled, time consumption and energy consumption is few, and the sulfhydryl modified graphene oxide prepared makes the synthesizing mean of Graphene derived material and sulfocompound and Application Areas widen further.
Accompanying drawing explanation
Fig. 1 is the XPS collection of illustrative plates of graphene oxide;
Fig. 2 is the XPS spectrum figure of sulfhydryl modified graphene oxide;
Fig. 3 is the infrared spectrogram of sulfhydryl modified graphene oxide;
Fig. 4 is the Raman spectrogram of sulfhydryl modified graphene oxide.
Embodiment
The present invention, using triethylamine as catalyzer, under the condition of nitrogen protection, introduces sulfydryl by open loop-shift reaction in graphene oxide laminated structure, and the field of Graphene derived material and sulfocompound is widened further.Below in conjunction with embodiment, the invention will be further described.Following examples are used for explaining and the present invention are described, instead of limit the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
embodiment 1
Take that DMF dissolves, powder size is that the 100mg/mL graphene oxide solution 2mL of 40 μm is in 25mL flask, add 12mL deionized water and 300 μ L triethylamines wherein, the sodium thioglycolate of 20mg is added in the logical nitrogen process of 20 minutes, at room temperature stirring reaction 2 days, obtains the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.Use XPS spectrum, FT-IR & FT-RAMAN spectra characterize obtained sulfhydryl modified graphite oxide ene product.The XPS collection of illustrative plates (Fig. 2) of sulfhydryl modified graphene oxide and the XPS collection of illustrative plates (Fig. 1) of graphene oxide are contrasted, can find to have occurred the element sulphur of 1.06% in sulfhydryl modified graphite oxide ene product, show that sulfydryl introduces possibility success; Can be obtained by the infrared spectrogram (Fig. 3) of sulfhydryl modified graphene oxide, after sulfhydryl modified, there is mercapto functional group in graphene oxide lamella surface, in conjunction with XPS collection of illustrative plates (Fig. 2), can obtain sulfydryl and introduce successfully; Can be obtained by the Raman spectrogram (Fig. 4) of sulfhydryl modified graphene oxide, after sulfhydryl modified, the carbon backbone structure of graphene oxide lamella does not become, and shows that this preparation method does not destroy the structure of Graphene, is a kind of reliable method introducing sulfydryl in graphene oxide laminated structure.
embodiment 2
Take that DMF dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 12mL deionized water and 300 μ L triethylamines wherein, 60 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 2 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 3
Take that DMSO dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 12mL deionized water and 300 μ L triethylamines wherein, 60 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 2 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 100mL, then use deionized water wash, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 4
Take that DMF dissolves, powder size is that the 5mg/mL graphene oxide solution 2mL of 40 μm is in 25mL flask, add DMF and the 300 μ L triethylamines of 12mL wherein, 10 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, stirring reaction 2 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 100mL, then use deionized water wash, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 5
Take that DMF dissolves, 300mg/mL graphene oxide solution 2mL is in 25mL flask, add DMF and the 200 μ L triethylamines of 12mL wherein, 60 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, stirring reaction 4 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 300mL, then use deionized water wash, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 6
Take that DMAc dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMF and the 200 μ L triethylamines of 4mL wherein, 30 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 7
Take that DMAc dissolves, powder size is that the 100mg/mL graphene oxide solution 2mL of 40 μm is in 25mL flask, add DMSO and the 300 μ L triethylamines of 10mL wherein, 30 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 8
Take H
2that O dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMSO and the 100 μ L triethylamines of 10mL wherein, in the logical nitrogen process of 20 minutes, add 30 μ L thioacetic acids, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 9
Take H
2that O dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add NMP and the 100 μ L triethylamines of 10mL wherein, in the logical nitrogen process of 20 minutes, add 30 μ L thioacetic acids, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 10
Take H
2that O dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMAc and the 100 μ L triethylamines of 10mL wherein, in the logical nitrogen process of 20 minutes, add 30 μ L thioacetic acids, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 300mL, then use deionized water wash, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 11
Take H
2o dissolves, 100mg/mL graphene oxide solution 2mL, in 25mL flask, adds 10mL deionized water and 60 μ L triethylamines wherein, adds 30 μ L thioacetic acids in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 300mL, then use deionized water wash, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 12
Take H
2that O dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 300 μ L triethylamines wherein, in the logical nitrogen process of 20 minutes, add 30 μ L thioacetic acids, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 13
Take that DMSO dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMSO and the 100 μ L triethylamines of 10mL wherein, in the logical nitrogen process of 20 minutes, add 6 μ L thioacetic acids, at room temperature stirring reaction 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 14
Take that DMSO dissolves, powder size is that the 100mg/mL graphene oxide solution 2mL of 40 μm is in 25mL flask, add DMSO and the 100 μ L triethylamines of 10mL wherein, 60 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, at room temperature stirring reaction 3 days, obtains the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 15
Take that DMSO dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMSO and the 100 μ L triethylamines of 10mL wherein, in the logical nitrogen process of 20 minutes, add 6mg sodium thioglycolate, at room temperature stirring reaction 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 16
Take that DMSO dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMSO and the 100 μ L triethylamines of 10mL wherein, 70mg thioacetic acid potassium is added in the logical nitrogen process of 20 minutes, at room temperature stirring reaction 3 days, obtains the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 17
Take that DMSO dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMSO and the 100 μ L triethylamines of 10mL wherein, in the logical nitrogen process of 20 minutes, add 30 μ L propane thioic acids, at room temperature stirring reaction 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 18
Take that DMSO dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add DMSO and the 100 μ L triethylamines of 10mL wherein, 30mg propane thioic acid sodium is added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 2 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 19
Take that DMF dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, 30 μ L thio-octanoic acid are added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 20
Take that DMF dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, 40mg thio-octanoic acid potassium is added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 300mL, then use deionized water wash, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 21
Take that DMF dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, 2 of 30 μ L are added in the logical nitrogen process of 20 minutes, 2-dimethyl sulphur-based butyric acid, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 300mL, then use deionized water wash, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 22
Take that DMF dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, 2 of 40mg is added in the logical nitrogen process of 20 minutes, 2-dimethyl sulphur-based Sodium propanecarboxylate, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 600mL, then use deionized water wash, stir 12 hours, obtain sulfhydryl modified graphene oxide.
embodiment 23
Take that DMF dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, 30 μ L thiobenzoic acids are added in the logical nitrogen process of 20 minutes, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 300mL, then use deionized water wash, stir 12 hours, obtain sulfhydryl modified graphene oxide.
embodiment 24
Take that DMAc dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, 40mg thiobenzoic acid sodium is added in the logical nitrogen process of 20 minutes, stirring reaction 3 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 300mL, then use deionized water wash, stir 12 hours, obtain sulfhydryl modified graphene oxide.
embodiment 25
Take that DMAc dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, the 2-furans bamic acid of 30 μ L is added in the logical nitrogen process of 20 minutes, stirring reaction 3 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 3% dilute hydrochloric acid 300mL, then use deionized water wash, stir 12 hours, obtain sulfhydryl modified graphene oxide.
embodiment 26
Take that DMAc dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, the 2-furans bamic acid potassium of 40mg is added in the logical nitrogen process of 20 minutes, stirring reaction 3 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 27
Take that DMAc dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, the 3-trifluoromethyl thio phenyl first S-acid of 30 μ L is added in the logical nitrogen process of 20 minutes, stirring reaction 3 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 28
Take that DMAc dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, the 3-trifluoromethyl thio phenyl first S-acid sodium of 40mg is added in the logical nitrogen process of 20 minutes, stirring reaction 3 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 29
Take H
2that O dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, in the logical nitrogen process of 20 minutes, add 30 μ L thioacetic acids, 10 degrees Celsius of lower stirring reactions 7 days, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 30
Take H
2that O dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, in the logical nitrogen process of 20 minutes, add 30 μ L thioacetic acids, 70 degrees Celsius of lower stirring reactions 1 day, obtain the latent sulphur graphene oxide of thioesters modification.By the product deionized water wash obtained, stir 24 hours, obtain sulfhydryl modified graphene oxide.
embodiment 31
Take H
2that O dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, in the logical nitrogen process of 20 minutes, add 30 μ L thioacetic acids, 40 degrees Celsius of lower stirring reactions 3 days, obtain the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 5% dilute hydrochloric acid 600mL, then use deionized water wash, stir 12 hours, obtain sulfhydryl modified graphene oxide.
embodiment 32
Take that NMP dissolves, 100mg/mL graphene oxide solution 2mL is in 25mL flask, add 10mL deionized water and 100 μ L triethylamines wherein, 30 μ L thioacetic acids are added in the logical nitrogen process of 20 minutes, stirring reaction 3 days at 60 c, obtains the latent sulphur graphene oxide of thioesters modification.In the product obtained, add 1% dilute hydrochloric acid 100mL, then use deionized water wash, stir 12 hours, obtain sulfhydryl modified graphene oxide.
Claims (3)
1. a sulfhydryl modified graphene oxide, is characterized in that: sulfydryl grafts in graphene oxide laminated structure.
2. a preparation method for sulfhydryl modified graphene oxide according to claim 1, is characterized in that, comprise the following steps:
(1) graphene oxide is dissolved in H
2in O, DMF, DMSO, DMAc or NMP, be mixed with the graphene oxide solution that concentration is 5-300 mg/mL;
(2), after the solvent of the graphene oxide solution of 1 volume, 2 ~ 6 volumes, the triethylamine of 0.03 ~ 0.15 volume being mixed, 3 × 10 are added under nitrogen protection
-3~ 3 × 10
-2the thiocarboxylic acid of volume or add and 3 × 10
-3~ 3 × 10
-2the dithionate of the thiocarboxylic acid equivalent of volume; Under 10-70 degree Celsius, react 1-7 days, obtain the latent sulphur graphene oxide of thioesters modification; Described solvent is H
2o, DMF, DMSO, DMAc or NMP;
(3) the latent sulphur graphene oxide deionized water centrifuge washing of thioesters modification step 2 prepared, obtains sulfhydryl modified graphene oxide; Or after the latent sulphur graphene oxide of the thioesters modification prepared by 1 debulking step 2 mixes with the dilute hydrochloric acid (massfraction is 1-5%) of 50-300 volume, then use deionized water centrifuge washing, obtain sulfhydryl modified graphene oxide.
3. preparation method according to claim 2, it is characterized in that: described thiocarboxylic acid is thioacetic acid, propane thioic acid, thio-octanoic acid, 2, 2-dimethyl sulphur-based butyric acid, thiobenzoic acid, 2-furans bamic acid, 3-trifluoromethyl thio phenyl first S-acid, described dithionate is sodium thioglycolate, thioacetic acid potassium, propane thioic acid sodium, propane thioic acid potassium, thio-octanoic acid sodium, thio-octanoic acid potassium, 2, 2-dimethyl sulphur-based Sodium propanecarboxylate, 2, 2-dimethyl sulphur-based potassium butyrate, thiobenzoic acid sodium, thiobenzoic acid potassium, 2-furans bamic acid sodium, 2-furans bamic acid potassium, 3-trifluoromethyl thio phenyl first S-acid sodium or 3-trifluoromethyl thio phenyl first S-acid potassium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510006305.8A CN104556012B (en) | 2015-01-07 | 2015-01-07 | A kind of sulfhydryl modified graphene oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510006305.8A CN104556012B (en) | 2015-01-07 | 2015-01-07 | A kind of sulfhydryl modified graphene oxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104556012A true CN104556012A (en) | 2015-04-29 |
| CN104556012B CN104556012B (en) | 2016-04-27 |
Family
ID=53073220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510006305.8A Active CN104556012B (en) | 2015-01-07 | 2015-01-07 | A kind of sulfhydryl modified graphene oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104556012B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199018A (en) * | 2016-03-18 | 2017-09-26 | 绿琪（北京）生物科技有限公司 | A kind of dithiocarbamates chelating agent modified graphene oxide and preparation method thereof |
| CN107325590A (en) * | 2017-07-04 | 2017-11-07 | 武汉大学 | A kind of cable shielding layer material of modified sulfur-bearing graphene doping and its application |
| CN108815009A (en) * | 2018-07-18 | 2018-11-16 | 山东利特纳米技术有限公司 | A kind of hair conditioner and preparation method thereof of containing graphene-albumen composite material |
| CN117239123A (en) * | 2023-11-15 | 2023-12-15 | 湖南镕锂新材料科技有限公司 | Graphene anode material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108380177B (en) * | 2018-03-09 | 2020-10-27 | 浙江农林大学 | Preparation method of magnetic modified graphene oxide hydrogel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913592A (en) * | 2010-08-10 | 2010-12-15 | 浙江大学 | Covalent functionalization graphene and preparation method thereof |
| CN102923700A (en) * | 2012-11-30 | 2013-02-13 | 南京大学 | Preparation method of thiol-modified graphene |
| WO2014008363A1 (en) * | 2012-07-05 | 2014-01-09 | Brigham And Women"S Hospital, Inc. | Detection, capture and quatification of biological moieties from unprocessed bodily fluids using nanoplasmonic platform |
| CN103675066A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Preparation of sulfydryl graphene modified electrode and trace heavy metal detection method thereof |
-
2015
- 2015-01-07 CN CN201510006305.8A patent/CN104556012B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913592A (en) * | 2010-08-10 | 2010-12-15 | 浙江大学 | Covalent functionalization graphene and preparation method thereof |
| WO2014008363A1 (en) * | 2012-07-05 | 2014-01-09 | Brigham And Women"S Hospital, Inc. | Detection, capture and quatification of biological moieties from unprocessed bodily fluids using nanoplasmonic platform |
| CN102923700A (en) * | 2012-11-30 | 2013-02-13 | 南京大学 | Preparation method of thiol-modified graphene |
| CN103675066A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Preparation of sulfydryl graphene modified electrode and trace heavy metal detection method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 于璐洋等: "巯基功能化石墨烯修饰玻碳电极测定水中痕量重金属镉", 《天津工业大学学报》 * |
| 陈邵鹏等: "碳原子线巯基化的红外光谱研究", 《南京师大学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199018A (en) * | 2016-03-18 | 2017-09-26 | 绿琪（北京）生物科技有限公司 | A kind of dithiocarbamates chelating agent modified graphene oxide and preparation method thereof |
| CN107325590A (en) * | 2017-07-04 | 2017-11-07 | 武汉大学 | A kind of cable shielding layer material of modified sulfur-bearing graphene doping and its application |
| CN108815009A (en) * | 2018-07-18 | 2018-11-16 | 山东利特纳米技术有限公司 | A kind of hair conditioner and preparation method thereof of containing graphene-albumen composite material |
| CN117239123A (en) * | 2023-11-15 | 2023-12-15 | 湖南镕锂新材料科技有限公司 | Graphene anode material and preparation method thereof |
| CN117239123B (en) * | 2023-11-15 | 2024-01-12 | 湖南镕锂新材料科技有限公司 | Graphene anode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104556012B (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104556012B (en) | A kind of sulfhydryl modified graphene oxide and preparation method thereof | |
| Blum et al. | Advances in photochemical and electrochemical incorporation of sulfur dioxide for the synthesis of value-added compounds | |
| BRPI0416835A (en) | silica gel / metal composition of group i, methods for preparing it, and for producing hydrogen gas, birch reduction of an aromatic compound in the presence of an alkali metal, dehalogenation reaction and wurtz reaction of a halogenated organic compound. presence of alkali metal, and desulphurization reaction of an organic compound containing a sulfide bond in the presence of alkali metal | |
| ATE502972T1 (en) | PRODUCTION PROCESS AND PURIFICATION PROCESS FOR POLYARYLENE SULFIDE AND PURIFICATION PROCESS FOR THE ORGANIC SOLUTION USED | |
| HUP0105025A2 (en) | Zinc sulphide electroluminophores and method for production thereof | |
| CN102408885A (en) | Efficient sulfur solving agent for sulfur deposits in sulfur-containing gas well | |
| CN102816287B (en) | Organic polymer gelator and preparation method and application thereof | |
| Chen et al. | A facile “off–on” fluorescence sensor for pentachlorophenol detection based on natural N and S co-doped carbon dots from crawfish shells | |
| CN105199696A (en) | Novel efficient polyether amine sulfur solvent and preparation method thereof | |
| CN104261394B (en) | The preparation method of Graphene | |
| CN106957431A (en) | The preparation method of poly arylidene thio-ester | |
| Drabowicz et al. | Asymmetric oxidation of sulfides to sulfoxides catalyzed by β-cyclodextrin | |
| RU2006126112A (en) | METHOD FOR PRODUCING SORBENT FOR SEWAGE TREATMENT FROM HEAVY METALS | |
| CN105801459A (en) | One-pot method of preparing aryl sulfonic fluoroform thioester series compounds through one-pot method | |
| Li et al. | Solar-driven synchronous photoelectrochemical sulfur recovery and pollutant degradation | |
| BRPI0418064A (en) | procedure for obtaining electrolytic manganese from ferroalloy waste | |
| CN105111066B (en) | 3,5 dichlorobenzoyl chloride synthetic methods | |
| CN107501145B (en) | A kind of preparation method of disulfide compound | |
| CN104829506B (en) | The industrialized preparing process of high-purity 2-nitryl-4-thiamphenicol benzoic acid | |
| RU2008139418A (en) | METHOD FOR PRODUCING POLYSULFIDES, POLYSULFIDES AND THEIR APPLICATION | |
| CN103038243B (en) | The method that single fluoromethylation organic substrates prepares biological activity organic compound | |
| CN105692547B (en) | A kind of hydrogen manufacturing nano-device and preparation method thereof and a kind of hydrogen production process | |
| Herlem et al. | About the reaction between asphaltenes and fluorosulfuric acid | |
| JP4551722B2 (en) | Method for producing pentabromothiophenol | |
| CN117142993A (en) | Reversible recovery method and application of aromatic alkane asymmetric disulfide |
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 |